WO2018072746A1 - 聚酯组合物及其制备方法和应用 - Google Patents

聚酯组合物及其制备方法和应用 Download PDF

Info

Publication number
WO2018072746A1
WO2018072746A1 PCT/CN2017/107106 CN2017107106W WO2018072746A1 WO 2018072746 A1 WO2018072746 A1 WO 2018072746A1 CN 2017107106 W CN2017107106 W CN 2017107106W WO 2018072746 A1 WO2018072746 A1 WO 2018072746A1
Authority
WO
WIPO (PCT)
Prior art keywords
repeating unit
polyester
mol
weight
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/107106
Other languages
English (en)
French (fr)
Inventor
郑萃
祝桂香
刘立志
张伟
姚雪容
任敏巧
韩翎
任毅
陈楠
史颖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201610922101.3A external-priority patent/CN107974052B/zh
Priority claimed from CN201710703435.6A external-priority patent/CN109401213B/zh
Priority claimed from CN201710703875.1A external-priority patent/CN109401216B/zh
Priority claimed from CN201710703774.4A external-priority patent/CN109401215B/zh
Priority claimed from CN201710703901.0A external-priority patent/CN109401217B/zh
Priority claimed from CN201710702760.0A external-priority patent/CN109401211B/zh
Priority claimed from CN201710703232.7A external-priority patent/CN109401212B/zh
Priority claimed from CN201710703617.3A external-priority patent/CN109401214B/zh
Priority to CA3040988A priority Critical patent/CA3040988A1/en
Priority to JP2019520899A priority patent/JP7584219B2/ja
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to US16/343,711 priority patent/US11466151B2/en
Priority to EP17862862.4A priority patent/EP3530694A4/en
Publication of WO2018072746A1 publication Critical patent/WO2018072746A1/zh
Anticipated expiration legal-status Critical
Priority to JP2024130717A priority patent/JP2024155925A/ja
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices ; Anti-rape devices
    • A61F5/01—Orthopaedic devices, e.g. long-term immobilising or pressure directing devices for treating broken or deformed bones such as splints, casts or braces
    • A61F5/0102—Orthopaedic devices, e.g. long-term immobilising or pressure directing devices for treating broken or deformed bones such as splints, casts or braces specially adapted for correcting deformities of the limbs or for supporting them; Ortheses, e.g. with articulations
    • A61F5/0104—Orthopaedic devices, e.g. long-term immobilising or pressure directing devices for treating broken or deformed bones such as splints, casts or braces specially adapted for correcting deformities of the limbs or for supporting them; Ortheses, e.g. with articulations without articulation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/07—Stiffening bandages
    • A61L15/12—Stiffening bandages containing macromolecular materials
    • A61L15/125—Mixtures of macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/07—Stiffening bandages
    • A61L15/14—Use of materials characterised by their function or physical properties
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B71/00—Games or sports accessories not covered in groups A63B1/00 - A63B69/00
    • A63B71/08—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions
    • A63B71/10—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the head
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/08—Methods for forming porous structures using a negative form which is filled and then removed by pyrolysis or dissolution
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B71/00—Games or sports accessories not covered in groups A63B1/00 - A63B69/00
    • A63B71/08—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions
    • A63B71/12—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the body or the legs, e.g. for the shoulders
    • A63B71/1225—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the body or the legs, e.g. for the shoulders for the legs, e.g. thighs, knees, ankles, feet
    • A63B2071/125—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the body or the legs, e.g. for the shoulders for the legs, e.g. thighs, knees, ankles, feet for the knee
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0049—Heat shrinkable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to the field of polymer materials, and in particular to a polyester composition, a method for preparing the polyester composition, and a shape memory material, a 3D printed wire, a heat shrinkable sleeve, a functional layer, and a medical limb fixed.
  • a polyester composition a method for preparing the polyester composition
  • a shape memory material a 3D printed wire
  • a heat shrinkable sleeve a functional layer
  • a medical limb fixed Uses for stents, heat shrinkable films, nonwovens, and elastic fibers.
  • Shape memory materials are a special class of smart materials.
  • the heat-induced shape memory material undergoes the initial shaping, is deformed by an external force at a certain temperature, and can maintain the deformed shape after cooling; and after reheating, the original shape can be restored.
  • Shape memory type polymers have the advantages of easy processing, light weight, low operating temperature, and low cost, so they are often used in many high value-added industries. Shape memory type polymers are classified into two types: reversible and irreversible.
  • CN103160948A discloses a cross-linked shape memory polymer. Its deformation fixation rate is about 90-98%, the shape recovery rate is between 85-95%, and their maximum deformation rate is usually between 20% and 400%. The initial shape of such shape memory polymers is not repeatable and reproducible.
  • CN105504474A discloses a shape memory polymer having a shape recovery rate of 80-95%, a shape fixing rate of about 90-98%, and a maximum deformation rate of about 50%. Although such shape-memory polymers are initially reproducible, their shape recovery rate and shape retention ratio are often inferior to irreversible shape-memory polymers, and the maximum deformation rate is much worse.
  • 3D printing provides unlimited possibilities for the design and manufacture of complex shape products, and has received much attention in recent years.
  • 3D printing technology mainly includes selection Laser sintering (SLS), photocuring (SLA), fused deposition (FDM), etc.
  • SLS Selection Laser sintering
  • SLA photocuring
  • FDM fused deposition
  • FDM 3D printed wires on the market are still relatively limited, and the most important consumables on the market are ABS and PLA.
  • the flexible consumables on the market are mainly polyurethane (TPU) materials, such as the polyurethane (TPU) materials described in CN104845353A, or as in CN104004377A.
  • TPU composite as described.
  • the TPU material described in CN104845353A, the printing temperature suggested in the examples is 220 ° C or higher.
  • the TPU composite material described in CN104004377A is recommended to have a printing temperature of 240-260 °C.
  • the recommended printing temperature for commercially available FDM polyurethane wires is generally above 190 ° C, such as 190-250 ° C.
  • CN103333402A discloses a halogen-free and non-red phosphorus heat-shrinkable tube formulation which is obtained by crosslinking using ethylene-acetic acid hexene copolymer and magnesium hydroxide as main components.
  • PVDF polyvinylidene fluoride
  • thermoplastic casings as a type of disposable products with a large amount of consumption, have potential demand for biodegradable treatment methods.
  • CN101049729A discloses a preparation method of a PET heat shrinkable tube, the main component of which is poly
  • PET ethylene terephthalate
  • the ethylene terephthalate (PET) mixed polyester elastomer can be extruded without cross-linking during the preparation process, but the degradation of PET is still difficult.
  • CN1580092A discloses a copolyester and a method for forming a heat shrinkable sleeve using the copolyester.
  • the polyester used is a material containing ethylene glycol as a comonomer, and has good shrinkage properties, but still does not have Biodegradability.
  • the sports protective gear market it is mainly divided into soft protective gear and hard protective gear.
  • the inner layer of most common hard protective gears on the market is the same as the soft protective material. It is fixed by the cotton, spandex and elastic fabrics surrounding the body, and then combined with the upper layer EVA or Buffer materials such as polyurethane, the outermost layer usually uses PP or PE or ABS to provide impact and scratch resistance.
  • the advantage of this kind of sports protective gear is that the price is relatively cheap, and the disadvantage is that the fixing is not firm, it is easy to fall off or slip during the movement, or the wearing of the hard outer layer and the protected position of the body is uncomfortable.
  • the finished tooth guard materials are mainly rubber, polyvinyl chloride, polyvinyl acetate-polyethylene copolymer.
  • the finished tooth care is inexpensive, can not be modified according to individual needs, is uncomfortable to wear, easily causes nausea, affects exercise, and has gradually been eliminated.
  • semi-finished products formed in the mouth are divided into two categories, one is hard shell soft capsule protection.
  • One type of tooth is a thermoplastic polymer material.
  • the hard-shell soft-bag guard is made of an acrylic material and EVA in a hard shell (polyvinyl chloride), which acts as a soft capsule and is integrally mounted on the teeth.
  • thermoplastic polymer material is usually a polyvinyl acetate-polyethylene copolymer, which is heated by hot water and then contained in the mouth to form a synthetic type.
  • These two forms of guard can provide a degree of protection, but because of the low plasticity and short thermoplastic time, resulting in less comfortable wear and repeated heating and oral saliva, these products have a short life span.
  • thermoplastic type tooth guard is mentioned in US 005 339 832 A, in which an elastic body for absorbing energy is embedded in the mouthpiece, but the disadvantage is still that the plasticity is not strong.
  • teeth that can be accurately molded and have memory function are products that are urgently needed on the market.
  • US4376438 proposes a polyurethane-based bandage product, and there are many improved patents on polymer bandages in China, such as CN102397133B.
  • the advantage of its contrast with plaster bandages is that it is stronger and can be transmitted through X-rays and is lighter.
  • All polymer bandages utilize the isocyanate prepolymer which is rapidly polymerized or crosslinked after water to achieve a fixed purpose. Its operation still needs to be opened and immersed in water for multiple extrusions, and then quickly shape and entangle the affected area.
  • a heat shrinkable film is a film which can be significantly reduced in size after heating.
  • heat shrinkable film is widely used.
  • Commonly used heat shrinkable films are polyvinyl chloride film, non-crosslinked polyethylene blown film, polypropylene film, polystyrene film, PET and PETG film. Such films can achieve large shrinkage in one direction (up to 75%) while on the other The shrinkage of the orientation is small (only 1%).
  • composite film is also widely used in heat shrinkable films, mainly in the following two types: (1) POF film.
  • Such films are typically coextruded using a polypropylene/polyethylene/polypropylene three layer and blown up by a double bubble process.
  • a class of polyolefin films incorporating photodegradable agents is also claimed to be a degradable film, as described in CN106519400A, but such films are not fully degradable and intelligently break up the polyolefin into small pieces.
  • Current degradable films are those based on hydroxyalkanoates as described in CN 103483789A, and films based on polylactic acid as described in CN 103625061 B. However, their performance does not reach the general performance of the general heat shrinkable film as described above, thus limiting their promotion.
  • Disposable textile products are mainly made of non-woven fabrics.
  • the materials for disposable surgical gown materials commonly available on the market are as follows: polypropylene wood pulp composite spunlaced nonwoven fabric, as described in CN205800418U; polypropylene, polyhydroxybutyrate and polylactic acid multilayer composite materials, such as CN204398434U and CN105054444A; polyethylene film and SMS non-woven composite material, as described in CN204317582U; non-woven fabric with resin reinforcing sheet, as mentioned in CN105015128B.
  • the disposable surgical protective suit becomes a medical waste. Disposal of medical waste will cause secondary pollution.
  • Most of the materials currently on the market are difficult to recycle. Therefore, how to conveniently recycle disposable medical textile products becomes a pressing issue.
  • Elastic fiber is a general term for a class of fibers with high elasticity, low modulus and high elastic recovery. These elastic fibers are roughly classified into two types, one is an elastic fiber obtained by utilizing the elasticity of the material itself, for example, natural rubber fiber, polyurethane fiber (spandex), polyacrylate fiber, poly Butylene terephthalate (PBT) fiber, polyether ester elastomer (TPEE) fiber, polytrimethylene terephthalate (PTT) fiber, polyolefin (XLA) fiber.
  • the elasticity of such elastic fibers is mostly determined by the material itself.
  • polyacrylate fiber, PBT fiber and PTT fiber have low elasticity and only slight elasticity; natural rubber fiber has strong elasticity but weak strength and easy aging; polyurethane fiber has weak strength; polyether ester elastomer fiber Excellent comprehensive performance, wide range of performance adjustment, but the cost is too high; XLA fiber has good elasticity, good heat resistance, and good mechanical strength, but the performance is relatively fixed and the adjustability is insufficient.
  • the other type is a multifilament composite elastic fiber, which utilizes the difference in shrinkage of the two materials to produce a helical elasticity, typically T400 fiber. The elasticity of such fibers can be controlled by the manufacturing process, but the value of the elastic force caused by the spiral is very low, usually far less than the elasticity of the material itself.
  • Another object of the present invention is to provide a polyester composition which is made using the polyester composition
  • the 3D printed wire should be a flexible wire and print at low temperatures with high gloss and degradability.
  • Another object of the present invention is to provide a polyester composition which has a heat shrinkable sleeve which has good heat shrinkage properties and insulating properties, and which is in the process of preparation. It does not need cross-linking and has good degradability, so it has a broad market space.
  • Another object of the present invention is to provide a polyester composition which, when used in a sports brace, should be shaped according to the difference in the application site, so that the brace is more conformable and comfortable. It is easy to make; in addition, if the sports protective gear is worn or slightly damaged, it should be able to restore the original appearance by softening and softening again.
  • Another object of the present invention is to provide a polyester composition whose hardness should vary with time and temperature, in particular, it has a lower hardness at a higher temperature and a shorter time after cooling.
  • the hardness is obviously increased, showing good plasticity and fixability, and thus is particularly suitable for preparing a medical limb fixation stent.
  • Another object of the present invention is to provide a polyester composition
  • the heat-shrinkable film produced using the polyester composition should not only have a high heat shrinkage rate, but also have a heat shrinkage rate in a large range.
  • the change meets different requirements; and the heat-shrinkable film should have suitable heat-sealing strength, the film surface is flat, the gloss is good, it can be degraded and can be repeatedly thermoplastically processed and recovered.
  • Another object of the present invention is to provide a polyester composition
  • the nonwoven fabric made of the polyester composition should have good water absorption, gas permeability, and easy sterility, and in particular, the nonwoven fabric should It can be sterilized in hot water (such as 100 ° C) and shrinks greatly, so it can be easily compressed to a small volume, convenient for the recovery and reproduction of materials (especially disposable materials), and re-produced non-woven
  • the cloth has similar properties to the first-time non-woven fabric and is suitable for continuing as a raw material for disposable non-woven products (especially disposable medical textile products), thereby solving the problem of material recycling.
  • Another object of the present invention is to provide a polyester composition which is composed of an elastic fiber which has both moderate elasticity and strength and a wide range of properties.
  • the above object is achieved by a polyester composition comprising a specific aliphatic-aromatic copolyester.
  • the present invention provides the following aspects.
  • the present invention provides a polyester composition comprising:
  • a first polyester the amount of the first polyester being 50% by weight to 100% by weight, based on the total weight of the first polyester and the second polyester, preferably 51% by weight to 99% by weight, the first
  • the polyester is selected from one or more of an aliphatic-aromatic copolyester containing a repeating unit A represented by the formula (I) and a repeat represented by the formula (II) Copolymer of unit B,
  • the content of the repeating unit A is 51 to 95% by mole based on the total moles of the repeating unit A and the repeating unit B in the aliphatic-aromatic copolyester, and the content of the repeating unit B is 5-49 mol%, preferably the content of the repeating unit A is 55-80 mol% and the content of the repeating unit B is 20-45 mol%;
  • m is 2-10, preferably 2-6, more preferably 2-
  • An integer of 4 and n are integers from 2 to 8, preferably from 2 to 4;
  • p is an integer from 2 to 10, preferably from 2 to 4; and
  • m, n and p are the same or different from each other;
  • an optional second polyester the amount of the second polyester being up to 50% by weight, based on the total weight of the first polyester and the second polyester, preferably from 1% to 49% by weight, the second polymerization
  • the ester is selected from the group consisting of an aliphatic polyester, an aromatic polyester, and one or more of an aliphatic-aromatic copolyester different from the first polyester;
  • polyester composition comprises at least two polyesters.
  • the aliphatic polyester as the second polyester contains a repeat represented by the formula (I"') Unit D,
  • m3 is the same as defined above for m
  • n3 is the same as defined above for n
  • m3 and n3 are the same or different from each other
  • the aliphatic polyester has a weight average molecular weight of 50,000 to 900,000, preferably 100,000 to 500,000.
  • the weight average molecular weight was measured by gel permeation chromatography (GPC).
  • the aromatic polyester as the second polyester is composed of the repeating unit B represented by the formula (II).
  • the aliphatic-aromatic copolyester different from the first polyester as the second polyester is a repeating unit A represented by the formula (I) and a repeating unit B represented by the formula (II) Copolymer.
  • the weight average molecular weight of the aliphatic-aromatic copolyester containing the repeating unit A represented by the formula (I) and the repeating unit B represented by the formula (II) as the first polyester or the second polyester is 50,000-900,000, preferably 100,000-500,000, the weight average molecular weight is measured by gel permeation chromatography (GPC); preferably the molecular weight distribution is 1.2-3, as measured by GPC.
  • GPC gel permeation chromatography
  • the aliphatic-aromatic copolyester as the first polyester may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer; as the second polyester
  • the aliphatic-aromatic copolyester may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer.
  • the polyester composition of the present invention may additionally comprise one or more additives selected from the group consisting of nucleating agents, fibrous fillers, and having the accelerated composition melt solidification, adjusting the mechanical strength of the composition, adjusting the color and gloss of the composition, Auxiliary fillers which improve the flame retardancy, oxidation resistance and the like of the composition, and erucamide and/or white oil.
  • the auxiliary filler may be selected from the group consisting of carbonates, silicates, sulfates, inorganic hollow microspheres, metal powder, carbon black, talc, erucamide, titanium dioxide, iron oxide, Metal carboxylate, metal phosphate, tetrabromobisphenol A, decabromodiphenyl ether, hexabromocyclododecane, low density polyethylene, polyphosphate or salt, phosphite, hindered phenol, hindered amine, At least one of dibenzyl sorbitol and its derivatives, hyperbranched polyamide, ethylene-methacrylic acid ionomer, ethylene bis stearamide, silicone powder and pentaerythritol stearate, preferably at least two; Preferred are calcium carbonate, anhydrous calcium sulfate, copper powder, iron oxide, carbon black, titanium dioxide, tris(2,3-dibromopropyl) phosphate, low density
  • the nucleating agent may be selected from the group consisting of talc, calcium oxide, carbon black, calcium carbonate, inorganic pigments, kaolin, metal carboxylates, metal phosphates, dibenzyl sorbitol and derivatives thereof, and polyvinylcyclohexane.
  • an alkane preferably one or more of an alkane, a polyvinylcyclopentane, a low density polyethylene, a hyperbranched polyamide, and an ethylene-methacrylic acid ionomer; preferably calcium carbonate, low density polyethylene, dibenzyl sorbitol, and One or more of its derivatives and hyperbranched polyamides, preferably in an amount of from 0.01 to 20% by weight, preferably from 0.2 to 5, based on the total weight of the polyester composition %.
  • the fibrous filler may be one or more of carbon fiber, glass fiber, basalt fiber, aramid fiber, and PET fiber, preferably one or more of glass fiber, carbon fiber, and basalt fiber; preferably,
  • the fibrous filler has a length of from 0.1 to 10 mm, preferably from 0.5 to 2 mm.
  • the polyester composition according to the invention comprises
  • Polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1).
  • Polyester B which is a copolymer containing the repeating unit C represented by the formula (I") and the repeating unit B represented by the formula (II-1),
  • n1 and n2 are independently of each other the same as the definition of m above
  • n1 and n2 are independently of each other the same as the definition of n above
  • m1 and n1 are the same or different from each other
  • m2 and n2 are the same or different from each other
  • N1 is less than n2;
  • the content of the repeating unit B is from 5 to 49 mol%, preferably from 10 to 45 mol%, more preferably 20, based on the total moles of the polyester A, the polyester B and the aliphatic polyester. - 40 mol%.
  • the content of the repeating unit A is 51 to 90% by mole based on the total moles of the repeating unit A and the repeating unit B in the polyester A; and the content of the repeating unit B is 10 to 49% by mole. ;
  • the content of the repeating unit C is 40 to 95 mol%, preferably 50 to 90 mol%, based on the total number of moles of the repeating unit C and the repeating unit B in the polyester B; the content of the repeating unit B It is 5 to 60% by mole, preferably 10 to 50% by mole.
  • the molar ratio of the polyester A, the polyester B to the aliphatic polyester is from 20 to 90:1 to 90:1 to 20; preferably from 20 to 90:1 to 70:1 to 20.
  • the polyester composition according to the invention comprises, based on the total weight of the components, the following components:
  • polyester A which is a copolymer containing the repeating unit A represented by the formula (I-1) and the repeating unit B represented by the formula (II-1), and
  • the content of the repeating unit A based on the total number of moles of the repeating unit A and the repeating unit B in the polyester A Is 56-80 mol%, preferably 60-75 mol%; the content of the repeating unit B is 20-44 mol%, preferably 25-40 mol%;
  • a polyester B which is a copolymer containing the repeating unit C represented by the formula (I') and the repeating unit D represented by the formula (IV'), and Based on the total number of moles of repeating unit C and repeating unit D in the polyester B, the content of the repeating unit C is 81 to 99 mol%, preferably 85 to 95 mol%, and the content of the repeating unit D is 1-19 mol%, preferably 5-15 mol%,
  • n1 is the same as defined above for n
  • m1 and n1 are the same or different from each other
  • a1 is the same as defined above, and a1 and m1 are identical or different from each other;
  • the content of the repeating unit E is 0 to 55 mol%, preferably 15 to 50 mol%, and the content of the repeating unit F is 45-100 mol%, preferably 50-85 mol%,
  • n2 is the same as defined above for n
  • m2 and n2 are the same or different from each other
  • a2 is the same as defined above for p
  • a2 and m2 are the same or different from each other.
  • the polyester composition contains 70 to 94% by weight of polyester A, 3 to 25% by weight of polyester B and 3 to 20% by weight of polyester C.
  • the polyester composition according to the invention comprises, based on the total weight of the components, the following components:
  • the polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit A and the repeating unit B in the polyester A is based on the content of the repeating unit A of 51 to 70% by mole, preferably 55 to 68% by mole, of the content of the repeating unit B. 30 to 49 mol%, preferably 32 to 45 mol%,
  • n1 is the same as defined above for n
  • m1 and n1 are the same or different; preferably, m1 is an integer of 2-4, and n1 is an integer of 2-4, preferably 2 ;
  • polyester B which is a copolymer containing repeating unit C represented by formula (I") and repeating unit B represented by formula (II-1), and
  • the total number of moles of the repeating unit C and the repeating unit B in the polyester B is based on the content of the repeating unit C of 1 to 50% by mole, preferably 20 to 45% by mole, of the content of the repeating unit B. 50-99 mol%, preferably 55-80 mol%,
  • n2 is the same as defined above for n
  • m2 and n2 are the same or different; preferably, m2 is an integer of 2-4, and n2 is an integer of 2-4, preferably 2 .
  • the polyester composition contains 80 to 95% by weight of polyester A and 5 to 20% by weight of polyester B.
  • the polyester composition according to the invention comprises, based on the total weight of the components, the following components:
  • polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit A and the repeating unit B in the polyester A is based on the content of the repeating unit A being 55 to 79 mol%, preferably 60 to 77 mol%, and the content of the repeating unit B. Is 21 to 45 mol%, preferably 23 to 40 mol%,
  • n1 is the same as defined above for n
  • m1 and n1 are the same or different from each other; preferably, m1 is an integer of 2-4, and n1 is an integer of 2-4, preferably 4;
  • polyester B which is a copolymer containing repeating unit C represented by formula (I") and repeating unit B represented by formula (II-1), and
  • the total number of moles of the repeating unit C and the repeating unit B in the polyester B is based on the content of the repeating unit C of 80 to 100% by mole, preferably 85 to 95% by mole, of the content of the repeating unit B. 0-20 mol%, preferably 5-15 mol%,
  • n2 is the same as defined above for n
  • m2 and n2 are the same or different from each other; preferably, m2 is an integer of 2-4, and n2 is an integer of 2-4, preferably 2;
  • the polyester composition contains 60 to 90% by weight of polyester A, 5 to 30% by weight of polyester B and 5 to 30% by weight of fibrous filler.
  • the polyester composition according to the invention comprises, based on the total weight of the components, the following components:
  • polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit A and the repeating unit B in the polyester A is based on the content of the repeating unit A being 60-80% by mole, preferably 62-78% by mole, and the content of the repeating unit B. 20-40% by mole, preferably 22-38% by mole,
  • n1 is the same as defined above for n
  • n1 and n1 are the same or different from each other; preferably m1 is an integer of 2-4, n1 is an integer of 2-4, preferably n1 Is 2;
  • polyester B which is a copolymer containing repeating unit C represented by formula (I") and repeating unit B represented by formula (II-1), and
  • the total number of moles of the repeating unit C and the repeating unit B in the polyester B is based on the content of the repeating unit C of 20 to 59 mol%, preferably 30 to 55 mol%, and the content of the repeating unit B. 41-80 mol%, preferably 45-70 mol%,
  • n2 is the same as defined above for n
  • m2 and n2 are the same or different from each other; preferably, m2 is an integer of 2-4, and n2 is an integer of 2-4, preferably N2 is 2.
  • the polyester composition contains 70 to 90% by weight of polyester A and 10 to 30% by weight of polyester B.
  • the polyester composition according to the invention comprises, based on the total weight of the components, the following components:
  • polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit A and the repeating unit B in the polyester A is based on the content of the repeating unit A being 60-80% by mole, preferably 62-72% by mole, and the content of the repeating unit B. 20-40% by mole, preferably 28-38% by mole,
  • n1 is the same as defined above for n
  • m1 and n1 are the same or different from each other; preferably, m1 is an integer of 2-4, and n1 is an integer of 2-4; N1 is 2;
  • polyester B which is a copolymer containing repeating unit C represented by formula (I") and repeating unit B represented by formula (II-1), and
  • the total number of moles of the repeating unit C and the repeating unit B in the polyester B is based on the content of the repeating unit C of 81 to 99 mol%, preferably 85 to 97 mol%, and the content of the repeating unit B. 1-19 mol%, preferably 3-15 mol%,
  • n2 is the same as defined above for n
  • m2 and n2 are the same or different from each other; preferably, m2 is an integer of 2-4, and n2 is an integer of 2-4, preferably N2 is 2.
  • the polyester composition contains 60 to 90% by weight of polyester A and 10 to 40% by weight of polyester B.
  • the polyester composition according to the present invention contains the following components based on the total weight of each component:
  • polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit A and the repeating unit B in the polyester A is based on the content of the repeating unit A being 75 to 95% by mole, preferably 81 to 95% by mole, and the content of the repeating unit B. 5 to 25 mol%, preferably 5 to 19 mol%,
  • n1 is the same as defined above for n
  • m1 and n1 are the same or different from each other; preferably, m1 is an integer of 2-4, and n1 is an integer of 2-4; N1 is 2;
  • polyester B which is a copolymer containing repeating unit C represented by formula (I") and repeating unit B represented by formula (II-1), and
  • the total number of moles of the repeating unit C and the repeating unit B in the polyester B is based on the content of the repeating unit C of 20 to 74 mol%, preferably 40 to 70 mol%, and the content of the repeating unit B. 26-80 mol%, preferably 30-60 mol%,
  • n2 is the same as defined above for n
  • m2 and n2 are the same or different from each other; preferably, m2 is an integer of 2-4, and n2 is an integer of 2-4, preferably N2 is 2.
  • the polyester composition contains 55 to 70% by weight of polyester A and 30 to 45% by weight of polyester B.
  • the polyester composition according to the present invention contains the following components based on the total weight of each component:
  • the polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit A and the repeating unit B in the polyester A is based on the content of the repeating unit A of 51 to 80% by mole, preferably 60 to 75% by mole; the content of the repeating unit B 20 to 49 mol%, preferably 25 to 40 mol%,
  • n1 is the same as defined above for n
  • m1 and n1 are the same or different from each other; preferably, m1 is an integer of 2-8 and n1 is an integer of 2-6, more Preferably, m1 is an integer of 2-4 and n1 is an integer of 2-4;
  • polyester B which is a copolymer containing the repeating unit C represented by the formula (I") and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit C and the repeating unit B in the polyester B is based on the content of the repeating unit C of 81 to 99 mol%, preferably 83 to 95 mol%, and the content of the repeating unit B. 1-19 mol%, preferably 5-17 mol%,
  • n2 is the same as defined above for n
  • m2 and n2 are the same or different from each other; preferably, m2 is an integer of 2-8, and n2 is an integer of 2-6; Preferably, m2 is an integer of 2-4, and n2 is an integer of 2-4;
  • n3 is the same as defined above for n
  • n3 and n3 are the same or different from each other; preferably, m3 is an integer of 2-8, and n3 is an integer of 2-6; Preferably, m3 is an integer from 2 to 4, and n3 is an integer from 2 to 4.
  • the polyester composition contains 60 to 93% by weight of polyester A, 5 to 38% by weight of polyester B and 1 to 20% by weight of polyester C.
  • the present invention provides a method of preparing a polyester composition according to the present invention comprising blending all components including a first polyester and a second polyester, and subjecting the resulting mixture to extrusion granulation To obtain a polyester composition, preferably the process of blending does not add a compatibilizer.
  • the blending is carried out under agitation.
  • the extrusion granulation is carried out in a twin-screw extruder; preferably at a temperature of 80-270 ° C, preferably 110-220 ° C; a screw speed of 10-70 rpm and a torque of 2-80 N*m get on.
  • the invention provides the use of a polyester composition according to the invention in one or more of the following aspects: shape memory material, 3D printed wire, heat shrinkable sleeve, work Energy layer (for example, functional layer for sports protective gear), sports protective gear (such as dental protectors, limb joint protectors, body large area protectors and head protectors), medical limb fixation bracket, heat shrinkable film, no Woven fabrics and nonwoven fabric articles (especially disposable nonwoven fabric articles, more preferably disposable medical nonwoven fabric articles).
  • work Energy layer for example, functional layer for sports protective gear
  • sports protective gear such as dental protectors, limb joint protectors, body large area protectors and head protectors
  • medical limb fixation bracket such as dental protectors, limb joint protectors, body large area protectors and head protectors
  • heat shrinkable film no Woven fabrics and nonwoven fabric articles (especially disposable nonwoven fabric articles, more preferably disposable medical nonwoven fabric articles).
  • the invention provides a shape memory material comprising the polyester composition according to the first preferred embodiment described above.
  • the invention provides a 3D printed wire comprising the polyester composition according to the second preferred embodiment described above, preferably the 3D printed wire has a diameter of from 0.1 to 10 mm, preferably from 1 to 4 mm.
  • the present invention provides a method of preparing a 3D printed wire according to the present invention comprising sequentially subjecting a polyester composition to extrusion and cooling to obtain a 3D printed wire; preferably, the extrusion temperature is 90-260 ° C, cooling The temperature is 0-60 ° C.
  • the invention provides a heat shrinkable sleeve comprising the polyester composition according to the third preferred embodiment described above.
  • the present invention provides a method of making a heat shrinkable sleeve according to the present invention comprising sequentially subjecting a polyester composition to extrusion, drawing, cooling and styling to obtain a heat shrinkable sleeve; preferably, the temperature of the extrusion is 90-240 ° C, preferably 120-180 ° C; and the cooling temperature is 0-60 ° C, preferably 20-40 ° C.
  • the method further comprises sequentially heating, expanding, re-cooling and setting the cooled pipe; preferably, the heating temperature is 65-120 ° C, preferably 70-90 ° C; preferably, The magnification of the expanded diameter is 1.5 to 5 times, preferably 3-5 times the original size; preferably, the temperature of the secondary cooling is 0 to 60 ° C, preferably 20 to 40 ° C.
  • the invention provides a functional layer comprising a polyester composition according to the fourth preferred embodiment described above, preferably a functional layer for a sports brace.
  • the invention provides a method of preparing a functional layer according to the invention comprising shaping a polyester composition, wherein the molding is preferably by extrusion or injection molding; preferably, the injection molding
  • the temperature is from 140 to 270 ° C, preferably from 170 to 185 ° C.
  • the present invention provides a medical limb fixation stent comprising the polyester composition according to the above fifth preferred embodiment; preferably, the medical limb fixation stent has a thickness of 0.2 to 10 mm, preferably 1 to 3 mm; preferably, The medical limb fixation stent has and/or has no pore structure, preferably has a pore structure; more preferably, the pore structure has a pore size of from 1 to 10 mm, preferably from 1 to 5 mm.
  • the present invention provides a method of preparing a medical limb fixation stent according to the present invention, comprising sequentially subjecting a polyester composition to extrusion, shaping, and optional perforation to obtain a medical limb fixation stent; preferably, the extrusion
  • the temperature is 90-230 ° C, preferably 110-170 ° C; preferably, the molding is by injection molding and/or compression molding; preferably, the molding is such that the thickness of the medical limb fixing bracket is 0.2- 10 mm, preferably 1-3 mm; preferably, the perforator used for perforating has a diameter of from 1 to 10 mm, preferably from 1 to 5 mm.
  • the invention provides a heat shrinkable film comprising the polyester composition according to the sixth preferred embodiment described above.
  • the present invention provides a method of preparing a heat-shrinkable film according to the present invention, comprising sequentially casting a polyester composition into a film, standing and stretching to obtain a heat-shrinkable film; preferably, the casting is carried out
  • the temperature of the film is from 80 to 220 ° C, preferably from 110 to 180 ° C; preferably, the standing time is from 30 minutes to 20 days, preferably from 4 to 24 hours; preferably, the stretching is one-way drawing Stretching or biaxial stretching; preferably, the stretching is carried out at a temperature of from 40 to 150 ° C, preferably from 60 to 120 ° C.
  • the present invention provides a nonwoven fabric comprising the polyester composition according to the seventh preferred embodiment described above.
  • the present invention provides a method of preparing a nonwoven fabric according to the present invention comprising preparing a nonwoven fabric by a spunbonding method; preferably, the spunbonding method comprises extrusion, spinning, web forming, and The process of strengthening; preferably, the process of extruding comprises three temperature zones, the temperature of the first temperature zone is 140-250 ° C, the temperature of the second temperature zone is 150-260 ° C, and the temperature of the third temperature zone is 170-260 ° C; preferably, the spinning temperature is 150-240 ° C, the spinning rate is 10-40 r / min; preferably, the rate of the netting is 5-30 r / min; The reinforcement is in the form of hot rolling, and the hot rolling temperature is 80-170 °C.
  • the present invention provides an elastic fiber comprising the polyester composition according to the above eighth preferred embodiment; preferably, the elastic fiber has a fineness of 5 to 500 dtex; a breaking strength of 3 to 19 cN/dtex; and an elongation at break It is 130-620%; the stress relaxation rate is 1-12%; and the permanent strain rate is 1-11%.
  • the present invention provides a method of preparing an elastic fiber according to the present invention comprising sequentially passing a polyester composition through filament formation, low temperature placement and stretching to obtain an elastic fiber; preferably, the method of forming the filament is a melt Spinning; preferably, the temperature of the filament formation is 120-270 ° C, preferably 150-220 ° C; preferably, the conditions for the low temperature placement include: a temperature of 20-55 ° C, preferably 25-45 ° C; The time is 2-120 min, preferably 15-60 min; preferably, the conditions of the stretching include: a temperature of 56-110 ° C, preferably 60-90 ° C; a stretching ratio of 1.2-10 times, preferably 2 -5 times.
  • the invention also provides the use of an aliphatic-aromatic copolyester as the first polyester described above for use in one or more of the following aspects: shape memory material, 3D printed wire, heat shrinkage Casing, functional layer (for example, functional layer for sports protective gear), sports protective gear (such as dental protectors, limb joint protectors, body large protective gear and head protectors), medical limb fixation bracket, heat shrinkage Films, nonwovens and non-woven products (especially disposable non-woven products, more preferably disposable medical non-woven products).
  • functional layer for example, functional layer for sports protective gear
  • sports protective gear such as dental protectors, limb joint protectors, body large protective gear and head protectors
  • medical limb fixation bracket such as dental protectors, limb joint protectors, body large protective gear and head protectors
  • heat shrinkage Films such as nonwovens and non-woven products (especially disposable non-woven products, more preferably disposable medical non-woven products).
  • 1 is a cross-sectional view of a finished dental care article obtained in Example IV-10 of the present invention, wherein 1 is an oral upper molar sleeve, and 2 is an oral lower molar sleeve;
  • Figure 2 is a side perspective view of the finished tooth protector obtained in Example IV-10 of the present invention.
  • FIG. 3 is a side perspective view of the knee care product obtained in Example IV-11 of the present invention, wherein 1 is the inner layer of the knee brace, 2 is the middle layer of the knee brace, 3 is the outer layer of the knee brace, and 4 is the convex part on the outer surface of the knee brace;
  • FIG. 4 is a front perspective view of the knee care product obtained in Example IV-11 of the present invention, wherein 1 is the inner layer of the knee brace, 2 is the middle layer of the knee brace, 3 is the outer layer of the knee brace, and 4 is the outer surface of the knee brace.
  • Raised portion 1 is the inner layer of the knee brace
  • 2 is the middle layer of the knee brace
  • 3 is the outer layer of the knee brace
  • 4 is the outer surface of the knee brace.
  • Figure 5 is a front perspective view of the upper body protector obtained in Example IV-12 of the present invention.
  • Figure 6 is a cross-sectional view of the upper body protector obtained in Example IV-12 of the present invention, wherein 1 is the inner layer of the upper body brace, 2 is the middle layer of the upper body brace, and 3 is the outer layer of the upper body brace;
  • Figure 7 is a side perspective view of the finished helmet obtained in Example IV-13 of the present invention, wherein 1 is the outer layer of the helmet, 2 is the middle layer of the helmet, 3 is the inner layer of the helmet, and 4 is a buckle.
  • FIGS. 8 and 9 are diagrams showing an example of a medical limb fixing bracket of the present invention.
  • the polyester composition of the present invention can be used for shape memory materials, 3D printed wires, heat shrinkable sleeves, functional layers, medical limb fixing stents, heat shrinkable films, nonwoven fabrics, and elastic fibers.
  • the polyester compositions of the present invention are described below for different applications.
  • the present invention provides a polyester composition comprising:
  • Polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1).
  • Polyester B which is a copolymer containing the repeating unit C represented by the formula (I") and the repeating unit B represented by the formula (II-1),
  • n1 is an integer of 2-10
  • n1 is an integer of 2-8
  • m1 and n1 are the same or different
  • the weight average molecular weight of the polyester A is 50,000-900,000
  • m2 is an integer of 2-10
  • n2 is An integer of 2-8
  • m2 and n2 are the same or different
  • the polyester B has a weight average molecular weight of 50,000 to 900,000; and, n1 is less than n2; and the polyester A, the polyester B, and the fat
  • the content of the repeating unit B is from 5 to 49 mol% based on the total moles of the group polyester.
  • m1 is an integer from 2 to 6
  • n1 is an integer from 2 to 4
  • m1 and n1 are the same or different
  • the polyester A has a weight average molecular weight of 100,000 to 500,000
  • m2 is 2 to 6.
  • n2 is an integer from 2 to 4, and m2 and n2 are the same or different, the polyester B has a weight average molecular weight of 100,000 to 500,000; and, n1 is less than n2; and the polyester A, the polyester B
  • the content of the repeating unit B is from 5 to 49 mol%, preferably from 10 to 45 mol%, more preferably from 20 to 40 mol%, still more preferably from 25 to 40, based on the total moles of the aliphatic polyester. Molar%, or 35-45 mol%.
  • the weight average molecular weight of the polymer is measured by gel permeation chromatography (GPC).
  • the polyester A may be at least one of a random copolymer, an alternating copolymer, a block copolymer and a graft copolymer, preferably a random copolymer and/or a block copolymer.
  • the source of the polyester A of the present invention is not particularly limited and can be obtained by a conventional means in the art, for example, commercially available, or can be produced according to the method disclosed in CN100429256C.
  • the preparation method of the polyester A may include the steps of: adding 1,4-butanediol, dimethyl benzoate, and a catalyst as described in US11312373 to a reactor, heating and stirring under a nitrogen atmosphere. Until a clear solution is obtained.
  • the polyester B may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, preferably a random copolymer and/or a block copolymer.
  • the source of the polyester B of the present invention is not particularly limited and can be obtained by a conventional means in the art, for example, commercially available, or can be produced by the method disclosed in CN100429256C.
  • the preparation method of the polyester B may include the steps of: adding 1,4-butanediol, dimethyl benzoate, and a catalyst as described in US11312373 to a reactor, heating and stirring under a nitrogen atmosphere. Until a clear solution is obtained.
  • the temperature was raised to 160-220 ° C to react.
  • adipic acid is added and the temperature is raised to 180-240 °C.
  • Most of the water was distilled off, and then the vacuum was slowly added, and the temperature was raised to 220-280 ° C. After 3-6 hours, the reaction was completed to obtain a product.
  • the content of the repeating unit A may be 40 to 95 mol%, preferably 45 to 90 mol%, more preferably based on the total number of moles of the repeating unit A and the repeating unit B in the polyester A. 45 to 70 mol%; the content of the repeating unit B may be 5 to 60 mol%, preferably 10 to 55 mol%, more preferably 30 to 55 mol%;
  • the content of the repeating unit C may be 40 to 95 mol%, preferably 50 to 90 mol%, more preferably 50 to 80, based on the total number of moles of the repeating unit C and the repeating unit B in the polyester B.
  • the molar unit content of the repeating unit B may be 5 to 60% by mole, preferably 10 to 50% by mole, more preferably 20 to 50% by mole.
  • the molar ratio of the polyester A, the polyester B and the aliphatic polyester may be from 20 to 90:1 to 90:1 to 20; preferably from 20 to 90:1 to 70:1. -20.
  • the kind and source of the aliphatic polyester are not particularly limited, and may be an aliphatic polyester conventionally used in the art.
  • the aliphatic polyester contains the repeating unit D represented by the formula (I"'),
  • m3 is an integer of from 2 to 10
  • n3 is an integer of from 2 to 8
  • m3 and n3 are the same or different
  • the aliphatic polyester has a weight average molecular weight of from 50,000 to 900,000; more preferably, m3 is from 2 to 6
  • An integer of n3 is an integer from 2 to 4, and m3 and n3 are the same or different, and the aliphatic polyester has a weight average molecular weight of 100,000, 500,000.
  • the aliphatic polyester can be obtained by a conventional means, for example, commercially available (for example, from BASF, under the designation 1111HTA4), or can be produced according to the method disclosed in CN104039865B, wherein The type of the reaction raw material can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of each repeating unit in the product are separately controlled by adjusting the amount of feed and the ratio of feed.
  • a conventional means for example, commercially available (for example, from BASF, under the designation 1111HTA4), or can be produced according to the method disclosed in CN104039865B, wherein
  • the type of the reaction raw material can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of each repeating unit in the product are separately controlled by adjusting the amount of feed and the ratio of feed.
  • the polyester composition may further comprise a nucleating agent; the nucleating agent is present in an amount of from 0.01 to 20% by weight, preferably from 0.01 to 10% by weight, based on the total weight of the polyester composition It is more preferably 0.2 to 5% by weight, still more preferably 1 to 5% by weight.
  • the nucleating agent may be a conventional choice in the art, and the nucleating agent may be selected from the group consisting of talc, calcium oxide, carbon black, calcium carbonate, and inorganic pigments (for example, purchased from Guangzhou Yingyi Plastic Pigment Co., Ltd.).
  • Yellow or green pigment Yellow or green pigment
  • kaolin metal carboxylate, metal phosphate, dibenzyl sorbitol and its derivatives, polyvinylcyclohexane, polyvinylcyclopentane, low density polyethylene, hyperbranched polyamide And one or more of ethylene-methacrylic acid ionomers; preferably one or more of calcium carbonate, low density polyethylene, dibenzyl sorbitol and derivatives thereof and hyperbranched polyamide; more preferably It is calcium carbonate and/or low density polyethylene.
  • the polyester composition may further contain other additives, for example, erucamide and/or white oil may also be contained.
  • the present invention also provides a method for preparing a polyester composition, which comprises: mixing polyester A, polyester B and aliphatic polyester, and extruding the obtained mixture to obtain a polyester combination. Things.
  • the above method may further comprise: a process of mixing the polyester A, the polyester B, the aliphatic polyester, and the nucleating agent in the presence of a nucleating agent and optionally other additives, wherein Other additives may be erucamide and/or white oil.
  • the mixing can be carried out under agitation; the agitation rate can be 6-60 rpm, and the agitation time can be 2-30 min.
  • the extrusion granulation process can be carried out according to a conventional extrusion granulation method, for example, the extrusion granulation can be carried out in a twin-screw extruder; preferably, the extrusion granulation Conditions include: a temperature of 160-220 ° C, a screw speed of 10-70 rpm, and a torque of 2-80 N*m; more preferably, the twin-screw extruder includes six temperature sections, and from the feed port to the extrusion The temperature of each section of the outlet is 160-190 ° C, 170-200 ° C, 180-210 ° C, 180-220 ° C, 180-220 ° C, 170-210 ° C.
  • the invention also provides for the use of the above polyester compositions in shape memory materials.
  • the present invention obtains a polyester composition suitable for use as a shape memory material by copolymerizing and blending polybutylene terephthalate (PBT).
  • the polyester composition is used for a shape memory material, and the shape fixing rate and the shape recovery rate of the shape memory material are both 92% or more, close to 100%, and the maximum deformation rate is as high as 400% or more.
  • the initial shaping temperature and the starting temperature of the shape memory material can be adjusted, which will be more advantageous for its application in daily life.
  • the present invention provides a polyester composition comprising the following components based on the total weight of each component:
  • the polyester A which is a copolymer containing the repeating unit A represented by the formula (I-1) and the repeating unit B represented by the formula (II-1), and
  • the content of the repeating unit A is 56-80 mol%, preferably 60-75 mol%, based on the total moles of the repeating unit A and the repeating unit B in the polyester A;
  • the repeating unit B The content is 20-44 Molar%, preferably 25-40 mol%;
  • the polyester A has a weight average molecular weight of 50,000-900,000, preferably 100,000-500,000;
  • a polyester B which is a copolymer containing the repeating unit C represented by the formula (I') and the repeating unit D represented by the formula (IV'), and Based on the total number of moles of repeating unit C and repeating unit D in the polyester B, the content of the repeating unit C is 81 to 99 mol%, preferably 85 to 95 mol%, and the content of the repeating unit D is 1-19 mol%, preferably 5-15 mol%,
  • the content of the repeating unit E is 0 to 55 mol%, preferably 15 to 50 mol%, and the content of the repeating unit F is 45-100 mol%, preferably 50-85 mol%,
  • m2 is an integer of 2-10, preferably an integer of 2-4; n2 is an integer of 2-8, preferably an integer of 2-4; and m2 and n2 are the same or different; a2 is an integer of 2-10, It is preferably an integer of 2 to 4; and a2 is the same as or different from m2, preferably the same; the polyester C has a weight average molecular weight of 50,000 to 900,000, preferably 100,000 to 500,000.
  • m1 and m2 may be the same or different, and n1 and n2 may be the same or different. However, when m1 and m2 are the same and n1 and n2 are also the same, the content of the repeating unit D in the polyester B is different from the content of the repeating unit F in the polyester C.
  • the polyester composition contains 70 to 94% by weight of polyester A, 3 to 25% by weight of polyester B and 3 to 20% by weight of polyester C.
  • the polyester A, the polyester B and the polyester C may each be at least one of a random copolymer, an alternating copolymer, a block copolymer and a graft copolymer, preferably It is a random copolymer and/or a block copolymer.
  • the source of the polyester A, the polyester B, and the polyester C is not particularly limited, and may be obtained by a conventional means in the art, commercially available, or may be in accordance with the embodiment of CN100429256C.
  • the method disclosed in B13-B21 is prepared. Specifically, the preparation method of the polyester A may include the following steps:
  • the preparation method of the polyester A comprises the following steps:
  • A' is terephthalic acid and/or an ester thereof, preferably at least one of terephthalic acid, dimethyl terephthalate and diethyl terephthalate; said first catalyst and The second catalyst is as described above and will not be described herein.
  • the molar ratio of the monomer A' to the first catalyst is 1:0.0001-0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003 .
  • the molar ratio of the first catalyst to the second catalyst is from 1:0.5 to 1.5, preferably from 1:0.8 to 1.2.
  • the kinds of the respective reactive monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of each repeating unit in the product are separately controlled by adjusting the amount of the feed and the ratio of the feed.
  • the temperature of the reaction in the step (S1), is preferably from 160 to 220 ° C; in the present invention, in the step (S2), the temperature of the reaction is preferably from 180 to 240 °C.
  • the preparation method of the polyester B comprises the following steps:
  • the monomer A is a C2-C8 diol (particularly a saturated linear diol);
  • the monomer B is terephthalic acid and/or an ester thereof, preferably terephthalic acid, At least one of dimethyl phthalate and diethyl terephthalate;
  • the monomer C is a C2-C10 diol (particularly a saturated linear diol); a C4-C10 dibasic acid (particularly a saturated linear dibasic acid);
  • the first catalyst being at least one of tetrabutyl titanate, titanium dioxide, diethoxy titanium and zinc acetate, preferably titanic acid Tetrabutyl ester;
  • the second catalyst is at least one of cerium acetylacetonate, cerium trichloride, triphenyloxy cerium and cerium propionate, preferably cerium acetylacetonate.
  • the molar ratio of the monomer B to the first catalyst is 1:0.0001-0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003.
  • the molar ratio of the monomer D to the first catalyst is 1:0.0001-0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003.
  • the total amount of the first catalyst (the sum of the amounts of the first catalysts in the step (1) and the step (2)) and the amount of the second catalyst are 1:0.5 - 1.5, preferably 1:0.8-1.2.
  • the kinds of the respective reactive monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of each repeating unit in the product are separately controlled by adjusting the amount of the feed and the ratio of the feed.
  • the temperature of the reaction in the step (1), is preferably 160-220 ° C; in the present invention, in the step (2), the temperature of the reaction is preferably 160-220 ° C; In the invention, in the step (3), the temperature of the reaction is preferably from 180 to 240 °C.
  • the polyester C can also be carried out in accordance with the above-mentioned preparation method of the polyester B, wherein the kinds of the respective reactive monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and by adjusting the amount of charge and the ratio of feed ratio The molecular weight of the product and the content of each repeating unit in the product were separately controlled to obtain a polyester C.
  • the polyester composition may further contain an auxiliary filler; preferably, the auxiliary filler is contained in an amount of from 0.1 to 50% by weight, more preferably 1 based on the total weight of the polyester composition. 25 wt%.
  • the auxiliary filler has the functions of accelerating the melt solidification of the composition, adjusting the mechanical strength of the composition, improving the flame retardancy, oxidation resistance, and adjusting the color and gloss of the composition, and can be conventional in the art.
  • the auxiliary filler is selected from the group consisting of calcium carbonate, carbon black, talc, erucamide, titanium dioxide, iron oxide, metal carboxylate, metal phosphate, tetrabromobisphenol A, decabromodiphenyl ether, and six Bromocyclododecane, low density polyethylene, polyphosphate or salt, phosphite, hindered phenol, hindered amine, dibenzyl sorbitol and its derivatives, hyperbranched polyamide, ethylene-methacrylic acid ionomer At least one of ethylene bis stearamide, silicone powder and pentaerythritol stearate; preferably calcium carbonate, carbon black, titanium dioxide, phosphoric acid tris(2,3- At least one of dibromopropyl)ester, low density polyethylene, hyperbranched polyamide, ethylene bis stearamide, and erucamide.
  • the present invention also provides a process for producing the above polyester composition, which comprises blending polyester A, polyester B and polyester C, and subjecting the resulting mixture to extrusion granulation.
  • the inventors unexpectedly found during the research that the polyester A, the polyester B and the polyester C have good compatibility, and therefore, no compatibilizer may be added during the blending.
  • the compatibilizer is a substance conventionally used in the art for improving the compatibility of a blending raw material, and for example, may be PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g- At least one of MAH and PP-g-MAH.
  • the process of blending can be carried out under agitation.
  • the conditions of the agitation of the present invention are not particularly limited as long as the raw materials can be uniformly mixed.
  • the stirring rate is 20-150 r/min, and the stirring time is 5-15 min.
  • the extrusion granulation process can be carried out in accordance with a conventional extrusion granulation method, for example, the extrusion granulation can be carried out in a screw extruder.
  • the temperature of the extrusion granulation is from 90 to 260 ° C, preferably from 110 to 180 ° C.
  • the present invention also provides a 3D printed wire comprising the above polyester composition, that is, the 3D printed wire is produced from the above polyester composition.
  • the 3D printed wire may have a diameter of from 0.1 to 10 mm, preferably from 1 to 4 mm.
  • the present invention also provides a method for preparing a 3D printed wire, the preparation method comprising: sequentially extruding and cooling a polyester composition to obtain a 3D printed wire; wherein the polyester composition is the above polyester combination Things.
  • the extrusion can be carried out using conventional extrusion methods, for example, the extrusion process can be carried out in a screw extruder.
  • the extrusion process is carried out in an extruder with a round hole die to obtain a 3D printed wire; more preferably, the resulting 3D printed wire has a diameter of 0.1 to 10 mm, preferably 1-4mm.
  • the extrusion temperature is from 90 to 260 °C.
  • the cooling temperature is from 0 to 60 °C.
  • the present invention comprises a specific polyester A, polyester B and polyester C according to a specific ratio (51-98% by weight of polyester A, 1-48% by weight of polyester B, 1-48% by weight of poly
  • the ester C) is blended to obtain a polyester composition which is made into a 3D printed wire with high gloss and can be printed at a lower temperature (105-165 ° C);
  • the 3D printed wire can be used as a flexible wire (Shore D hardness of 35-50), and can be degraded, and has good environmental advantages and application prospects.
  • the present invention provides a polyester composition comprising the following components based on the total weight of each component:
  • the polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit A and the repeating unit B in the polyester A is based on the content of the repeating unit A of 51 to 70% by mole, preferably 55 to 68% by mole, of the content of the repeating unit B. 30 to 49 mol%, preferably 32 to 45 mol%,
  • n1 is an integer from 2 to 4, preferably 2; and m1 and n1 are the same or different, and the polyester A has a weight average molecular weight of 50,000 to 900,000, preferably 100,000 to 500,000;
  • polyester B which is a copolymer containing repeating unit C represented by formula (I") and repeating unit B represented by formula (II-1), and
  • the content of the repeating unit C is from 1 to 50 mol%, preferably from 20 to 45 mol%, and the content of the repeating unit B is from 50 to 99 mol%, Preferably it is 55-80 mol%,
  • m1 and m2 may be the same or different, and n1 and n2 may be the same or different. However, when m1 and m2 are the same and n1 and n2 are also the same, the content of the repeating unit B in the polyester A is different from the content of the repeating unit B in the polyester B.
  • the polyester composition contains 80 to 95% by weight of polyester A and 5 to 20% by weight of polyester B.
  • the composition of the polymer is determined by the amount of the raw material charged.
  • the polyester A and the polyester B may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, preferably a random copolymer and/or Or block copolymer.
  • the present invention is not particularly limited in the source of the polyester A and the polyester B, and can be obtained by a conventional means in the art, commercially available, or can be disclosed in accordance with the method disclosed in Example B13-B21 of CN100429256C. Prepared. Specifically, the preparation method of the polyester A may include the following steps:
  • the monomer A is butanediol; the monomer B is terephthalic acid and/or an ester thereof, preferably terephthalic acid, dimethyl terephthalate and diethyl terephthalate At least one of the monomers C is a C2-C4 diol (particularly a saturated linear diol); the monomer D is a C4-C6 dibasic acid (especially a saturated linear two)
  • the first catalyst is at least one of tetrabutyl titanate, titanium dioxide, titanium diethoxyoxide and zinc acetate, preferably tetrabutyl titanate; the second catalyst is cesium acetylacetonate, At least one of barium trichloride, triphenyloxyanthracene and cesium propionate is preferably cesium acetylacetonate.
  • the molar ratio of the monomer B to the first catalyst is 1:0.0001-0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003.
  • the molar ratio of the monomer D to the first catalyst is 1:0.0001-0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003.
  • the total amount of the first catalyst (the sum of the amounts of the first catalysts in the step (1) and the step (2)) and the amount of the second catalyst are 1:0.5 - 1.5, preferably 1:0.8-1.2.
  • the kinds of the respective reactive monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of each repeating unit in the product are separately controlled by adjusting the amount of the feed and the ratio of the feed.
  • the temperature of the reaction in the step (1), is preferably 160-220 ° C; in the present invention, in the step (2), the temperature of the reaction is preferably 160-220 ° C; In the invention, in the step (3), the temperature of the reaction is preferably from 180 to 240 °C.
  • the preparation method of the polyester A comprises the following steps:
  • A' is terephthalic acid and/or an ester thereof, preferably at least one of terephthalic acid, dimethyl terephthalate and diethyl terephthalate; monomer B' is C4- a dibasic acid of C6 (particularly a saturated linear dibasic acid); the first catalyst and the second catalyst are as described above and will not be further described herein.
  • the molar ratio of the monomer A' to the first catalyst is 1:0.0001-0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003 .
  • the molar ratio of the first catalyst to the second catalyst is from 1:0.5 to 1.5, preferably from 1:0.8 to 1.2.
  • the kinds of the respective reactive monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of each repeating unit in the product are separately controlled by adjusting the amount of the feed and the ratio of the feed.
  • the temperature of the reaction in the step (S1), is preferably from 160 to 220 ° C; in the present invention, in the step (S2), the temperature of the reaction is preferably from 180 to 240 °C.
  • the polyester B can be carried out according to the above-mentioned preparation method of the polyester A, wherein the kinds of the respective reactive monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the amount of the feed and the ratio of the feed ratio can be adjusted respectively.
  • the molecular weight of the product and the content of each repeating unit in the product are controlled to obtain polyester B.
  • the polyester composition may further contain an auxiliary filler; preferably, the auxiliary filler is contained in an amount of from 0.1 to 60% by weight, more preferably 1 based on the total weight of the polyester composition. 20% by weight.
  • the auxiliary filler has a function of adjusting the mechanical strength of the composition, improving the flame retardancy, oxidation resistance of the composition, adjusting the color and gloss of the composition, and the like, and can be a conventional choice in the art, for example,
  • the auxiliary filler may be selected from the group consisting of calcium carbonate, carbon black, talc, erucamide, titanium dioxide, iron oxide, metal carboxylate, metal phosphate, tetrabromobisphenol A, decabromodiphenyl ether, and hexabromocyclohexane.
  • TDBPP tris(2,3-dibromopropyl) phosphate
  • the present invention also provides a process for producing the above polyester composition, which comprises blending the above polyester A with polyester B, and subjecting the resulting mixture to extrusion granulation.
  • the inventors unexpectedly found during the research that the polyester A has good compatibility with the polyester B, and therefore, no compatibilizer may be added during the blending process.
  • the compatibilizer is a substance conventionally used in the art for improving the compatibility of a blending raw material, and for example, may be PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g- At least one of MAH and PP-g-MAH.
  • the process of blending is as described above.
  • the agitation rate is from 20 to 150 r/min and the agitation time is from 5 to 15 min.
  • the extrusion granulation process is as described above.
  • the temperature of the extrusion granulation is from 160 to 220 ° C;
  • the rotation speed of the screw of the screw extruder is from 10 to 70 rpm; and
  • the torque of the screw is from 2 to 80 N*m.
  • the present invention also provides a heat shrinkable sleeve comprising the above polyester composition and/or the polyester composition obtained by the above preparation method, that is, the heat shrinkable sleeve is composed of the above polyester combination And/or a polyester composition obtained by the above production method.
  • the heat shrinkable sleeve may have a thickness of 0.3 to 10 mm, a shrinkage ratio of 5:1 to 4.5, good insulation, and a breakdown strength of ⁇ 25 kV/mm.
  • the present invention also provides a method for preparing a heat shrinkable sleeve, the method comprising: sequentially extruding, drawing, cooling, and shaping a polyester composition to obtain a heat shrinkable sleeve; wherein the polyester combination
  • the composition is the above polyester composition.
  • the extrusion process is carried out on a screw extruder equipped with a die and a mandrel. More preferably, the temperature of the extrusion is from 90 to 240 ° C, further preferably from 120 to 180 ° C.
  • the cooling may be carried out at a temperature of 0 to 60 ° C, preferably 20 to 40 ° C.
  • the preparation method further comprises: sequentially heating, expanding, re-cooling, and shaping the cooled pipe.
  • the heating temperature is 65-120 ° C, more preferably 70-90 ° C.
  • the magnification of the expanded diameter is preferably 1.5 to 5 times, more preferably 3-5 times, the original size (i.e., before the diameter expansion).
  • the temperature of the secondary cooling may be 0 to 60 ° C, preferably 20 to 40 ° C.
  • the present invention provides a polyester composition comprising the following components based on the total weight of each component:
  • polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit A and the repeating unit B in the polyester A is based on the content of the repeating unit A being 55 to 79 mol%, preferably 60 to 77 mol%, and the content of the repeating unit B. Is 21 to 45 mol%, preferably 23 to 40 mol%,
  • n1 is an integer of 2-4, preferably 4; and m1 and n1 are the same or different; and the polyester A has a weight average molecular weight of 50,000 to 900,000, preferably 100,000-500,000;
  • polyester B which is a copolymer containing repeating unit C represented by formula (I") and repeating unit B represented by formula (II-1), and
  • the total number of moles of the repeating unit C and the repeating unit B in the polyester B is based on the content of the repeating unit C of 80 to 100% by mole, preferably 85 to 95% by mole, of the content of the repeating unit B. 0-20 mol%, preferably 5-15 mol%,
  • m1 and m2 may be the same or different, and n1 and n2 may be the same or different. However, when m1 and m2 are the same and n1 and n2 are also the same, the content of the repeating unit B in the polyester A is different from the content of the repeating unit B in the polyester B.
  • the content of the repeating unit B in the polyester A is greater than the content of the repeating unit B in the polyester B.
  • the polyester composition contains 60 to 90% by weight of polyester A, 5 to 30% by weight of polyester B and 5 to 30% by weight of fibrous filler.
  • the polyester A and the polyester B may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, preferably a random copolymer and/or Or block copolymer.
  • the source of the polyester A and the polyester B in the present invention is not particularly limited, and the source and preparation method are as described above.
  • the fiber filler may be one or more of carbon fiber, glass fiber, basalt fiber, aramid fiber and polyethylene terephthalate fiber, preferably glass fiber, carbon fiber. And one or more of basalt fibers.
  • the fibrous filler has a length of from 0.1 to 10 mm, preferably from 0.5 to 2 mm.
  • the polyester composition may further comprise an auxiliary filler; preferably, the auxiliary filler is present in an amount of from 0.1 to 25% by weight, more preferably 1 - based on the total weight of the polyester composition 20% by weight.
  • the auxiliary filler has an effect of accelerating the melt solidification of the composition, adjusting the mechanical strength of the composition, adjusting the color and gloss of the composition, and the like, and may be a conventional choice in the art, for example, the auxiliary filler may be carbonic acid.
  • a salt inorganic filler, a silicate inorganic filler, a sulfate inorganic filler, an inorganic hollow microsphere, and a metal powder preferably a carbonate inorganic filler, a silicate inorganic filler, sulfuric acid
  • One or more of the salt inorganic filler and the metal powder are more preferably at least one of anhydrous calcium sulfate, calcium carbonate and copper powder.
  • the present invention also provides a process for producing the above polyester composition, which comprises blending polyester A, polyester B and a fibrous filler, and subjecting the resulting mixture to extrusion granulation.
  • the inventors unexpectedly found during the research that the polyester A, the polyester B and the fibrous filler have good compatibility, and therefore, no compatibilizer may be added during the blending.
  • the compatibilizer is a substance conventionally used in the art for improving the compatibility of a blending raw material, and for example, may be PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g- At least one of MAH and PP-g-MAH.
  • the process of blending is as described above.
  • the agitation rate is from 20 to 150 r/min and the agitation time is from 5 to 15 min.
  • the extrusion granulation process is as described above.
  • the temperature of the extrusion granulation is from 120 to 240 ° C, preferably from 150 to 200 ° C.
  • the present invention also provides a functional layer, wherein the functional layer contains the above polyester composition, that is, the functional layer is produced from the above polyester composition.
  • the functional layer has low temperature plasticity and shape memory, specifically, under the condition of T 1 (80 to 100 ° C), the functional layer has a Shore D hardness value of 0-35; Under the condition of 2 (-20 to 50 ° C), the functional layer has a Shore D hardness value of 40-80. That is to say, the functional layer can be softened under the condition of T 1 (80 to 100 ° C), and it can be shaped by applying an external force to obtain a desired shape, and after the shaping is completed, the temperature is lowered to T 2 ( Under the condition of -20 to 50 ° C), the hardness of the functional layer is increased to maintain the shape.
  • the present invention also provides a method for preparing a functional layer, which comprises: molding the above polyester composition.
  • the shaping can be by extrusion or injection molding, preferably injection molding.
  • the temperature of the injection molding is from 140 to 270 ° C, preferably from 170 to 185 ° C.
  • the invention also provides the above polyester composition and the above functional layer in the sports protective device; preferably, the sports protective device is a dental protector, a limb joint protector, a body large area protector and a head protector One or more of them.
  • the term "teeth protector” refers to a protector that protects the teeth during exercise.
  • the dental shield may contain the functional layer, preferably consisting of the functional layer.
  • the dental protector has low temperature plasticity and shape memory, specifically, under the condition of T 1 (80 ⁇ 100 ° C), the tooth protector has a Shore D hardness value of 0-35; The tooth protector has a Shore D hardness value of 40-80 under conditions of T 2 (-20 to 50 ° C).
  • the present invention also provides a method for preparing the dental protector, the preparation method comprising sequentially softening, shaping and cooling the functional layer provided by the present invention.
  • the preparation method comprises: the functional layer in the T Soften under conditions of 1 (80 to 100 ° C) and shape it by applying an external force (such as a tooth occlusion) to obtain the desired shape (such as tooth shape); after shaping is completed, cool down to T 2 (-20 Under the condition of ⁇ 50 ° C), the hardness of the dental protector is increased to maintain the shape.
  • the term "extremity joint brace” refers to a brace that protects the joints of the extremities (for example, knee joints, elbow joints, shoulder joints, wrist joints, etc.) during exercise.
  • the limb joint protector contains the functional layer.
  • the limb joint protector comprises an optional outer layer, an intermediate layer and an optional inner layer, wherein the intermediate layer is the functional layer;
  • the outer layer may be a hard material, such as And may be at least one of a metal material, a hard plastic (excluding the polyester composition of the invention), ceramics and wood;
  • the inner layer may be a soft material, for example, may be a sponge, a foam, a soft silicone And at least one of soft rubber.
  • the outer layer, the intermediate layer and the inner layer are connected; preferably, the connection is achieved by bonding (such as using glue), threading or snapping. More preferably, the outer layer, the intermediate layer and the inner layer are all detachable.
  • the invention also provides a preparation method of the limb joint protection device, which comprises: softening, shaping and cooling the functional layer provided by the invention to obtain an intermediate layer of the limb joint protection device, specifically
  • the preparation method comprises: softening the functional layer under the condition of T 1 (80 to 100 ° C), and shaping it by applying an external force (such as pressing on a surface of the joint) to obtain a desired shape ( If the shape is in contact with the joint; after the shaping is completed, the temperature is lowered to a condition of T 2 (-20 to 50 ° C), the hardness of the functional layer is increased, and the shape is maintained to obtain the joint protection of the limbs. middle layer.
  • the method for preparing the limb joint protector further comprises: connecting the outer layer and/or the inner layer to the outer surface and/or the inner surface of the intermediate layer, respectively.
  • the outer layer and the inner layer are as described above, and are not described herein again.
  • the term "large area body protector” refers to a protector that protects a main part of the body (for example, the chest, the back, the waist, the abdomen, the front of the thigh, the front of the calf, etc.) during exercise.
  • the body large area protector contains the functional layer.
  • the body large area protector comprises an outer layer, an intermediate layer and an optional inner layer, wherein the intermediate layer is the functional layer;
  • the outer layer may be a hard material, for example, It is at least one of a metal material, a hard plastic (excluding the polyester composition of the invention), ceramics and wood;
  • the inner layer may be a soft material, for example, may be sponge, foam, soft silicone, and soft At least one of the rubbers.
  • the outer layer, the intermediate layer and the inner layer are connected; preferably, the inner layer and the intermediate layer are connected by adhesion; the intermediate layer and the outer layer are buckled, attached or The bandage is attached in a fixed manner. More preferably, The outer layer, the intermediate layer and the inner layer are all detachable.
  • the invention also provides a preparation method of the body large-area protective device, which comprises: softening, shaping and cooling the functional layer provided by the invention in order to obtain an intermediate layer of the body large-area protective device.
  • the preparation method comprises: softening the functional layer under conditions of T 1 (80 to 100 ° C), and shaping it by applying an external force (such as pressing on a surface of a body part to be applied) to Obtaining the desired shape (such as a shape conforming to the body part); after the shaping is completed, cooling to a condition of T 2 (-20 to 50 ° C), the hardness of the functional layer is increased, and the shape is maintained to obtain
  • the intermediate layer of the large area of the body is attached to the outer layer of the intermediate layer.
  • the method for preparing the body large area protector further comprises: connecting an inner layer on an inner surface of the intermediate layer. Wherein, the outer layer and the inner layer are as described above, and are not described herein again.
  • the term "head protector” refers to a protector that protects the head during exercise.
  • the head protector is a helmet.
  • the head protector contains the functional layer.
  • the head protector comprises an optional outer layer, an intermediate layer and an optional inner layer, wherein the intermediate layer is the functional layer;
  • the outer layer may be a hard material, such as And may be at least one of a metal material, a hard plastic (excluding the polyester composition of the invention), ceramics and wood;
  • the inner layer may be a soft material, for example, may be a sponge, a foam, a soft silicone And at least one of soft rubber.
  • the outer layer, the intermediate layer and the inner layer are connected; preferably, the inner layer and the intermediate layer are connected by adhesion; the intermediate layer and the outer layer are buckled, attached or The bandage is attached in a fixed manner. More preferably, the outer layer, the intermediate layer and the inner layer are all detachable.
  • the present invention also provides a method for preparing the head protector, which comprises: softening, shaping and cooling the functional layer provided by the present invention to obtain an intermediate layer of the head protector, specifically
  • the preparation method comprises: softening the functional layer under the condition of T 1 (80 to 100 ° C), and shaping it by applying an external force (such as pressing on a surface of the head) to obtain a desired shape. (the head was bonded shape); after the shaping is completed, cooling to T 2 (-20 ⁇ 50 °C) conditions, the hardness of the functional layer is increased, shape retaining, said head guard to give With the middle layer.
  • the method for preparing the head protector further comprises: connecting an inner layer and/or an outer layer on an inner surface and/or an outer surface of the intermediate layer, respectively. Wherein, the outer layer and the inner layer are as described above, and are not described herein again.
  • the present invention has a specific structure of polyester A, polyester B and fibrous filler according to a specific ratio (50-98% by weight of polyester A, 1-49% by weight of polyester B, 1-49% by weight
  • the fiber filler) is used in combination to obtain a polyester composition which can be sufficiently softened (hardness reduction) under high temperature conditions (for example, 80-100 ° C), and the softened polyester composition can be formed into any form according to the target portion.
  • the functional layer of the shape allows it to be better fitted to the target area; then the hardness is significantly increased at lower temperatures (eg -20-50 ° C) for shaping purposes.
  • the polyester composition provided by the present invention also has good shape memory performance, and the deformation fixing rate is 90% or more, the deformation recovery rate is as high as 90% or more, and the maximum deformation rate is as high as 280% or more.
  • the above-mentioned softening and shaping process of the polyester composition provided by the present invention is reversible, and when it is made into a sports brace, when the sports brace is worn or slightly damaged, it can be softened again by warming and low temperature. Reshaping allows the brace to return to its original appearance. Therefore, the sports protector made by the functional layer provided by the present invention has a good application prospect.
  • the polyester composition of the present invention has good low temperature plasticity and shape memory properties. Therefore, when the polyester composition provided by the present invention is used for a sports brace, it can be shaped according to the difference of the application parts, so that the brace is more conformable to the body, more comfortable and convenient to manufacture.
  • polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the content of the repeating unit A is 60-80 mol%, preferably 62-78 mol%, and the content of the repeating unit B is 20-40 mol%, based on the total number of moles of the repeating unit A and the repeating unit B. Preferably it is 22-38 mol%,
  • n1 is an integer from 2 to 4, preferably 2; and m1 and n1 are the same or different; and the polyester A has a weight average molecular weight of 50,000 to 900,000, preferably 100,000 to 500,000;
  • polyester B which is a copolymer containing repeating unit C represented by formula (I") and repeating unit B represented by formula (II-1), and
  • the total number of moles of the repeating unit C and the repeating unit B in the polyester B is based on the content of the repeating unit C of 20 to 59 mol%, preferably 30 to 55 mol%, and the content of the repeating unit B. 41-80 mol%, preferably 45-70 mol%,
  • m1 and m2 may be the same or different, and n1 and n2 may be the same or different. However, when m1 and m2 are the same and n1 and n2 are also the same, the content of the repeating unit B in the polyester A is different from the content of the repeating unit B in the polyester B.
  • the polyester composition contains 70 to 90% by weight of polyester A and 10 to 30% by weight of polyester B; more preferably, the polyester composition contains 70 to 80% by weight Polyester A and 20-30% by weight of polyester B.
  • the polyester A and the polyester B may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, preferably a random copolymer and/or Or block copolymer.
  • the source of the polyester A and the polyester B in the present invention is not particularly limited, and the source and preparation method are as described above.
  • the polyester composition may further contain an auxiliary filler; preferably, the auxiliary filler is contained in an amount of from 0.1 to 60% by weight, more preferably 1 based on the total weight of the polyester composition. 20% by weight.
  • the auxiliary filler has a function of adjusting the curing time of the composition, adjusting the mechanical strength of the composition, improving the flame retardancy and oxidation resistance of the composition, and adjusting the color and gloss of the composition.
  • the auxiliary filler may be selected from the group consisting of calcium carbonate, carbon black, talc, erucamide, titanium dioxide, iron oxide, metal carboxylate, metal phosphate, tetrabromobisphenol A, decabromo Phenyl ether, hexabromocyclododecane, low density polyethylene, polyphosphate or ester, phosphite, hindered phenol, hindered amine, dibenzyl sorbitol and its derivatives, hyperbranched polyamide and ethylene-methyl At least one of acrylic acid ionomers; preferably at least one of calcium carbonate, carbon black, erucamide, titanium dioxide, polyphosphate or ester, low density polyethylene, and hyperbranched polyamide and ethylene-methyl At least one of
  • the present invention also provides a process for producing the above polyester composition, characterized in that the preparation method comprises: blending the above polyester A with polyester B, and subjecting the obtained mixture to extrusion granulation.
  • the inventors unexpectedly found during the research that the polyester A has good compatibility with the polyester B, and therefore, no compatibilizer may be added during the blending process.
  • the compatibilizer is a substance conventionally used in the art for improving the compatibility of a blending raw material, and for example, may be PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g- At least one of MAH and PP-g-MAH.
  • the process of blending is as described above.
  • the agitation rate is from 20 to 150 r/min and the agitation time is from 5 to 15 min.
  • the extrusion granulation process is as described above.
  • the temperature of the extrusion granulation is from 110 to 260 ° C, preferably from 160 to 220 ° C.
  • the present invention also provides a medical limb fixation stent comprising the above polyester composition, that is, the medical limb fixation stent is produced from the above polyester composition.
  • the medical limb fixing bracket may have a thickness of 0.2 to 10 mm, preferably 1 to 3 mm.
  • the medical limb fixation stent has and/or has no pore structure, preferably has a pore structure.
  • the hole structure is distributed along the medical limb fixing bracket to improve the gas permeability of the medical limb fixing bracket.
  • the pore structure has a pore diameter of from 1 to 10 mm, preferably from 1 to 5 mm.
  • the medical limb fixing bracket can be used for fixing any limb part, for example, it can be used for various body parts such as a finger, a limb, a neck, a back, and the like.
  • the invention also provides a method for preparing a medical limb fixing bracket, the preparation method comprising: sequentially extruding, molding and optionally punching a polyester composition to obtain a medical limb fixing bracket; wherein the gathering The ester composition is the above polyester composition.
  • the extrusion is preferably melt extrusion; more preferably, the extrusion temperature is from 90 to 230 ° C, preferably from 110 to 170 ° C.
  • the molding may be by injection molding and/or compression molding.
  • the shaping is such that the medical limb fixation stent has a thickness of from 0.2 to 10 mm, preferably from 1 to 3 mm.
  • the punching may be performed using a puncher; preferably, the puncher used has a diameter of 1-10 mm, preferably 1-5 mm.
  • the preparation method can also This involves cutting the shaped material to obtain a medical limb fixation bracket of appropriate size and shape.
  • the present invention blends specific copolymers (Polyester A and Polyester B) according to a specific ratio (content of polyester A is 51-99% by weight, content of polyester B is 1-49% by weight).
  • a polyester composition having a hardness which can vary with temperature and time is obtained.
  • the medical limb fixing bracket made by using the polyester composition provided by the invention can be fully softened under high temperature conditions (such as hot water, especially boiling water), and the softened material is easy to be cut, and cut into appropriate size and The shape is wound around the part of the limb to be fixed and can be hardened and self-adhesive for good shaping and fixing purposes.
  • the above process is reversible, and can be reshaped according to the limb part, and the medical limb fixing bracket is convenient for disassembly and cleaning; at the same time, it has good degradation performance, and the preparation process is processed by thermoplastic processing (no cross-linking agent is used), trimming material It can also be recycled and reused.
  • the medical limb fixing bracket of the invention has the following advantages: no special packaging such as water isolation is needed in the process of storage and transportation, and the bag can still be kept for at least two years after being opened; the weight and the polymer bandage are similar, only The gypsum bandage weighs about 1/5; it has excellent X-ray permeability; it is perfectly water-repellent because it does not involve reaction with water, and it is not afraid of moisture before storage.
  • the hardness of the polyester composition provided by the present invention varies with time and temperature. Specifically, it has a lower hardness at a higher temperature, and the hardness is remarkably increased in a shorter time after cooling, exhibiting good plasticity and fixability.
  • the polyester compositions provided by the present invention are particularly useful in the preparation of medical limb fixation stents.
  • the present invention provides a polyester composition wherein the polyester composition contains the following components based on the total weight of each component:
  • polyester A which contains a repeat represented by formula (I') a copolymer of the unit A and the repeating unit B represented by the formula (II-1), and based on the total number of moles of the repeating unit A and the repeating unit B in the polyester A, the content of the repeating unit A is 60-80 mol%, preferably 62-72 mol%, and the content of the repeating unit B is 20-40 mol%, preferably 28-38 mol%,
  • n1 is an integer from 2 to 4, preferably 2; and m1 and n1 are the same or different; and the polyester A has a weight average molecular weight of 50,000 to 900,000, preferably 100,000 to 500,000;
  • polyester B which is a copolymer containing repeating unit C represented by formula (I") and repeating unit B represented by formula (II-1), and
  • the total number of moles of the repeating unit C and the repeating unit B in the polyester B is based on the content of the repeating unit C of 81 to 99 mol%, preferably 85 to 97 mol%, and the content of the repeating unit B. 1-19 mol%, preferably 3-15 mol%,
  • m1 and m2 may be the same or different, and n1 and n2 may be the same or different. However, when m1 and m2 are the same and n1 and n2 are also the same, the content of the repeating unit B in the polyester A is different from the content of the repeating unit B in the polyester B.
  • the content of the repeating unit B in the polyester A is greater than the content of the repeating unit B in the polyester B.
  • the polyester composition contains 60 to 90% by weight of polyester A and 10 to 40% by weight of polyester B.
  • the polyester A and the polyester B may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, preferably a random copolymer and/or Or block copolymer.
  • the source of the polyester A and the polyester B in the present invention is not particularly limited, and the source and preparation method are as described above.
  • the polyester composition may further contain an auxiliary filler; preferably, the auxiliary filler is contained in an amount of from 0.1 to 20% by weight, more preferably from 10% by weight based on the total mass of the polyester composition. 20% by weight.
  • the auxiliary filler has the functions of accelerating the melt solidification of the composition, adjusting the mechanical strength of the composition, improving the flame retardancy, oxidation resistance, and adjusting the color and gloss of the composition, and can be conventional in the art.
  • the auxiliary filler may be selected from the group consisting of calcium carbonate, carbon black, talc, erucamide, titanium dioxide, iron oxide, metal carboxylate, metal phosphate, tetrabromobisphenol A, decabromodiphenyl ether, Hexabromocyclododecane, low density polyethylene, polyphosphate or salt, phosphite, hindered phenol, hindered amine, dibenzyl sorbitol and its derivatives, hyperbranched polyamide and ethylene-methacrylic acid ionomerization At least one of; preferably at least one of calcium carbonate, carbon black, erucamide, titanium dioxide, polyphosphate, low density polyethylene, and hyperbranched polyamide; more preferably calcium carbonate, carbon black, At least two of erucamide, titanium dioxide, tris(2,3-dibromopropyl) phosphate, low density polyethylene, and hyperbranched polyamide.
  • the present invention also provides a process for producing the above polyester composition, which comprises blending the above polyester A with polyester B, and subjecting the resulting mixture to extrusion granulation.
  • the inventors unexpectedly found during the research that the polyester A has good compatibility with the polyester B, and therefore, no compatibilizer may be added during the blending process.
  • the compatibilizer is a substance conventionally used in the art for improving the compatibility of a blending raw material, and for example, may be PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g- At least one of MAH and PP-g-MAH.
  • the process of blending is as described above.
  • the agitation rate is 10-150 r/min and the agitation time is 5-15 min.
  • the extrusion granulation process is as described above.
  • the temperature of the extrusion granulation is from 80 to 220 ° C, preferably from 110 to 180 ° C.
  • the present invention also provides a heat shrinkable film comprising the above polyester composition, that is, the heat shrinkable film is produced from the above polyester composition.
  • the heat-shrinkable film may have a thickness of 5 to 1000 ⁇ m, and the heat shrinkage rate can be changed within a wide range by adjustment of the formulation and the polyester structure, for example, the heat shrinkage film has a heat shrinkage ratio of 10 -80%, which can meet different needs; and the heat-shrinkable film has a heat-sealing strength of 11 to 19 N/15 mm, and the heat-shrinkable film has good degradable properties.
  • the present invention also provides a method for preparing a heat shrinkable film, the method comprising: sequentially casting a polyester composition into a film, standing and stretching to obtain a heat shrinkable film; wherein the polyester combination
  • the composition is the above polyester composition.
  • the process of casting the film is not particularly limited, and for example, it can be carried out on a casting machine.
  • the temperature of the cast film formation is from 80 to 220 ° C, preferably from 110 to 180 ° C.
  • the process of the standing is not particularly limited, and for example, it can be placed in a room temperature (25 ° C) environment.
  • the standing time is from 30 minutes to 20 days, preferably from 4 to 24 hours.
  • the stretching may be uniaxial stretching or biaxial stretching.
  • the stretching temperature is from 40 to 150 ° C, preferably from 60 to 120 ° C.
  • the present invention blends specific copolymers (Polyester A and Polyester B) according to a specific ratio (content of polyester A is 51-99% by weight, content of polyester B is 1-49% by weight). Not only can a heat shrinkable film having a heat shrinkage rate of more than 70% be obtained, but also a film having a heat shrinkage rate of 10% can be obtained, which shows that the heat of the film can be changed over a wide range by the adjustment of the formulation and the polyester structure. Shrinkage; and, the heat shrinkable film obtained by the present invention has suitable The heat sealing strength (up to 11-19N/15mm), the film surface is flat, the gloss is good, it can be degraded and can be repeatedly thermoplastically processed and recycled, so it has obvious environmental advantages and industrial application prospects.
  • the present invention provides a polyester composition wherein the polyester composition contains the following components based on the total weight of each component:
  • polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit A and the repeating unit B in the polyester A is based on the content of the repeating unit A of 75 to 99 mol%, preferably 81 to 95 mol%, and the content of the repeating unit B. 1 to 25 mol%, preferably 5 to 19 mol%,
  • n1 is an integer from 2 to 4, preferably 2; and m1 and n1 are the same or different, and the polyester A has a weight average molecular weight of 50,000 to 900,000, preferably 100,000 to 500,000;
  • polyester B which is a copolymer containing repeating unit C represented by formula (I") and repeating unit B represented by formula (II-1), and
  • the total number of moles of the repeating unit C and the repeating unit B in the polyester B is based on the content of the repeating unit C of 20 to 74 mol%, preferably 40 to 70 mol%, and the content of the repeating unit B. 26-80 mol%, preferably 30-60 mol%,
  • m1 and m2 may be the same or different, and n1 and n2 may be the same or different. However, when m1 and m2 are the same and n1 and n2 are also the same, the content of the repeating unit B in the polyester A is different from the content of the repeating unit B in the polyester B.
  • the polyester composition contains from 55 to 70% by weight of polyester A and from 30 to 45% by weight of polyester B.
  • the polyester A and the polyester B may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, preferably a random copolymer and/or Or block copolymer.
  • the source of the polyester A and the polyester B in the present invention is not particularly limited, and the source and preparation method are as described above.
  • the polyester composition may further comprise an auxiliary filler; preferably, the auxiliary filler is present in an amount of from 0.1 to 25% by weight, more preferably 1 - based on the total weight of the polyester composition 20% by weight.
  • the auxiliary filler has an effect of accelerating the composition spinning and solidification molding, adjusting the mechanical strength of the woven fabric or the nonwoven fabric, improving the flame retardancy, oxidation resistance, and adjusting the color and gloss of the product, and
  • the auxiliary filler may be selected from the group consisting of calcium carbonate, carbon black, talc, erucamide, titanium dioxide, iron oxide, metal carboxylate, metal phosphate, tetrabromobisphenol A, decabromo Diphenyl ether, hexabromocyclododecane, low density polyethylene, polyphosphate or ester, phosphite, hindered phenol, hindered amine, dibenzyl sorbitol and its derivatives, hyperbranched polyamide and ethylene-A At least one of the acrylic acid ionomers; preferably hindered phenol, calcium carbonate, carbon black, erucamide, titanium dioxide, tris(2,3-d
  • the present invention also provides a process for producing the above polyester composition, wherein the preparation method comprises: blending the above polyester A with polyester B, and subjecting the obtained mixture to extrusion granulation.
  • the inventors unexpectedly found during the research that the polyester A has good compatibility with the polyester B, and therefore, no compatibilizer may be added during the blending process.
  • the compatibilizer is a substance conventionally used in the art for improving the compatibility of a blending raw material, and for example, may be PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g- At least one of MAH and PP-g-MAH.
  • the process of blending is as described above.
  • the agitation rate is from 20 to 150 r/min and the agitation time is from 5 to 15 min.
  • the extrusion granulation process is as described above.
  • the temperature of the extrusion granulation is from 140 to 220 ° C, preferably from 160 to 200 ° C.
  • the present invention also provides a nonwoven fabric, wherein the nonwoven fabric contains the above polyester composition, that is, the nonwoven fabric is obtained from the above polyester composition.
  • the nonwoven fabric may have a filament diameter of 5 to 100 ⁇ m, preferably 20 to 50 ⁇ m.
  • the present invention also provides a method for preparing a nonwoven fabric, which comprises preparing a nonwoven fabric by the above-mentioned polyester composition by a spunbonding method.
  • the apparatus used in the spunbonding method of the present invention is not particularly limited, and for example, a spunbonding machine conventionally used in the art can be used.
  • the spunbond process comprises a process of extrusion, spinning, web forming and consolidation. More preferably, the extrusion process comprises three temperature zones, the temperature of the first temperature zone is 140-250 ° C, preferably 160-210 ° C; the temperature of the second temperature zone is 150-260 ° C, preferably 165 -220 ° C; the temperature in the third temperature zone is 170-260 ° C, preferably 180-230 ° C.
  • the spinning conditions are not particularly limited, for example, the spinning temperature may be 150-240 ° C, preferably 170-220 ° C; the spinning rate may be 10-40 r /min, preferably 15-30 r/min.
  • the conditions for the web formation are not particularly limited, and for example, the rate of the web formation may be 5 to 30 r/min, preferably 10 to 20 r/min.
  • the reinforcement is preferably in the form of hot rolling, and the temperature of the hot rolling is 80-170 ° C, preferably 90-120 ° C.
  • the present invention also provides the use of the above polyester composition and the above nonwoven fabric in a nonwoven fabric article, preferably in a disposable nonwoven fabric article, more preferably in a disposable medical nonwoven fabric article.
  • the disposable medical nonwoven article is selected from at least one of a disposable surgical gown, a disposable medical respirator, a disposable medical cap, a disposable medical bed sheet, and a disposable surgical towel.
  • the present invention provides a polyester composition comprising the following components based on the total weight of each component:
  • the polyester A which is a copolymer containing the repeating unit A represented by the formula (I') and the repeating unit B represented by the formula (II-1), and
  • the total number of moles of the repeating unit A and the repeating unit B in the polyester A is based on the content of the repeating unit A of 51 to 80% by mole, preferably 60 to 75% by mole; the content of the repeating unit B 20 to 49 mol%, preferably 25 to 40 mol%,
  • the molecular weight is 50,000-900,000, preferably 100,000-500,000;
  • m2 is an integer of 2-8, preferably an integer of 2-4; n2 is an integer of 2-6, preferably an integer of 2-4; and m2 and n2 are the same or different;
  • the molecular weight is 50,000-900,000, preferably 100,000-500,000;
  • m3 is an integer of 2-8, preferably an integer of 2-4; n3 is an integer of 2-6, preferably an integer of 2-4; and m3 and n3 are the same or different; the weight average of the polyester C
  • the molecular weight is from 50,000 to 900,000, preferably from 100,000 to 500,000.
  • m1, m2 and m3 may be the same or different, and n1, n2 and n3 may be the same or different. However, when m1, m2 and m3 are all the same, and n1, n2 and n3 are all the same, the content of the repeating unit B in the polyester A, the polyester B and the polyester C is different.
  • the polyester composition contains from 60 to 93% by weight of polyester A, from 5 to 38% by weight of polyester B and from 1 to 20% by weight of polyester C.
  • the polyester A, the polyester B and the polyester C may each be at least one of a random copolymer, an alternating copolymer, a block copolymer and a graft copolymer, preferably It is a random copolymer and/or a block copolymer.
  • the source of the polyester A, the polyester B, and the polyester C of the present invention is not particularly limited, and the source and preparation method are as described above.
  • the polyester composition may further comprise an auxiliary filler; preferably, the auxiliary filler is present in an amount of from 1 to 20% by weight, more preferably from 2, based on the total weight of the polyester composition 10% by weight.
  • the auxiliary filler may have an effect of accelerating the melt solidification of the composition, adjusting the mechanical strength of the composition, improving the flame retardancy, oxidation resistance of the composition, adjusting the color and gloss of the composition, and the like.
  • the auxiliary filler is selected from the group consisting of calcium carbonate, carbon black, talc, erucamide, titanium dioxide, low density polyethylene, polyphosphate or ester, phosphite, hindered phenol, hindered amine, two One or more of benzyl sorbitol and its derivatives, hyperbranched polyamide and ethylene-methacrylic acid ionomer; preferably calcium carbonate, carbon black, erucamide, titanium dioxide, phosphoric acid three (2, 3- One or more of dibromopropyl) ester (TDBPP) and low density polyethylene.
  • TDBPP dibromopropyl
  • the present invention also provides a process for producing the above polyester composition, which comprises blending polyester A, polyester B and polyester C, and subjecting the resulting mixture to extrusion granulation.
  • the inventors unexpectedly found during the research that the polyester A, the polyester B and the polyester C have good compatibility, and therefore, no compatibilizer may be added during the blending.
  • the compatibilizer is a substance conventionally used in the art for improving the compatibility of a blending raw material, and for example, may be PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g- At least one of MAH and PP-g-MAH.
  • the process of blending is as described above.
  • the agitation rate is 10-150 r/min and the agitation time is 5-15 min.
  • the extrusion granulation process is as described above.
  • the temperature of the extrusion granulation is from 110 to 270 ° C, preferably from 130 to 230 ° C.
  • the present invention also provides an elastic fiber, wherein the elastic fiber comprises the above polyester composition and/or the polyester composition obtained by the above production method, that is, the elastic fiber is composed of the above polyester composition and/or The polyester composition obtained by the above production method is obtained.
  • the elastic fibers may have a fineness of from 5 to 500 dtex. Breaking strength ⁇ 1cN/dtex, preferably 3-19cN/dtex; elongation at break ⁇ 100%, preferably 130-620%; stress relaxation rate ⁇ 12%, preferably 1-12%; permanent strain rate ⁇ 12%, preferably It is 1-11%.
  • the fineness can be detected using a conventional denier.
  • the present invention also provides a method for preparing an elastic fiber, the preparation method comprising: sequentially passing a polyester composition through filament formation, low temperature placement and stretching to obtain an elastic fiber; wherein the polyester composition is the above-mentioned poly Ester composition.
  • the manner of filament formation can be a conventional choice in the art, preferably melt spinning.
  • the temperature of the filaments is from 120 to 270 ° C, preferably from 150 to 220 ° C.
  • the conditions for the low temperature placement include a temperature of 20 to 55 ° C, preferably 25 to 45 ° C; a time of 2 to 120 min, preferably 15 to 60 min.
  • the conditions for stretching include a temperature of 56 to 110 ° C, preferably 60 to 90 ° C; and a stretching ratio of 1.2 to 10 times, preferably 2 to 5 times.
  • the invention adopts specific polyester A, polyester B and polyester C according to a specific ratio (30-98% by weight of polyester A, 1-69 wt% of polyester B, 1-69 wt% of poly
  • the ester C) is blended to obtain a polyester composition
  • the elastic fiber made using the polyester composition has a breaking strength of ⁇ 1 cN/dtex, and can be changed over a wide range by the adjustment of the formulation and molecular structure, and the maximum fracture
  • the strength of the elastic fiber provided by the present invention is as high as 130% or more, and the stress relaxation and the permanent strain rate are both ⁇ 12%, which indicates that the elastic fiber provided by the present invention has moderate elasticity and It has a wide range of strength and performance, so it has a good application prospect.
  • the present invention particularly prepares elastic fibers by using high temperature filament-low temperature placement-high temperature stretching methods and conditions, which can further improve the breaking strength of elastic fibers, expand the adjustable range of properties, and reduce the stress relaxation and permanent properties of elastic fibers. Strain rate.
  • the measurement criteria for some parameters in the present invention are as follows:
  • Denier directly measured with a spiral micrometer, and the corresponding value is calculated by the JIS L0104-2000 method.
  • Plastic spline strength GB/T 1040.2-2006/ISO 527-2:1993
  • the weight average molecular weight of the polymer was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent on a Waters-208 (with a Waters 2410 RI detector, 1.5 mL/min flow rate, 30 ° C) instrument for polymerization.
  • GPC gel permeation chromatography
  • THF tetrahydrofuran
  • Waters-208 with a Waters 2410 RI detector, 1.5 mL/min flow rate, 30 ° C
  • polyester A The microstructures of polyester A, polyester B, polyester C and aliphatic polyester and aromatic polyester were determined by an AVANCE DRX 400 MHz NMR spectrometer from Bruker, Switzerland, using deuterated chloroform as a solvent;
  • the composition of the polyester composition is determined by the feeding of the raw materials
  • the deformation memory properties of the polyester composition were measured using an Instron 5965 tensile tester (with an incubator) as follows:
  • the initial length of the polyester composition spline at room temperature is a; the temperature of the incubator is raised to 80 ° C, Fully softened, stretched to a length b at a tensile speed of 50 mm / min; maintain external force to make the stretch length unchanged, cool down, to be solidified, remove the external force, at this time the length of the spline is c; Raise the strip to 80 ° C again, and the strip is fully retracted, at which time the length of the strip is d;
  • Deformation fixation rate (%) (c-a) / (b-a) ⁇ 100%;
  • Shape recovery rate (%) (c-d) / (c - a) ⁇ 100%;
  • the maximum deformation rate (%) b max / a ⁇ 100%, where b max is the maximum b value that can be reached before the spline is damaged;
  • the aliphatic-aromatic copolyester used in the present invention is prepared by itself according to the method disclosed in Example B13-B21 of CN100429256C, wherein the reaction can be adjusted accordingly according to the composition and molecular weight of the target product, unless otherwise specified.
  • the type of raw material, and the molecular weight of the product and the content of each repeating unit in the product are controlled by adjusting the amount of feed and the ratio of feed.
  • a butylene terephthalate (BT)-butyl succinate (BS) copolyester (weight average molecular weight of 100,000, wherein The content of the BT repeating unit is 30 mol% based on the total moles of the BT repeating unit and the BS repeating unit, and the butylene terephthalate (BT)-butylene adipate (BA) copolyester ( Purchased from BASF under the trade name ecoflex, where BT repeat unit content is 50 mol% based on the total moles of BT repeat unit and BA repeat unit) and polybutylene succinate (PBS) From BASF, grade 1111HTA4) was mixed at a 40:40:20 molar ratio and 1% by weight calcium carbonate was added (based on the total weight of the mixture).
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 190 ° C. , 200 ° C, 210 ° C, 220 ° C, 220 ° C, 210 ° C, made polyester Composition I-A1.
  • a polyester composition was prepared according to the method of Example I-1, except that the same molar amount of polybutylene terephthalate (PBT) (purchased from DuPont, under the designation Crastin SC164 NC010) was used instead of the implementation.
  • PBT polybutylene terephthalate
  • the BT-BS copolyester used in Example I-1 was used to prepare a polyester composition I-D1.
  • polyester composition was prepared according to the method of Example I-1, except that the same molar amount of PBT (available from DuPont, under the designation Crastin SC164 NC010) was used instead of the BT-BA used in Example I-1. Polyester, polyester composition I-D2 was obtained.
  • PBT available from DuPont, under the designation Crastin SC164 NC010
  • a polyester composition was prepared according to the method of Example I-1 except that the PBS used in Example I-1 was not added to obtain a polyester composition I-D3.
  • a polyester composition was prepared according to the method of Example I-1, except that BT-BS copolyester, BT-BA copolyester and PBS were mixed at a molar ratio of 2:2:96 to obtain a polyester.
  • BT-BS copolyester weight average molecular weight is 100,000 under stirring conditions (a stirring rate of 30 rpm, time 10 min), wherein BT repeats based on the total number of moles of BT repeating unit and BS repeating unit a content of the unit of 55 mol%), a BT-BA copolyester (weight average molecular weight of 100,000, wherein the content of the BT repeating unit is 20 mol% based on the total number of moles of the BT repeating unit and the BA repeating unit)
  • the PBS was mixed at a molar ratio of 20:70:10 and 1% by weight of calcium carbonate (based on the total weight of the mixture) was added.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 190 ° C. , 200 ° C, 210 ° C, 220 ° C, 220 ° C, 210 ° C, the polyester composition I-A2.
  • BT-BS copolyester weight average molecular weight is 100,000 under stirring conditions (a stirring rate of 30 rpm, time 10 min), wherein BT repeats based on the total number of moles of BT repeating unit and BS repeating unit
  • the content of the unit is 30 mol%)
  • BT-BA copolyester purchased from BASF, under the trade name ecoflex
  • the content of the BT repeating unit is 50 mol based on the total moles of the BT repeating unit and the BA repeating unit.
  • PBS were mixed at a molar ratio of 50:49:1, and 1% by weight of calcium carbonate (based on the total weight of the mixture) was added.
  • Polyester composition I-A3 was obtained at 200 ° C, 210 ° C, 220 ° C, 220 ° C, and 210 ° C.
  • BT-BS copolyester weight average molecular weight is 100,000 under stirring conditions (a stirring rate of 30 rpm, time 10 min), wherein BT repeats based on the total number of moles of BT repeating unit and BS repeating unit
  • the content of the unit is 40 mol%), BT-BA copolyester (purchased from BASF, under the trade name ecoflex), wherein the content of the BT repeating unit is 50 mol based on the total number of moles of the BT repeating unit and the BA repeating unit.
  • PBS were mixed at a molar ratio of 90:1:9, and 1% by weight of calcium carbonate (based on the total weight of the mixture) was added.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 160 ° C.
  • the polyester composition I-A4 was obtained at 170 ° C, 180 ° C, 180 ° C, 180 ° C, and 170 ° C.
  • BT-BS copolyester weight average molecular weight of 100,000 under stirring conditions (30 rpm stirring time, 10 min), wherein BT repeating unit and BS repeating unit Based on the total moles, the BT repeat unit content is 40% by mole
  • BT-BA copolyester purchased from BASF, under the trade name ecoflex
  • the content of the BT repeating unit was 50% by mole
  • PBS were mixed at a molar ratio of 90:1:9, and 5% by weight of calcium carbonate (based on the total weight of the mixture) was added.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 160 ° C.
  • the polyester composition I-A5 was obtained at 170 ° C, 180 ° C, 180 ° C, 180 ° C, and 170 ° C.
  • BT-BS copolyester weight average molecular weight is 100,000 under stirring conditions (a stirring rate of 30 rpm, time 10 min), wherein BT repeats based on the total number of moles of BT repeating unit and BS repeating unit
  • the content of the unit is 40 mol%), BT-BA copolyester (purchased from BASF, under the trade name ecoflex), wherein the content of the BT repeating unit is 50 mol based on the total number of moles of the BT repeating unit and the BA repeating unit.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 160 ° C.
  • the polyester composition I-A6 was obtained at 170 ° C, 180 ° C, 180 ° C, 180 ° C, and 170 ° C.
  • a polyester composition was prepared according to the method of Example I-1 except that the calcium carbonate used in Example I-1 was not added to obtain a polyester composition I-A7.
  • a polyester composition was prepared according to the method of Example I-1, except that the same molar amount of ethylene terephthalate (ET)-succinic acid ethylene glycol (ES) copolyester was used (weight average The molecular weight is 100,000, wherein, based on the total number of moles of the ET repeating unit and the ES repeating unit, The content of the ET repeating unit was 50% by mole.
  • ETD ethylene terephthalate
  • ES ethylene glycol
  • a polyester composition was prepared according to the method of Example I-1, except that the same molar amount of poly(butylene succinate) (PHS) (prepared according to the method disclosed in CN104039865B, having a weight average molecular weight of 100,000) was used. Instead of the PBS used in Example I-1, a polyester composition I-A9 was obtained.
  • PBS poly(butylene succinate)
  • polyester compositions prepared in Examples I-1 to I-9 and Comparative Examples I-1 to I-4 were respectively formed into stamping splines, and the formed punched splines were subjected to morphological memory performance test, and the results were as follows Table 1 shows.
  • the polyester composition prepared by the above Examples I-1 to I-9 was used for a shape memory material having a deformation fixation rate and a shape recovery ratio of 92% or more and maximum deformation.
  • the rate is as high as 400% or more.
  • the initial shaping temperature and the starting temperature of the shape memory material can be adjusted, which will be more advantageous for its application in daily life.
  • BT-BS copolyester A weight average molecular weight of 300,000, wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, content of BT repeating unit is 30 mol%) particles
  • 50 g of BT-BS copolyester B weight average molecular weight is 200,000, wherein BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit a content of 10 mol%) particles
  • 50 g of BT-BS copolyester C weight average molecular weight of 200,000, wherein the content of the BT repeating unit is 80 mol% based on the total number of moles of the BT repeating unit and the BS repeating unit
  • the granules were mixed with 100 g of titanium dioxide, and the mixture was then added to a twin-screw extruder, melt extruded at a temperature of 180
  • the above polyester composition II-A1 was added to an extruder, and the line was extruded through a round hole die at 180 ° C, and the line was cooled at 0 ° C by air or a water tank to obtain a 3D printed wire II having a diameter of 1.75 mm. B1.
  • BT-BS copolyester A weight average molecular weight of 300,000, wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, content of BT repeating unit is 40 mol%) particles
  • 110 g of BT-BS copolyester B weight average molecular weight is 200,000, wherein BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit a content of 15 mol%) particles
  • 110 g of BT-BS copolyester C weight average molecular weight of 200,000, wherein the content of the BT repeating unit is 85 mol% based on the total number of moles of the BT repeating unit and the BS repeating unit
  • the granules were mixed with 100 g of titanium dioxide.
  • the mixture is then added to a twin-screw extruder at a temperature of 180 ° C.
  • the above polyester composition II-A2 was added to an extruder, and the line was extruded through a round hole die at 180 ° C, and the line was cooled at 0 ° C by air or a water tank to obtain a 3D printed wire II having a diameter of 1.75 mm. B2.
  • BT-BS copolyester A weight average molecular weight of 300,000, wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, content of BT repeating unit is 25 mol%) particles
  • 165 g of BT-BS copolyester B weight average molecular weight is 200,000, wherein the content of BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit 5 mol%) of particles
  • 165 g of BT-BS copolyester C weight average molecular weight of 200,000, wherein the content of BT repeating unit is 50 mol% based on the total moles of BT repeating unit and BS repeating unit
  • the above polyester composition II-A3 was added to an extruder, and the line was extruded through a round hole die at 180 ° C, and the line was cooled at 0 ° C through air or a water tank to obtain a 3D printed wire II having a diameter of 1.75 mm. B3.
  • BT-BS copolyester A weight average molecular weight of 300,000, based on the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 44 mol%) particles
  • 275 g of BT-BS copolyester B weight average molecular weight is 200,000, wherein the content of the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • the above polyester composition II-A4 was added to an extruder, and the line was extruded through a round hole die at 180 ° C, and the line was cooled at 0 ° C by air or a water tank to obtain a 3D printed wire II having a diameter of 1.75 mm. B4.
  • BT-BS copolyester A weight average molecular weight of 300,000, wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, the content of the BT repeating unit is 20 mol%) particles
  • 11 g of BT-BS copolyester B weight average molecular weight is 200,000, wherein, based on the total number of moles of the BT repeating unit and the BS repeating unit, the BT repeating unit a content of 1 mol%) particles
  • 11 g of BT-BS copolyester C weight average molecular weight of 200,000, wherein the content of the BT repeating unit is 45 mol% based on the total number of moles of the BT repeating unit and the BS repeating unit
  • the granules were mixed with 100 g of titanium dioxide, and the mixture was then added to a twin-screw extruder, melt extru
  • the above polyester composition II-A5 was added to an extruder, and the line was extruded through a round hole die at 180 ° C, and the line was cooled at 0 ° C through air or a water tank to obtain a 3D printed wire II having a diameter of 1.75 mm. B5.
  • Example II-1 The procedure of Example II-1 was carried out except that the polyester B was a BT-BA copolyester (weight average molecular weight was 200,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit. The content of the unit is 10 mol%); the polyester C is a BT-BA copolyester (weight average molecular weight is 200,000, wherein the content of the BT repeating unit is 80 based on the total number of moles of the BT repeating unit and the BA repeating unit. Molar%). Polyester composition II-A6 and 3D printed wire II-B6 were obtained.
  • Example II-1 The procedure of Example II-1 was carried out except that the polyester B was an ET-EA (ethylene adipate) copolyester (weight average molecular weight was 200,000, wherein ET repeating unit and EA) The content of the ET repeating unit is 10 mol% based on the total number of moles of the repeating unit; the polyester C is an ET-EA copolyester (weight average molecular weight is 200,000, wherein the total molar amount of the ET repeating unit and the EA repeating unit) Based on the number, the content of the ET repeating unit was 80% by mole). Polyester Composition II-A7 and 3D printed wire II-B7 were obtained.
  • ET-EA ethylene adipate copolyester
  • Example II-1 The procedure of Example II-1 was carried out except that the polyester B was an ET-BS copolyester (weight average molecular weight was 200,000, wherein ET was repeated based on the total number of moles of the ET repeating unit and the BS repeating unit. The content of the unit is 10 mol%); the polyester C is a BT-EA copolyester (weight average molecular weight is 200,000), wherein the content of the BT repeating unit is 80 based on the total number of moles of the BT repeating unit and the EA repeating unit. Molar%). Polyester Composition II-A8 and 3D printed wire II-B8 were obtained.
  • ET-BS copolyester weight average molecular weight was 200,000, wherein ET was repeated based on the total number of moles of the ET repeating unit and the BS repeating unit. The content of the unit is 10 mol%)
  • the polyester C is a BT-EA copolyester (weight average molecular weight is 200,000), wherein the
  • Example II-1 The procedure of Example II-1 was carried out except that the same weight of calcium carbonate was used instead of the titanium oxide of Example II-1. Polyester Composition II-A9 and 3D printed wire II-B9 were obtained.
  • Example II-1 The procedure of Example II-1 was carried out except that 100 g of titanium dioxide was not added. Polyester composition II-A10 and 3D printed wire II-B10 were obtained.
  • Example II-1 The procedure of Example II-1 was carried out except that 1 kg of the polyester A used in Example II-1, 100 g of the polyester B used in Example II-1 and 100 g of titanium oxide were mixed without adding Example II- 1 used polyester C. Wire material II-D1 was obtained.
  • Example II-1 The procedure of Example II-1 was carried out except that 1 kg of the polyester A used in Example II-1, 100 g of the polyester C used in Example II-1 and 100 g of titanium oxide were mixed without adding Example II- 1 used polyester B. Wire material II-D2 was obtained.
  • Example II-1 The procedure of Example II-1 was carried out except that 550 g of the polyester B used in Example II-1, 550 g of the polyester C used in Example II-1 and 100 g of titanium oxide were mixed without adding Example II- 1 used polyester A. Wires II-D3 were obtained.
  • Example II-1 The procedure of Example II-1 was carried out except that 50 g of the polyester A used in Example II-1, 1 kg of the polyester B used in Example II-1, and 50 g of the polyester C used in Example II-1 were used. Mixed with 100g of titanium dioxide. Wires II-D4 were obtained.
  • Example II-1 The procedure of Example II-1 was carried out except that the same weight of PBS (available from BASF Corporation under the designation 1111HTA4) was used instead of the polyester A used in Example II-1. Wires II-D5 were obtained.
  • PBS available from BASF Corporation under the designation 1111HTA4
  • Example II-1 The procedure of Example II-1 was carried out except that the same weight of PBS (available from BASF Corporation under the designation 1111HTA4) was used instead of the polyester C used in Example II-1. Wires II-D6 were obtained.
  • PBS available from BASF Corporation under the designation 1111HTA4
  • Example II-1 The procedure of Example II-1 was carried out except that 1.1 kg of the polyester A used in Example II-1 and 100 g of titanium oxide were mixed. Wires II-D7 were obtained.
  • Example II-1 The procedure of Example II-1 was carried out except that 1.1 kg of the polyester B used in Example II-1 and 100 g of titanium oxide were mixed. Wires II-D8 were obtained.
  • Example II-1 The procedure of Example II-1 was carried out except that 1.1 kg of the polyester C used in Example II-1 and 100 g of titanium oxide were mixed. Wires II-D9 were obtained.
  • Example II-1 follows the method of Example II-1, except that 1.1 kg of PBT (purchased from DuPont) Division, graded Crastin SC164 NC010) mixed with 100g titanium dioxide. Wires II-D10 were obtained.
  • polyester composition pellets obtained in Examples II-1 to II-10 and Comparative Examples II-1 to II-10 were cast on a room temperature (25 ° C) plate by a Haake mini-casting machine, to be flowed After the stent was completely cooled and solidified, the surface that did not contact the cooling plate was tested for gloss.
  • the gloss of the cast sheets obtained in Examples II-1 to II-10 and Comparative Examples II-1 to II-10 was evaluated in accordance with the GBT9754-2007 standard. The results are shown in Table 2.
  • the wires obtained in Examples II-1 to II-10 and Comparative Examples II-1 to II-10 were cut into granules, and the granules were melt-heated on a melting point to a sheet of 7 cm ⁇ 7 cm ⁇ 4 mm by a Carver hot press.
  • the Shore D hardness of the sheets obtained in Examples II-1 to II-10 and Comparative Examples II-1 to II-10 was evaluated in accordance with the method of GB/T2411-2008. The results are shown in Table 2.
  • the wires obtained in Examples II-1 to II-10 and Comparative Examples II-1 to II-10 were respectively loaded on a Makerbot Replicator 2X printer, and the nozzle temperature was raised until the speed at which the wires flowed out through the nozzles reached 2.4 m/min. This temperature is defined as the lowest print temperature.
  • the preset 3D printing shape can be finally printed, and the printing effect is “good”, and the actual printing shape is deviated from the preset 3D printing shape. not good”.
  • the results of the minimum print temperature and printing results are shown in Table 2.
  • the biodegradation of the films prepared in Examples II-1 to II-10 and Comparative Examples II-1 to II-10 was tested as follows: using the compost (secondary age of 2 months) provided by Beijing Nangong Composting Plant, 18 g, 3 g of the wire to be tested was added, mixed with an appropriate amount of distilled water and appropriately stirred, and then placed at normal temperature (25 ° C). Whether the biodegradation is qualified by measuring whether the weight loss is more than 50% in 3 months Standard. The results are shown in Table 2.
  • the 3D printed wires obtained in Examples II-1 to II-10 can be stored for at least one year without any significant change in a clean environment at normal temperature and humidity, only in the case of soil, eutrophication or composting. Significant degradation will occur.
  • the present invention has a specific ratio of polyester A, polyester B and polyester C according to a specific ratio (51-98% by weight of polyester A, 1-48% by weight of poly
  • the ester B, 1-48% by weight of the polyester C) is blended to obtain a polyester composition, which is made into a 3D printed wire having a high gloss and can be at a lower temperature ( 105-165 ° C) printing; at the same time, the 3D printed wire can be used as a flexible wire (Shore D hardness of 35-50), and can be degraded, with good environmental advantages and application prospects.
  • polyester composition III-A1 pellets were placed in a screw extruder equipped with a die and a mandrel, extruded into a tube at 180 ° C, and water-cooled at 40 ° C. The mixture was further heated to 90 ° C, expanded to an inner diameter of 5 times the original size, and cooled at 40 ° C to form a heat shrinkable sleeve III-B1.
  • BT-BS copolyester A weight average molecular weight of 100,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 45 mol%)
  • 0.25 kg of BT-BS copolyester B weight average molecular weight is 100,000, wherein the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • the content is 80% by mole), 0.05kg of antioxidant 300 (hindered phenolic antioxidant produced by the Materials Synthesis Research Institute of the Ministry of Chemical Industry), 0.05kg of carbon black, mixed and extruded, drawn and air cooled by a twin-screw extruder. Pelletizing, wherein the temperature in each section of the twin-screw extruder from the feed port to the extrusion port is 190 ° C, 200 ° C, 210 ° C, 220 ° C, 220 ° C, 210 ° C, the screw rotation speed is 20 rpm, the torque is 10N*m.
  • Polyester Composition III-A2 Made of polyester Composition III-A2.
  • polyester composition III-A2 pellets were placed in a screw extruder equipped with a die and a mandrel, extruded into a tube at 120 ° C, and water-cooled at 20 ° C.
  • the mixture was further heated to 70 ° C, expanded to an inner diameter of 5 times the original size, and cooled and set at 20 ° C to obtain a heat shrinkable sleeve III-B2.
  • BT-BS copolyester A weight average molecular weight of 100,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 40 mol%)
  • 0.75 kg of BT-BS copolyester B weight average molecular weight is 100,000, wherein the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • polyester composition III-A3 pellets were placed in a screw extruder equipped with a die and a mandrel, extruded into a tube at 160 ° C, and water-cooled at 25 ° C.
  • the mixture was further heated to 80 ° C, expanded to an inner diameter of 5 times the original size, and cooled and set at 25 ° C to obtain a heat shrinkable sleeve III-B3.
  • BT-BS copolyester A weight average molecular weight of 100,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 49 mol%)
  • 0.05 kg of BT-BS copolyester B weight average molecular weight is 100,000, wherein the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • polyester composition III-A4 pellets were placed in a screw extruder equipped with a die and a mandrel, extruded into a tube at 180 ° C, and water-cooled at 25 ° C. The mixture was further heated to 90 ° C, expanded to an inner diameter of 5 times the original size, and cooled at 25 ° C to form a heat shrinkable sleeve III-B4.
  • BT-BS copolyester A weight average molecular weight of 100,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 30 mol%)
  • 2.45 kg of BT-BS copolyester B weight average molecular weight is 100,000, wherein the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • antioxidant 300 hindered phenolic antioxidant produced by the Materials Synthesis Institute of the Ministry of Chemical Industry
  • carbon black 0.05kg of carbon black, mixed and extruded, drawn, air-cooled, by twin-screw extruder, Pelletizing, wherein the temperature in each section of the twin-screw extruder from the feed port to the extrusion port is 190 ° C, 200 ° C, 210 ° C, 220 ° C, 220 ° C, 210 ° C, the screw rotation speed is 10 rpm, the torque is 20N*m.
  • a polyester composition III-A5 was obtained.
  • the above polyester composition III-A5 pellets were placed in a screw extruder equipped with a die and a mandrel, extruded into a tube at 180 ° C, and water-cooled at 25 ° C. The mixture was further heated to 90 ° C, expanded to an inner diameter of 5 times the original size, and cooled at 25 ° C to form a heat shrinkable sleeve III-B5.
  • Example III-1 The procedure of Example III-1 was carried out except that the polyester A was a BT-BA copolyester (weight average molecular weight was 100,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit. The content of the unit is 45 mol%); the polyester B is a BT-BA copolyester (weight average molecular weight is 100,000, wherein the content of the BT repeating unit is 70 based on the total number of moles of the BT repeating unit and the BA repeating unit; Molar%). Obtaining polyester composition III-A6 And heat shrinkable sleeve III-B6.
  • Example III-1 The procedure of Example III-1 was carried out except that the polyester A was a BT-ES (succinic acid glycol) copolyester (weight average molecular weight was 200,000, wherein the BT repeating unit and the ES repeating unit were used. Based on the total moles, the content of the BT repeating unit is 45 mol%); the polyester B is a BT-ES copolyester (weight average molecular weight is 200,000, wherein, based on the total moles of the BT repeating unit and the ES repeating unit) The content of the BT repeating unit was 70% by mole). Polyester composition III-A7 and heat shrinkable sleeve III-B7 were obtained.
  • BT-ES succinic acid glycol copolyester
  • Example III-1 The procedure of Example III-1 was carried out except that the polyester A was a BT-BA copolyester (weight average molecular weight was 500,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit. The content of the unit is 45 mol%); the polyester B is a BT-ES copolyester (weight average molecular weight is 500,000, wherein the content of the BT repeating unit is 70 based on the total number of moles of the BT repeating unit and the ES repeating unit. Molar%). Polyester composition III-A8 and heat shrinkable sleeve III-B8 were obtained.
  • Example III-1 The procedure of Example III-1 was followed except that 0.05 kg of titanium dioxide was used instead of 0.05 kg of carbon black used in Example III-1. Polyester composition III-A9 and heat shrinkable sleeve III-B9 were obtained.
  • Example III-1 The procedure of Example III-1 was followed except that 0.05 kg of antioxidant 300 and 0.05 kg of carbon black were not added. Polyester composition III-A10 and heat shrinkable sleeve III-B10 were obtained.
  • Example III-1 The procedure of Example III-1 was carried out except that the polyester A in Example III-1 was directly formed into the sleeve III-DB1, and the blending with the polyester B in Example III-1 was not included. process.
  • Example III-1 The procedure of Example III-1 was carried out except that the polyester B of Example III-1 was directly formed into the sleeve III-DB2, and the blend of the polyester A in Example III-1 was not included. process.
  • Example III-1 The procedure of Example III-1 was carried out except that the same weight of PBT (purchased from DuPont, under the designation Crastin SC164 NC010, the same below) was used instead of the polyester A used in Example III-1.
  • Example III-1 The procedure was carried out in the same manner as in Example III-1 except that the same weight of PBT was used instead of the polyester B used in Example III-1 to obtain a sleeve III-DB4.
  • Example III-1 The procedure of Example III-1 was carried out except that the same weight of PBS (purchased from BASF Corporation, brand No. 1111HTA4, the same below) was used instead of the polyester A used in Example III-1 to obtain a sleeve III. -DB5.
  • PBS purchased from BASF Corporation, brand No. 1111HTA4, the same below
  • Example III-1 The procedure of Example III-1 was carried out except that the same weight of PBS was used instead of the polyester B used in Example III-1 to prepare a sleeve III-DB6.
  • Example III-1 The procedure was carried out in the same manner as in Example III-1 except that the amount of the polyester A was 1 kg and the amount of the polyester B was 4 kg to obtain a sleeve III-DB7.
  • Example III-1 The procedure of Example III-1 was carried out except that the amount of the polyester A was 2.5 kg and the amount of the polyester B was 2.5 kg, and the sleeve III-DB8 was obtained.
  • Example III-1 The procedure of Example III-1 was followed except that the PBT was directly formed into a sleeve III-DB9.
  • Example III-1 The procedure of Example III-1 was followed except that PBS was directly formed into cannula III-DB10.
  • Shrinkage ratio test Measure the outer diameter of the heat-shrinkable tube before shrinking at 25 ° C using a vernier caliper; place the heat-shrink tube in an oven at 80 ° C for 1 hour, remove it and naturally cool it to 25 ° C, and measure the shrinkage of the heat-shrinkable tube using a vernier caliper After the outer diameter, the shrinkage ratio result was recorded as "diameter before shrinkage: diameter after shrinkage”.
  • the shrinkage ratios of the sleeves prepared in Examples III-1 to III-10 and Comparative Examples III-1 to III-10 were measured in this manner, and the results are shown in Table 3.
  • Puncture strength test The puncture strength of the sleeve materials prepared in Examples III-1 to III-10 and Comparative Examples III-1 to III-10 were tested in accordance with the national standard GB T1408.1-2006. The results show that the sleeves produced in Examples III-1 to III-10 have a breakdown strength of ⁇ 25 kV/mm, which indicates that the sleeve obtained by the present invention has good insulation properties.
  • Degradability test 18kg of compost (2 months fat) provided by Beijing Nangong Composting Plant, plus 3g of film to be tested, mixed with appropriate amount of distilled water and stirred properly, then placed at room temperature, whether it loses more than 50% in 3 months As a measure of eligibility for biodegradation.
  • heat shrinkable sleeves prepared in Examples III-1 to III-10 can be stored for at least one year without any significant change in a clean environment at normal temperature and humidity, only in the case of soil, eutrophication or composting. Significant degradation will occur.
  • the present invention is based on a specific ratio of the specific copolymer (polyester A and polyester B) (the content of the polyester A is 51 to 99% by weight, the content of the polyester B). Blending from 1 to 49% by weight to obtain a heat shrinkage ratio (up to 5:4.5 or more) and A heat shrinkable sleeve with high insulation. Moreover, the heat shrinkable sleeve does not need to be crosslinked during the preparation process, and has good degradability, so it has a broad market space.
  • BT-BA copolyester A weight average molecular weight of 100,000, based on the total moles of BT repeating unit and BA repeating unit, The content of the BT repeating unit is 25 mol%) particles
  • 20 g of BT-BS copolyester B weight average molecular weight is 110,000, wherein the content of the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • BT-BA copolyester A weight average molecular weight of 100,000, based on the total moles of BT repeating unit and BA repeating unit, The content of the BT repeating unit is 40 mol%) particles, 9.5 g of BT-BS copolyester B (weight average molecular weight is 110,000, wherein the content of the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit. 15 mol%) granules, 9.5 g of glass fibers and 10 g of anhydrous calcium sulfate were thoroughly mixed.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 40 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 180 ° C.
  • the polyester composition IV-A2 was obtained at 190 ° C, 195 ° C, 195 ° C, 195 ° C, and 195 ° C.
  • BT-BA copolyester A weight average molecular weight of 100,000, based on the total moles of BT repeating unit and BA repeating unit, The content of the BT repeating unit is 23 mol%) particles
  • 57 g of BT-BS copolyester B weight average molecular weight is 110,000, wherein the content of the BT repeating unit is 5 based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • Molar%) granules, 19 g of glass fibers and 10 g of anhydrous calcium sulphate were thoroughly mixed.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 40 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 180 ° C.
  • the polyester composition IV-A3 was obtained at 190 ° C, 195 ° C, 195 ° C, 195 ° C, and 195 ° C.
  • BT-BA copolyester A weight average molecular weight of 100,000, based on the total moles of BT repeating unit and BA repeating unit, The content of the BT repeating unit is 45 mol%) particles
  • 85.5 g of BT-BS copolyester B weight average molecular weight is 110,000, wherein the content of the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit 20 mol%) of the granules, 9.5 g of basalt fiber and 10 g of anhydrous calcium sulfate were thoroughly mixed.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 40 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 180 ° C.
  • the polyester composition IV-A4 was obtained at 190 ° C, 195 ° C, 195 ° C, 195 ° C, and 195 ° C.
  • BT-BA copolyester A weight average molecular weight of 100,000, wherein BT is based on the total moles of BT repeating unit and BA repeating unit, BT The content of the repeating unit was 20 mol%), 9.5 g of PBT (available from DuPont, under the designation Crastin SC164 NC010) particles, 85.5 g of basalt fiber and 10 g of anhydrous calcium sulfate were thoroughly mixed.
  • the obtained mixture was subjected to extrusion granulation by a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 40 N*m, and the twin-screw extruder was used.
  • the temperature of each section of the feed port to the extrusion port was 180 ° C, 190 ° C, 195 ° C, 195 ° C, 195 ° C, and 195 ° C to obtain a polyester composition IV-A5.
  • Example IV-1 The procedure of Example IV-1 was carried out except that the polyester A was a BT-BA copolyester (weight average molecular weight was 100,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit. The content of the unit is 25 mol%); the polyester B is a BT-BA copolyester (weight average molecular weight is 110,000, wherein the content of the BT repeating unit is 10 based on the total number of moles of the BT repeating unit and the BA repeating unit. Molar%).
  • a polyester composition IV-A6 was obtained.
  • Example IV-1 The procedure of Example IV-1 was carried out except that the polyester A was a BT-ES copolyester (weight average molecular weight was 200,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the ES repeating unit. The content of the unit is 25 mol%); the polyester B is a BT-ES copolyester (weight average molecular weight is 200,000, wherein the content of the BT repeating unit is 10 based on the total number of moles of the BT repeating unit and the ES repeating unit. Molar%).
  • a polyester composition IV-A7 was obtained.
  • Example IV-1 The procedure of Example IV-1 was carried out except that the polyester A was a BT-BA copolyester (weight average molecular weight was 500,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit. The content of the unit is 25 mol%); the polyester B is a BT-ES copolyester (weight average molecular weight is 500,000, wherein the content of the BT repeating unit is 10 based on the total number of moles of the BT repeating unit and the ES repeating unit. Molar%).
  • a polyester composition IV-A8 was obtained.
  • Example IV-1 The procedure of Example IV-1 was followed except that anhydrous calcium sulfate was not added. A polyester composition IV-A9 was obtained.
  • Example IV-1 The procedure of Example IV-1 was followed except that 170 g of the polyester A used in Example IV-1, 20 g of glass fiber and 10 g of anhydrous calcium sulfate were mixed without adding the example IV-1. Polyester B used. A polyester composition IV-D1 was obtained.
  • Example IV-1 The procedure of Example IV-1 was followed except that 170 g of the polyester B used in Example IV-1, 20 g of glass fiber and 10 g of anhydrous calcium sulfate were mixed without adding the polyester used in Example IV-1. A. A polyester composition IV-D2 was obtained.
  • Example IV-1 The procedure of Example IV-1 was followed except that the same weight of PBT (available from DuPont, under the designation Crastin SC164 NC010) was used instead of the polyester A used in Example IV-1.
  • a polyester composition IV-D3 was obtained.
  • Example IV-1 The procedure of Example IV-1 was followed except that the same weight of PBT (available from DuPont, under the designation Crastin SC164 NC010) was used instead of the polyester B used in Example IV-1. A polyester composition IV-D4 was obtained.
  • PBT available from DuPont, under the designation Crastin SC164 NC010
  • Example IV-1 The procedure of Example IV-1 was carried out except that the same weight of PBS (available from BASF, under the designation 1111HTA4, the same below) was used instead of the polyester A used in Example IV-1 to prepare a polyester composition.
  • PBS available from BASF, under the designation 1111HTA4, the same below
  • Example IV-1 The procedure of Example IV-1 was followed except that no glass fibers were added. A polyester composition IV-D6 was obtained.
  • Example IV-1 The procedure of Example IV-1 was carried out except that the amount of the polyester A was 20 g and the amount of the polyester B was 150 g. A polyester composition IV-D7 was obtained.
  • Example IV-1 The procedure of Example IV-1 was followed except that 190 g of PBT and 10 g of anhydrous calcium sulfate were mixed. A polyester composition IV-D8 was obtained.
  • Example IV-1 The procedure of Example IV-1 was followed except that 190 g of PBS and 10 g of anhydrous calcium sulfate were mixed. A polyester composition IV-D9 was obtained.
  • polyester compositions prepared in Examples IV-1 to IV-9 and Comparative Examples IV-1 to IV-9 were respectively melted, treated at 170 ° C and 1000 MPa for 5 minutes, and pressed into a thickness of 4 mm and a side length of 7 cm. Plate.
  • the hot plate was taken out, and the plate was quenched with a cold iron block placed at room temperature for 1 min, taken out, and left at room temperature (25 ° C) for 1 h.
  • the placed panels were measured using a Drick shore D hand hardness tester and the measurements were recorded after 15 seconds. Subsequently, the sheet was heated to 90 ° C on a hot plate, and the Shore D hardness was measured again in the same manner.
  • Table 4 The results are shown in Table 4.
  • polyester compositions prepared in Examples IV-1 to IV-9 and Comparative Examples IV-1 to IV-9 were respectively made into stamping splines, and the formed punched splines were subjected to shape memory performance test, and the results were as follows. Table 4 shows.
  • the shape memory properties of the polyester composition were measured using an Instron 5965 tensile tester (with an incubator) as follows:
  • the initial length of the polyester composition spline at room temperature is a; the incubator is heated to 80 ° C, fully softened, stretched to a length b at a tensile speed of 50 mm / min; The length is constant, the temperature is lowered, the sample strip is solidified, and the external force is removed. At this time, the length of the spline is c; the spline is heated again to 80 ° C, and the spline is fully retracted, and the length of the spline is d;
  • Deformation fixation rate (%) (c-a) / (b-a) ⁇ 100%;
  • the maximum deformation rate (%) b max / a ⁇ 100%, where b max is the maximum b that can be reached before the spline is damaged.
  • the polyester compositions of Examples IV-1 to IV-9 had lower hardness at higher temperatures (90 ° C) than Comparative Examples IV-1 to IV-9. However, the hardness at a lower temperature (25 ° C) is significantly increased, and it is easy to shape. Further, the polyester compositions of Examples IV-1 to IV-9 have a high deformation fixing ratio (up to 90% or more), a deformation recovery ratio (up to 90% or more), and a maximum deformation rate (up to 280% or more). The above results indicate that the polyester composition provided by the present invention has good low temperature plasticity and shape memory properties.
  • the polyester composition IV-A1 obtained in Example IV-1 was molded into a dental protector by injection molding at a temperature of 170 ° C, injected into an aluminum mold, and released into a U-shaped mold at normal temperature (25 ° C).
  • the obtained U-shaped mold is softened in hot water at 90 ° C, and then rapidly cooled to 0 ° C, containing the inlet, the upper and lower teeth are bitten to form a tooth contour, and after repeated grinding, the finished tooth protector is obtained. As shown in Figures 1 and 2.
  • the dental protector When the dental protector is worn or uncomfortable, the dental protector is softened again in hot water at 90 ° C, and then rapidly cooled to 0 ° C, containing the entrance, the upper and lower teeth are bite to form a tooth contour, which is re-grinded after repeated grinding.
  • a finished tooth protector that is more conformable to the shape of the teeth.
  • the polyester composition IV-A1 obtained in Example IV-1 was formed into a knee-protecting intermediate layer by injection molding at a temperature of 175 ° C, injected into an aluminum mold, and subjected to mold release at room temperature (25 ° C) to obtain a mold.
  • the obtained mold was softened in hot water at 90 ° C, then rapidly cooled to 0 ° C, placed on the surface of the knee joint to form a knee joint profile, and the intermediate layer of the knee brace was obtained after repeated grinding.
  • the inner surface of the obtained middle layer of the knee protector is connected to the inner layer of the cotton material through a tape, and the outer surface of the middle layer of the knee protector is connected to the outer layer of the aluminum alloy material by a hook and can be taken out at any time.
  • the outer layer, the intermediate layer and the inner layer are assembled together into a knee care product. As shown in Figures 3 and 4.
  • the knee pads When the knee pads are worn or uncomfortable, the knee pads are softened again in hot water at 90 ° C, then rapidly cooled to 0 ° C, placed on the surface of the knee joint to form a knee joint contour, which is re-finished after repeated grinding.
  • the knee joint is more conformable to the middle layer of the knee.
  • the polyester composition IV-A1 obtained in Example IV-1 was formed into an intermediate layer of the upper body protector by injection molding, and the processing temperature of the injection molding was 180 ° C, which was injected into an aluminum mold, and after being released at room temperature (25 ° C). Get the mold.
  • the obtained mold is softened in hot water at 90 ° C, and then rapidly cooled to 0 ° C, pressed around the surface of the upper body to form an upper body contour, which is repeatedly polished. Go to the middle layer of the upper body protector.
  • the inner surface of the obtained intermediate layer of the upper body protector is connected to the inner layer of the spandex material through a tape, and the outer surface of the middle layer of the upper body protector is connected to the outer layer of the PBS material by a hook and can be taken out at any time.
  • the outer layer, the intermediate layer and the inner layer are assembled together into a finished upper body protector. As shown in Figures 5 and 6.
  • the upper body protector When the upper body protector is worn or uncomfortable, the upper body protector is softened again in hot water at 90 ° C, then rapidly cooled to 0 ° C, pressed around the surface of the upper body to form the upper body contour, which is re-obtained after repeated grinding.
  • the middle layer of the upper body protector that conforms to the upper body.
  • the polyester composition IV-A1 obtained in Example IV-1 was formed into an intermediate layer of a helmet by injection molding, and the processing temperature of the injection molding was 185 ° C, which was poured into an aluminum mold, and a mold was obtained after demolding at room temperature (25 ° C).
  • the obtained mold was softened in hot water at 90 ° C, then rapidly cooled to 0 ° C, placed on the surface of the head to press to form a head contour, and after repeated grinding, an intermediate layer of the helmet was obtained.
  • the inner surface of the obtained intermediate layer of the helmet is connected to the inner layer of the sponge material by a hook, and the outer surface of the middle layer of the knee protector is connected with the outer layer of the aluminum alloy material through the hook.
  • the outer layer, the middle layer and the inner layer are also fixed by snaps and assembled together into a finished helmet. As shown in Figure 7.
  • the helmet When the helmet is worn or uncomfortable, the helmet is softened again in hot water at 90 ° C, then rapidly cooled to 0 ° C, placed on the surface of the head to press to form the head contour, after repeated grinding to get the shape and The middle layer of the helmet that fits the head more closely.
  • polyester composition provided by the present invention when used for a sports brace, it can be shaped according to the difference of the applied parts, so that the protective device is more conformable to the body and more
  • the utility model is comfortable and convenient to manufacture; in addition, if the sports safety device of the invention wears or is slightly damaged, the protective device can be restored to the original appearance by warming softening and low temperature reshaping again.
  • BT-BS copolyester A weight average molecular weight of 130,000, based on the total moles of BT repeating unit and BS repeating unit, The content of the BT repeating unit is 30 mol%) particles
  • 3 kg of BT-BA copolyester B weight average molecular weight is 100,000, wherein the content of the BT repeating unit is based on the total number of moles of the BT repeating unit and the BA repeating unit. 70 mol%) particles were mixed with 1 kg of iron oxide.
  • the obtained mixture was subjected to extrusion granulation by a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 150 ° C.
  • the polyester composition V-A1 was obtained at 160 ° C, 170 ° C, 170 ° C, 170 ° C, and 170 ° C.
  • BT-BS copolyester A weight average molecular weight of 200,000, based on the total moles of BT repeating unit and BS repeating unit, The content of the BT repeating unit is 25 mol%) particles
  • 2 kg of BT-BA copolyester B weight average molecular weight is 200,000, wherein the content of the BT repeating unit is based on the total number of moles of the BT repeating unit and the BA repeating unit. 50 mol%) particles were mixed with 1 kg of titanium dioxide.
  • the obtained mixture was subjected to extrusion granulation by a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 150 ° C.
  • the polyester composition V-A2 was obtained at 160 ° C, 170 ° C, 170 ° C, 170 ° C, and 170 ° C.
  • BT-BS copolyester A weight average molecular weight of 130,000, based on the total moles of BT repeating unit and BS repeating unit, The content of the BT repeating unit is 30 mol%) particles, 1 kg of BT-BS copolyester B (weight average molecular weight is 100,000, wherein the content of the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit. 60 mol%) granules and 1 kg of titanium dioxide.
  • the obtained mixture is subjected to extrusion granulation through a twin-screw extruder, and the speed of the screw is controlled.
  • the system has a capacity of 10 rpm and a torque of 20 N*m.
  • the temperature of each section from the feed port to the extrusion port in the twin-screw extruder is 150 ° C, 160 ° C, 170 ° C, 170 ° C, 170 ° C, 170 ° C to obtain a polymer.
  • BT-BS copolyester A weight average molecular weight of 130,000, based on the total moles of BT repeating unit and BS repeating unit, The content of the BT repeating unit is 40 mol%) particles
  • BT-BA copolyester B weight average molecular weight is 100,000, wherein the content of the BT repeating unit is based on the total number of moles of the BT repeating unit and the BA repeating unit. 80 mol%) particles were mixed with 1 kg of iron oxide.
  • the obtained mixture was subjected to extrusion granulation by a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 150 ° C.
  • the polyester composition V-A4 was obtained at 160 ° C, 170 ° C, 170 ° C, 170 ° C, and 170 ° C.
  • BT-BS copolyester A weight average molecular weight of 130,000, based on the total moles of BT repeating unit and BS repeating unit
  • BT repeating unit content 20 mol% particles
  • BT-BA copolyester B weight average molecular weight of 100,000, wherein, based on the total number of moles of BT repeating unit and BA repeating unit, BT repeating unit The content was 41 mol%) and the particles were mixed with 1 kg of iron oxide.
  • the obtained mixture was subjected to extrusion granulation by a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 150 ° C.
  • the polyester composition V-A5 was obtained at 160 ° C, 170 ° C, 170 ° C, 170 ° C, and 170 ° C.
  • Example V-1 The procedure of Example V-1 was carried out except that the polyester A was a BT-BA copolyester (weight average molecular weight was 130,000, wherein the total number of moles of the BT repeating unit and the BA repeating unit) For the reference, the content of the BT repeating unit is 30 mol%); the polyester B is a BT-BA copolyester (weight average molecular weight is 100,000, wherein BT repeats based on the total number of moles of the BT repeating unit and the BA repeating unit) The content of the unit was 70% by mole).
  • a polyester composition V-A6 was obtained.
  • Example V-1 The procedure of Example V-1 was carried out except that the polyester A was a BT-ES copolyester (weight average molecular weight was 200,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the ES repeating unit. The content of the unit is 30 mol%); the polyester B is a BT-ES copolyester (weight average molecular weight is 200,000, wherein the content of the BT repeating unit is 70 based on the total number of moles of the BT repeating unit and the ES repeating unit; Molar%).
  • a polyester composition V-A7 was obtained.
  • Example V-1 The procedure of Example V-1 was carried out except that the polyester A was a BT-BA copolyester (weight average molecular weight was 500,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit. The content of the unit is 30 mol%); the polyester B is a BT-ES copolyester (weight average molecular weight is 500,000, wherein the content of the BT repeating unit is 70 based on the total number of moles of the BT repeating unit and the ES repeating unit; Molar%).
  • a polyester composition V-A8 was obtained.
  • Example V-1 The procedure of Example V-1 was followed except that no iron oxide was added. A polyester composition V-A9 was obtained.
  • Example V-1 The procedure of Example V-1 was carried out except that 10 kg of the polyester A used in Example V-1 and 1 kg of iron oxide were mixed without the addition of the polyester B used in Example V-1.
  • Composition V-D1 was prepared.
  • Example V-1 The procedure of Example V-1 was carried out except that 10 kg of the polyester B used in Example V-1 and 1 kg of iron oxide were mixed without the addition of the polyester A used in Example V-1.
  • Composition V-D2 was prepared.
  • Example V-1 The procedure of Example V-1 was followed except that the same weight of PBT (available from DuPont, under the designation Crastin SC164 NC010) was used instead of the polyester A used in Example V-1.
  • Composition V-D3 was prepared.
  • Example V-1 The procedure of Example V-1 was followed except that the same weight of PBT (available from DuPont, under the designation Crastin SC164 NC010) was used instead of the polyester B used in Example V-1.
  • Composition V-D4 was prepared.
  • Example V-1 The procedure of Example V-1 was carried out except that the same weight of PBS (available from BASF Corporation, brand No. 1111HTA4, the same hereinafter) was used instead of the polyester A used in Example V-1 to prepare a composition V- D5.
  • PBS available from BASF Corporation, brand No. 1111HTA4, the same hereinafter
  • Example V-1 The procedure of Example V-1 was carried out except that the same weight of PBS was used instead of the polyester B used in Example V-1.
  • Composition V-D6 was prepared.
  • Example V-1 The procedure of Example V-1 was carried out except that the amount of the polyester A was 3 kg and the amount of the polyester B was 7 kg. Composition V-D7 was prepared.
  • Example V-1 The procedure of Example V-1 was carried out except that the amount of the polyester A was 5 kg and the amount of the polyester B was 5 kg. Composition V-D8 was prepared.
  • Example V-1 The procedure of Example V-1 was carried out except that 10 kg of PBT and 1 kg of iron oxide were mixed. Composition V-D9 was prepared.
  • Example V-1 The procedure of Example V-1 was followed except that 10 kg of PBS and 1 kg of iron oxide were used. mixing. Composition V-D10 was prepared.
  • Examples V-1 to V-9 and Comparative Examples V-1 to V-11 were respectively melted, and then treated at 170 ° C and 1000 MPa for 5 minutes, and pressed into a sheet having a thickness of 4 mm and a side length of 7 cm.
  • the hot plate was taken out, and the plate was quenched with a cold iron block placed at room temperature for 1 min and time zero was recorded.
  • the quenched sheet was subjected to a test of Shore A hardness with time (measured with a Drick shore A hand hardness tester and measured after 3 seconds), and the results are shown in Table 5-1 below.
  • the polyester compositions V-A1 to V-A9 obtained in Examples V-1 to V-9 had a low hardness at the start of the test (higher temperature), and the treatment was cold. The post hardness increases slowly with time.
  • the materials V-D1 to V-D11 obtained in the comparative examples V-1 to V-11 had a high temperature at the start of the test and did not change with time.
  • the polyester compositions V-A1 to V-A9 obtained in Examples V-1 to V-9 have good plasticity and fixability, and are suitable for the preparation of medical limb fixation stents.
  • Examples V-1 to V-9 and Comparative Examples V-1 to V-11 were respectively melted, treated at 170 ° C, 1000 MPa for 5 min, pressed into 2 mm thick, and cut into square pieces having a side length of 1 cm. .
  • the cut sheet was placed on a Bruker D8Discovery 2D WAXD scatterometer, measured by transmission method, and the scattering curve of scattering intensity versus scattering angle was obtained, and then the peak area within the scattering angle of 5° to 30° was integrated. The value is Int-1.
  • the polyester composition provided by the present invention has good water-repellent properties, so that it does not require special packaging such as water-proof during storage and transportation; and, at room temperature, at least It remains unchanged for two years and has a small weight, which is only about 1/5 of the weight of a conventional plate made of calcium sulfate. At the same time, it has excellent X-ray permeability.
  • the polyester composition V-A1 obtained in Example V-1 was melted, and then pressed at 170 ° C and 1000 MPa to obtain a sheet having a thickness of 2 mm and a side length of 7 cm. Heat the hole with a diameter of 7 mm and evenly apply 4 holes on the plate. Waiting for about 1 hour to completely harden the plate, it can be used as a medical limb fixation bracket.
  • the medical limb fixation stent is placed in hot water (about 100 ° C) for about 10 s, and the medical limb fixation stent is fully softened. Then, the medical limb fixing bracket is taken out and cooled with cold water until it is not hot, dried and wrapped around a limb part (such as a finger) to be fixed, and gently pressed to bind the medical limb fixing bracket to the limb. Wait for about 5 minutes, and the medical limb fixation bracket is partially hardened and fixed to maintain the shape of the limb. Continue to avoid large movements of the limbs, wait for about 30 minutes, until the medical limb fixation bracket will completely harden, to achieve the purpose of protecting and fixing the limb.
  • the specific cured medical limb fixation bracket is shown in Figs. 8 and 9.
  • the cured medical limb fixation bracket can be placed in hot water at 100 ° C to soften it again, and then re-wound to be fixed.
  • the limb part, after it is hardened, remains in conformity with the shape of the limb.
  • the medical limb fixing bracket made by using the polyester composition provided by the invention can be fully softened under high temperature conditions (such as hot water, especially boiling water), and the softened material is easy to be cut and cut into Appropriate size and shape are wound around the part of the limb that needs to be fixed and can be hardened and self-adhesive for good shaping and fixing purposes.
  • the above process is reversible and can be reshaped according to the limb part.
  • the medical limb fixing bracket is easy to disassemble and clean; and has good degradation at the same time Performance, preparation process Because of the thermoplastic processing (no cross-linking agent), the scrap can also be recycled.
  • the above polyester composition VI-A1 pellet was passed through a casting machine and cast at 150 ° C to obtain a film having a thickness of 0.2 mm.
  • the film was allowed to stand at room temperature (25 ° C) for 10 hours, and then stretched to 5 times the original length at 60 ° C on a uniaxial stretching machine to prepare a heat-shrinkable film VI-B1.
  • BT-BS copolyester A weight average molecular weight of 100,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 38 mol%)
  • BT-BS copolyester B weight average molecular weight is 100,000, wherein BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit Content of 3 mol%)
  • the temperatures to the respective sections of the extrusion port were 170 ° C, 180 ° C, 190 ° C, 190 ° C, 190 ° C, and 190 ° C, respectively.
  • a polyester composition weight average molecular weight of 100,000, wherein the total number of moles of BT repeating unit
  • the above polyester composition VI-A2 pellets were passed through a casting machine and cast at 150 ° C to obtain a thickness. It is a 0.2 mm film. The film was allowed to stand at room temperature (25 ° C) for 10 hours, and then stretched to a ratio of 4.5 times the original length at 60 ° C on a uniaxial stretching machine to prepare a heat-shrinkable film VI-B2.
  • BT-BS copolyester A weight average molecular weight of 100,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 28 mol%)
  • BT-BS copolyester B weight average molecular weight is 100,000, wherein the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • the above polyester composition VI-A3 pellets were passed through a casting machine and cast at 150 ° C to obtain a film having a thickness of 0.2 mm.
  • the film was allowed to stand at room temperature (25 ° C) for 10 hours, and then stretched to 4 times the original length at 60 ° C on a uniaxial stretching machine to prepare a heat-shrinkable film VI-B3.
  • BT-BS copolyester A weight average molecular weight of 100,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 40 mol%)
  • 0.03 kg of BT-BS copolyester B weight average molecular weight is 100,000, wherein BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit Content of 20 mol%)
  • the temperatures to the respective sections of the extrusion port were 170 ° C, 180 ° C, 190 ° C, 190 ° C, 190 ° C, and 190 ° C, respectively.
  • a polyester composition VI weight average molecular weight of 100,000, wherein the total number of moles of
  • the above polyester composition VI-A4 pellets were passed through a casting machine and cast at 150 ° C to obtain a film having a thickness of 0.2 mm.
  • the film was allowed to stand at room temperature (25 ° C) for 10 hours, and then stretched at 60 ° C for 4 times on the uniaxial stretching machine to obtain a heat shrinkable film VI-B4.
  • BT-BS copolyester A weight average molecular weight of 100,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 20 mol%)
  • 1.47 kg of BT-BS copolyester B weight average molecular weight is 100,000, wherein the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • the above polyester composition VI-A5 pellets were passed through a casting machine and cast at 150 ° C to obtain a film having a thickness of 0.2 mm.
  • the film was allowed to stand at room temperature (25 ° C) for 10 hours, and then stretched to 1.5 times the original length at 60 ° C on a uniaxial stretching machine to prepare a heat-shrinkable film VI-B5.
  • Example VI-1 The procedure of Example VI-1 was carried out except that the polyester A was a BT-BA copolyester (weight average molecular weight was 100,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit. The content of the unit is 35 mol%); the polyester B is a BT-BA copolyester (weight average molecular weight is 100,000, wherein the content of the BT repeating unit is 15 based on the total number of moles of the BT repeating unit and the BA repeating unit. Molar%). Polyester composition VI-A6 and heat shrinkable film VI-B6 were obtained.
  • the polyester A was a BT-BA copolyester (weight average molecular weight was 100,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit. The content of the unit is 35 mol%); the polyester B is a BT-BA copolyester (weight average molecular weight is 100,000,
  • Example VI-1 The procedure of Example VI-1 was carried out except that the polyester A was a BT-ES copolyester (weight average molecular weight was 200,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the ES repeating unit. The content of the unit is 35 mol%); the polyester B is a BT-ES copolyester (weight average molecular weight is 200,000, wherein the content of the BT repeating unit is 15 based on the total number of moles of the BT repeating unit and the ES repeating unit. Molar%). Polyester composition VI-A7 and heat shrinkable film VI-B7 were obtained.
  • the polyester A was a BT-ES copolyester (weight average molecular weight was 200,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the ES repeating unit. The content of the unit is 35 mol%); the polyester B is a BT-ES copolyester (weight average mo
  • Example VI-1 The procedure of Example VI-1 was carried out except that the polyester A was a BT-BO (butylene phthalate) copolyester (having a weight average molecular weight of 500,000, wherein the BT repeating unit and the BO repeating unit were used. Based on the total moles, the content of the BT repeating unit is 35 mol%); the polyester B is a BT-ES copolyester (weight average molecular weight is 500,000, wherein, based on the total moles of the BT repeating unit and the ES repeating unit) The content of the BT repeating unit was 15 mol%). Polyester composition VI-A8 and heat shrinkable film VI-B8 were obtained.
  • BT-BO butylene phthalate copolyester
  • Example VI-1 The procedure of Example VI-1 was followed except that 0.2 kg of carbon black and 0.2 kg of titanium dioxide were used in place of 0.5 kg of calcium carbonate and 0.01 kg of erucamide used in Example VI-1.
  • a polyester composition VI-A9 and a heat shrinkable film VI-B9 were obtained.
  • Example VI-1 The procedure of Example VI-1 was followed except that 0.5 kg of calcium carbonate and 0.01 kg of erucamide were not added. Polyester composition VI-A10 and heat shrinkable film VI-B10 were obtained.
  • Example VI-1 The procedure of Example VI-1 was carried out except that the polyester A in Example VI-1 was directly formed into the film VI-DB1, and the blending process with the polyester B in Example VI-1 was not included. .
  • Example VI-1 The procedure of Example VI-1 was carried out except that the polyester B of Example VI-1 was directly formed into the film VI-DB2, and the process of blending with the polyester A in Example VI-1 was not included. .
  • Example VI-1 The procedure of Example VI-1 was carried out except that the same weight of PBT (available from DuPont, under the designation Crastin SC164 NC010, the same below) was used instead of the polyester A used in Example VI-1 to prepare a film.
  • PBT available from DuPont, under the designation Crastin SC164 NC010, the same below
  • Example VI-1 The method of Example VI-1 was carried out except that the same weight of PBT was used instead.
  • the polyester B used in Example VI-1 was used to prepare a film VI-DB4.
  • Example VI-1 The procedure of Example VI-1 was carried out except that the same weight of PBS (available from BASF Corporation, brand No. 1111HTA4, the same hereinafter) was used instead of the polyester A used in Example VI-1 to prepare a film VI- DB5.
  • PBS available from BASF Corporation, brand No. 1111HTA4, the same hereinafter
  • Example VI-1 The procedure of Example VI-1 was carried out except that the same weight of PBS was used instead of the polyester B used in Example VI-1 to obtain a film VI-DB6.
  • Example VI-1 The procedure of Example VI-1 was carried out except that the amount of the polyester A was 1 kg and the amount of the polyester B was 2 kg to prepare a film VI-DB7.
  • Example VI-1 The procedure was carried out in the same manner as in Example VI-1 except that the amount of the polyester A was 1.5 kg and the amount of the polyester B was 1.5 kg to obtain a film VI-DB8.
  • Example VI-1 The procedure of Example VI-1 was carried out except that PBT was directly formed into a film VI-DB9.
  • Example VI-1 The procedure of Example VI-1 was carried out except that PBS was directly formed into a film VI-DB10.
  • Thermal Shrinkage Test Films prepared in Examples VI-1 to VI-10 and Comparative Examples VI-1 to VI-10 were tested by heating on a Labthink Thermotek 2710 heat shrinkage apparatus at 70 ° C for 5 s. Heat shrinkage rate (%);
  • Heat seal strength test On a Brugger Munchen HSG-C heat sealer, after wrapping with 25 ⁇ m of PTFE, the corresponding film is heated at a pressure of 100 N per layer at 90 ° C. After sealing for 2 s, the samples of Examples VI-1 to VI-10 and Comparative Examples VI-1 to VI-10 were respectively tested by an Instron 5965 tensile tester (50 mm/min speed) according to the test method of QB/T 2358-1998. Heat sealing strength of the film (N/15mm);
  • Biodegradation test The biodegradation of the films prepared in Examples VI-1 to VI-10 and Comparative Examples VI-1 to VI-10 was tested according to the following methods, specifically, the compost provided by Beijing Nangong Composting Plant (fertilizer) 18 g of age 2), plus 3 g of film to be tested, mixed with appropriate amount of distilled water and stirred appropriately, and then placed at room temperature (25 ° C). Whether or not the weight loss is more than 50% in 3 months is a measure of whether biodegradation is acceptable.
  • heat-shrinkable films prepared in Examples VI-1 to VI-10 can be stored for at least one year without any significant change in a clean environment at normal temperature and humidity, only in the case of soil, eutrophication or composting. Significant degradation will occur.
  • the present invention is based on a specific ratio of the specific copolymer (polyester A and polyester B) (the content of the polyester A is 51 to 99% by weight, the content of the polyester B).
  • the content of the polyester A is 51 to 99% by weight, the content of the polyester B.
  • the present invention is adjusted by the formulation and the structure of the polyester.
  • the heat shrinkage rate of the film can be changed within a wide range; and the heat shrinkable film obtained by the present invention has a suitable heat seal strength (up to 11-19 N/15 mm), the film surface is flat, the gloss is good, and the film can be degraded and can be repeated.
  • Thermoplastic processing and recycling so it has obvious environmental advantages and industrial application prospects.
  • the above polyester polymer VII-A1 was added into the screw of the spunbonding machine.
  • the temperature of the screw area was 185 ° C
  • the temperature of the two zones was 190 ° C
  • the temperature of the three zones was 205 ° C
  • the spinning temperature was 195 ° C
  • the speed of the metering pump was 20 r / min.
  • the forming speed was 17 m/min
  • the hot rolling temperature was 105 ° C to obtain a nonwoven fabric VII-B1.
  • BT-BS copolyester A weight average molecular weight of 120,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 5 mol%)
  • 1.5 kg of BT-BS copolyester B weight average molecular weight is 100,000, wherein the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • the above polyester polymer VII-A2 was added into the screw of the spunbonding machine.
  • the temperature of the screw area was 185 ° C
  • the temperature of the second zone was 190 ° C
  • the temperature of the three zones was 205 ° C
  • the spinning temperature was 195 ° C
  • the speed of the metering pump was 20 r / min.
  • the forming speed was 17 m/min
  • the hot rolling temperature was 105 ° C to obtain a nonwoven fabric VII-B2.
  • BT-BS copolyester A weight average molecular weight of 120,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 12 mol%)
  • 2.25 kg of the BT-BS copolyester B weight average molecular weight is 100,000, wherein the BT repeating unit is based on the total number of moles of the BT repeating unit and the BS repeating unit.
  • BT-BS copolyester A weight average molecular weight of 120,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 25 mol%)
  • 0.05 kg of BT-BS copolyester B weight average molecular weight is 100,000, wherein the total number of moles of the BT repeating unit and the BS repeating unit is based on the BT repeating unit
  • the content is 80 mol%)
  • 0.25 kg of antioxidant 300 after mixing, extrusion, drawing, air-cooling and pelletizing by a twin-screw extruder, wherein the twin-screw extruder is from the feed port to the sections of the extrusion port.
  • the temperatures were 170 ° C, 180 ° C, 185 ° C, 185 ° C, 190 ° C, and 190 ° C.
  • the above polyester polymer VII-A4 was added into the screw of the spunbonding machine.
  • the temperature of the screw area was 185 ° C
  • the temperature of the second zone was 190 ° C
  • the temperature of the three zones was 205 ° C
  • the spinning temperature was 195 ° C
  • the speed of the metering pump was 20 r / min.
  • the forming speed was 17 m/min
  • the hot rolling temperature was 105 ° C to obtain a nonwoven fabric VII-B4.
  • BT-BS copolyester A weight average molecular weight of 120,000, wherein the total number of moles of BT repeating unit and BS repeating unit
  • the content of the BT repeating unit is 1 mol%)
  • 2.45 kg of BT-BS copolyester B weight average molecular weight is 100,000, wherein BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit Content of 26 mol%)
  • 0.25 kg of antioxidant 300 after mixing, extrusion, drawing, air cooling, pelletizing by twin-screw extruder, wherein the section from the feed port to the extrusion port in the twin-screw extruder
  • the temperatures were 170 ° C, 180 ° C, 185 ° C, 185 ° C, 190 ° C, and 190 ° C.
  • the polyester composition VII-A5 was obtained.
  • the above polyester polymer VII-A5 was added to the screw of the spunbonding machine.
  • the temperature of the screw area was 185 ° C
  • the temperature of the two zones was 190 ° C
  • the temperature of the three zones was 205 ° C
  • the spinning temperature was 195 ° C
  • the speed of the metering pump was 20 r / min.
  • the forming speed was 17 m/min
  • the hot rolling temperature was 105 ° C to obtain a nonwoven fabric VII-B5.
  • Example VII-1 The procedure of Example VII-1 was carried out except that the polyester A was a BT-BA copolyester (weight average molecular weight was 120,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit. The content of the unit is 18 mol%); the polyester B is a BT-BA copolyester (weight average molecular weight is 100,000, wherein the content of the BT repeating unit is 50 based on the total number of moles of the BT repeating unit and the BA repeating unit. Molar%). Polyester composition VII-A6 and non-woven fabric VII-B6 were obtained.
  • Example VII-1 The procedure of Example VII-1 was carried out except that the polyester A was a BT-ES copolyester (weight average molecular weight was 200,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the ES repeating unit. The content of the unit is 18 mol%); the polyester B is a BT-ES copolyester (weight average molecular weight is 200,000, wherein the content of the BT repeating unit is 50 based on the total number of moles of the BT repeating unit and the ES repeating unit. Molar%). Polyester composition VII-A7 and non-woven fabric VII-B7 were obtained.
  • Example VII-1 The procedure of Example VII-1 was carried out except that the polyester A was a BT-BO copolyester (weight average molecular weight was 500,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BO repeating unit. The content of the unit is 18 mol%); the polyester B is a BT-ES copolyester (weight average molecular weight is 500,000, wherein the content of the BT repeating unit is 50 based on the total number of moles of the BT repeating unit and the ES repeating unit. Molar%). Polyester composition VII-A8 and non-woven fabric VII-B8 were obtained.
  • Example VII-1 The procedure of Example VII-1 was carried out except that 0.25 kg of titanium dioxide of the same weight was used instead of 0.25 kg of the antioxidant 300 used in Example VII-1. Polyester composition VII-A9 and non-woven fabric VII-B9 were obtained.
  • Example VII-1 The procedure of Example VII-1 was followed except that 0.25 kg of antioxidant 300 was not added. A polyester composition VII-A10 and a heat shrinkable film VII-B10 were obtained.
  • Example VII-1 The procedure of Example VII-1 was carried out except that the polyester A of Example VII-1 was directly formed into the nonwoven fabric VII-DB1, and did not include the total of the polyester B in Example VII-1. Mixing process.
  • Example VII-1 The procedure of Example VII-1 was carried out except that the polyester B of Example VII-1 was directly formed into the nonwoven fabric VII-DB2, and did not include the total of the polyester A in Example VII-1. Mixing process.
  • Example VII-1 The procedure of Example VII-1 was carried out except that the same weight of PBT (available from DuPont, under the designation Crastin SC164 NC010, the same below) was used instead of the polyester A used in Example VII-1. Textile VII-DB3.
  • PBT available from DuPont, under the designation Crastin SC164 NC010, the same below
  • Example VII-1 The procedure of Example VII-1 was carried out except that the same weight of PBT was used instead of the polyester B used in Example VII-1 to obtain a nonwoven fabric VII-DB4.
  • Example VII-1 The procedure of Example VII-1 was carried out except that the same weight of PBS (available from BASF Corporation, brand No. 1111HTA4, the same below) was used instead of the polyester A used in Example VII-1 to obtain a nonwoven fabric. VII-DB5.
  • PBS available from BASF Corporation, brand No. 1111HTA4, the same below
  • Example VII-1 The procedure of Example VII-1 was carried out except that the same weight of PBS was used instead of the polyester B used in Example VII-1 to obtain a nonwoven fabric VII-DB6.
  • Example VII-1 The procedure of Example VII-1 was carried out except that the amount of the polyester A was 2 kg, and the polymerization was carried out. The amount of the ester B was 3 kg, and a nonwoven fabric VII-DB7 was obtained.
  • Example VII-1 The procedure of Example VII-1 was carried out except that the amount of the polyester A was 2.5 kg and the amount of the polyester B was 2.5 kg to obtain a film VII-DB8.
  • Example VII-1 The procedure of Example VII-1 was carried out except that PBT was directly formed into a nonwoven fabric VII-DB9.
  • Example VII-1 The procedure of Example VII-1 was carried out except that PBS was directly formed into a nonwoven fabric VII-DB10.
  • the water absorption test was verified by two methods, namely the non-woven drip test and the contact angle test of the material itself on water.
  • the specific test process is as follows.
  • Drip test use a dropper to drop a drop of deionized water on the surface of the prepared non-woven fabric. If the water droplets permeate freely through the non-woven fabric, the result is marked as "seepage”; if the water droplets float on the surface and maintain a good shape, similar to the load The water droplets on the surface of the leaf have a shape, and the result is marked as "drop”.
  • Gas permeability test A balloon was bundled on a thin tube having an inner diameter of about 1 mm and filled with gas to the same size. The balloon is free to deflate through the thin tube, and the time is counted as t 1 . A small piece of the nonwoven fabric in the examples or comparative examples was then placed in a thin tube mouth and then tested for emptying time, denoted as t 2 . If t 2 is less than 2 ⁇ t 1 , the result is marked as "breathable”, otherwise marked as "impermeable”.
  • Ethanol resistance test The ethanol resistance test is used to indicate whether the non-woven fabric reacts with ethanol during ethanol sterilization or dissolves in ethanol to reflect the easy sterilization of the non-woven fabric. Specifically, 2 g of the nonwoven fabric sample was placed in 75 vol% ethanol, left at room temperature for 24 hours, and then air-dried, and the surface of the nonwoven fabric sample was observed and weighed. If the sample satisfies (1) no significant change in appearance, and (2) the weight is not less than 99% of the original weight, the result is marked as "OK", otherwise it is marked as "No".
  • Heat shrinkage test A 10 cm ⁇ 10 cm nonwoven fabric was placed in hot water (80 ° C, 90 ° C, 95 ° C) for 10 s, then taken out, the size was measured, and then the area of the reduced nonwoven fabric was calculated. The percentage of the initial area.
  • Non-woven fabric Drip experiment Contact angle experiment Breathability test Ethanol resistance test Test
  • Example VII-1 VII-B1 Seepage Hydrophilic Breathable can Test
  • Example VII-2 VII-B2 Seepage Hydrophilic Breathable can Test
  • Example VII-3 VII-B3 Seepage Hydrophilic Breathable can Test
  • Example VII-4 VII-B4 Seepage Hydrophilic Breathable can Test
  • Example VII-5 VII-B5 Seepage Hydrophilic Breathable can Test
  • Example VII-6 VII-B6 Seepage Hydrophilic Breathable can Test
  • Example VII-7 VII-B7 Seepage Hydrophilic Breathable can Test
  • Example VII-8 VII-B8 Seepage Hydrophilic Breathable can Test
  • Example VII-9 VII-B9 Seepage Hydrophilic Breathable can Test
  • Example VII-10 VII-B10 Seepage Hydrophilic Breathable can Test
  • Example VII-11 VII-DB1 a Seepage Hydrophilic Breathable can Test
  • the non-woven fabrics prepared in Examples VII-1 to VII-10 and Comparative Examples VII-1 to VII-10 were respectively made into disposable surgical gowns, and after clinical use, the disposable disposable surgical gowns were immersed in boiling water for disinfection. .
  • the disposable surgical gowns made of the nonwoven fabrics VII-B1 to VII-B10 obtained in Examples VII-1 to VII-10 were greatly shrunk in boiling water, and the volume was remarkably reduced to facilitate recovery. Further, the recovered material was again added to a spunbonding machine as a raw material for preparing a nonwoven fabric, and a nonwoven fabric was newly obtained in accordance with the conditions of the spunbonding method in Example VII-1. It has also been found that the re-made nonwoven fabric has similar properties to the nonwoven fabrics VII-B1 to VII-B10 prepared in the above Examples VII-1 to VII-10, and is suitable for continuing as a raw material for disposable medical textile products. Thereby achieving material recycling.
  • the disposable surgical gowns made of the nonwoven fabrics VII-DB1 to VII-DB10 obtained in Comparative Examples VII-1 to VII-10 had almost no change in volume in boiling water, which would make the recycling work very cumbersome.
  • the recovered material was again added to a spunbonding machine as a raw material for preparing a nonwoven fabric, and a nonwoven fabric was newly obtained in accordance with the conditions of the spunbonding method in Example VII-1. As a result, it was found that some were not well formed, while others did not have good heat shrinkage properties and were not suitable for continuing as raw materials for disposable medical textile products.
  • the present invention by specific copolymers (Polyester A and Polyester B) according to a specific ratio (The content of polyester A is 51-99% by weight, and the content of polyester B is 1-49% by weight), and the obtained nonwoven fabric has good water absorbability, gas permeability and easy sterilizability, in particular
  • the non-woven fabric of the present invention can be sterilized in hot water (for example, 100 ° C) and shrunk greatly, so that it can be easily compressed to a small volume, facilitating the recovery and reproduction of materials (especially disposable materials), and
  • the remanufactured nonwoven fabric has similar properties to the first-use nonwoven fabric and is suitable for continuing as a raw material for disposable nonwoven fabric products (especially disposable medical textile products), thereby solving the material well. Recycling issues.
  • BT-BS copolyester A weight average molecular weight of 130,000, wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, content of BT repeating unit is 30 mol%) particles
  • 30 g of BT-BS copolyester B weight average molecular weight is 100,000, wherein BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit a content of 10 mol%) particles
  • 20 g of BT-BA copolyester C weight average molecular weight of 100,000, wherein, based on the total number of moles of BT repeating unit and BA repeating unit, wherein the content of BT repeating unit is 60 mol
  • the pellets, 10 g of titanium dioxide were mixed and stirred at 10 r/min for 10 min, then added to a twin-screw extruder, melt extruded at 220 ° C
  • polyester polymer VIII-A1 was spun into a fiber having a fineness of 72 dtex by melt spinning at 170 °C.
  • the fibers were allowed to stand at 40 ° C for 60 min, then warmed to 70 ° C and stretched to 4 times the original length. After cooling, the elastic fiber VIII-B1 was obtained.
  • BT-BS copolyester A weight average molecular weight of 130,000, wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, content of BT repeating unit is 30 mol%) particles
  • 12 g of BT-BS copolyester B weight average molecular weight is 100,000, wherein BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit a content of 10 mol%) particles
  • 4 g of BT-BA copolyester C weight average molecular weight of 100,000, wherein, based on the total moles of BT repeating units and BA repeating units, wherein the content of BT repeating units is 60 moles %) granules, 10g of titanium dioxide mixed and stirred at 10r/min for 10min, then added to the twin screw In an extruder, melt extrusion and granulation were carried out at
  • polyester polymer VIII-A2 was spun into a fiber having a fineness of 72 dtex by melt spinning at 170 °C.
  • the fibers were allowed to stand at 40 ° C for 60 min, then warmed to 70 ° C and stretched to 4 times the original length. After cooling, the elastic fiber VIII-B2 was obtained.
  • BT-BS copolyester A weight average molecular weight of 130,000, wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, content of BT repeating unit is 40 mol%) particles
  • 40 g of BT-BS copolyester B weight average molecular weight is 100,000, wherein BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit a content of 17 mol%) particles
  • 40 g of BT-BA copolyester C weight average molecular weight of 100,000, wherein, based on the total number of moles of BT repeating unit and BA repeating unit, wherein the content of BT repeating unit is 85 mol
  • the pellets, 10 g of titanium dioxide were mixed and stirred at 10 r/min for 10 min, then added to a twin-screw extruder, melt extruded at 220 °
  • the above polyester polymer VIII-A3 was spun into a fiber having a fineness of 72 dtex by melt spinning at 170 °C.
  • the fibers were allowed to stand at 40 ° C for 60 min, then warmed to 70 ° C and stretched to 4 times the original length. After cooling, the elastic fiber VIII-B3 was obtained.
  • BT-BS copolyester A weight average molecular weight of 130,000, wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, BT repeat unit content of 25 mol%) particles
  • 70 g BT-BS copolyester B weight average molecular weight of 100,000, wherein BT repeat unit and BS Based on the total moles of repeating units, the content of BT repeating units is 5 mol%) particles
  • 10 g of BT-BA copolyester C weight average molecular weight is 100,000, wherein the total number of moles of BT repeating units and BA repeating units
  • 10 g of titanium dioxide is mixed and stirred at 10 r/min for 10 min, then added to a twin-screw extruder, melt extruded and granulated at 220 ° C.
  • the polyester composition VIII weight average molecular weight of 130,000, wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, BT repeat
  • polyester polymer VIII-A4 was spun into a fiber having a fineness of 72 dtex by melt spinning at 170 °C.
  • the fibers were allowed to stand at 40 ° C for 60 min, then warmed to 70 ° C and stretched to 4 times the original length. After cooling, the elastic fiber VIII-B4 was obtained.
  • BT-BS copolyester A weight average molecular weight of 130,000 under stirring conditions (rate of agitation of 10r/min, time of 10min), wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, content of BT repeating unit is 49 mol%) particles
  • 138 g of BT-BS copolyester B weight average molecular weight is 100,000, wherein BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit Particles of 19 mol%)
  • 2 g of PBT available from DuPont, under the designation Crastin SC164 NC010
  • 10 g of titanium dioxide mixed and stirred at 10 r/min for 10 min then added to a twin-screw extruder at 220 ° C
  • the mixture was melt extruded and granulated to obtain a polyester composition VIII-A5.
  • polyester polymer VIII-A5 was spun into a fiber having a fineness of 72 dtex by melt spinning at 170 °C.
  • the fibers were allowed to stand at 40 ° C for 60 min, then warmed to 70 ° C and stretched to 4 times the original length. After cooling, the elastic fiber VIII-B5 was obtained.
  • BT-BS copolyester A weight average molecular weight: 130,000, wherein the content of BT repeating unit is 20 mol% based on the total moles of BT repeating unit and BS repeating unit
  • 2 g of BT-BS copolyester B weight average molecular weight is 100,000, wherein the content of BT repeating unit is 1 mol% based on the total moles of BT repeating unit and BS repeating unit
  • 138 g of BT-BA copolyester C weight average molecular weight is 100,000, wherein, based on the total moles of the BT repeating unit and the BA repeating unit, wherein the content of the BT repeating unit is 51 mol%)
  • 10 g of titanium dioxide is mixed and stirred at a rate of 10 r/min for 10 min, and then a twin screw is added.
  • melt extrusion and granulation were carried out at a twin screw is added.
  • polyester polymer VIII-A6 was spun into a fiber having a fineness of 72 dtex by melt spinning at 170 °C.
  • the fibers were allowed to stand at 40 ° C for 60 min, then warmed to 70 ° C and stretched to 4 times the original length. After cooling, the elastic fiber VIII-B6 was obtained.
  • BT-BS copolyester A weight average molecular weight of 130,000, wherein the total number of moles of BT repeating unit and BS repeating unit is Benchmark, content of BT repeating unit is 30 mol%) particles
  • 2 g of BT-BS copolyester B weight average molecular weight is 100,000, wherein BT repeating unit is based on the total number of moles of BT repeating unit and BS repeating unit a content of 10 mol%) particles
  • 2 g of BT-BA copolyester C weight average molecular weight of 100,000, wherein, based on the total number of moles of BT repeating unit and BA repeating unit, wherein the content of BT repeating unit is 60 mol
  • the pellets, 10 g of titanium dioxide were mixed and stirred at 10 r/min for 10 min, then added to a twin-screw extruder, melt extruded at 220 °
  • the above polyester polymer A7 was spun into a fiber having a fineness of 72 dtex by melt spinning at 170 °C.
  • the fibers were placed at 40 ° C for 60 min, then warmed to 70 ° C and stretched to the original 4 times longer. After cooling, the elastic fiber VIII-B7 was obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out except that the polyester A was a BT-BA copolyester (weight average molecular weight was 130,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit.
  • the polyester A was a BT-BA copolyester (weight average molecular weight was 130,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the BA repeating unit.
  • the content of the unit is 30 mol%);
  • the polyester B is a BT-ES ester (weight average molecular weight is 100,000, wherein the content of the BT repeating unit is 10 mol% based on the total number of moles of the BT repeating unit and the ES repeating unit
  • Polyester C is a BT-ES ester (having a weight average molecular weight of 100,000, wherein the content of the BT repeating unit is 60 mol% based on the total number of moles of the BT repeating unit and the ES repeating unit).
  • Polyester composition VIII-A8 and elastic fiber VIII-B8 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out except that the polyester A was a BT-ES copolyester (weight average molecular weight was 130,000, wherein BT was repeated based on the total number of moles of the BT repeating unit and the ES repeating unit.
  • the content of the unit is 30 mol%);
  • the polyester B is a BT-BA ester (weight average molecular weight is 100,000, wherein the content of the BT repeating unit is 10 mol% based on the total number of moles of the BT repeating unit and the BA repeating unit
  • Polyester C is a BT-BA ester (having a weight average molecular weight of 100,000, wherein the content of the BT repeating unit is 60 mol% based on the total number of moles of the BT repeating unit and the BA repeating unit).
  • Polyester composition VIII-A9 and elastic fiber VIII-B9 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was followed except that the same weight of calcium carbonate was used in place of the titanium dioxide of Example VIII-1. Polyester composition VIII-A10 and elastic fiber VIII-B10 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was followed except that 10 g of titanium dioxide was not added. Polyester composition VIII-A11 and elastic fiber VIII-B11 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out to give the polyester composition VIII-A1.
  • polyester polymer VIII-A1 was spun into a fiber having a fineness of 72 dtex by melt spinning at 170 °C.
  • the fibers were placed at 55 ° C for 120 min, then warmed to 110 ° C and stretched to 10 times the original length. After cooling, the elastic fiber VIII-B12 was obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out to give the polyester composition VIII-A1.
  • polyester polymer VIII-A1 was spun into a fiber having a fineness of 72 dtex by melt spinning at 170 °C.
  • the fibers were placed at 20 ° C for 2 min, then warmed to 56 ° C and stretched to 1.2 times the original length. After cooling, the elastic fiber VIII-B13 was obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out to give the polyester composition VIII-A1.
  • polyester polymer VIII-A1 was spun into a fiber having a fineness of 72 dtex by melt spinning at 170 °C. It was then directly cooled to 70 ° C and stretched to 4 times the original length, without including the procedure of placing at 40 ° C in Example VIII-1. After cooling, the elastic fiber VIII-B14 was obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out, except that in step (1), 150 g of the polyester A used in Example VIII-1, 50 g of the polyester B used in Example VIII-1, and 10 g of titanium oxide were mixed. The polyester C used in Example VIII-1 was not added. Polyester composition VIII-DA1 and elastic fiber VIII-DB1 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out, except that in the step (1), 150 g of the polyester A used in Example VIII-1, 50 g of the polyester C used in Example VIII-1, and 10 g of titanium oxide were mixed. The polyester B used in Example VIII-1 was not added. Polyester composition VIII-DA2 and elastic fiber VIII-DB2 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out, except that in step (1), 120 g of the polyester B used in Example VIII-1, 80 g of the polyester C used in Example VIII-1 and 10 g of titanium oxide were mixed. The polyester A used in Example VIII-1 was not added. Polyester composition VIII-DA3 and elastic fiber VIII-DB3 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was followed except that in the step (1), 20 g of the polyester A used in Example VIII-1, 160 g of the polyester B used in Example VIII-1, and 20 g of Example VIII were used. -1 used polyester C and 10 g of titanium dioxide mixed. Polyester composition VIII-DA4 and elastic fiber VIII-DB4 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out, except that in the step (1), the same weight of PBS (purchased from BASF Corporation, brand No. 1111HTA4) was used instead of the polyester A used in Example VIII-1. Polyester composition VIII-DA5 and elastic fiber VIII-DB5 were obtained.
  • PBS purchased from BASF Corporation, brand No. 1111HTA4
  • Example VIII-1 The procedure of Example VIII-1 was carried out, except that in the step (1), the same weight of PBS (purchased from BASF Corporation, brand No. 1111HTA4) was used instead of the polyester B used in Example VIII-1. Polyester composition VIII-DA6 and elastic fiber VIII-DB6 were obtained.
  • PBS purchased from BASF Corporation, brand No. 1111HTA4
  • Example VIII-1 The procedure of Example VIII-1 was carried out, except that in the step (1), the same weight of PBA was used instead of the polyester C used in Example VIII-1, wherein the preparation of PBA was carried out.
  • the method comprises the following steps: reacting adipic acid and butanediol in a nitrogen atmosphere in the presence of tetrabutyl titanate and acetylacetonate, and stirring at 240 ° C; adipic acid, butanediol, titanium The ratio VIII- of tetrabutyl acrylate and acetylacetonate ⁇ is 1800:2000:1:1. After 2 hours of reaction, the system was evacuated until the pressure stabilized at 100 Pa for half an hour. The remaining material in the system is the product. Polyester composition VIII-DA7 and elastic fiber VIII-DB7 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out, except that in the step (1), 200 g of the polyester A used in Example VIII-1 and 10 g of titanium oxide were mixed. Polyester composition VIII-DA8 and elastic fiber VIII-DB8 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out, except that in the step (1), 200 g of the polyester B used in Example VIII-1 and 10 g of titanium oxide were mixed. Polyester composition VIII-DA9 and elastic fiber VIII-DB9 were obtained.
  • Example VIII-1 The procedure of Example VIII-1 was carried out, except that in the step (1), 200 g of the polyester C used in Example VIII-1 and 10 g of titanium oxide were mixed. Polyester composition VIII-DA10 and elastic fiber VIII-DB10 were obtained.
  • a sample having a length of 2 cm (L1) was stretched to 2 times the original length (strain of 100%) on an Instron 5965 stretcher at a speed of 50 mm/min, and the stress at this time was recorded as E1. . Then, after maintaining the length for 20 s, the stress at this time is denoted as E2. The strain is then reduced until the stress is zero, at which time the length of the sample is L2. Then, the sample is at a speed of 50 mm/min. Stretching until fracture, the length of the sample at break is L3, and the stress value is E3.
  • the formula for calculating the above parameters is as follows:
  • the present invention has a specific ratio of polyester A, polyester B and polyester C according to a specific ratio (30-98% by weight of polyester A, 1-69 wt% of poly
  • the ester B, 1-69 wt% of the polyester C) is blended to obtain a polyester composition
  • the elastic fiber prepared using the polyester composition has good elastic properties, a breaking strength of ⁇ 1 cN/dtex, and
  • the adjustment of the molecular structure can be changed within a wide range, and the maximum breaking strength is close to 20 cN/dtex; and the elastic fiber provided by the invention has an elongation at break of more than 130%, and the stress relaxation and permanent strain rate can be ⁇ 12%.
  • This shows that the elastic fiber provided by the invention has moderate elasticity and strength, and has wide range of performance adjustability, so it has a good application prospect.
  • Example VIII-1 particularly produces an elastic fiber by a method and a condition of high-temperature filament-low temperature placement-high temperature stretching.
  • the breaking strength of the elastic fiber can be further increased, the performance adjustable range can be expanded, and the stress relaxation and permanent strain rate of the elastic fiber can be reduced.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Nursing (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Materials For Medical Uses (AREA)
  • Artificial Filaments (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Moulding By Coating Moulds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Nonwoven Fabrics (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

一种聚酯组合物，包含：(1)第一聚酯，选自脂肪族-芳香族共聚酯中的一种或多种，为含有式(I)所示的重复单元A和式(II)所示的重复单元B的共聚物， m为2-10的整数和n为2-8的整数；p为2-10的整数；且m、n和p彼此相同或不同； (2)任选的第二聚酯；其中所述聚酯组合物包含至少两种聚酯。所述聚酯组合物可用于形状记忆材料、3D打印线材、热收缩套管、功能层、医用肢体固定支架、热收缩薄膜、无纺布和弹性纤维等方面中。

Description

聚酯组合物及其制备方法和应用 技术领域
本发明涉及高分子材料领域，具体地，涉及一种聚酯组合物，该聚酯组合物的制备方法，及其在形状记忆材料、3D打印线材、热收缩套管、功能层、医用肢体固定支架、热收缩薄膜、无纺布和弹性纤维等方面的用途。
背景技术
形状记忆材料是一类特殊的智能材料。热致感应型形状记忆材料经历最初的赋形后，在一定的温度下受外力变形，冷却后能保持变形后的形状；而再次加热后，能恢复原来的形状。形状记忆型高分子具有加工容易，质量轻，操作温度低，以及价格低廉等优势，因此在许多高附加值的产业常有其应用于研究。形状记忆型高分子分为可逆和不可逆的两种。
CN103160948A揭示了一种基于交联的形状记忆高分子。它的形变固定率约为90-98％，形状回复率在85-95％之间，它们的最大形变率通常在20％-400％之间。这类形状记忆高分子的最初赋形都不可重复和再生。
CN105504474A揭示的一种形状记忆高分子，它的形状回复率为80-95％，形状固定率约为90-98％，最大形变率约为50％。这类形状记忆型高分子虽然最初赋形可重复，但它们的形状回复率和形状固定率往往不如不可逆的形状记忆型高分子，而最大形变率更差得多。
目前市场上并没有一种可大形变，并且形状回复率和形状固定率都接近100％的可逆形状记忆型高分子。
3D打印作为一种增材制造技术，为复杂形状产品的设计、制造提供了无限的可能，近年来备受人们的关注。目前3D打印技术主要包括选择 性激光烧结(SLS)、光固化成型(SLA)、熔融沉积成型(FDM)等。其中，FDM是最简单便捷、设备成本低的一种3D打印方式。目前市场上的FDM 3D打印线材还比较有限，市场上最主要的耗材是ABS和PLA。随着FDM 3D打印技术在不同领域的应用推广，人们对3D打印制品的性能和工艺需求也越来越多。
目前市场上主打的耗材都是硬材料，而柔软有弹性的材料还很有限，市场上柔性耗材主要是聚氨酯(TPU)材料，如CN104845353A中所述的聚氨酯(TPU)材料，或者如CN104004377A中所述的TPU复合材料。CN104845353A中所述的TPU材料，实施例中建议的打印温度为220℃以上。CN104004377A中所述的TPU复合材料，建议打印温度在240-260℃。市售FDM聚氨酯线材的建议打印温度一般在190℃以上，如190-250℃。
因此，开发可低温打印的柔性线材对于扩大3D打印在不同场合的应用、提高打印的安全性并降低能耗等都很有意义。
热收缩套管方面，目前市场上主要由辐照交联聚烯烃材料制成，在扩张定型后经过加热会恢复初始形状。
CN103333402A公开了无卤无红磷热缩管配方，使用乙烯-醋酸已烯共聚物以及氢氧化镁等作为主要组分，交联后制得。
另外还有一些特种热缩管来满足特殊需求，如耐化学腐蚀性较高的聚偏氟乙烯(PVDF)热缩管，透明度高的光纤热缩管，介电性能好的硅胶热缩管等等以满足不同需求。
然而，这些市面上的产品均采用交联的高分子材料制成，废弃后处理困难，特别是交联后的高分子网络难于分解。
针对目前日益严重的环境问题，热塑套管作为一类用量较大的一次性产品，对可生物降解的处理方式具有潜在需求。
CN101049729A公开了一种PET热缩管的制备方法，主要成份为聚 对苯二甲酸乙二醇酯(PET)混合聚酯弹性体，制备过程可以挤塑成型无需交联，然而PET的降解仍存在难度。
CN1580092A公开一种共聚酯及使用这种共聚酯制成热收缩套管的方法，使用的聚酯为含有乙二醇作为共聚单体的材料，具有较好的收缩性能，然而仍不具备生物降解性能。
因此，目前急需寻找既具有良好热收缩性能，又可以降解的热收缩套管。
运动护具市场上，目前主要分为软质护具及硬质护具。市面上大多数的普通的硬质护具的内层材料与软质护具材料一致，通过棉、氨纶和橡筋的织物包围住身体的部位，起到固定作用，再配合上中间层EVA或聚氨酯等缓冲材料，最外层通常使用PP或PE或ABS提供抗冲击和刮擦。该种运动护具的优势在于价格相对便宜，而缺点在于，固定不牢固，容易运动过程中脱落或滑移，或者由于硬质外层与身体受保护位置形状配合不佳导致佩戴不舒服。
在运动护具的开发中，美国Dow Corning公司提出了一种新的专利抗冲击技术-Dow Corning积极防护系统(Active Protection System)，英国D3O Lab公司研制出一种特殊衣料，例如US0157083中提到一种使用了D3O的运动防护头盔，瑞典POC公司独立开发的一种装甲防护材料，美国Rogers公司开发的poron护具材料。上述这些材料成本较高，而且这些材料不具备低温可塑功能，人体穿着之后无法根据个人需求进行塑型调整。并且，这些材料不具备高温记忆恢复功能，出现刮擦痕迹后十分影响外观和后续使用。
另外，护齿在运动护具中的作用也十分重要。成品护齿材料主要为橡胶、聚氯乙烯、聚乙酸乙烯脂-聚乙烯共聚物。成品护齿价格低廉，无法根据个人需求修改，佩戴不舒服，容易引起恶心，影响运动，已经逐渐被淘汰。目前，口内成型的半成品产品分为两类，一类是硬壳软囊护 齿，一类是热塑高分子材料。硬壳软囊护齿是在硬壳(聚氯乙烯)内注入丙烯酸类材料和EVA，充当软囊，整体安装在牙齿上。热塑高分子材料通常为聚乙酸乙烯脂-聚乙烯共聚物，通过热水加热然后含在口中咬合成型。这两种形式的护齿可以提供一定程度的保护作用，但是因为可塑性不高和热塑时间过短，导致佩戴欠舒适，且受到反复加热以及口腔唾液影响，该类产品寿命短。
US005339832A中提到了一种热塑型护齿，具有吸收能量的弹性体内嵌在牙套中，但其缺点仍然在于可塑性不强。
另外，在儿童护齿领域，因为儿童口腔发育持续改变形状，可以精确塑型并且具有记忆功能的护齿是市场上急缺的产品。
医用肢体固定支架方面，目前市场上主要有两类，一是石膏绷带，二是聚氨酯高分子绷带。另外，还有一种在医院中少量使用的、较昂贵的交联型绷带，主要由交联聚己内酯制备而成。
US4376438提出了一种基于聚氨酯的绷带产品，国内关于高分子绷带也有不少改良的专利，如CN102397133B。它对比与石膏绷带的优点是强度更大，可透过X射线，更轻。所有高分子绷带利用的都是异氰酸酯预聚物遇水后快速聚合或交联固化来达到固定的目的。它的操作仍然需要打开包装后浸泡在水中多次挤压，然后快速对患处进行塑形和缠绕。
另外，不论是石膏绷带还是聚氨酯高分子绷带，它们废弃之后都不可回收，且不可降解，将作为医疗垃圾处理。
因此，急需寻找易塑形、固定效果好、方便拆卸且可以回收的适用于医用肢体固定支架的材料。
热收缩薄膜是一种加热后能在尺寸上有明显缩小的薄膜。在包装行业，热收缩薄膜应用十分广泛。常用的热收缩薄膜有聚氯乙烯薄膜、非交联聚乙烯吹塑薄膜、聚丙烯薄膜、聚苯乙烯薄膜、PET和PETG薄膜。这类薄膜可以在单向达到很大的收缩率(最高达到75％)，而在另一方 向的收缩率很小(仅1％)。近年来，除了纯材料薄膜外，复合材料薄膜也大量地用于热收缩薄膜，主要有如下两种：(1)POF薄膜。这种薄膜典型地采用聚丙烯/聚乙烯/聚丙烯三层共挤出，并用双泡法吹涨得到。(2)多层共挤出交联聚乙烯薄膜。市场需求的热收缩薄膜可具备的几个关键性能有：较大的收缩率，环保(例如，可回收、燃烧无害等)，热封强度大，表面光泽好等。而目前市场上并没有这些性能同时都较优秀的薄膜。
另外，目前市场上并没有较为成熟的可降解的热收缩薄膜的解决方案。有一类加入了光降解剂的聚烯烃薄膜也声称属于可降解薄膜，如CN106519400A所述，但这类薄膜并不能完全降解，智能使聚烯烃碎裂成小块。目前的可降解薄膜有如CN103483789A中所述的，以羟基烷酸酯为基础的薄膜，以及如CN103625061B中所述的，以聚乳酸为基础的薄膜。但它们的性能并不能达到如前所述的通用热收缩薄膜的一般性能，因此限制了它们的推广使用。
一次性纺织制品，特别是一次性医用纺织制品，主要由无纺布制成。目前市场上常见的一次性手术服材料材质有如下几种：聚丙烯木浆复合水刺非织造布，如CN205800418U中所述；聚丙烯、聚羟基丁酸酯与聚乳酸多层复合材料，如CN204398434U和CN105054444A中所述；聚乙烯膜与SMS无纺布复合材料，如CN204317582U中所述；带有树脂加强片的无纺布，如CN105015128B提到。一次性手术防护服经过一次手术使用后，就成为了一种医疗废弃物。医疗废弃物的处置会带来二次污染。而目前市场上的这些材料大都是难以回收的材料。因此如何方便地回收一次性医用纺织制品成为很紧迫的问题。
弹性纤维是一类有着高弹性、低模量、高弹性回复的纤维的总称。这些弹性纤维大致分为两类，一类是利用材料本身的弹性得到的弹性纤维，例如，天然橡胶纤维、聚氨酯纤维(氨纶)、聚丙烯酸酯纤维、聚 对苯二甲酸丁二酯(PBT)纤维、聚醚酯弹性体(TPEE)纤维、聚对苯二甲酸丙二醇酯(PTT)纤维、聚烯烃(XLA)纤维。此类弹性纤维的弹性大多由材料本身决定。其中，聚丙烯酸酯纤维、PBT纤维和PTT纤维的弹性较低，只具有轻微的弹性；天然橡胶纤维的弹性强但强度弱，且易老化；聚氨酯纤维的强度较弱；聚醚酯弹性体纤维综合性能优秀，性能可调节范围广，但成本太高；XLA纤维弹性好，耐热性能好，力学强度尚可，但性能较为固定，可调节性不足。另一类是多丝复合的弹性纤维，利用两种材料收缩率的不同产生的螺旋弹性，典型的就是T400纤维。这类纤维的弹性可以由制备工艺来控制，但由螺旋导致的弹性力值很低，通常远不如材料本身所带来的弹性。
目前，市场上还缺乏这样一种弹性纤维，它在有着较低成本的基础上，同时兼具适中的弹性和强度，并且性能可调节范围广，能够适应多样化产品的需求。
总之，持续需求不具有上述缺点的改进的形状记忆材料、3D打印线材、热收缩套管、功能层、医用肢体固定支架、热收缩薄膜、无纺布和弹性纤维。
发明内容
发明概述
因此，本发明的目的是，为了克服现有的形状记忆产品、3D打印线材、热收缩套管、功能层、医用肢体固定支架、热收缩薄膜、无纺布和弹性纤维具有的上述缺陷，提供了一种聚酯组合物及其制备方法，以及该聚酯组合物在这些材料中的应用。
尤其是，本发明的目的是提供一种聚酯组合物，该聚酯组合物应具有良好的低温可塑性和形状记忆性能。
本发明的另一目的是提供一种聚酯组合物，使用该聚酯组合物制成 的3D打印线材应为柔性线材，且在低温下可打印，同时具有高光泽度和可降解性。
本发明的另一目的是提供一种聚酯组合物，使用该聚酯组合物制成的热收缩套管应具有良好的热收缩性能和绝缘性能，且该热收缩套管在制备的过程中无需进行交联，具有良好的可降解性，因此其具有广阔的市场空间。
本发明的另一目的是提供一种聚酯组合物，将该聚酯组合物用于运动护具时，应该可以根据应用部位的差异进行塑形，使得护具更贴合身体、更舒适且制作方便；另外，该运动护具如果出现磨损或者轻微损坏以后，应可以再次通过升温软化和低温再塑形使得护具恢复原貌。
本发明的另一目的是提供一种聚酯组合物，该聚酯组合物的硬度应随时间和温度发生变化，具体地，其在较高温度下硬度较低，冷却后在较短时间内硬度明显升高，表现出良好的可塑性和固定性，从而特别适用于制备医用肢体固定支架。
本发明的另一目的是提供一种聚酯组合物，使用该聚酯组合物制成的热收缩薄膜应该不仅具有较高的热收缩率，而且其热收缩率还可以在较大的范围内变化，满足不同的需求；并且，该热收缩薄膜应具有合适的热封强度，薄膜表面平整、光泽度良好，可降解且可以反复热塑加工并可回收。
本发明的另一目的是提供一种聚酯组合物，由该聚酯组合物制成的无纺布应具有良好的吸水性、透气性、易灭菌性，特别是，该无纺布应可以在热水(如100℃)中消毒并大幅度收缩，因此很容易被压缩至很小的体积，方便材料(特别是一次性材料)的回收以及再生产，并且，重新生产制得的无纺布与首次使用的无纺布具有相似的性能，适于继续作为一次性无纺布制品(特别是一次性医用纺织制品)的原材料，从而很好地解决材料的再回收利用问题。
本发明的另一目的是提供一种聚酯组合物，使用该聚酯组合物制成的弹性纤维应兼具适中的弹性和强度，并且性能可调节范围广。
根据本发明，通过包含特定的脂肪族-芳香族共聚酯的聚酯组合物实现了上述目的。
具体地，本发明提供以下方面。
第一方面，本发明提供一种聚酯组合物，包含：
(1)第一聚酯，该第一聚酯的量为基于第一聚酯和第二聚酯的总重量计50重量％至100重量％，优选51重量％至99重量％，该第一聚酯选自脂肪族-芳香族共聚酯中的一种或多种，该脂肪族-芳香族共聚酯为含有式(I)所示的重复单元A和式(II)所示的重复单元B的共聚物，
Figure PCTCN2017107106-appb-000001
其中以所述脂肪族-芳香族共聚酯中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为51-95摩尔％，所述重复单元B的含量为5-49摩尔％，优选所述重复单元A的含量为55-80摩尔％和所述重复单元B的含量为20-45摩尔％；m为2-10，优选2-6，更优选2-4的整数和n为2-8，优选2-4的整数；p为2-10，优选2-4的整数；且m、n和p彼此相同或不同；
(2)任选的第二聚酯，该第二聚酯的量基于第一聚酯和第二聚酯的总重量计最多50重量％，优选1重量％至49重量％，该第二聚酯选自脂肪族聚酯、芳香族聚酯和不同于第一聚酯的脂肪族-芳香族共聚酯中的一种或多种；
其中所述聚酯组合物包含至少两种聚酯。
优选地，作为第二聚酯的所述脂肪族聚酯含有式(I”’)所示的重复 单元D，
Figure PCTCN2017107106-appb-000002
其中m3与上文中对m的定义相同，n3与上文中对n的定义相同，且m3和n3彼此相同或不同，所述脂肪族聚酯的重均分子量为50,000-900,000，优选100,000-500,000，该重均分子量根据凝胶渗透色谱法(GPC)测得。
优选地，作为第二聚酯的所述芳香族聚酯由式(II)所示的重复单元B组成。
优选地，作为第二聚酯的所述不同于第一聚酯的脂肪族-芳香族共聚酯为含有式(I)所示的重复单元A和式(II)所示的重复单元B的共聚物。
优选地，作为第一聚酯或第二聚酯的含有式(I)所示的重复单元A和式(II)所示的重复单元B的脂肪族-芳香族共聚酯的重均分子量为50,000-900,000，优选100,000-500,000，该重均分子量根据凝胶渗透色谱法(GPC)测得；优选分子量分布为1.2-3，由GPC测得。
作为第一聚酯的所述脂肪族-芳香族共聚酯可以是无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种；作为第二聚酯的所述脂肪族-芳香族共聚酯可以是无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种。
本发明的聚酯组合物可以另外包含一种或多种选自以下的添加剂：成核剂，纤维填料，和具有加速组合物熔体固化、调节组合物力学强度、调节组合物颜色和光泽、改善组合物的阻燃性、抗氧化性等方面的作用的辅助填料，以及芥酸酰胺和/或白油。
例如，所述辅助填料可以选自碳酸盐类、硅酸盐类、硫酸盐类、无机质中空微球、金属粉、炭黑、滑石粉、芥酸酰胺、二氧化钛、氧化铁、 羧酸金属盐、磷酸金属盐、四溴双酚A、十溴二苯醚、六溴环十二烷、低密度聚乙烯、多聚磷酸酯或盐、亚磷酸酯、受阻酚、受阻胺、二苄山梨醇及其衍生物、超支化聚酰胺、乙烯-甲基丙烯酸离聚物、乙撑双硬脂酰胺、硅酮粉和季戊四醇硬脂酸酯中的至少一种，优选至少两种；优选为碳酸钙、无水硫酸钙、铜粉、氧化铁、炭黑、二氧化钛、磷酸三(2,3-二溴丙基)酯、低密度聚乙烯、超支化聚酰胺、乙撑双硬脂酰胺和芥酸酰胺中的至少一种，优选至少两种，优选以所述聚酯组合物的总重量为基准，所述辅助填料的含量为0.1-60重量％，优选0.1-50重量％，更优选为1-25重量％，更优选1-20重量％，更优选2-10重量％。
例如，所述成核剂可以选自滑石粉、氧化钙、炭黑、碳酸钙、无机颜料、高岭土、羧酸金属盐、磷酸金属盐、二苄山梨醇及其衍生物、聚乙烯基环己烷、聚乙烯基环戊烷、低密度聚乙烯、超支化聚酰胺和乙烯-甲基丙烯酸离聚物中的一种或几种；优选为碳酸钙、低密度聚乙烯、二苄山梨醇及其衍生物和超支化聚酰胺中的一种或几种，优选以所述聚酯组合物的总重量为基准，所述成核剂的含量为0.01-20重量％，优选为0.2-5重量％。
例如，所述纤维填料可以为碳纤维、玻璃纤维、玄武岩纤维、芳纶纤维和PET纤维中的一种或几种，优选为玻璃纤维、碳纤维和玄武岩纤维中的一种或几种；优选地，所述纤维填料的长度为0.1-10mm，优选为0.5-2mm。
在第一优选实施方案中，根据本发明的聚酯组合物包含
(1)聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，
Figure PCTCN2017107106-appb-000003
Figure PCTCN2017107106-appb-000004
(2)聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，
Figure PCTCN2017107106-appb-000005
(3)脂肪族聚酯，
其中，m1和m2彼此独立地与上文中对m的定义相同，n1和n2彼此独立地与上文中对n的定义相同,且m1和n1彼此相同或不同，m2和n2彼此相同或不同，并且n1小于n2；
以所述聚酯A、所述聚酯B和所述脂肪族聚酯的总摩尔数为基准，所述重复单元B的含量为5-49摩尔％，优选10-45摩尔％，更优选20-40摩尔％。
优选，以所述聚酯A中重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为51-90摩尔％；所述重复单元B的含量为10-49摩尔％；
以所述聚酯B中重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为40-95摩尔％，优选为50-90摩尔％；所述重复单元B的含量为5-60摩尔％，优选为10-50摩尔％。
优选，所述聚酯A、所述聚酯B与所述脂肪族聚酯的摩尔比为20-90：1-90：1-20；优选为20-90：1-70：1-20。
在第二优选实施方案中，根据本发明的聚酯组合物，以各组分的总重量为基准，含有以下组分：
(1)51-98重量％的聚酯A，所述聚酯A为含有式(I-1)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量 为56-80摩尔％，优选为60-75摩尔％；所述重复单元B的含量为20-44摩尔％，优选为25-40摩尔％；
Figure PCTCN2017107106-appb-000006
(2)1-48重量％的聚酯B，所述聚酯B为含有式(I’)所示的重复单元C和式(IV’)所示的重复单元D的共聚物，且以所述聚酯B中的重复单元C和重复单元D的总摩尔数为基准，所述重复单元C的含量为81-99摩尔％，优选为85-95摩尔％，所述重复单元D的含量为1-19摩尔％，优选为5-15摩尔％，
Figure PCTCN2017107106-appb-000007
其中，m1与上文中对m的定义相同，n1与上文中对n的定义相同，且m1和n1彼此相同或不同；a1与上文中p的定义相同，且a1与m1彼此相同或不同；
(3)1-48重量％的聚酯C，所述聚酯C为含有式(I”)所示的重复单元E和式(IV”)所示的重复单元F的共聚物，且以所述聚酯C中的重复单元E和重复单元F的总摩尔数为基准，所述重复单元E的含量为0-55摩尔％，优选为15-50摩尔％，所述重复单元F的含量为45-100摩尔％，优选为50-85摩尔％，
Figure PCTCN2017107106-appb-000008
其中，m2与上文中对m的定义相同，n2与上文中对n的定义相同，且m2和n2彼此相同或不同；a2与上文中p的定义相同，且a2与m2彼此相同或不同。
优选，所述聚酯组合物含有70-94重量％的聚酯A、3-25重量％的聚酯B和3-20重量％的聚酯C。
在第三优选实施方案中，根据本发明的聚酯组合物，以各组分的总重量为基准，含有以下组分：
(1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为51-70摩尔％，优选为55-68摩尔％，所述重复单元B的含量为30-49摩尔％，优选为32-45摩尔％，
Figure PCTCN2017107106-appb-000009
其中，m1与上文中对m的定义相同，n1与上文中对n的定义相同，且m1和n1相同或不同；优选，m1为2-4的整数，n1为2-4的整数，优选2；
(2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为1-50摩尔％，优选为20-45摩尔％，所述重复单元B的含量为50-99摩尔％，优选为55-80摩尔％，
Figure PCTCN2017107106-appb-000010
其中，m2与上文中对m的定义相同，n2与上文中对n的定义相同，且m2和n2相同或不同；优选，m2为2-4的整数，n2为2-4的整数，优选2。
优选，所述聚酯组合物含有80-95重量％的聚酯A和5-20重量％的聚酯B。
在第四优选实施方案中，根据本发明的聚酯组合物，以各组分的总重量为基准，含有以下组分：
(1)50-98重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为55-79摩尔％，优选为60-77摩尔％，所述重复单元B的含量为21-45摩尔％，优选为23-40摩尔％，
Figure PCTCN2017107106-appb-000011
其中，m1与上文中对m的定义相同，n1与上文中对n的定义相同，且m1和n1彼此相同或不同；优选，m1为2-4的整数，n1为2-4的整数，优选4；
(2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为80-100摩尔％，优选为85-95摩尔％，所述重复单元B的含量为0-20摩尔％，优选为5-15摩尔％，
Figure PCTCN2017107106-appb-000012
其中，m2与上文中对m的定义相同，n2与上文中对n的定义相同，且m2和n2彼此相同或不同；优选，m2为2-4的整数，n2为2-4的整数，优选2；
(3)1-49重量％的纤维填料。
优选，所述聚酯组合物含有60-90重量％的聚酯A、5-30重量％的聚酯B和5-30重量％的纤维填料。
在第五优选实施方案中，根据本发明的聚酯组合物，以各组分的总重量为基准，含有以下组分：
(1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为60-80摩尔％，优选为62-78摩尔％，所述重复单元B的含量为20-40摩尔％，优选为22-38摩尔％，
Figure PCTCN2017107106-appb-000013
其中，m1与上文中对m的定义相同，n1与上文中对n的定义相同，且m1和n1彼此相同或不同；优选m1为2-4的整数，n1为2-4的整数，优选n1为2；
(2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为20-59摩尔％，优选为30-55摩尔％，所述重复单元B的含量为41-80摩尔％，优选为45-70摩尔％，
Figure PCTCN2017107106-appb-000014
其中，m2与上文中对m的定义相同，n2与上文中对n的定义相同，且m2和n2彼此相同或不同；优选，m2为2-4的整数，n2为2-4的整数，优选n2为2。
优选，所述聚酯组合物含有70-90重量％的聚酯A和10-30重量％的聚酯B。
在第六优选实施方案中，根据本发明的聚酯组合物，以各组分的总重量为基准，含有以下组分：
(1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为60-80摩尔％，优选为62-72摩尔％，所述重复单元B的含量为20-40摩尔％，优选为28-38摩尔％，
Figure PCTCN2017107106-appb-000015
其中，m1与上文中对m的定义相同，n1与上文中对n的定义相同，且m1和n1彼此相同或不同；优选，m1为2-4的整数，n1为2-4的整数；优选n1为2；
(2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为81-99摩尔％，优选为85-97摩尔％，所述重复单元B的含量为1-19摩尔％，优选为3-15摩尔％，
Figure PCTCN2017107106-appb-000016
其中，m2与上文中对m的定义相同，n2与上文中对n的定义相同，且m2和n2彼此相同或不同；优选，m2为2-4的整数，n2为2-4的整数，优选n2为2。
优选，所述聚酯组合物含有60-90重量％的聚酯A和10-40重量％的聚酯B。
在第七优选实施方案中，根据本发明的聚酯组合物，以各组分的总重量为基准，含有以下组分：
(1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为75-95摩尔％，优选为81-95摩尔％，所述重复单元B的含量为5-25摩尔％，优选为5-19摩尔％，
Figure PCTCN2017107106-appb-000017
其中，m1与上文中对m的定义相同，n1与上文中对n的定义相同，且m1和n1彼此相同或不同；优选，m1为2-4的整数，n1为2-4的整数；优选n1为2；
(2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为20-74摩尔％，优选为40-70摩尔％，所述重复单元B的含量为26-80摩尔％，优选为30-60摩尔％，
Figure PCTCN2017107106-appb-000018
其中，m2与上文中对m的定义相同，n2与上文中对n的定义相同，且m2和n2彼此相同或不同；优选，m2为2-4的整数，n2为2-4的整数，优选n2为2。
优选，所述聚酯组合物含有55-70重量％的聚酯A和30-45重量％的聚酯B。
在第八优选实施方案中，根据本发明的聚酯组合物，以各组分的总重量为基准，含有以下组分：
(1)30-98重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为51-80摩尔％，优选为60-75摩尔％；所述重复单元B的含量为20-49摩尔％，优选为25-40摩尔％，
Figure PCTCN2017107106-appb-000019
其中，m1与上文中对m的定义相同，n1与上文中对n的定义相同，且m1和n1彼此相同或不同；优选，m1为2-8的整数和n1为2-6的整数，更优选m1为2-4的整数和n1为2-4的整数；
(2)1-69重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为81-99摩尔％，优选为83-95摩尔％，所述重复单元B的含量为1-19摩尔％，优选为5-17摩尔％，
Figure PCTCN2017107106-appb-000020
其中，m2与上文中对m的定义相同，n2与上文中对n的定义相同，且m2和n2彼此相同或不同；优选，m2为2-8的整数，n2为2-6的整数；更优选，m2为2-4的整数，n2为2-4的整数；
(3)1-69重量％的聚酯C，所述聚酯C为含有式(I”’)所示的重复单元D和式(II-1)所示的重复单元B的共聚物，且以所述聚酯C中的重复单元D和重复单元B的总摩尔数为基准，所述重复单元D的含量为0-49摩尔％，优选为15-45摩尔％，所述重复单元B的含量为51-100摩尔％，优选为55-85摩尔％，
Figure PCTCN2017107106-appb-000021
其中，m3与上文中对m的定义相同，n3与上文中对n的定义相同，且m3和n3彼此相同或不同；优选，m3为2-8的整数，n3为2-6的整数；更优选，m3为2-4的整数，n3为2-4的整数。
优选，所述聚酯组合物含有60-93重量％的聚酯A、5-38重量％的聚酯B和1-20重量％的聚酯C。
另一方面，本发明提供制备根据本发明的聚酯组合物的方法，包括将包括第一聚酯和第二聚酯在内的所有组分共混，并将得到的混合物进行挤出造粒，以得到聚酯组合物，优选所述共混的过程不加入相容剂。
优选，所述共混在搅拌的条件下进行。
优选，所述挤出造粒在双螺杆挤出机中进行；优选地，在温度为80-270℃，优选为110-220℃；螺杆转速为10-70rpm，扭矩为2-80N*m下进行。
另一方面，本发明提供根据本发明的聚酯组合物用于以下方面中一个或多个方面中的用途：形状记忆材料、3D打印线材、热收缩套管、功 能层(例如用于运动护具的功能层)、运动护具(例如牙齿护具、四肢关节护具、身体大面积护具和头部护具)、医用肢体固定支架、热收缩薄膜、无纺布和无纺布制品(尤其是一次性无纺布制品，更优选一次性医用无纺布制品)。
另一方面，本发明提供形状记忆材料，其包含根据上述第一优选实施方案的聚酯组合物。
另一方面，本发明提供3D打印线材，其包含根据上述第二优选实施方案的聚酯组合物，优选所述3D打印线材的直径为0.1-10mm，优选为1-4mm。
另一方面，本发明提供制备根据本发明的3D打印线材的方法，包括将聚酯组合物依次经过挤出和冷却，以得到3D打印线材；优选，挤出的温度为90-260℃，冷却的温度为0-60℃。
另一方面，本发明提供热收缩套管，包含根据上述第三优选实施方案的聚酯组合物。
另一方面，本发明提供制备根据本发明的热收缩套管的方法，包括将聚酯组合物依次经过挤出、牵引、冷却和定型，以得到热收缩套管；优选，挤出的温度为90-240℃，优选为120-180℃；并且冷却的温度为0-60℃，优选为20-40℃。
优选，所述方法还包括将冷却后的管材依次进行加热、扩径、二次冷却和定型；优选地，所述加热的温度为65-120℃，优选为70-90℃；优选地，所述扩径的倍率为原尺寸的1.5-5倍，优选为3-5倍；优选地，所述二次冷却的温度为0-60℃，优选为20-40℃。
另一方面，本发明提供功能层，包含根据上述第四优选实施方案的聚酯组合物，优选用于运动护具的功能层。
另一方面，本发明提供制备根据本发明的功能层的方法，包括将聚酯组合物成型，其中成型的方式优选为挤出或注塑；优选地，所述注塑 的温度为140-270℃，优选为170-185℃。
另一方面，本发明提供医用肢体固定支架，包含根据上述第五优选实施方案的聚酯组合物；优选，所述医用肢体固定支架的厚度为0.2-10mm，优选为1-3mm；优选地，所述医用肢体固定支架具有和/或不具有孔结构，优选为具有孔结构；更优选地，所述孔结构的孔径为1-10mm，优选为1-5mm。
另一方面，本发明提供制备根据本发明的医用肢体固定支架的方法，包括将聚酯组合物依次经过挤出、成型和可选的打孔，以得到医用肢体固定支架；优选，所述挤出的温度为90-230℃，优选为110-170℃；优选地，所述成型的方式为注塑和/或压塑；优选地，所述成型使得所述医用肢体固定支架的厚度为0.2-10mm，优选为1-3mm；优选地，所述打孔使用的打孔器的直径为1-10mm，优选为1-5mm。
另一方面，本发明提供热收缩薄膜，包含根据上述第六优选实施方案的聚酯组合物。
另一方面，本发明提供制备根据本发明的热收缩薄膜的方法，包括将聚酯组合物依次经过流延成膜、静置和拉伸，以得到热收缩薄膜；优选，所述流延成膜的温度为80-220℃，优选为110-180℃；优选地，所述静置的时间为30分钟-20天，优选为4-24小时；优选地，所述拉伸为单向拉伸或双向拉伸；优选地，所述拉伸的温度为40-150℃，优选为60-120℃。
另一方面，本发明提供无纺布，包含根据上述第七优选实施方案的聚酯组合物。
另一方面，本发明提供制备根据本发明的无纺布的方法，包括将聚酯组合物通过纺粘法制得无纺布；优选，所述纺粘法包括挤出、纺丝、成网和加固的过程；优选地，所述挤出的过程包括三个温区，第一温区的温度为140-250℃，第二温区的温度为150-260℃，第三温区的温度为 170-260℃；优选地，所述纺丝的温度为150-240℃，所述纺丝的速率为10-40r/min；优选地，所述成网的速率为5-30r/min；优选地，所述加固采用热轧的方式，所述热轧的温度为80-170℃。
另一方面，本发明提供弹性纤维，包含根据上述第八优选实施方案的聚酯组合物；优选，所述弹性纤维的纤度为5-500dtex；断裂强度为3-19cN/dtex；断裂伸长率为130-620％；应力松弛率1-12％；永久应变率为1-11％。
另一方面，本发明提供制备根据本发明的弹性纤维的方法，包括将聚酯组合物依次经过成丝、低温放置和拉伸，以得到弹性纤维；优选，所述成丝的方式为熔体纺丝；优选地，所述成丝的温度为120-270℃，优选为150-220℃；优选地，所述低温放置的条件包括：温度为20-55℃，优选为25-45℃；时间为2-120min，优选为15-60min；优选地，所述拉伸的条件包括：温度为56-110℃，优选为60-90℃；拉伸的倍率为1.2-10倍，优选为2-5倍。
另一方面，本发明也提供上文所述作为第一聚酯的脂肪族-芳香族共聚酯用于以下方面中一个或多个方面中的用途：形状记忆材料、3D打印线材、热收缩套管、功能层(例如用于运动护具的功能层)、运动护具(例如牙齿护具、四肢关节护具、身体大面积护具和头部护具)、医用肢体固定支架、热收缩薄膜、无纺布和无纺布制品(尤其是一次性无纺布制品，更优选一次性医用无纺布制品)。
附图说明
图1是本发明的实施例IV-10得到的牙齿护具成品的横切面图，其中，1为口腔上颚牙套，2为口腔下颚牙套；
图2是本发明的实施例IV-10得到的牙齿护具成品的侧面立体图；
图3是本发明的实施例IV-11得到的护膝成品的侧面立体图，其中， 1为护膝的内层，2为护膝的中间层，3为护膝的外层，4为护膝外层表面上的凸起部分；
图4是本发明的实施例IV-11得到的护膝成品的正面立体图，其中，1为护膝的内层，2为护膝的中间层，3为护膝的外层，4为护膝外层表面上的凸起部分；
图5是本发明的实施例IV-12得到的上半身护具成品的正面立体图；
图6是本发明的实施例IV-12得到的上半身护具成品的剖面图，其中，1为上半身护具的内层，2为上半身护具的中间层，3为上半身护具的外层；
图7是本发明的实施例IV-13得到的头盔成品的侧面立体图，其中，1为头盔的外层，2为头盔的中间层，3为头盔的内层，4为卡扣。
图8和图9是本发明的医用肢体固定支架的实例图。
发明详述
本发明的聚酯组合物可以用于形状记忆材料、3D打印线材、热收缩套管、功能层、医用肢体固定支架、热收缩薄膜、无纺布和弹性纤维等方面。下面针对不同的应用描述本发明的聚酯组合物。
形状记忆材料
本发明提供了一种聚酯组合物，该聚酯组合物包括：
(1)聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，
Figure PCTCN2017107106-appb-000022
(2)聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，
Figure PCTCN2017107106-appb-000023
(3)脂肪族聚酯，
其中，m1为2-10的整数，n1为2-8的整数，且m1和n1相同或不同，所述聚酯A的重均分子量为50,000-900,000；m2为2-10的整数，n2为2-8的整数，且m2和n2相同或不同，所述聚酯B的重均分子量为50,000-900,000；并且，n1小于n2；以所述聚酯A、所述聚酯B和所述脂肪族聚酯的总摩尔数为基准，所述重复单元B的含量为5-49摩尔％。
在优选的情况下，m1为2-6的整数，n1为2-4的整数，且m1和n1相同或不同，所述聚酯A的重均分子量为100,000-500,000；m2为2-6的整数，n2为2-4的整数，且m2和n2相同或不同，所述聚酯B的重均分子量为100,000-500,000；并且，n1小于n2；以所述聚酯A、所述聚酯B和所述脂肪族聚酯的总摩尔数为基准，所述重复单元B的含量为5-49摩尔％，优选为10-45摩尔％，更优选20-40摩尔％，更优选为25-40摩尔％，或35-45摩尔％。
在本发明中，聚合物的重均分子量根据凝胶渗透色谱法(GPC)测得。
在本发明中，所述聚酯A可以为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种，优选为无规共聚物和/或嵌段共聚物。本发明对所述聚酯A的来源没有特别的限定，可以通过本领域的常规手段获得，例如，可以通过商购获得，或者，可以按照CN100429256C中公开的方法制备得到。具体地，所述聚酯A的制备方法可以包括以下步骤：将1,4-丁二醇、苯甲酸二甲酯和如US11312373中所述的催化剂加入反应器中，在氮气氛围下加热和搅拌，直至得到透明的溶液。随后，将 温度升至160-220℃反应。当体系中绝大多数蒸馏出的甲醇被除去后，加入丁二酸，升温至180-240℃。蒸馏除去大部分水，然后缓慢加上真空环境，并将体系升温至220-280℃，3-6小时后反应完成，得到产品。
在本发明中，所述聚酯B可以为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种，优选为无规共聚物和/或嵌段共聚物。本发明对所述聚酯B的来源没有特别的限定，可以通过本领域的常规手段获得，例如，可以通过商购获得，或者，可以按照CN100429256C中公开的方法制备得到。具体地，所述聚酯B的制备方法可以包括以下步骤：将1,4-丁二醇、苯甲酸二甲酯和如US11312373中所述的催化剂加入反应器中，在氮气氛围下加热和搅拌，直至得到透明的溶液。随后，将温度升至160-220℃反应。当体系中绝大多数蒸馏出的甲醇被除去后，加入己二酸，升温至180-240℃。蒸馏除去大部分水，然后缓慢加上真空环境，并将体系升温至220-280℃，3-6小时后反应完成，得到产品。
根据本发明，以所述聚酯A中重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量可以为40-95摩尔％，优选为45-90摩尔％，更优选为45-70摩尔％；所述重复单元B的含量可以为5-60摩尔％，优选为10-55摩尔％，更优选为30-55摩尔％；
以所述聚酯B中重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量可以为40-95摩尔％，优选为50-90摩尔％，更优选为50-80摩尔％；所述重复单元B的含量可以为5-60摩尔％，优选为10-50摩尔％，更优选为20-50摩尔％。
根据本发明，所述聚酯A、所述聚酯B与所述脂肪族聚酯的摩尔比可以为20-90：1-90：1-20；优选为20-90：1-70：1-20。
在本发明中，对所述脂肪族聚酯的种类和来源没有特别的限定，可以为本领域常规使用的脂肪族聚酯。
在优选的情况下，所述脂肪族聚酯含有式(I”’)所示的重复单元D，
Figure PCTCN2017107106-appb-000024
其中，m3为2-10的整数，n3为2-8的整数，且m3和n3相同或不同，所述脂肪族聚酯的重均分子量为50,000-900,000；更优选地，m3为2-6的整数，n3为2-4的整数，且m3和n3相同或不同，所述脂肪族聚酯的重均分子量为100,000,500,000。
在本发明中，所述脂肪族聚酯可以通过常规的手段获得，例如，可以通过商购获得(如购自巴斯夫公司，牌号为1111HTA4)，或者，可以按照CN104039865B公开的方法制备得到，其中，可以根据目标产品的组成和分子量，相应地调整反应原料的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量。
根据本发明，所述聚酯组合物还可以含有成核剂；以所述聚酯组合物的总重量为基准，所述成核剂的含量为0.01-20重量％，优选0.01-10重量％，更优选为0.2-5重量％，更优选为1-5重量％。
根据本发明，所述成核剂可以为本领域的常规选择，所述成核剂可以选自滑石粉、氧化钙、炭黑、碳酸钙、无机颜料(如购自广州颖毅塑胶颜料有限公司的黄色或绿色颜料)、高岭土、羧酸金属盐、磷酸金属盐、二苄山梨醇及其衍生物、聚乙烯基环己烷、聚乙烯基环戊烷、低密度聚乙烯、超支化聚酰胺和乙烯-甲基丙烯酸离聚物中的一种或几种；优选为碳酸钙、低密度聚乙烯、二苄山梨醇及其衍生物和超支化聚酰胺中的一种或几种；更优选为碳酸钙和/或低密度聚乙烯。
在本发明中，所述聚酯组合物还可以含有其他添加剂，例如还可以含有芥酸酰胺和/或白油。
本发明还提供了一种聚酯组合物的制备方法，该方法包括：将聚酯A、聚酯B和脂肪族聚酯混合，并将得到的混合物进行挤出造粒，以得到聚酯组合物。
在本发明中，上述方法还可以包括：将聚酯A、聚酯B、脂肪族聚酯和成核剂混合的过程在成核剂和任选的其他添加剂的存在下进行，其中，所述其他添加剂可以为芥酸酰胺和/或白油。
根据本发明，所述混合可以在搅拌的条件下进行；所述搅拌的速率可以为6-60rpm，所述搅拌的时间可以为2-30min。
根据本发明，所述挤出造粒过程可以按照常规的挤出造粒方法实施，例如，所述挤出造粒可以在双螺杆挤出机中进行；优选地，所述挤出造粒的条件包括：温度为160-220℃，螺杆转速为10-70rpm，扭矩为2-80N*m；更优选地，所述双螺杆挤出机包括六个温度区段，且从进料口到挤出口各区段的温度依次为160-190℃、170-200℃、180-210℃、180-220℃、180-220℃、170-210℃。
本发明还提供了上述聚酯组合物在形状记忆材料中的应用。
本发明通过对聚对苯二甲酸丁二醇酯(PBT)进行共聚和共混改性，得到了一种适用于用作形状记忆材料的聚酯组合物。将该聚酯组合物用于形状记忆材料，该形状记忆材料的形变固定率和形状回复率均达到92％以上，接近100％，最大形变率高达400％以上。另外，该形状记忆材料的最初赋形温度和启动温度均可以调节，这将更有利于其在日常生活中的应用。
3D打印材料
本发明提供了一种聚酯组合物，以各组分的总重量为基准，该聚酯组合物含有以下组分：
(1)51-98重量％的聚酯A，所述聚酯A为含有式(I-1)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为56-80摩尔％，优选为60-75摩尔％；所述重复单元B的含量为20-44 摩尔％，优选为25-40摩尔％；所述聚酯A的重均分子量为50,000-900,000，优选为100,000-500,000；
Figure PCTCN2017107106-appb-000025
(2)1-48重量％的聚酯B，所述聚酯B为含有式(I’)所示的重复单元C和式(IV’)所示的重复单元D的共聚物，且以所述聚酯B中的重复单元C和重复单元D的总摩尔数为基准，所述重复单元C的含量为81-99摩尔％，优选为85-95摩尔％，所述重复单元D的含量为1-19摩尔％，优选为5-15摩尔％，
Figure PCTCN2017107106-appb-000026
其中，m1为2-10的整数，优选为2-4的整数；n1为2-8的整数，优选为2-4的整数；且m1和n1相同或不同；a1为2-10的整数，优选为2-4的整数；且a1与m1相同或不同，优选为相同；所述聚酯B的重均分子量为50,000-900,000，优选为100,000-500,000；
(3)1-48重量％的聚酯C，所述聚酯C为含有式(I”)所示的重复单元E和式(IV”)所示的重复单元F的共聚物，且以所述聚酯C中的重复单元E和重复单元F的总摩尔数为基准，所述重复单元E的含量为0-55摩尔％，优选为15-50摩尔％，所述重复单元F的含量为45-100摩尔％，优选为50-85摩尔％，
Figure PCTCN2017107106-appb-000027
Figure PCTCN2017107106-appb-000028
其中，m2为2-10的整数，优选为2-4的整数；n2为2-8的整数，优选为2-4的整数；且m2和n2相同或不同；a2为2-10的整数，优选为2-4的整数；且a2与m2相同或不同，优选为相同；所述聚酯C的重均分子量为50,000-900,000，优选为100,000-500,000。
在本发明中，m1和m2可以相同或不同，n1和n2可以相同或不同。但当m1和m2相同且n1和n2也相同时，在所述聚酯B中重复单元D的含量与在所述聚酯C中重复单元F的含量不同。
在优选的情况下，所述聚酯组合物含有70-94重量％的聚酯A、3-25重量％的聚酯B和3-20重量％的聚酯C。
在本发明中，所述聚酯A、所述聚酯B和所述聚酯C均可以为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种，优选为无规共聚物和/或嵌段共聚物。本发明对所述聚酯A、所述聚酯B和所述聚酯C的来源没有特别的限定，可以通过本领域常规的手段获得，可以通过商购获得，或者，可以按照CN100429256C中实施例B13-B21公开的方法制备得到。具体地，所述聚酯A的制备方法可以包括以下步骤：
在本发明优选的实施方式中，当m1为4时，所述聚酯A的制备方法包括以下步骤：
(S1)在惰性气氛中，将丁二醇和单体A’在第一催化剂的存在下进行反应；
(S2)将由步骤(S1)得到的反应产物和丁二酸在第二催化剂的存在下进行反应；
其中，A’为对苯二甲酸和/或其酯，优选为对苯二甲酸、对苯二甲酸二甲酯和对苯二甲酸二乙酯中的至少一种；所述第一催化剂和所述第二催化剂如上所述，在此不再赘述。
在本发明中，在步骤(S1)中，所述单体A’与所述第一催化剂的摩尔比为1：0.0001-0.02：0.0001-0.02，更优选为1：0.001-0.003：0.001-0.003。
在优选的情况下，所述第一催化剂的用量与所述第二催化剂的用量的摩尔比为1：0.5-1.5，优选为1：0.8-1.2。
在本发明中，可以根据目标产品的组成和分子量，相应地调整各反应单体的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量。
在本发明中，在步骤(S1)中，所述反应的温度优选为160-220℃；在本发明中，在步骤(S2)中，所述反应的温度优选为180-240℃。
在优选的情况下，所述聚酯B的制备方法包括以下步骤：
(1)在惰性气氛中，将单体A和单体B在第一催化剂的存在下进行反应；
(2)在惰性气氛中，将单体C和单体D在第一催化剂的存在下进行反应；
(3)将由步骤(1)得到的反应产物和由步骤(2)得到的反应产物在第二催化剂的存在下进行反应；
其中，所述单体A为C2-C8的二元醇(特别是饱和直链二元醇)；所述单体B为对苯二甲酸和/或其酯，优选为对苯二甲酸、对苯二甲酸二甲酯和对苯二甲酸二乙酯中的至少一种；所述单体C为C2-C10的二元醇(特别是饱和直链二元醇)；所述单体D为C4-C10的二元酸(特别是饱和直链二元酸)；所述第一催化剂为钛酸四丁酯、二氧化钛、二乙氧基钛和乙酸锌中的至少一种，优选为钛酸四丁酯；所述第二催化剂为乙酰丙酮镧、三氯化镧、三苯氧基镧和丙酸镧中的至少一种，优选为乙酰丙酮镧。
在本发明中，在步骤(1)中，所述单体B与所述第一催化剂的摩尔比为1：0.0001-0.02：0.0001-0.02，更优选为1：0.001-0.003：0.001-0.003。
在本发明中，在步骤(2)中，所述单体D与所述第一催化剂的摩尔比为1：0.0001-0.02：0.0001-0.02，更优选为1：0.001-0.003：0.001-0.003。
在优选的情况下，所述第一催化剂的总用量(步骤(1)和步骤(2)中的第一催化剂的用量之和)与所述第二催化剂的用量的摩尔比为1：0.5-1.5，优选为1：0.8-1.2。
在本发明中，可以根据目标产品的组成和分子量，相应地调整各反应单体的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量。
在本发明中，在步骤(1)中，所述反应的温度优选为160-220℃；在本发明中，在步骤(2)中，所述反应的温度优选为160-220℃；在本发明中，在步骤(3)中，所述反应的温度优选为180-240℃。
根据本发明，所述聚酯C也可以按照上述聚酯B的制备方法进行，其中，可以根据目标产品的组成和分子量，相应地调整各反应单体的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量，以获得聚酯C。
根据本发明，所述聚酯组合物还可以含有辅助填料；优选地，以所述聚酯组合物的总重量为基准，所述辅助填料的含量为0.1-50重量％，更优选为1-25重量％。
根据本发明，所述辅助填料具有加速组合物熔体固化，调节组合物力学强度，改善组合物阻燃性、抗氧化性，调节组合物颜色和光泽等方面的作用，可以为本领域的常规选择，例如，所述辅助填料选自碳酸钙、炭黑、滑石粉、芥酸酰胺、二氧化钛、氧化铁、羧酸金属盐、磷酸金属盐、四溴双酚A、十溴二苯醚、六溴环十二烷、低密度聚乙烯、多聚磷酸酯或盐、亚磷酸酯、受阻酚、受阻胺、二苄山梨醇及其衍生物、超支化聚酰胺、乙烯-甲基丙烯酸离聚物、乙撑双硬脂酰胺、硅酮粉和季戊四醇硬脂酸酯中的至少一种；优选为碳酸钙、炭黑、二氧化钛、磷酸三(2,3- 二溴丙基)酯、低密度聚乙烯、超支化聚酰胺、乙撑双硬脂酰胺和芥酸酰胺中的至少一种。
本发明还提供了上述聚酯组合物的制备方法，该制备方法包括：将聚酯A、聚酯B和聚酯C共混，并将得到的混合物进行挤出造粒。
在本发明中，发明人在研究过程中意外地发现：所述聚酯A、聚酯B和聚酯C具有良好的相容性，因此，在共混的过程中可以不加入相容剂。所述相容剂为本领域常规使用的用于提高共混原料的相容性的物质，例如，可以为PE-g-ST、PP-g-ST、ABS-g-MAH、PE-g-MAH和PP-g-MAH中的至少一种。
根据本发明，所述共混的过程可以在搅拌的条件下进行。本发明对搅拌的条件没有特别的限定，只要可以将原料混合均匀即可，在优选的情况下，所述搅拌的速率为20-150r/min，所述搅拌的时间为5-15min。
根据本发明，所述挤出造粒过程可以按照常规的挤出造粒方法实施，例如，所述挤出造粒可以在螺杆挤出机中进行。在优选的情况下，所述挤出造粒的温度为90-260℃，优选为110-180℃。
本发明还提供了一种3D打印线材，该3D打印线材含有上述聚酯组合物，也即所述3D打印线材由上述聚酯组合物制得。
根据本发明，所述3D打印线材的直径可以为0.1-10mm，优选为1-4mm。
本发明还提供了一种3D打印线材的制备方法，该制备方法包括：将聚酯组合物依次经过挤出和冷却，以得到3D打印线材；其中，所述聚酯组合物为上述聚酯组合物。
根据本发明，所述挤出可以采用常规的挤出方法进行，例如，所述挤出的过程可以在螺杆挤出机中进行。在优选的情况下，所述挤出的过程在带有圆孔模头的挤出机中进行，以得到3D打印线材；更优选地，得到的3D打印线材的直径为0.1-10mm，优选为1-4mm。
在本发明的3D打印线材的制备方法中，所述挤出的温度为90-260℃。优选地，所述冷却的温度为0-60℃。
本发明通过将特定的聚酯A、聚酯B和聚酯C按照特定的配比(51-98重量％的聚酯A，1-48重量％的聚酯B，1-48重量％的聚酯C)进行共混后得到聚酯组合物，将该聚酯组合物制成3D打印线材具有较高的光泽度，且可以在较低的温度下(105-165℃)进行打印；同时，该3D打印线材可以作为柔性线材(邵氏D硬度为35-50)，并且可以降解，具有良好的环保优势和应用前景。
热收缩管
本发明提供了一种聚酯组合物，以各组分的总重量为基准，该聚酯组合物含有以下组分：
(1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为51-70摩尔％，优选为55-68摩尔％，所述重复单元B的含量为30-49摩尔％，优选为32-45摩尔％，
Figure PCTCN2017107106-appb-000029
其中，m1为2-4的整数；n1为2-4的整数，优选为2；且m1和n1相同或不同，所述聚酯A的重均分子量为50,000-900,000，优选为100,000-500,000；
(2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的 重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为1-50摩尔％，优选为20-45摩尔％，所述重复单元B的含量为50-99摩尔％，优选为55-80摩尔％，
Figure PCTCN2017107106-appb-000030
其中，m2为2-4的整数；n2为2-4的整数，优选为2；且m2和n2相同或不同，所述聚酯B的重均分子量为50,000-900,000，优选为100,000-500,000。
在本发明中，m1和m2可以相同或不同，n1和n2可以相同或不同。但当m1和m2相同且n1和n2也相同时，在所述聚酯A中重复单元B的含量与在所述聚酯B中重复单元B的含量不同。
在优选的情况下，所述聚酯组合物含有80-95重量％的聚酯A和5-20重量％的聚酯B。
在本发明中，所述聚合物的组成通过原料的投料量进行确定。
在本发明中，所述聚酯A和所述聚酯B可以为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种，优选为无规共聚物和/或嵌段共聚物。本发明对所述聚酯A和所述聚酯B的来源没有特别的限定，可以通过本领域常规的手段获得，可以通过商购获得，或者，可以按照CN100429256C中实施例B13-B21公开的方法制备得到。具体地，所述聚酯A的制备方法可以包括以下步骤：
(1)在惰性气氛中，将单体A和单体B在第一催化剂的存在下进行反应；
(2)在惰性气氛中，将单体C和单体D在第一催化剂的存在下进行反应；
(3)将由步骤(1)得到的反应产物和由步骤(2)得到的反应产物在第二催化剂的存在下进行反应；
其中，所述单体A为丁二醇；所述单体B为对苯二甲酸和/或其酯，优选为对苯二甲酸、对苯二甲酸二甲酯和对苯二甲酸二乙酯中的至少一种；所述单体C为C2-C4的二元醇(特别是饱和直链二元醇)；所述单体D为C4-C6的二元酸(特别是饱和直链二元酸)；所述第一催化剂为钛酸四丁酯、二氧化钛、二乙氧基钛和乙酸锌中的至少一种，优选为钛酸四丁酯；所述第二催化剂为乙酰丙酮镧、三氯化镧、三苯氧基镧和丙酸镧中的至少一种，优选为乙酰丙酮镧。
在本发明中，在步骤(1)中，所述单体B与所述第一催化剂的摩尔比为1：0.0001-0.02：0.0001-0.02，更优选为1：0.001-0.003：0.001-0.003。
在本发明中，在步骤(2)中，所述单体D与所述第一催化剂的摩尔比为1：0.0001-0.02：0.0001-0.02，更优选为1：0.001-0.003：0.001-0.003。
在优选的情况下，所述第一催化剂的总用量(步骤(1)和步骤(2)中的第一催化剂的用量之和)与所述第二催化剂的用量的摩尔比为1：0.5-1.5，优选为1：0.8-1.2。
在本发明中，可以根据目标产品的组成和分子量，相应地调整各反应单体的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量。
在本发明中，在步骤(1)中，所述反应的温度优选为160-220℃；在本发明中，在步骤(2)中，所述反应的温度优选为160-220℃；在本发明中，在步骤(3)中，所述反应的温度优选为180-240℃。
在本发明优选的实施方式中，当m1为4时，所述聚酯A的制备方法包括以下步骤：
(S1)在惰性气氛中，将丁二醇和单体A’在第一催化剂的存在下进行反应；
(S2)将由步骤(S1)得到的反应产物和单体B’在第二催化剂的存在下进行反应；
其中，A’为对苯二甲酸和/或其酯，优选为对苯二甲酸、对苯二甲酸二甲酯和对苯二甲酸二乙酯中的至少一种；单体B’为C4-C6的二元酸(特别是饱和直链二元酸)；所述第一催化剂和所述第二催化剂如上所述，在此不再赘述。
在本发明中，在步骤(S1)中，所述单体A’与所述第一催化剂的摩尔比为1：0.0001-0.02：0.0001-0.02，更优选为1：0.001-0.003：0.001-0.003。
在优选的情况下，所述第一催化剂的用量与所述第二催化剂的用量的摩尔比为1：0.5-1.5，优选为1：0.8-1.2。
在本发明中，可以根据目标产品的组成和分子量，相应地调整各反应单体的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量。
在本发明中，在步骤(S1)中，所述反应的温度优选为160-220℃；在本发明中，在步骤(S2)中，所述反应的温度优选为180-240℃。
根据本发明，所述聚酯B可以按照上述聚酯A的制备方法进行，其中，可以根据目标产品的组成和分子量，相应地调整各反应单体的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量，以获得聚酯B。
根据本发明，所述聚酯组合物还可以含有辅助填料；优选地，以所述聚酯组合物的总重量为基准，所述辅助填料的含量为0.1-60重量％，更优选为1-20重量％。
根据本发明，所述辅助填料具有调节组合物的力学强度，改善组合物的阻燃性、抗氧化性，调节组合物的颜色和光泽等方面的作用，可以为本领域的常规选择，例如，所述辅助填料可以选自碳酸钙、炭黑、滑石粉、芥酸酰胺、二氧化钛、氧化铁、羧酸金属盐、磷酸金属盐、四溴双酚A、十溴二苯醚、六溴环十二烷、低密度聚乙烯、多聚磷酸盐或酯、亚磷酸酯、受阻胺、受阻酚、二苄山梨醇及其衍生物、超支化聚酰胺和 乙烯-甲基丙烯酸离聚物中的至少一种；优选为炭黑、受阻酚、碳酸钙、芥酸酰胺、二氧化钛、多磷酸酯、低密度聚乙烯和超支化聚酰胺中的至少一种；更优选为炭黑、受阻酚、碳酸钙、芥酸酰胺、二氧化钛、磷酸三(2,3-二溴丙基)酯(TDBPP)、低密度聚乙烯和超支化聚酰胺中的至少两种。
本发明还提供了一种上述聚酯组合物的制备方法，该方法包括：将上述聚酯A与聚酯B共混，并将得到的混合物进行挤出造粒。
在本发明中，发明人在研究过程中意外地发现：所述聚酯A与所述聚酯B具有良好的相容性，因此，在共混的过程中可以不加入相容剂。所述相容剂为本领域常规使用的用于提高共混原料的相容性的物质，例如，可以为PE-g-ST、PP-g-ST、ABS-g-MAH、PE-g-MAH和PP-g-MAH中的至少一种。
根据本发明，所述共混的过程如上文所述。在优选的情况下，所述搅拌的速率为20-150r/min，所述搅拌的时间为5-15min。
根据本发明，所述挤出造粒过程如上文所述。在优选的情况下，所述挤出造粒的温度为160-220℃；所述螺杆挤出机的螺杆的转速为10-70rpm；螺杆的扭矩为2-80N*m。
本发明还提供了一种热收缩套管，该热收缩套管含有上述聚酯组合物和/或由上述制备方法得到的聚酯组合物，也即所述热收缩套管由上述聚酯组合物和/或由上述制备方法得到的聚酯组合物制得。
在本发明中，所述热收缩套管的厚度可以为0.3-10mm，收缩比率为5：1-4.5，绝缘性良好，击穿强度≥25kV/mm。
本发明还提供了一种热收缩套管的制备方法，该制备方法包括：将聚酯组合物依次经过挤出、牵引、冷却和定型，以得到热收缩套管；其中，所述聚酯组合物为上述聚酯组合物。
在本发明的热收缩套管的制备方法中，对所述挤出的过程没有特别 的限定，可以在常规的螺旋挤出机上进行，以得到管材。优选地，所述挤出的过程在安装有口模和芯模的螺杆挤出机上进行。更优选地，所述挤出的温度为90-240℃，进一步优选为120-180℃。
在本发明的热收缩套管的制备方法中，所述冷却的温度可以为0-60℃，优选为20-40℃。
在优选的情况下，所述制备方法还包括：将所述冷却后的管材依次进行加热、扩径、二次冷却和定型。优选地，所述加热的温度为65-120℃，更优选为70-90℃。
在本发明中，所述扩径的倍率优选为原尺寸(即扩径前)的1.5-5倍，更优选为3-5倍。
在本发明中，所述二次冷却的温度可以为0-60℃，优选为20-40℃。
功能层(运动护具)
本发明提供了一种聚酯组合物，以各组分的总重量为基准，该聚酯组合物含有以下组分：
(1)50-98重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为55-79摩尔％，优选为60-77摩尔％，所述重复单元B的含量为21-45摩尔％，优选为23-40摩尔％，
Figure PCTCN2017107106-appb-000031
其中，m1为2-4的整数；n1为2-4的整数，优选为4；且m1和n1相同或不同；所述聚酯A的重均分子量为50,000-900,000，优选为 100,000-500,000；
(2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为80-100摩尔％，优选为85-95摩尔％，所述重复单元B的含量为0-20摩尔％，优选为5-15摩尔％，
Figure PCTCN2017107106-appb-000032
其中，m2为2-4的整数；n2为2-4的整数，优选为2；且m2和n2相同或不同；所述聚酯B的重均分子量为50,000-900,000，优选为100,000-500,000；在所述聚酯A中重复单元B的含量大于在所述聚酯B中重复单元B的含量；
(3)1-49重量％的纤维填料。
在本发明中，m1和m2可以相同或不同，n1和n2可以相同或不同。但当m1和m2相同且n1和n2也相同时，在所述聚酯A中重复单元B的含量与在所述聚酯B中重复单元B的含量不同。
在优选的情况下，在所述聚酯A中重复单元B的含量大于在所述聚酯B中重复单元B的含量。
在优选的情况下，所述聚酯组合物含有60-90重量％的聚酯A、5-30重量％的聚酯B和5-30重量％的纤维填料。
在本发明中，所述聚酯A和所述聚酯B可以为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种，优选为无规共聚物和/或嵌段共聚物。本发明对所述聚酯A和所述聚酯B的来源没有特别的限定，来源和制备方法如上文所述。
所述纤维填料可以为碳纤维、玻璃纤维、玄武岩纤维、芳纶纤维和聚对苯二甲酸乙二醇酯纤维中的一种或几种，优选为玻璃纤维、碳纤维 和玄武岩纤维中的一种或几种。优选地，所述纤维填料的长度为0.1-10mm，优选为0.5-2mm。
根据本发明，所述聚酯组合物还可以含有辅助填料；优选地，以所述聚酯组合物的总重量为基准，所述辅助填料的含量为0.1-25重量％，更优选为1-20重量％。
根据本发明，所述辅助填料具有加速组合物熔体固化、调节组合物力学强度、调节组合物颜色和光泽等方面的作用，可以为本领域的常规选择，例如，所述辅助填料可以为碳酸盐类无机填料、硅酸盐类无机填料、硫酸盐类无机填料、无机质中空微球和金属粉中的一种或几种，优选为碳酸盐类无机填料、硅酸盐类无机填料、硫酸盐类无机填料和金属粉中的一种或几种，更优选为无水硫酸钙、碳酸钙和铜粉中的至少一种。
本发明还提供了上述聚酯组合物的制备方法，该制备方法包括：将聚酯A、聚酯B和纤维填料共混，并将得到的混合物进行挤出造粒。
在本发明中，发明人在研究过程中意外地发现：所述聚酯A、聚酯B和纤维填料具有良好的相容性，因此，在共混的过程中可以不加入相容剂。所述相容剂为本领域常规使用的用于提高共混原料的相容性的物质，例如，可以为PE-g-ST、PP-g-ST、ABS-g-MAH、PE-g-MAH和PP-g-MAH中的至少一种。
根据本发明，所述共混的过程如上文所述。在优选的情况下，所述搅拌的速率为20-150r/min，所述搅拌的时间为5-15min。
根据本发明，所述挤出造粒过程如上文所述。在优选的情况下，所述挤出造粒的温度为120-240℃，优选为150-200℃。
本发明还提供了一种功能层，其中，该功能层含有上述聚酯组合物，也即所述功能层由上述聚酯组合物制得。
在本发明中，所述功能层具有低温可塑性和形状记忆性，具体地，在T1(80～100℃)条件下，所述功能层的邵氏D型硬度值为0-35；在 T2(-20～50℃)条件下，所述功能层的邵氏D型硬度值为40-80。也就是说，所述功能层可以在T1(80～100℃)条件下软化，此时可以通过施加外力对其进行塑形以获得预期的形状，待塑形完成后，降温至T2(-20～50℃)条件，所述功能层的硬度升高，保持形状。
本发明还提供了一种功能层的制备方法，该制备方法包括：将上述聚酯组合物成型。
在本发明中，可以根据应用目的的不同通过成型制得任意形状和大小的功能层。
根据本发明，所述成型的方式可以为挤出或注塑，优选为注塑。优选地，所述注塑的温度为140-270℃，优选为170-185℃。
本发明还提供了上述聚酯组合物和上述功能层在运动护具中的应用；优选地，所述运动护具为牙齿护具、四肢关节护具、身体大面积护具和头部护具中的一种或多种。
在本发明中，术语“牙齿护具”是指在运动过程中对牙齿起到保护作用的护具。所述牙齿护具可以含有所述功能层，优选由所述功能层组成。
在本发明中，所述牙齿护具具有低温可塑性和形状记忆性，具体地，在T1(80～100℃)条件下，所述牙齿护具的邵氏D型硬度值为0-35；在T2(-20～50℃)条件下，所述牙齿护具的邵氏D型硬度值为40-80。
本发明还提供了所述牙齿护具的制备方法，该制备方法包括将本发明提供的功能层依次进行软化、塑形和降温处理，具体地，该制备方法包括：将所述功能层在T1(80～100℃)条件下软化，并通过施加外力(如牙齿咬合)对其进行塑形，以获得预期的形状(如齿形)；待塑形完成后，降温至T2(-20～50℃)条件，所述牙齿护具的硬度升高，保持形状。
在本发明中，术语“四肢关节护具”是指在运动过程中，对四肢关节(例如，膝关节、肘关节、肩关节、腕关节等)起到保护作用的护具。所述四肢关节护具含有所述功能层。
在优选的情况下，所述四肢关节护具含有可选的外层、中间层和可选的内层，其中，所述中间层为上述功能层；所述外层可以为硬质材料，例如，可以为金属材料、硬质塑料(不包括本发明的聚酯组合物)、陶瓷和木材中的至少一种；所述内层可以为软质材料，例如，可以为海绵、泡沫、软硅胶和软橡胶中的至少一种。并且，所述外层、中间层和内层相连接；优选地，所述连接通过粘合(如使用胶)、螺纹或卡扣的方式实现。更优选地，所述外层、中间层和内层均是可拆卸的。
本发明还提供了所述四肢关节护具的制备方法，该制备方法包括：将本发明提供的功能层依次进行软化、塑形和降温处理，以得到所述四肢关节护具的中间层，具体地，该制备方法包括：将所述功能层在T1(80～100℃)条件下软化，并通过施加外力(如放置于关节的表面按压)对其进行塑形，以获得预期的形状(如呈与关节贴合的形状)；待塑形完成后，降温至T2(-20～50℃)条件，所述功能层的硬度升高，保持形状，以得到所述四肢关节护具的中间层。可选地，所述四肢关节护具的制备方法还包括：分别在所述中间层的外表面和/或内表面连接外层和/或内层。其中，所述外层和所述内层如上所述，在此不再赘述。
在本发明中，术语“身体大面积护具”是指在运动过程中对身体主要部位(例如，胸部、背部、腰部、腹部、大腿正面、小腿正面等)起到保护作用的护具。所述身体大面积护具含有所述功能层。
在优选的情况下，所述身体大面积护具含有外层、中间层和可选的内层，其中，所述中间层为上述功能层；所述外层可以为硬质材料，例如，可以为金属材料、硬质塑料(不包括本发明的聚酯组合物)、陶瓷和木材中的至少一种；所述内层可以为软质材料，例如，可以为海绵、泡沫、软硅胶和软橡胶中的至少一种。并且，所述外层、中间层和内层相连接；优选地，所述内层与所述中间层通过粘合的方式连接；所述中间层与所述外层通过卡扣、贴合或绷带固定的方式连接。更优选地，所 述外层、中间层和内层均是可拆卸的。
本发明还提供了所述身体大面积护具的制备方法，该制备方法包括：将本发明提供的功能层依次进行软化、塑形和降温处理，以得到所述身体大面积护具的中间层，具体地，该制备方法包括：将所述功能层在T1(80～100℃)条件下软化，并通过施加外力(如放置于应用的身体部位的表面按压)对其进行塑形，以获得预期的形状(如呈与身体部位贴合的形状)；待塑形完成后，降温至T2(-20～50℃)条件，所述功能层的硬度升高，保持形状，以得到所述身体大面积护具的中间层，并在中间层的外表面连接外层。可选地，所述身体大面积护具的制备方法还包括：在所述中间层的内表面连接内层。其中，所述外层和所述内层如上所述，在此不再赘述。
在本发明中，术语“头部护具”是指在运动过程中对头部起到保护作用的护具。优选地，所述头部护具为头盔。
在本发明中，所述头部护具含有所述功能层。
在优选的情况下，所述头部护具含有可选的外层、中间层和可选的内层，其中，所述中间层为上述功能层；所述外层可以为硬质材料，例如，可以为金属材料、硬质塑料(不包括本发明的聚酯组合物)、陶瓷和木材中的至少一种；所述内层可以为软质材料，例如，可以为海绵、泡沫、软硅胶和软橡胶中的至少一种。并且，所述外层、中间层和内层相连接；优选地，所述内层与所述中间层通过粘合的方式连接；所述中间层与所述外层通过卡扣、贴合或绷带固定的方式连接。更优选地，所述外层、中间层和内层均是可拆卸的。
本发明还提供了所述头部护具的制备方法，该制备方法包括：将本发明提供的功能层依次进行软化、塑形和降温处理，以得到所述头部护具的中间层，具体地，该制备方法包括：将所述功能层在T1(80～100℃)条件下软化，并通过施加外力(如放置于头部的表面按压)对其进行塑 形，以获得预期的形状(如呈与头部贴合的形状)；待塑形完成后，降温至T2(-20～50℃)条件，所述功能层的硬度升高，保持形状，以得到所述头部护具的中间层。可选地，所述头部护具的制备方法还包括：分别在所述中间层的内表面和/或外表面连接内层和/或外层。其中，所述外层和所述内层如上所述，在此不再赘述。
本发明通过将具有特定结构的聚酯A、聚酯B和纤维填料按照特定的配比(50-98重量％的聚酯A，1-49重量％的聚酯B，1-49重量％的纤维填料)配合使用得到聚酯组合物，该聚酯组合物高温条件下(如80-100℃)可以充分软化(硬度下降)，软化后的聚酯组合物可以根据目标部位通过成型制成任意形状的功能层，使其可以与目标部位更好地贴合；然后在较低的温度下(如-20-50℃)硬度明显升高，从而实现塑形的目的。并且，本发明提供的聚酯组合物还具有良好的形状记忆性能，其形变固定率为90％以上，形变回复率高达90％以上，最大形变率高达280％以上。另外，本发明提供的聚酯组合物的上述软化和塑形过程是可逆的，当将其制成运动护具的时候，当运动护具出现磨损或轻微损坏以后，可以再次通过升温软化和低温再塑形使得护具恢复原貌。因此，由本发明提供的功能层制得的运动护具具有良好的应用前景。
本发明的聚酯组合物具有良好的低温可塑性和形状记忆性能。因此，将本发明提供的聚酯组合物用于运动护具时，可以根据应用部位的差异进行塑形，使得护具更贴合身体、更舒适且制作方便。
医用肢体固定支架
本发明提供了一种聚酯组合物，其特征在于，以各组分的总重量为基准，该聚酯组合物含有以下组分：
(1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的 重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为60-80摩尔％，优选为62-78摩尔％，所述重复单元B的含量为20-40摩尔％，优选为22-38摩尔％，
Figure PCTCN2017107106-appb-000033
其中，m1为2-4的整数；n1为2-4的整数，优选为2；且m1和n1相同或不同；所述聚酯A的重均分子量为50,000-900,000，优选为100,000-500,000；
(2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为20-59摩尔％，优选为30-55摩尔％，所述重复单元B的含量为41-80摩尔％，优选为45-70摩尔％，
Figure PCTCN2017107106-appb-000034
其中，m2为2-4的整数；n2为2-4的整数，优选为2；且m2和n2相同或不同；所述聚酯B的重均分子量为50,000-900,000，优选为100,000-500,000。
在本发明中，m1和m2可以相同或不同，n1和n2可以相同或不同。但当m1和m2相同且n1和n2也相同时，在所述聚酯A中重复单元B的含量与在所述聚酯B中重复单元B的含量不同。
在优选的情况下，所述聚酯组合物含有70-90重量％的聚酯A和10-30重量％的聚酯B；更优选地，所述聚酯组合物含有70-80重量％的聚酯A和20-30重量％的聚酯B。
在本发明中，所述聚酯A和所述聚酯B可以为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种，优选为无规共聚物和/或嵌段共聚物。本发明对所述聚酯A和所述聚酯B的来源没有特别的限定，来源和制备方法如上文中所述。
根据本发明，所述聚酯组合物还可以含有辅助填料；优选地，以所述聚酯组合物的总重量为基准，所述辅助填料的含量为0.1-60重量％，更优选为1-20重量％。
根据本发明，所述辅助填料具有调节组合物的固化时间，调节组合物的力学强度，改善组合物的阻燃性、抗氧化性，调节组合物的颜色和光泽等方面的作用，可以为本领域的常规选择，例如，所述辅助填料可以选自碳酸钙、炭黑、滑石粉、芥酸酰胺、二氧化钛、氧化铁、羧酸金属盐、磷酸金属盐、四溴双酚A、十溴二苯醚、六溴环十二烷、低密度聚乙烯、多聚磷酸盐或酯、亚磷酸酯、受阻酚、受阻胺、二苄山梨醇及其衍生物、超支化聚酰胺和乙烯-甲基丙烯酸离聚物中的至少一种；优选为碳酸钙、炭黑、芥酸酰胺、二氧化钛、多聚磷酸盐或酯、低密度聚乙烯和超支化聚酰胺中的至少一种；更优选为氧化铁、二氧化钛、碳酸钙、炭黑、芥酸酰胺、磷酸三(2,3-二溴丙基)酯(TDBPP)、低密度聚乙烯和超支化聚酰胺中的至少一种。
本发明还提供了上述聚酯组合物的制备方法，其特征在于，该制备方法包括：将上述聚酯A与聚酯B共混，并将得到的混合物进行挤出造粒。
在本发明中，发明人在研究过程中意外地发现：所述聚酯A与所述聚酯B具有良好的相容性，因此，在共混的过程中可以不加入相容剂。所述相容剂为本领域常规使用的用于提高共混原料的相容性的物质，例如，可以为PE-g-ST、PP-g-ST、ABS-g-MAH、PE-g-MAH和PP-g-MAH中的至少一种。
根据本发明，所述共混的过程如上文所述。在优选的情况下，所述搅拌的速率为20-150r/min，所述搅拌的时间为5-15min。
根据本发明，所述挤出造粒过程如上文所述。在优选的情况下，所述挤出造粒的温度为110-260℃，优选为160-220℃。
本发明还提供了一种医用肢体固定支架，该医用肢体固定支架含有上述聚酯组合物，也即所述医用肢体固定支架由上述聚酯组合物制得。
根据本发明，所述医用肢体固定支架的厚度可以为0.2-10mm，优选为1-3mm。
根据本发明，所述医用肢体固定支架具有和/或不具有孔结构，优选为具有孔结构。
在本发明中，所述孔结构沿所述医用肢体固定支架贯穿分布，以提高医用肢体固定支架的透气性。优选地，所述孔结构的孔径为1-10mm，优选为1-5mm。
在本发明中，所述医用肢体固定支架可以用于任意肢体部位的固定，例如，可以用于手指、四肢、颈部、背部等各个身体部位。
本发明还提供了一种医用肢体固定支架的制备方法，该制备方法包括：将聚酯组合物依次经过挤出、成型和可选的打孔，以得到医用肢体固定支架；其中，所述聚酯组合物为上述聚酯组合物。
在本发明的医用肢体固定支架的制备方法中，所述挤出优选为熔融挤出；更优选地，所述挤出的温度为90-230℃，优选为110-170℃。
在本发明的医用肢体固定支架的制备方法中，所述成型的方式可以为注塑和/或压塑。在优选的情况下，所述成型使得所述医用肢体固定支架的厚度为0.2-10mm，优选为1-3mm。
在本发明的医用肢体固定支架的制备方法中，所述打孔可以使用打孔器进行；优选地，使用的打孔器的直径为1-10mm，优选为1-5mm。
在本发明的医用肢体固定支架的制备方法中，所述制备方法还可以 包括将成型得到的材料进行切割，以获得大小和形状合适的医用肢体固定支架。
本发明通过将特定的共聚物(聚酯A和聚酯B)按照特定的配比(聚酯A的含量为51-99重量％，聚酯B的含量为1-49重量％)进行共混，得到硬度可以随温度和时间变化的聚酯组合物。使用本发明提供的聚酯组合物制成的医用肢体固定支架在高温条件下(如热水中，特别是沸水中)可以充分软化，软化后的材料易于剪裁，将其剪裁成适当的尺寸和形状缠绕于需要固定的肢体部位可以发生硬化且可自行粘合，从而达到良好的塑形和固定目的。并且，上述过程是可逆的，可以重新按照肢体部位进行塑形，且该医用肢体固定支架方便拆卸和清洗；同时具有良好的降解性能，制备过程由于采用热塑性加工(未使用交联剂)，边角料亦可以回收再利用。
另外，本发明的医用肢体固定支架还具有以下优势：在保存和运输的过程中不需隔水等特殊包装，开袋后仍可保持至少两年不变质；重量和高分子绷带相近，仅有石膏绷带重量的约1/5；具有极好的X射线透过性；由于不涉及和水的反应，具有完美的防水性，使用前的储存也不惧怕潮湿。
本发明提供的聚酯组合物的硬度随时间和温度发生变化，具体地，其在较高温度下硬度较低，冷却后在较短时间内硬度明显升高，表现出良好的可塑性和固定性，因此，本发明提供的聚酯组合物特别适用于制备医用肢体固定支架。
热收缩膜
本发明提供了一种聚酯组合物，其中，以各组分的总重量为基准，该聚酯组合物含有以下组分：
(1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复 单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为60-80摩尔％，优选为62-72摩尔％，所述重复单元B的含量为20-40摩尔％，优选为28-38摩尔％，
Figure PCTCN2017107106-appb-000035
其中，m1为2-4的整数；n1为2-4的整数，优选为2；且m1和n1相同或不同；所述聚酯A的重均分子量为50,000-900,000，优选为100,000-500,000；
(2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为81-99摩尔％，优选为85-97摩尔％，所述重复单元B的含量为1-19摩尔％，优选为3-15摩尔％，
Figure PCTCN2017107106-appb-000036
其中，m2为2-4的整数；n2为2-4的整数，优选为2；且m2和n2相同或不同；所述聚酯B的重均分子量为50,000-900,000，优选为100,000-500,000。
在本发明中，m1和m2可以相同或不同，n1和n2可以相同或不同。但当m1和m2相同且n1和n2也相同时，在所述聚酯A中重复单元B的含量与在所述聚酯B中重复单元B的含量不同。
在优选的情况下，在所述聚酯A中重复单元B的含量大于在所述聚酯B中重复单元B的含量。
在优选的情况下，所述聚酯组合物含有60-90重量％的聚酯A和10-40重量％的聚酯B。
在本发明中，所述聚酯A和所述聚酯B可以为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种，优选为无规共聚物和/或嵌段共聚物。本发明对所述聚酯A和所述聚酯B的来源没有特别的限定，来源和制备方法如上文中所述。
根据本发明，所述聚酯组合物还可以含有辅助填料；优选地，以所述聚酯组合物的总重量为基准，所述辅助填料的含量为0.1-20重量％，更优选为10-20重量％。
根据本发明，所述辅助填料具有加速组合物熔体固化,调节组合物力学强度,改善组合物阻燃性、抗氧化性，调节组合物颜色和光泽等方面的作用，可以为本领域的常规选择，例如，所述辅助填料可以选自碳酸钙、炭黑、滑石粉、芥酸酰胺、二氧化钛、氧化铁、羧酸金属盐、磷酸金属盐、四溴双酚A、十溴二苯醚、六溴环十二烷、低密度聚乙烯、多聚磷酸酯或盐、亚磷酸酯、受阻酚、受阻胺、二苄山梨醇及其衍生物、超支化聚酰胺和乙烯-甲基丙烯酸离聚物中的至少一种；优选为碳酸钙、炭黑、芥酸酰胺、二氧化钛、多聚磷酸盐、低密度聚乙烯和超支化聚酰胺中的至少一种；更优选为碳酸钙、炭黑、芥酸酰胺、二氧化钛、磷酸三(2,3-二溴丙基)酯、低密度聚乙烯和超支化聚酰胺中的至少两种。
本发明还提供了一种上述聚酯组合物的制备方法，该方法包括：将上述聚酯A与聚酯B共混，并将得到的混合物进行挤出造粒。
在本发明中，发明人在研究过程中意外地发现：所述聚酯A与所述聚酯B具有良好的相容性，因此，在共混的过程中可以不加入相容剂。所述相容剂为本领域常规使用的用于提高共混原料的相容性的物质，例如，可以为PE-g-ST、PP-g-ST、ABS-g-MAH、PE-g-MAH和PP-g-MAH中的至少一种。
根据本发明，所述共混的过程如上文所述。在优选的情况下，所述搅拌的速率为10-150r/min，所述搅拌的时间为5-15min。
根据本发明，所述挤出造粒过程如上文所述。在优选的情况下，所述挤出造粒的温度为80-220℃，优选为110-180℃。
本发明还提供了一种热收缩薄膜，该热收缩薄膜含有上述聚酯组合物，也即所述热收缩薄膜由上述聚酯组合物制得。
在本发明中，所述热收缩薄膜的厚度可以为5-1000μm，热收缩率通过配方和聚酯结构的调节能够在较大范围内改变，例如，所述热收缩薄膜的热收缩率为10-80％，可以满足不同的需求；并且，所述热收缩薄膜的热封强度为11-19N/15mm，且所述热收缩薄膜具有良好的可降解性能。
本发明还提供了一种热收缩薄膜的制备方法，该制备方法包括：将聚酯组合物依次经过流延成膜、静置和拉伸，以得到热收缩薄膜；其中，所述聚酯组合物为上述聚酯组合物。
根据本发明，对所述流延成膜的过程没有特别的限定，例如，可以在流延机上进行。在优选的情况下，所述流延成膜的温度为80-220℃，优选为110-180℃。
在本发明中，对所述静置的过程没有特别的限定，例如，可以在室温(25℃)环境中放置。在优选的情况下，所述静置的时间为30分钟-20天，优选为4-24小时。
在本发明中，所述拉伸可以为单向拉伸或双向拉伸。在优选的情况下，所述拉伸的温度为40-150℃，优选为60-120℃。
本发明通过将特定的共聚物(聚酯A和聚酯B)按照特定的配比(聚酯A的含量为51-99重量％，聚酯B的含量为1-49重量％)进行共混，不仅可以得到热收缩率高达70％以上的热收缩薄膜，还可以得到热收缩率为10％的薄膜，这说明本发明通过配方和聚酯结构的调节能够在较大范围内改变薄膜的热收缩率；并且，本发明得到的热收缩薄膜具有合适 的热封强度(高达11-19N/15mm)，薄膜表面平整、光泽度良好，可降解且可以反复热塑加工并可回收，因此其具有明显的环保优势和工业应用前景。
无纺布
本发明提供了一种聚酯组合物，其中，以各组分的总重量为基准，该聚酯组合物含有以下组分：
(1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为75-99摩尔％，优选为81-95摩尔％，所述重复单元B的含量为1-25摩尔％，优选为5-19摩尔％，
Figure PCTCN2017107106-appb-000037
其中，m1为2-4的整数；n1为2-4的整数，优选为2；且m1和n1相同或不同，所述聚酯A的重均分子量为50,000-900,000，优选为100,000-500,000；
(2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为20-74摩尔％，优选为40-70摩尔％，所述重复单元B的含量为26-80摩尔％，优选为30-60摩尔％，
Figure PCTCN2017107106-appb-000038
其中，m2为2-4的整数；n2为2-4的整数，优选为2；且m2和n2相同或不同；所述聚酯B的重均分子量为50,000-900,000，优选为100,000-500,000。
在本发明中，m1和m2可以相同或不同，n1和n2可以相同或不同。但当m1和m2相同且n1和n2也相同时，在所述聚酯A中重复单元B的含量与在所述聚酯B中重复单元B的含量不同。
在优选的情况下，所述聚酯组合物含有55-70重量％的聚酯A和30-45重量％的聚酯B。
在本发明中，所述聚酯A和所述聚酯B可以为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种，优选为无规共聚物和/或嵌段共聚物。本发明对所述聚酯A和所述聚酯B的来源没有特别的限定，来源和制备方法如上文所述。
根据本发明，所述聚酯组合物还可以含有辅助填料；优选地，以所述聚酯组合物的总重量为基准，所述辅助填料的含量为0.1-25重量％，更优选为1-20重量％。
根据本发明，所述辅助填料具有加速组合物纺丝固化成型，调节织物或无纺布的力学强度，改善制品阻燃性、抗氧化性，调节制品的颜色和光泽等方面的作用，可以为本领域的常规选择，例如，所述辅助填料可以选自碳酸钙、炭黑、滑石粉、芥酸酰胺、二氧化钛、氧化铁、羧酸金属盐、磷酸金属盐、四溴双酚A、十溴二苯醚、六溴环十二烷、低密度聚乙烯、多聚磷酸盐或酯、亚磷酸酯、受阻酚、受阻胺、二苄山梨醇及其衍生物、超支化聚酰胺和乙烯-甲基丙烯酸离聚物中的至少一种；优选为受阻酚、碳酸钙、炭黑、芥酸酰胺、二氧化钛、磷酸三(2,3-二溴丙基)酯(TDBPP)、低密度聚乙烯和超支化聚酰胺中的至少一种。
本发明还提供了上述聚酯组合物的制备方法，其中，该制备方法包括：将上述聚酯A与聚酯B共混，并将得到的混合物进行挤出造粒。
在本发明中，发明人在研究过程中意外地发现：所述聚酯A与所述聚酯B具有良好的相容性，因此，在共混的过程中可以不加入相容剂。所述相容剂为本领域常规使用的用于提高共混原料的相容性的物质，例如，可以为PE-g-ST、PP-g-ST、ABS-g-MAH、PE-g-MAH和PP-g-MAH中的至少一种。
根据本发明，所述共混的过程如上文所述。在优选的情况下，所述搅拌的速率为20-150r/min，所述搅拌的时间为5-15min。
根据本发明，所述挤出造粒过程如上文所述。在优选的情况下，所述挤出造粒的温度为140-220℃，优选为160-200℃。
本发明还提供了一种无纺布，其中，该无纺布含有上述聚酯组合物，也即所述无纺布由上述聚酯组合物制得。
在本发明中，所述无纺布的长丝直径可以为5-100μm，优选为20-50μm。
本发明还提供了一种无纺布的制备方法，该制备方法包括：将上述聚酯组合物通过纺粘法制得无纺布。本发明对所述纺粘法使用的装置没有特别的限定，例如，可以使用本领域常规使用的纺粘机。
在优选的情况下，所述纺粘法包括挤出、纺丝、成网和加固的过程。更优选地，所述挤出的过程包括三个温区，第一温区的温度为140-250℃，优选为160-210℃；第二温区的温度为150-260℃，优选为165-220℃；第三温区的温度为170-260℃，优选为180-230℃。
在本发明中，对所述纺丝的条件没有特别的限定，例如，所述纺丝的温度可以为150-240℃，优选为170-220℃；所述纺丝的速率可以为10-40r/min，优选为15-30r/min。
在本发明中，对所述成网的条件没有特别的限定，例如，所述成网的速率可以为5-30r/min，优选为10-20r/min。
在本发明中，所述加固优选采用热轧的方式，所述热轧的温度为 80-170℃，优选为90-120℃。
本发明还提供了上述聚酯组合物和上述无纺布在无纺布制品中的应用，优选在一次性无纺布制品中的应用，更优选在一次性医用无纺布制品中的应用。
在优选情况下，所述一次性医用无纺布制品选自一次性手术服、一次性医用口罩、一次性医用帽子、一次性医用床单和一次性手术洞巾中的至少一种。
弹性纤维
本发明提供了一种聚酯组合物，以各组分的总重量为基准，该聚酯组合物含有以下组分：
(1)30-98重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为51-80摩尔％，优选为60-75摩尔％；所述重复单元B的含量为20-49摩尔％，优选为25-40摩尔％，
Figure PCTCN2017107106-appb-000039
其中，m1为2-8的整数，优选为2-4的整数；n1为2-6的整数，优选为2-4的整数；且m1和n1相同或不同；所述聚酯A的重均分子量为50,000-900,000，优选为100,000-500,000；
(2)1-69重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为 81-99摩尔％，优选为83-95摩尔％，所述重复单元B的含量为1-19摩尔％，优选为5-17摩尔％，
Figure PCTCN2017107106-appb-000040
其中，m2为2-8的整数，优选为2-4的整数；n2为2-6的整数，优选为2-4的整数；且m2和n2相同或不同；所述聚酯B的重均分子量为50,000-900,000，优选为100,000-500,000；
(3)1-69重量％的聚酯C，所述聚酯C为含有式(I”’)所示的重复单元D和式(II-1)所示的重复单元B的共聚物，且以所述聚酯C中的重复单元D和重复单元B的总摩尔数为基准，所述重复单元D的含量为0-49摩尔％，优选为15-45摩尔％，所述重复单元B的含量为51-100摩尔％，优选为55-85摩尔％，
Figure PCTCN2017107106-appb-000041
其中，m3为2-8的整数，优选为2-4的整数；n3为2-6的整数，优选为2-4的整数；且m3和n3相同或不同；所述聚酯C的重均分子量为50,000-900,000，优选为100,000-500,000。
在本发明中，m1、m2和m3可以相同或不同，n1、n2和n3可以相同或不同。但当m1、m2和m3均相同，n1、n2和n3均相同时，在所述聚酯A、所述聚酯B和所述聚酯C中重复单元B的含量各不相同。
在优选的情况下，所述聚酯组合物含有60-93重量％的聚酯A、5-38重量％的聚酯B和1-20重量％的聚酯C。
在本发明中，所述聚酯A、所述聚酯B和所述聚酯C均可以为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种，优选为无规共聚物和/或嵌段共聚物。本发明对所述聚酯A、所述聚酯B和所述聚酯C的来源没有特别的限定，来源和制备方法如上文所述。
根据本发明，所述聚酯组合物还可以含有辅助填料；优选地，以所述聚酯组合物的总重量为基准，所述辅助填料的含量为1-20重量％，更优选为2-10重量％。
在本发明中，所述辅助填料可以具有加速组合物熔体固化，调节组合物力学强度，改善组合物阻燃性、抗氧化性，调节组合物颜色和光泽等方面的作用，可以为本领域的常规选择，例如，所述辅助填料选自碳酸钙、炭黑、滑石粉、芥酸酰胺、二氧化钛、低密度聚乙烯、多聚磷酸盐或酯、亚磷酸酯、受阻酚、受阻胺、二苄山梨醇及其衍生物、超支化聚酰胺和乙烯-甲基丙烯酸离聚物中的一种或几种；优选为碳酸钙、炭黑、芥酸酰胺、二氧化钛、磷酸三(2、3-二溴丙基)酯(TDBPP)和低密度聚乙烯中的一种或几种。
本发明还提供了上述聚酯组合物的制备方法，该制备方法包括：将聚酯A、聚酯B和聚酯C共混，并将得到的混合物进行挤出造粒。
在本发明中，发明人在研究过程中意外地发现：所述聚酯A、聚酯B和聚酯C具有良好的相容性，因此，在共混的过程中可以不加入相容剂。所述相容剂为本领域常规使用的用于提高共混原料的相容性的物质，例如，可以为PE-g-ST、PP-g-ST、ABS-g-MAH、PE-g-MAH和PP-g-MAH中的至少一种。
根据本发明，所述共混的过程如上文所述。在优选的情况下，所述搅拌的速率为10-150r/min，所述搅拌的时间为5-15min。
根据本发明，所述挤出造粒过程如上文所述。在优选的情况下，所述挤出造粒的温度为110-270℃，优选为130-230℃。
本发明还提供了一种弹性纤维，其中，该弹性纤维含有上述聚酯组合物和/或由上述制备方法得到的聚酯组合物，也即所述弹性纤维由上述聚酯组合物和/或由上述制备方法得到的聚酯组合物制得。
根据本发明，所述弹性纤维的纤度可以为5-500dtex。断裂强度 ≥1cN/dtex，优选为3-19cN/dtex；断裂伸长率≥100％，优选为130-620％；应力松弛率≤12％，优选为1-12％；永久应变率≤12％，优选为1-11％。在本发明中，纤度可以使用常规的纤度仪进行检测。
本发明还提供了一种弹性纤维的制备方法，该制备方法包括：将聚酯组合物依次经过成丝、低温放置和拉伸，以得到弹性纤维；其中，所述聚酯组合物为上述聚酯组合物。
根据本发明，所述成丝的方式可以为本领域常规的选择，优选为熔体纺丝。在优选的情况下，所述成丝的温度为120-270℃，优选为150-220℃。
根据本发明，所述低温放置的条件包括：温度为20-55℃，优选为25-45℃；时间为2-120min，优选为15-60min。
根据本发明，所述拉伸的条件包括：温度为56-110℃，优选为60-90℃；拉伸的倍率为1.2-10倍，优选为2-5倍。
本发明通过将特定的聚酯A、聚酯B和聚酯C按照特定的配比(30-98重量％的聚酯A，1-69重量％的聚酯B，1-69重量％的聚酯C)进行共混后得到聚酯组合物，使用该聚酯组合物制成的弹性纤维的断裂强度≥1cN/dtex，且通过配方和分子结构的调节能够在较大范围内改变，最大断裂强度接近20cN/dtex；并且，本发明提供的弹性纤维的断裂伸长率高达130％以上，应力松弛和永久应变率均可以≤12％，这说明本发明提供的弹性纤维兼具适中的弹性和强度，且性能可调节性范围广，因此其具有良好的应用前景。
另外，本发明特别采用高温成丝-低温放置-高温拉伸的方法和条件制备得到弹性纤维，该方法可以进一步提高弹性纤维的断裂强度，扩大性能可调节范围，降低弹性纤维的应力松弛和永久应变率。
本发明中一些参数的测量标准如下：
纤度：直接用螺旋测微器测量，并用JIS L0104-2000法算出相应的数值。
纤维断裂强度：GB/T 14337-2008
纤维断裂伸长率：GB/T 14337-2008
应力松弛率：GB/T 14337-2008
永久应变率：GB/T 14337-2008
塑料样条强度：GB/T 1040.2-2006/ISO 527-2:1993
塑料样条断裂伸长率：GB/T 1040.2-2006/ISO 527-2:1993
邵氏硬度：GB/T 2411-2008/ISO 868:2003
具体实施方式
以下将通过实施例对本发明进行详细描述，应当理解的是，这些实施例仅用于举例说明本发明，并不意于限制本发明的范围。
实施例
在以下实施例和对比例中，
聚合物的重均分子量采用凝胶渗透色谱法(GPC)，以四氢呋喃(THF)为溶剂，在Waters-208(带Waters 2410RI检测器，1.5mL/min流速，30℃)仪器上测量，以聚苯乙烯标样校准；
聚酯A、聚酯B、聚酯C和脂肪族聚酯以及芳香族聚酯的微观结构采用瑞士Bruker公司的AVANCE DRX 400MHz核磁共振波谱仪测定，以氘代氯仿作为溶剂；
聚酯组合物的组成通过原料的投料确定；
聚酯组合物的形变记忆性能采用Instron5965拉伸仪(带恒温箱)测量，具体如下：
聚酯组合物样条在室温下的初始长度为a；将恒温箱升温至80℃， 使其充分软化，在拉伸速度为50mm/min的条件下拉伸至长度b；保持外力使拉伸长度不变，降温，待样条固化，撤去外力，此时样条的长度为c；再次将样条升温至80℃，待样条充分回缩，此时样条的长度为d；
形变固定率(％)＝(c-a)/(b-a)×100％；
形状回复率(％)＝(c-d)/(c-a)×100％；
最大形变率(％)＝bmax/a×100％，其中，bmax为样条损坏前能达到的最大b值；
在没有特别说明的情况下，本发明使用的脂肪族-芳香族共聚酯按照CN100429256C中实施例B13-B21公开的方法自行制备得到，其中，可以根据目标产品的组成和分子量，相应地调整反应原料的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量。
形状记忆材料
实施例I-1
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将对苯二甲酸丁二醇(BT)-丁二酸丁二醇(BS)共聚酯(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)、对苯二甲酸丁二醇(BT)-己二酸丁二醇(BA)共聚酯(购自巴斯夫公司，牌号为ecoflex，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)和聚丁二酸丁二醇酯(PBS)(购自巴斯夫公司，牌号为1111HTA4)按照40：40：20的摩尔比进行混合，并加入1重量％碳酸钙(以混合物的总重量为基准)。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为190℃、200℃、210℃、220℃、220℃、210℃，制得聚酯 组合物I-A1。
对比例I-1
按照实施例I-1的方法制备聚酯组合物，所不同的是，使用相同摩尔量的聚对苯二甲酸丁二醇酯(PBT)(购自杜邦公司，牌号为Crastin SC164 NC010)代替实施例I-1中使用的BT-BS共聚酯，制得聚酯组合物I-D1。
对比例I-2
按照实施例I-1的方法制备聚酯组合物，所不同的是，使用相同摩尔量的PBT(购自杜邦公司，牌号为Crastin SC164 NC010)代替实施例I-1中使用的BT-BA共聚酯，制得聚酯组合物I-D2。
对比例I-3
按照实施例I-1的方法制备聚酯组合物，所不同的是，不加入实施例I-1中使用的PBS，制得聚酯组合物I-D3。
对比例I-4
按照实施例I-1的方法制备聚酯组合物，所不同的是，BT-BS共聚酯、BT-BA共聚酯和PBS按照2：2：96的摩尔比进行混合，制得聚酯组合物I-D4。
实施例I-2
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将BT-BS共聚酯(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为55摩尔％)、BT-BA共聚酯(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为20摩尔％)和PBS按照20：70：10的摩尔比进行混合，并加入1重量％碳酸钙(以混合物的总重量为基准)。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为190℃、200℃、210℃、220℃、220℃、210℃，制得聚酯组合物 I-A2。
实施例I-3
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将BT-BS共聚酯(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)、BT-BA共聚酯(购自巴斯夫公司，牌号为ecoflex，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)和PBS按照50：49：1的摩尔比进行混合，并加入1重量％碳酸钙(以混合物的总重量为基准)。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为190℃、200℃、210℃、220℃、220℃、210℃，制得聚酯组合物I-A3。
实施例I-4
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将BT-BS共聚酯(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为40摩尔％)、BT-BA共聚酯(购自巴斯夫公司，牌号为ecoflex，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)和PBS按照90：1：9的摩尔比进行混合，并加入1重量％碳酸钙(以混合物的总重量为基准)。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为160℃、170℃、180℃、180℃、180℃、170℃，制得聚酯组合物I-A4。
实施例I-5
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将BT-BS共聚酯(重均分子量为100,000，其中，以BT重复单元和BS重复单元 的总摩尔数为基准，BT重复单元的含量为40摩尔％)、BT-BA共聚酯(购自巴斯夫公司，牌号为ecoflex，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)和PBS按照90：1：9的摩尔比进行混合，并加入5重量％碳酸钙(以混合物的总重量为基准)。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为160℃、170℃、180℃、180℃、180℃、170℃，制得聚酯组合物I-A5。
实施例I-6
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将BT-BS共聚酯(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为40摩尔％)、BT-BA共聚酯(购自巴斯夫公司，牌号为ecoflex，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)和PBS按照90：1：9的摩尔比进行混合，并加入5重量％低密度聚乙烯(以混合物的总重量为基准，购自中石化燕山石化公司，牌号为LD607)。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为160℃、170℃、180℃、180℃、180℃、170℃，制得聚酯组合物I-A6。
实施例I-7
按照实施例I-1的方法制备聚酯组合物，所不同的是，不加入实施例I-1中使用的碳酸钙，制得聚酯组合物I-A7。
实施例I-8
按照实施例I-1的方法制备聚酯组合物，所不同的是，使用相同摩尔量的对苯二甲酸乙二醇(ET)-丁二酸乙二醇(ES)共聚酯(重均分子量为100,000，其中，以ET重复单元和ES重复单元的总摩尔数为基准， ET重复单元的含量为50摩尔％)代替实施例I-1中使用的BT-BS共聚酯，制得聚酯组合物I-A8。
实施例I-9
按照实施例I-1的方法制备聚酯组合物，所不同的是，使用相同摩尔量的聚丁二酸己二醇酯(PHS)(按照CN104039865B公开的方法制备得到，重均分子量为100,000)代替实施例I-1中使用的PBS，制得聚酯组合物I-A9。
形态记忆性能测试例
将实施例I-1至I-9和对比例I-1至I-4制得的聚酯组合物分别制成冲压样条，并将制成的冲压样条进行形态记忆性能测试，结果如下表1所示。
表1
Figure PCTCN2017107106-appb-000042
将以上由实施例I-1至I-9制备得到的聚酯组合物用于形状记忆材料，该形状记忆材料的形变固定率和形状回复率均达到92％以上，最大形变 率高达400％以上。另外，该形状记忆材料的最初赋形温度和启动温度均可以调节，这将更有利于其在日常生活中的应用。
3D打印材料
实施例II-1
在搅拌的条件下(搅拌的速率为50r/min，时间为10min)，将1kg BT-BS共聚酯A(重均分子量为300,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)颗粒、50g BT-BS共聚酯B(重均分子量为200,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)颗粒、50g BT-BS共聚酯C(重均分子量为200,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为80摩尔％)颗粒和100g二氧化钛混合，然后将混合物加入双螺杆挤出机中，在180℃温度下熔融挤出并造粒，得到聚酯组合物II-A1。
将以上聚酯组合物II-A1加入到挤出机中，在180℃下经过圆孔模头挤出线条，线条经过空气或者水槽在0℃冷却，得到直径为1.75mm的3D打印线材II-B1。
实施例II-2
在搅拌的条件下(搅拌的速率为50r/min，时间为10min)，将880g BT-BS共聚酯A(重均分子量为300,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为40摩尔％)颗粒、110g BT-BS共聚酯B(重均分子量为200,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为15摩尔％)颗粒、110g BT-BS共聚酯C(重均分子量为200,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为85摩尔％)颗粒和100g二氧化钛混合。然后将混合物加入双螺杆挤出机中，在180℃温度 下熔融挤出并造粒，得到聚酯组合物II-A2。
将以上聚酯组合物II-A2加入到挤出机中，在180℃下经过圆孔模头挤出线条，线条经过空气或者水槽在0℃冷却，得到直径为1.75mm的3D打印线材II-B2。
实施例II-3
在搅拌的条件下(搅拌的速率为50r/min，时间为10min)，将770g BT-BS共聚酯A(重均分子量为300,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为25摩尔％)颗粒、165gBT-BS共聚酯B(重均分子量为200,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为5摩尔％)颗粒、165g BT-BS共聚酯C(重均分子量为200,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)颗粒和100g二氧化钛混合，然后将混合物加入双螺杆挤出机中，在180℃温度下熔融挤出并造粒，得到聚酯组合物II-A3。
将以上聚酯组合物II-A3加入到挤出机中，在180℃下经过圆孔模头挤出线条，线条经过空气或者水槽在0℃冷却，得到直径为1.75mm的3D打印线材II-B3。
实施例II-4
在搅拌的条件下(搅拌的速率为50r/min，时间为10min)，将605gBT-BS共聚酯A(重均分子量为300,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为44摩尔％)颗粒、275gBT-BS共聚酯B(重均分子量为200,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为19摩尔％)颗粒、220gPBT(聚酯C，购自杜邦公司，牌号为Crastin SC164 NC010)颗粒和100g二氧化钛混合，然后将混合物加入双螺杆挤出机中，在180℃温度下熔融挤出并造粒，得到聚酯组合物II-A4。
将以上聚酯组合物II-A4加入到挤出机中，在180℃下经过圆孔模头挤出线条，线条经过空气或者水槽在0℃冷却，得到直径为1.75mm的3D打印线材II-B4。
实施例II-5
在搅拌的条件下(搅拌的速率为50r/min，时间为10min)，将1078g BT-BS共聚酯A(重均分子量为300,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为20摩尔％)颗粒、11g BT-BS共聚酯B(重均分子量为200,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为1摩尔％)颗粒、11g BT-BS共聚酯C(重均分子量为200,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为45摩尔％)颗粒和100g二氧化钛混合，然后将混合物加入双螺杆挤出机中，在180℃温度下熔融挤出并造粒，得到聚酯组合物II-A5。
将以上聚酯组合物II-A5加入到挤出机中，在180℃下经过圆孔模头挤出线条，线条经过空气或者水槽在0℃冷却，得到直径为1.75mm的3D打印线材II-B5。
实施例II-6
按照实施例II-1的方法进行，不同的是，聚酯B为BT-BA共聚酯(重均分子量为200,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)；聚酯C为BT-BA共聚酯(重均分子量为200,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为80摩尔％)。得到聚酯组合物II-A6和3D打印线材II-B6。
实施例II-7
按照实施例II-1的方法进行，不同的是，聚酯B为ET-EA(己二酸乙二醇)共聚酯(重均分子量为200,000，其中，以ET重复单元和EA 重复单元的总摩尔数为基准，ET重复单元的含量为10摩尔％)；聚酯C为ET-EA共聚酯(重均分子量为200,000，其中，以ET重复单元和EA重复单元的总摩尔数为基准，ET重复单元的含量为80摩尔％)。得到聚酯组合物II-A7和3D打印线材II-B7。
实施例II-8
按照实施例II-1的方法进行，不同的是，聚酯B为ET-BS共聚酯(重均分子量为200,000，其中，以ET重复单元和BS重复单元的总摩尔数为基准，ET重复单元的含量为10摩尔％)；聚酯C为BT-EA共聚酯(重均分子量为200,000，其中，以BT重复单元和EA重复单元的总摩尔数为基准，BT重复单元的含量为80摩尔％)。得到聚酯组合物II-A8和3D打印线材II-B8。
实施例II-9
按照实施例II-1的方法进行，不同的是，使用相同重量的碳酸钙代替实施例II-1中的二氧化钛。得到聚酯组合物II-A9和3D打印线材II-B9。
实施例II-10
按照实施例II-1的方法进行，不同的是，未加入100g二氧化钛。得到聚酯组合物II-A10和3D打印线材II-B10。
对比例II-1
按照实施例II-1的方法进行，不同的是，将1kg实施例II-1使用的聚酯A、100g实施例II-1使用的聚酯B和100g二氧化钛混合，而不加入实施例II-1使用的聚酯C。得到线材II-D1。
对比例II-2
按照实施例II-1的方法进行，不同的是，将1kg实施例II-1使用的聚酯A、100g实施例II-1使用的聚酯C和100g二氧化钛混合，而不加入实施例II-1使用的聚酯B。得到线材II-D2。
对比例II-3
按照实施例II-1的方法进行，不同的是，将550g实施例II-1使用的聚酯B、550g实施例II-1使用的聚酯C和100g二氧化钛混合，而不加入实施例II-1使用的聚酯A。得到线材II-D3。
对比例II-4
按照实施例II-1的方法进行，不同的是，将50g实施例II-1使用的聚酯A、1kg实施例II-1使用的聚酯B、50g实施例II-1使用的聚酯C和100g二氧化钛混合。得到线材II-D4。
对比例II-5
按照实施例II-1的方法进行，不同的是，使用相同重量的PBS(购自巴斯夫公司，牌号为1111HTA4)代替实施例II-1中使用的聚酯A。得到线材II-D5。
对比例II-6
按照实施例II-1的方法进行，不同的是，使用相同重量的PBS(购自巴斯夫公司，牌号为1111HTA4)代替实施例II-1中使用的聚酯C。得到线材II-D6。
对比例II-7
按照实施例II-1的方法进行，不同的是，将1.1kg实施例II-1中使用的聚酯A和100g二氧化钛混合。得到线材II-D7。
对比例II-8
按照实施例II-1的方法进行，不同的是，将1.1kg实施例II-1中使用的聚酯B和100g二氧化钛混合。得到线材II-D8。
对比例II-9
按照实施例II-1的方法进行，不同的是，将1.1kg实施例II-1中使用的聚酯C和100g二氧化钛混合。得到线材II-D9。
对比例II-10
按照实施例II-1的方法进行，不同的是，将1.1kg PBT(购自杜邦公 司，牌号为Crastin SC164 NC010)和100g二氧化钛混合。得到线材II-D10。
测试例II-1至II-20
1、光泽度评价
将实施例II-1至II-10和对比例II-1至II-10得到的聚酯组合物粒料，用Haake小型流延机流延在一个室温(25℃)的平板上，待流延片完全冷却固化后，对不接触冷却平板的那个表面测试其光泽度。按照GBT9754-2007标准对实施例II-1至II-10和对比例II-1至II-10得到的流延片的光泽度进行评价。结果如表2所示。
2、硬度(或柔性)评价
将实施例II-1至II-10和对比例II-1至II-10得到的线材剪成颗粒，用Carver热压机把颗粒在熔点之上熔融热压成7cm×7cm×4mm的片，按照GB/T2411-2008方法分别对实施例II-1至II-10和对比例II-1至II-10得到的片的邵氏D硬度进行评价。结果如表2所示。
3、最低打印温度和打印效果
在Makerbot Replicator 2X打印机上分别加载实施例II-1至II-10和对比例II-1至II-10得到的线材，提高喷嘴温度直至线材经过喷嘴往下流出的速度达到2.4m/min，则该温度定义为最低打印温度。在3D打印时采用仪器默认打印条件设置进行层层堆积时，最终可以打出预设的3D打印形状，则打印效果“好”，实际打印形状与预设的3D打印形状有偏差的则打印效果“不好”。最低打印温度和打印效果的结果如表2所示。
4、降解性
按照如下方法分别测试实施例II-1至II-10和对比例II-1至II-10制得的薄膜的生物降解情况：采用北京南宫堆肥厂提供的堆肥(肥龄2个月)18g，加待测线材3g，加入适量蒸馏水混合并适当搅拌，然后置于常温(25℃)下。以3个月是否失重50％以上作为衡量生物降解是否合格 的标准。结果如表2所示。
另外，实施例II-1至II-10得到的3D打印线材，在常温常湿的干净环境下，至少可以保存一年并无明显的变化，只有在土壤、富营养或是堆肥的情况下才会发生显著的降解。
表2
Figure PCTCN2017107106-appb-000043
由以上表2的结果可以看出，本发明通过将特定的聚酯A、聚酯B和聚酯C按照特定的配比(51-98重量％的聚酯A，1-48重量％的聚酯B，1-48重量％的聚酯C)进行共混后得到聚酯组合物，将该聚酯组合物制成3D打印线材具有较高的光泽度，且可以在较低的温度下(105-165℃)进行打印；同时，该3D打印线材可以作为柔性线材(邵氏D硬度为35-50)，并且可以降解，具有良好的环保优势和应用前景。
热收缩管
实施例III-1
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将4kg BT-BS共聚聚酯A(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为32摩尔％)，1kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为55摩尔％)，0.05kg抗氧化剂300(化工部材料合成研究院生产的受阻酚抗氧剂)，0.05kg炭黑，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为190℃、200℃、210℃、220℃、220℃、210℃，螺杆的转速为10rpm，扭矩为20N*m。制得聚酯组合物III-A1。
将以上聚酯组合物III-A1粒料投入安装有口模和芯模的螺杆挤出机，在180℃下挤出成管，40℃下水冷定型。再加热至90℃，扩径至内径为原尺寸的5倍，40℃下冷却定型，制得热收缩套管III-B1。
实施例III-2
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将4.75kg BT-BS共聚聚酯A(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为45摩尔％)，0.25kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为80摩尔％)，0.05kg抗氧化剂300(化工部材料合成研究院生产的受阻酚抗氧剂)，0.05kg炭黑，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为190℃、200℃、210℃、220℃、220℃、210℃，螺杆的转速为20rpm，扭矩为10N*m。制得聚酯 组合物III-A2。
将以上聚酯组合物III-A2粒料投入安装有口模和芯模的螺杆挤出机，在120℃下挤出成管，20℃下水冷定型。再加热至70℃，扩径至内径为原尺寸的5倍，20℃下冷却定型，制得热收缩套管III-B2。
实施例III-3
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将4.25kg BT-BS共聚聚酯A(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为40摩尔％)，0.75kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为70摩尔％)，0.05kg抗氧化剂300(化工部材料合成研究院生产的受阻酚抗氧剂)，0.05kg炭黑，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为190℃、200℃、210℃、220℃、220℃、210℃，螺杆的转速为10rpm，扭矩为20N*m。制得聚酯组合物III-A3。
将以上聚酯组合物III-A3粒料投入安装有口模和芯模的螺杆挤出机，在160℃下挤出成管，25℃下水冷定型。再加热至80℃，扩径至内径为原尺寸的5倍，25℃下冷却定型，制得热收缩套管III-B3。
实施例III-4
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将4.95kg BT-BS共聚聚酯A(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为49摩尔％)，0.05kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为99摩尔％)，0.05kg抗氧化剂300(化工部材料合成研究院生产的受阻酚抗氧剂)，0.05kg炭黑，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆 挤出机中从进料口到挤出口各区段的温度依次为190℃、200℃、210℃、220℃、220℃、210℃，螺杆的转速为10rpm，扭矩为20N*m。制得聚酯组合物III-A4。
将以上聚酯组合物III-A4粒料投入安装有口模和芯模的螺杆挤出机，在180℃下挤出成管，25℃下水冷定型。再加热至90℃，扩径至内径为原尺寸的5倍，25℃下冷却定型，制得热收缩套管III-B4。
实施例III-5
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将2.55kg BT-BS共聚聚酯A(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)，2.45kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)，0.05kg抗氧化剂300(化工部材料合成研究院生产的受阻酚抗氧剂)，0.05kg炭黑，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为190℃、200℃、210℃、220℃、220℃、210℃，螺杆的转速为10rpm，扭矩为20N*m。制得聚酯组合物III-A5。
将以上聚酯组合物III-A5粒料投入安装有口模和芯模的螺杆挤出机，在180℃下挤出成管，25℃下水冷定型。再加热至90℃，扩径至内径为原尺寸的5倍，25℃下冷却定型，制得热收缩套管III-B5。
实施例III-6
按照实施例III-1的方法进行，不同的是，聚酯A为BT-BA共聚酯(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为45摩尔％)；聚酯B为BT-BA共聚酯(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为70摩尔％)。得到聚酯组合物III-A6 和热收缩套管III-B6。
实施例III-7
按照实施例III-1的方法进行，不同的是，聚酯A为BT-ES(丁二酸乙二醇)共聚酯(重均分子量为200,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为45摩尔％)；聚酯B为BT-ES共聚酯(重均分子量为200,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为70摩尔％)。得到聚酯组合物III-A7和热收缩套管III-B7。
实施例III-8
按照实施例III-1的方法进行，不同的是，聚酯A为BT-BA共聚酯(重均分子量为500,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为45摩尔％)；聚酯B为BT-ES共聚酯(重均分子量为500,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为70摩尔％)。得到聚酯组合物III-A8和热收缩套管III-B8。
实施例III-9
按照实施例III-1的方法进行，不同的是，使用0.05kg二氧化钛代替实施例III-1中使用的0.05kg炭黑。得到聚酯组合物III-A9和热收缩套管III-B9。
实施例III-10
按照实施例III-1的方法进行，不同的是，未加入0.05kg抗氧化剂300和0.05kg炭黑。得到聚酯组合物III-A10和热收缩套管III-B10。
对比例III-1
按照实施例III-1的方法进行，不同的是，将实施例III-1中的聚酯A直接制成套管III-DB1，而不包括实施例III-1中与聚酯B的共混过程。
对比例III-2
按照实施例III-1的方法进行，不同的是，将实施例III-1中的聚酯B直接制成套管III-DB2，而不包括实施例III-1中与聚酯A的共混过程。
对比例III-3
按照实施例III-1的方法进行，不同的是，使用相同重量的PBT(购自杜邦公司，牌号为Crastin SC164 NC010，下同)代替实施例III-1中使用的聚酯A，制得套管III-DB3。
对比例III-4
按照实施例III-1的方法进行，不同的是，使用相同重量的PBT代替实施例III-1中使用的聚酯B，制得套管III-DB4。
对比例III-5
按照实施例III-1的方法进行，不同的是，使用相同重量的PBS(购自巴斯夫公司，牌号为1111HTA4，下同)代替实施例III-1中使用的聚酯A，制得套管III-DB5。
对比例III-6
按照实施例III-1的方法进行，不同的是，使用相同重量的PBS代替实施例III-1中使用的聚酯B，制得套管III-DB6。
对比例III-7
按照实施例III-1的方法进行，不同的是，聚酯A的用量为1kg，聚酯B的用量为4kg，制得套管III-DB7。
对比例III-8
按照实施例III-1的方法进行，不同的是，聚酯A的用量为2.5kg，聚酯B的用量为2.5kg，制得套管III-DB8。
对比例III-9
按照实施例III-1的方法进行，不同的是，将PBT直接制成套管III-DB9。
对比例10
按照实施例III-1的方法进行，不同的是，将PBS直接制成套管III-DB10。
测试例III-1至III-20
收缩比率测试：在25℃下，使用游标卡尺测量热缩管收缩前的外径；将热缩管放入80℃烘箱中恒温1小时，取出自然冷却至25℃后，使用游标卡尺测量热缩管收缩后的外径，收缩比率结果记录为“收缩前直径：收缩后直径”。按此方法分别测量实施例III-1至III-10和对比例III-1至III-10制得的套管的收缩比率，结果如表3所示。
击穿强度测试：按照国标GB T1408.1-2006方法分别测试实施例III-1至III-10和对比例III-1至III-10制得的套管材料的击穿强度。结果表明，实施例III-1至III-10制得的套管的击穿强度均≥25kv/mm，这说明本发明得到的套管的绝缘性良好。
降解性测试：采用北京南宫堆肥厂提供的堆肥(肥龄2个月)18kg，加待测薄膜3g，加入适量蒸馏水混合并适当搅拌，然后置于常温下，以3个月是否失重50％以上作为衡量生物降解是否合格的标准。
以上收缩比率测试和降解性测试的结果如表3所示。
另外，实施例III-1至III-10制得的热收缩套管，在常温常湿的干净环境下，至少可以保存一年并无明显的变化，只有在土壤、富营养或是堆肥的情况下才会发生显著的降解。
表3
  套管 收缩比率 降解性
测试例III-1 III-B1 5：1 合格
测试例III-2 III-B2 5：1 合格
测试例III-3 III-B3 5：1 合格
测试例III-4 III-B4 5：2 合格
测试例III-5 III-B5 5：2 合格
测试例III-6 III-B6 5：4.5 合格
测试例III-7 III-B7 5：4.5 合格
测试例III-8 III-B8 5：4.5 合格
测试例III-9 III-B9 5：1 合格
测试例III-10 III-B10 5：1 合格
测试例III-11 III-DB1 无热收缩性 合格
测试例III-12 III-DB2 无热收缩性 不合格
测试例III-13 III-DB3 无热收缩性 不合格
测试例III-14 III-DB4 无热收缩性 合格
测试例III-15 III-DB5 无热收缩性 合格
测试例III-16 III-DB6 无热收缩性 合格
测试例III-17 III-DB7 无热收缩性 不合格
测试例III-18 III-DB8 无热收缩性 不合格
测试例III-19 III-DB9 无热收缩性 不合格
测试例III-20 III-DB10 无热收缩性 合格
由以上表3的结果可以看出，本发明通过将特定的共聚物(聚酯A和聚酯B)按照特定的配比(聚酯A的含量为51-99重量％，聚酯B的含量为1-49重量％)进行共混，得到热收缩比率(高达5：4.5以上)和 绝缘性均较高的热收缩套管。并且，该热收缩套管在制备的过程中无需进行交联，具有良好的可降解性，因此其具有广阔的市场空间。
功能层(运动护具)
实施例IV-1
在搅拌的条件下(搅拌的速率为30rpm，时间为5min)，将150g BT-BA共聚酯A(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为25摩尔％)颗粒、20g BT-BS共聚酯B(重均分子量为110,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)颗粒、20g玻璃纤维(泰山玻璃纤维有限公司，型号为T536，下同)和10g无水硫酸钙(天津市致远化学试剂有限公司，分析纯，下同)充分混合。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为40N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为180℃、190℃、195℃、195℃、195℃、195℃，制得聚酯组合物IV-A1。
实施例IV-2
在搅拌的条件下(搅拌的速率为30rpm，时间为5min)，将171g BT-BA共聚酯A(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为40摩尔％)颗粒、9.5gBT-BS共聚酯B(重均分子量为110,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为15摩尔％)颗粒、9.5g玻璃纤维和10g无水硫酸钙充分混合。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为40N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为180℃、190℃、195℃、195℃、195℃、195℃，制得聚酯组合物IV-A2。
实施例IV-3
在搅拌的条件下(搅拌的速率为30rpm，时间为5min)，将114g BT-BA共聚酯A(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为23摩尔％)颗粒、57gBT-BS共聚酯B(重均分子量为110,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为5摩尔％)颗粒、19g玻璃纤维和10g无水硫酸钙充分混合。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为40N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为180℃、190℃、195℃、195℃、195℃、195℃，制得聚酯组合物IV-A3。
实施例IV-4
在搅拌的条件下(搅拌的速率为30rpm，时间为5min)，将95g BT-BA共聚酯A(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为45摩尔％)颗粒、85.5g BT-BS共聚酯B(重均分子量为110,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为20摩尔％)颗粒、9.5g玄武岩纤维和10g无水硫酸钙充分混合。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为40N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为180℃、190℃、195℃、195℃、195℃、195℃，制得聚酯组合物IV-A4。
实施例IV-5
在搅拌的条件下(搅拌的速率为30rpm，时间为5min)，将95gBT-BA共聚酯A(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为20摩尔％)颗粒、9.5gPBT(购自杜邦公司，牌号为Crastin SC164 NC010)颗粒、85.5g玄武岩纤维和10g无水硫酸钙充分混合。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为40N*m，双螺杆挤出机中从 进料口到挤出口各区段的温度依次为180℃、190℃、195℃、195℃、195℃、195℃，制得聚酯组合物IV-A5。
实施例IV-6
按照实施例IV-1的方法进行，不同的是，聚酯A为BT-BA共聚酯(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为25摩尔％)；聚酯B为BT-BA共聚酯(重均分子量为110,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)。制得聚酯组合物IV-A6。
实施例IV-7
按照实施例IV-1的方法进行，不同的是，聚酯A为BT-ES共聚酯(重均分子量为200,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为25摩尔％)；聚酯B为BT-ES共聚酯(重均分子量为200,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)。制得聚酯组合物IV-A7。
实施例IV-8
按照实施例IV-1的方法进行，不同的是，聚酯A为BT-BA共聚酯(重均分子量为500,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为25摩尔％)；聚酯B为BT-ES共聚酯(重均分子量为500,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)。制得聚酯组合物IV-A8。
实施例IV-9
按照实施例IV-1的方法进行，不同的是，未加入无水硫酸钙。制得聚酯组合物IV-A9。
对比例IV-1
按照实施例IV-1的方法进行，不同的是，将170g实施例IV-1使用的聚酯A、20g玻璃纤维和10g无水硫酸钙混合，而不加入实施例IV-1 使用的聚酯B。制得聚酯组合物IV-D1。
对比例IV-2
按照实施例IV-1的方法进行，不同的是，将170g实施例IV-1使用的聚酯B、20g玻璃纤维和10g无水硫酸钙混合，而不加入实施例IV-1使用的聚酯A。制得聚酯组合物IV-D2。
对比例IV-3
按照实施例IV-1的方法进行，不同的是，使用相同重量的PBT(购自杜邦公司，牌号为Crastin SC164 NC010)代替实施例IV-1中使用的聚酯A。制得聚酯组合物IV-D3。
对比例IV-4
按照实施例IV-1的方法进行，不同的是，使用相同重量的PBT(购自杜邦公司，牌号为Crastin SC164 NC010)代替实施例IV-1中使用的聚酯B。制得聚酯组合物IV-D4。
对比例IV-5
按照实施例IV-1的方法进行，不同的是，使用相同重量的PBS(购自巴斯夫公司，牌号为1111HTA4，下同)代替实施例IV-1中使用的聚酯A制得聚酯组合物IV-D5。
对比例IV-6
按照实施例IV-1的方法进行，不同的是，不加入玻璃纤维。制得聚酯组合物IV-D6。
对比例IV-7
按照实施例IV-1的方法进行，不同的是，聚酯A的用量为20g，聚酯B的用量为150g。制得聚酯组合物IV-D7。
对比例IV-8
按照实施例IV-1的方法进行，不同的是，将190g PBT和10g无水硫酸钙混合。制得聚酯组合物IV-D8。
对比例IV-9
按照实施例IV-1的方法进行，不同的是，将190gPBS和10g无水硫酸钙混合。制得聚酯组合物IV-D9。
测试例IV-1至IV-18
1、硬度检测
分别将实施例IV-1至IV-9和对比例IV-1至IV-9制得的聚酯组合物熔融后，于170℃、1000MPa下处理5min，压制成4mm厚，边长为7cm的板材。将热板材取出，用长期放置于室温的冷铁块将板材淬冷1min后取出并在室温(25℃)下放置1h。将放置后的板材使用Drick shore D手持硬度计进行测量，15s后记录测量结果。随后，将该板材在热台上加热至90℃，用同样的方法再次测量邵氏D硬度。结果如表4所示。
2、形状记忆性能检测
将实施例IV-1至IV-9和对比例IV-1至IV-9制得的聚酯组合物分别制成冲压样条，并将制成的冲压样条进行形状记忆性能测试，结果如表4所示。聚酯组合物的形状记忆性能采用Instron5965拉伸仪(带恒温箱)测量，具体如下：
聚酯组合物样条在室温下的初始长度为a；将恒温箱升温至80℃，使其充分软化，在拉伸速度为50mm/min的条件下拉伸至长度b；保持外力使拉伸长度不变，降温，待样条固化，撤去外力，此时样条的长度为c；再次将样条升温至80℃，待样条充分回缩，此时样条的长度为d；
形变固定率(％)＝(c-a)/(b-a)×100％；
形变回复率(％)＝(c-d)/(c-a)×100％；
最大形变率(％)＝bmax/a×100％，其中，bmax为样条损坏前能达到的最大b。
表4
Figure PCTCN2017107106-appb-000044
由以上表4的结果可以看出，与对比例IV-1至IV-9相比，实施例IV-1至IV-9的聚酯组合物在较高温度下(90℃)的硬度较低，而在较低温度下(25℃)的硬度明显升高，易于塑形。并且，实施例IV-1至IV-9的聚酯组合物具有较高的形变固定率(高达90％以上)、形变回复率(高达90％以上)和最大形变率(高达280％以上)。以上结果表明，本发明提供的聚酯组合物具有良好的低温可塑性和形状记忆性能。
实施例IV-10
将实施例IV-1得到的聚酯组合物IV-A1通过注塑的方式形成牙齿护具，注塑的温度为170℃，注入铝制模具中，常温(25℃)脱模成U型模具。将得到的U型模具在90℃的热水中软化，然后迅速冷却至0℃，含入口中，上下牙齿咬合后形成牙齿轮廓，经反复打磨后得到牙齿护具成品。如图1和2所示。
当牙齿护具磨损或者使用不舒适时，将牙齿护具再次在90℃的热水中软化，然后迅速冷却至0℃，含入口中，上下牙齿咬合后形成牙齿轮廓，经反复打磨后重新得到形状与牙齿更贴合的牙齿护具成品。
实施例IV-11
将实施例IV-1得到的聚酯组合物IV-A1通过注塑的方式形成护膝中间层，注塑的温度为175℃，注入铝制模具中，常温(25℃)脱模成型后得到模具。将得到的模具在90℃的热水中软化，然后迅速冷却至0℃，放置于膝关节表面按压，以形成膝关节轮廓，经反复打磨后得到护膝的中间层。然后将得到的护膝中间层的内表面通过胶带与棉质材料的内层连接，护膝中间层的外表面通过粘扣与铝合金材质的外层连接，可以随时取出。从而将外层、中间层和内层一起组装成护膝成品。如图3和4所示。
当护膝磨损或者使用不舒适时，将护膝再次在90℃的热水中软化，然后迅速冷却至0℃，放置于膝关节表面按压，以形成膝关节轮廓，经反复打磨后得到重新得到形状与膝关节更贴合的护膝中间层。
实施例IV-12
将实施例IV-1得到的聚酯组合物IV-A1通过注塑的方式形成上半身护具的中间层，注塑的加工温度为180℃，注入铝制模具中，常温(25℃)脱模成型后得到模具。将得到的模具在90℃的热水中软化，然后迅速冷却至0℃，围绕上半身的表面按压，以形成上半身轮廓，经反复打磨后得 到上半身护具的中间层。然后将得到的上半身护具的中间层的内表面通过胶带与氨纶材料的内层连接，上半身护具的中间层的外表面通过粘扣与PBS材质的外层连接，可以随时取出。从而将外层、中间层和内层一起组装成上半身护具成品。如图5和6所示。
当上半身护具磨损或者使用不舒适时，将上半身护具再次在90℃的热水中软化，然后迅速冷却至0℃，围绕上半身的表面按压，以形成上半身轮廓，经反复打磨后得到重新得到形状与上半身更贴合的上半身护具的中间层。
实施例IV-13
将实施例IV-1得到的聚酯组合物IV-A1通过注塑的方式形成头盔中间层，注塑的加工温度为185℃，注入铝制模具中，常温(25℃)脱模成型后得到模具。将得到的模具在90℃的热水中软化，然后迅速冷却至0℃，放置于头部表面按压，以形成头部轮廓，经反复打磨后得到头盔的中间层。然后将得到的头盔中间层的内表面通过粘扣与海绵材质的内层连接，护膝中间层的外表面通过粘扣与铝合金材质的外层连接。外层、中间层和内层还通过卡扣固定，一起组装成头盔成品。如图7所示。
当头盔磨损或者使用不舒适时，将头盔再次在90℃的热水中软化，然后迅速冷却至0℃，放置于头部表面按压，以形成头部轮廓，经反复打磨后得到重新得到形状与头部更贴合的头盔中间层。
由以上实施例IV-10至IV-13可以看出，将本发明提供的聚酯组合物用于运动护具时，可以根据应用部位的差异进行塑形，使得护具更贴合身体、更舒适且制作方便；另外，本发明的运动护具如果出现磨损或者轻微损坏以后，可以再次通过升温软化和低温再塑形使得护具恢复原貌。
医用肢体固定支架
实施例V-1
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将7kg BT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)颗粒、3kg BT-BA共聚酯B(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为70摩尔％)颗粒和1kg氧化铁混合。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为150℃、160℃、170℃、170℃、170℃、170℃，制得聚酯组合物V-A1。
实施例V-2
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将8kg BT-BS共聚酯A(重均分子量为200,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为25摩尔％)颗粒、2kg BT-BA共聚酯B(重均分子量为200,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)颗粒和1kg二氧化钛混合。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为150℃、160℃、170℃、170℃、170℃、170℃，制得聚酯组合物V-A2。
实施例V-3
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将9kg BT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)颗粒、1kg BT-BS共聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为60摩尔％)颗粒和1kg二氧化钛。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控 制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为150℃、160℃、170℃、170℃、170℃、170℃，制得聚酯组合物V-A3。
实施例V-4
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将9.9kgBT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为40摩尔％)颗粒、0.1kgBT-BA共聚酯B(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为80摩尔％)颗粒和1kg氧化铁混合。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为150℃、160℃、170℃、170℃、170℃、170℃，制得聚酯组合物V-A4。
实施例V-5
在搅拌的条件下(搅拌的速率为30rpm，时间为10min)，将5.1kg BT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为20摩尔％)颗粒、4.9kg BT-BA共聚酯B(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为41摩尔％)颗粒和1kg氧化铁混合。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为150℃、160℃、170℃、170℃、170℃、170℃，制得聚酯组合物V-A5。
实施例V-6
按照实施例V-1的方法进行，不同的是，聚酯A为BT-BA共聚酯(重均分子量为130,000，其中，以BT重复单元和BA重复单元的总摩尔数 为基准，BT重复单元的含量为30摩尔％)；聚酯B为BT-BA共聚酯(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为70摩尔％)。制得聚酯组合物V-A6。
实施例V-7
按照实施例V-1的方法进行，不同的是，聚酯A为BT-ES共聚酯(重均分子量为200,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)；聚酯B为BT-ES共聚酯(重均分子量为200,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为70摩尔％)。制得聚酯组合物V-A7。
实施例V-8
按照实施例V-1的方法进行，不同的是，聚酯A为BT-BA共聚酯(重均分子量为500,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)；聚酯B为BT-ES共聚酯(重均分子量为500,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为70摩尔％)。制得聚酯组合物V-A8。
实施例V-9
按照实施例V-1的方法进行，不同的是，未加入氧化铁。制得聚酯组合物V-A9。
对比例V-1
按照实施例V-1的方法进行，不同的是，将10kg实施例V-1使用的聚酯A和1kg氧化铁混合，而不加入实施例V-1使用的聚酯B。制得组合物V-D1。
对比例V-2
按照实施例V-1的方法进行，不同的是，将10kg实施例V-1使用的聚酯B和1kg氧化铁混合，而不加入实施例V-1使用的聚酯A。制得组合物V-D2。
对比例V-3
按照实施例V-1的方法进行，不同的是，使用相同重量的PBT(购自杜邦公司，牌号为Crastin SC164 NC010)代替实施例V-1中使用的聚酯A。制得组合物V-D3。
对比例V-4
按照实施例V-1的方法进行，不同的是，使用相同重量的PBT(购自杜邦公司，牌号为Crastin SC164 NC010)代替实施例V-1中使用的聚酯B。制得组合物V-D4。
对比例V-5
按照实施例V-1的方法进行，不同的是，使用相同重量的PBS(购自巴斯夫公司，牌号为1111HTA4，下同)代替实施例V-1中使用的聚酯A制得组合物V-D5。
对比例V-6
按照实施例V-1的方法进行，不同的是，使用相同重量的PBS代替实施例V-1中使用的聚酯B。制得组合物V-D6。
对比例V-7
按照实施例V-1的方法进行，不同的是，聚酯A的用量为3kg，聚酯B的用量为7kg。制得组合物V-D7。
对比例V-8
按照实施例V-1的方法进行，不同的是，聚酯A的用量为5kg，聚酯B的用量为5kg。制得组合物V-D8。
对比例V-9
按照实施例V-1的方法进行，不同的是，将10kg PBT和1kg氧化铁混合。制得组合物V-D9。
对比例V-10
按照实施例V-1的方法进行，不同的是，将10kg PBS和1kg氧化铁 混合。制得组合物V-D10。
对比例V-11
直接将医用硫酸钙颗粒(Osteoset颗粒，美国Wright公司)作为V-D11。
测试例V-1至V-20
1、邵氏A硬度测试
分别将实施例V-1至V-9和对比例V-1至V-11得到的物料熔融后，于170℃、1000MPa下处理5min，压制成4mm厚，边长为7cm的板材。将热板材取出，用长期放置于室温的冷铁块将板材淬冷1min并记时间零点。将淬冷后的板材进行邵氏A硬度随时间变化的测试(用Drick shoreA手持硬度计测量，取3s后的测量结果)，结果如下表5-1所示。
表5-1
Figure PCTCN2017107106-appb-000045
注：“-”表示由于无法压制成片，从而无法测出。
由以上表5-1的结果可以看出，实施例V-1至V-9得到的聚酯组合物V-A1至V-A9在测试开始时(温度较高)的硬度较低，待遇冷后硬度随时间缓慢地升高。而对比例V-1至V-11得到的物料V-D1至V-D11在测试开始时的温度很高，且不随时间变化。通过比较可知，实施例V-1至V-9得到的聚酯组合物V-A1至V-A9具有良好的可塑性和固定性，适用于制备医用肢体固定支架。
2、防水性测试
分别将实施例V-1至V-9和对比例V-1至V-11得到的物料熔融后，于170℃、1000MPa下处理5min，压制成2mm厚，边长为7cm的板材。将板材称重、测量尺寸、拍照并观察外观。将板材浸入25℃的水中24h，然后取出晾干，观察称重、测量尺寸、拍照并观察外观。如果浸水后板材的外观与浸入前相比并无变化，则记录为“无变化”，否则记录为“有变化”。如果浸水后板材的尺寸与浸入前相比，变化程度在±2％以内，则记录为“无变化”，否则记录为“有变化”。如果浸水后板材的重量与浸入前相比，变化程度在±2％以内，则记录为“无变化”，否则记录为“有变化”。结果如表5-2所示。
3、保存时间测试
分别将实施例V-1至V-9和对比例V-1至V-11得到的物料熔融后，于170℃、1000MPa下处理5min，压制成2mm厚，边长为7cm的板材。将板材称重、测量尺寸、拍照并观察外观。然后，将得到的板材于室温(25℃)常压环境中放置2年，将板材称重、测量尺寸、拍照并观察外观。如果放置2年后板材的外观与放置前相比并无变化，则记录为“无变化”，否则记录为“有变化”。如果放置2年后板材的尺寸与放置前相比并无变化，则记录为“无变化”，否则记录为“有变化”。如果放置2年后板材的重量与放置前相比，变化程度在±2％以内，则记录为“无变化”，否则记 录为“有变化”。结果如表5-2所示。
4、X射线透过性测试
分别将实施例V-1至V-9和对比例V-1至V-11得到的物料熔融后，于170℃、1000MPa下处理5min，压制成2mm厚，裁剪成边长为1cm的方形片。将裁剪后的板材置于Bruker D8Discovery 2D WAXD散射仪上，采用透射方法测量，并得到散射强度对散射角的散射曲线，然后对5°到30°的散射角之内的峰面积进行积分，积分值为Int-1。另外，将对比例V-11中的无水硫酸钙加上少量水调成糊状，置于1cm×1cm的方形槽中，槽深度为2mm，等待约15min，制成1cm×1cm×2mm的石膏片。将该石膏片按照上述同样的方法进行X射线散射测量，得到的峰面积积分值为Int-2。若Int-1/Int-2的值大于10，则证明试样具有优秀的X射线透过率，记录为“优秀”；若该比值为2-10之间，则证明X射线透过率普通，记录为“普通”；若该比值小于2，则证明试样不具有X射线透过性，记录为“不透过”。结果如表5-2所示。
表5-2
Figure PCTCN2017107106-appb-000046
注：“-”表示由于无法压制成片，从而无法测出。
通过以上表5-2的结果可以看出，本发明提供的聚酯组合物具有良好的防水性能，因此其在保存和运输的过程中不需要隔水等特殊包装；并且，在室温条件下至少保持两年不变质，且重量较小，仅为常规的由硫酸钙制成的板材重量的1/5左右；同时，具有极好的X射线透过性。
实施例V-10
将实施例V-1得到的聚酯组合物V-A1，熔融后于170℃、1000MPa下压制成2mm厚，边长为7cm的板材。趁热用直径为7mm的打孔器在该板材上均匀打上4个孔。等待约1小时使该板材完全硬化，即可作为医用肢体固定支架。
使用时，将该医用肢体固定支架置于热水(约100℃)中约10s，医用肢体固定支架充分软化。然后将医用肢体固定支架取出并用冷水冷却至不烫手，擦干并缠绕于需要固定的肢体部位(如手指)处，轻轻按压使医用肢体固定支架贴合肢体。等待约5分钟，待医用肢体固定支架部分硬化而固定，保持贴合肢体的形状。继续避免肢体大幅运动，等待约30分钟，待医用肢体固定支架将完全硬化，达到保护和固定肢体的目的。具体硬化后的医用肢体固定支架如图8和图9所示。
如果硬化后的医用肢体固定支架与肢体的贴合度不是十分理想，则可以将硬化后的医用肢体固定支架重新放于100℃的热水中，使其重新软化，之后重新缠绕于需要固定的肢体部位，待其硬化后，保持贴合肢体的形状。
以上结果说明，使用本发明提供的聚酯组合物制成的医用肢体固定支架在高温条件下(如热水中，特别是沸水中)可以充分软化，软化后的材料易于剪裁，将其剪裁成适当的尺寸和形状缠绕于需要固定的肢体部位可以发生硬化且可自行粘合，从而达到良好的塑形和固定目的。并且，上述过程是可逆的，可以重新按照肢体部位进行塑形。
另外，该医用肢体固定支架方便拆卸和清洗；同时具有良好的降解 性能，制备过程由于采用热塑性加工(未使用交联剂)，边角料亦可以回收再利用。
热收缩薄膜
实施例VI-1
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将2kg BT-BS共聚聚酯A(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为35摩尔％)，1kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为15摩尔％)，0.5kg碳酸钙，0.01kg芥酸酰胺，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为170℃、180℃、190℃、190℃、190℃、190℃。制得聚酯组合物VI-A1。
将以上聚酯组合物VI-A1粒料通过流延机，在150℃流延得到厚度为0.2mm的薄膜。该薄膜在室温(25℃)放置10小时后，在单向拉伸机上于60℃，拉伸为原长的5倍，制得热收缩薄膜VI-B1。
实施例VI-2
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将1.8kg BT-BS共聚聚酯A(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为38摩尔％)，1.2kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为3摩尔％)，0.5kg碳酸钙，0.01kg芥酸酰胺，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为170℃、180℃、190℃、190℃、190℃、190℃。制得聚酯组合物VI-A2。
将以上聚酯组合物VI-A2粒料通过流延机，在150℃流延得到厚度 为0.2mm的薄膜。该薄膜在室温(25℃)放置10小时后，在单向拉伸机上于60℃，拉伸为原长的4.5倍，制得热收缩薄膜VI-B2。
实施例VI-3
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将2.7kg BT-BS共聚聚酯A(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为28摩尔％)，0.3kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为15摩尔％)，0.5kg碳酸钙，0.01kg芥酸酰胺，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为170℃、180℃、190℃、190℃、190℃、190℃。制得聚酯组合物VI-A3。
将以上聚酯组合物VI-A3粒料通过流延机，在150℃流延得到厚度为0.2mm的薄膜。该薄膜在室温(25℃)放置10小时后，在单向拉伸机上于60℃，拉伸为原长的4倍，制得热收缩薄膜VI-B3。
实施例VI-4
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将2.97kg BT-BS共聚聚酯A(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为40摩尔％)，0.03kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为20摩尔％)，0.5kg碳酸钙，0.01kg芥酸酰胺，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为170℃、180℃、190℃、190℃、190℃、190℃。制得聚酯组合物VI-A4。
将以上聚酯组合物VI-A4粒料通过流延机，在150℃流延得到厚度为0.2mm的薄膜。该薄膜在室温(25℃)放置10小时后，在单向拉伸机上于60℃，拉伸为原长的4倍，制得热收缩薄膜VI-B4。
实施例VI-5
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将1.53kg BT-BS共聚聚酯A(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为20摩尔％)，1.47kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为1摩尔％)，0.5kg碳酸钙，0.5kg芥酸酰胺，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为170℃、180℃、190℃、190℃、190℃、190℃。制得聚酯组合物VI-A5。
将以上聚酯组合物VI-A5粒料通过流延机，在150℃流延得到厚度为0.2mm的薄膜。该薄膜在室温(25℃)放置10小时后，在单向拉伸机上于60℃，拉伸为原长的1.5倍，制得热收缩薄膜VI-B5。
实施例VI-6
按照实施例VI-1的方法进行，不同的是，聚酯A为BT-BA共聚酯(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为35摩尔％)；聚酯B为BT-BA共聚酯(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为15摩尔％)。得到聚酯组合物VI-A6和热收缩薄膜VI-B6。
实施例VI-7
按照实施例VI-1的方法进行，不同的是，聚酯A为BT-ES共聚酯(重均分子量为200,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为35摩尔％)；聚酯B为BT-ES共聚酯(重均分子量为200,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为15摩尔％)。得到聚酯组合物VI-A7和热收缩薄膜VI-B7。
实施例VI-8
按照实施例VI-1的方法进行，不同的是，聚酯A为BT-BO(乙二酸丁二醇)共聚酯(重均分子量为500,000，其中，以BT重复单元和BO重复单元的总摩尔数为基准，BT重复单元的含量为35摩尔％)；聚酯B为BT-ES共聚酯(重均分子量为500,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为15摩尔％)。得到聚酯组合物VI-A8和热收缩薄膜VI-B8。
实施例VI-9
按照实施例VI-1的方法进行，不同的是，使用0.2kg炭黑和0.2kg二氧化钛代替实施例VI-1中使用的0.5kg碳酸钙和0.01kg芥酸酰胺。得到聚酯组合物VI-A9和热收缩薄膜VI-B9。
实施例VI-10
按照实施例VI-1的方法进行，不同的是，未加入0.5kg碳酸钙和0.01kg芥酸酰胺。得到聚酯组合物VI-A10和热收缩薄膜VI-B10。
对比例VI-1
按照实施例VI-1的方法进行，不同的是，将实施例VI-1中的聚酯A直接制成薄膜VI-DB1，而不包括实施例VI-1中与聚酯B的共混过程。
对比例VI-2
按照实施例VI-1的方法进行，不同的是，将实施例VI-1中的聚酯B直接制成薄膜VI-DB2，而不包括实施例VI-1中与聚酯A的共混过程。
对比例VI-3
按照实施例VI-1的方法进行，不同的是，使用相同重量的PBT(购自杜邦公司，牌号为Crastin SC164 NC010，下同)代替实施例VI-1中使用的聚酯A，制得薄膜VI-DB3。
对比例VI-4
按照实施例VI-1的方法进行，不同的是，使用相同重量的PBT代替 实施例VI-1中使用的聚酯B，制得薄膜VI-DB4。
对比例VI-5
按照实施例VI-1的方法进行，不同的是，使用相同重量的PBS(购自巴斯夫公司，牌号为1111HTA4，下同)代替实施例VI-1中使用的聚酯A，制得薄膜VI-DB5。
对比例VI-6
按照实施例VI-1的方法进行，不同的是，使用相同重量的PBS代替实施例VI-1中使用的聚酯B，制得薄膜VI-DB6。
对比例VI-7
按照实施例VI-1的方法进行，不同的是，聚酯A的用量为1kg，聚酯B的用量为2kg，制得薄膜VI-DB7。
对比例VI-8
按照实施例VI-1的方法进行，不同的是，聚酯A的用量为1.5kg，聚酯B的用量为1.5kg，制得薄膜VI-DB8。
对比例VI-9
按照实施例VI-1的方法进行，不同的是，将PBT直接制成薄膜VI-DB9。
对比例VI-10
按照实施例VI-1的方法进行，不同的是，将PBS直接制成薄膜VI-DB10。
测试例VI-1至VI-20
热收缩率测试：在Labthink Thermotek 2710热收缩率仪器上，在70℃的环境下加热5s，分别测试实施例VI-1至VI-10和对比例VI-1至VI-10制得的薄膜的热收缩率(％)；
热封强度测试：在Brugger Munchen HSG-C热封仪上，用25μm的聚四氟乙烯包裹后，将相应薄膜每两层在90℃条件下以100N的压力热 封2s，之后按照QB/T 2358-1998的测试方法，用Instron 5965拉伸仪(50mm/min速度)分别测试实施例VI-1至VI-10和对比例VI-1至VI-10制得的薄膜的热封强度(N/15mm)；
生物降解测试：按照以下方法分别测试实施例VI-1至VI-10和对比例VI-1至VI-10制得的薄膜的生物降解情况，具体地，采用北京南宫堆肥厂提供的堆肥(肥龄2个月)18g，加待测薄膜3g，加入适量蒸馏水混合并适当搅拌，然后置于常温下(25℃)。以3个月是否失重50％以上作为衡量生物降解是否合格的标准。
上述测试的结果如表6所示。
另外，实施例VI-1至VI-10制得的热收缩薄膜，在常温常湿的干净环境下，至少可以保存一年并无明显的变化，只有在土壤、富营养或是堆肥的情况下才会发生显著的降解。
表6
Figure PCTCN2017107106-appb-000047
注：“a”表示流延成膜后无法完成单向拉伸过程，以得到完整的热收缩薄膜；
“b”表示无法流延成膜；
“c”表示成膜性不好，在流延过程中不易操控，易破膜；
“d”表示拉伸过程不易操控，易破膜；
“-”表示无法测出。
由以上表6的结果可以看出，本发明通过将特定的共聚物(聚酯A和聚酯B)按照特定的配比(聚酯A的含量为51-99重量％，聚酯B的含量为1-49重量％)进行共混，不仅可以得到热收缩率高达70％以上的热收缩薄膜，还可以得到热收缩率为10％的薄膜，这说明本发明通过配方和聚酯结构的调节能够在较大范围内改变薄膜的热收缩率；并且，本发明得到的热收缩薄膜具有合适的热封强度(高达11-19N/15mm)，薄膜表面平整、光泽度良好，可降解且可以反复热塑加工并可回收，因此其具有明显的环保优势和工业应用前景。
无纺布
实施例VII-1
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将3kg BT-BS共聚聚酯A(重均分子量为120,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为18摩尔％)，2kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)，0.25kg抗氧化剂300(化工部材料合成研究院生产的受阻酚抗氧剂，下同)，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为170℃、180℃、185℃、185℃、 190℃、190℃。得到聚酯组合物VII-A1。
将以上聚酯聚合物VII-A1，加入纺粘机的螺杆中，螺杆一区温度185℃，二区温度190℃，三区温度205℃，纺丝温度195℃，计量泵转速20r/min，成网速度17m/min，热轧温度105℃，得到无纺布VII-B1。
实施例VII-2
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将3.5kg BT-BS共聚聚酯A(重均分子量为120,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为5摩尔％)，1.5kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为60摩尔％)，0.25kg抗氧化剂300，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为170℃、180℃、185℃、185℃、190℃、190℃。得到聚酯组合物VII-A2。
将以上聚酯聚合物VII-A2，加入纺粘机的螺杆中，螺杆一区温度185℃，二区温度190℃，三区温度205℃，纺丝温度195℃，计量泵转速20r/min，成网速度17m/min，热轧温度105℃，得到无纺布VII-B2。
实施例VII-3
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将2.75kg BT-BS共聚聚酯A(重均分子量为120,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为12摩尔％)，2.25kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)，0.25kg抗氧化剂300，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为170℃、180℃、185℃、185℃、190℃、190℃。得到聚酯组合物VII-A3。
将以上聚酯聚合物VII-A3，加入纺粘机的螺杆中，螺杆一区温度 185℃，二区温度190℃，三区温度205℃，纺丝温度195℃，计量泵转速20r/min，成网速度17m/min，热轧温度105℃，得到无纺布VII-B3。
实施例VII-4
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将4.95kg BT-BS共聚聚酯A(重均分子量为120,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为25摩尔％)，0.05kgBT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为80摩尔％)，0.25kg抗氧化剂300，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为170℃、180℃、185℃、185℃、190℃、190℃。得到聚酯组合物VII-A4。
将以上聚酯聚合物VII-A4，加入纺粘机的螺杆中，螺杆一区温度185℃，二区温度190℃，三区温度205℃，纺丝温度195℃，计量泵转速20r/min，成网速度17m/min，热轧温度105℃，得到无纺布VII-B4。
实施例VII-5
在搅拌的条件下(搅拌的速率为30r/min，时间为10min)，将2.55kg BT-BS共聚聚酯A(重均分子量为120,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为1摩尔％)，2.45kg BT-BS共聚聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为26摩尔％)，0.25kg抗氧化剂300，混合后通过双螺杆挤出机挤出、拉丝、风冷、切粒，其中，双螺杆挤出机中从进料口到挤出口各区段的温度依次为170℃、180℃、185℃、185℃、190℃、190℃。得到聚酯组合物VII-A5。
将以上聚酯聚合物VII-A5，加入纺粘机的螺杆中，螺杆一区温度185℃，二区温度190℃，三区温度205℃，纺丝温度195℃，计量泵转速20r/min，成网速度17m/min，热轧温度105℃，得到无纺布VII-B5。
实施例VII-6
按照实施例VII-1的方法进行，不同的是，聚酯A为BT-BA共聚酯(重均分子量为120,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为18摩尔％)；聚酯B为BT-BA共聚酯(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)。得到聚酯组合物VII-A6和无纺布VII-B6。
实施例VII-7
按照实施例VII-1的方法进行，不同的是，聚酯A为BT-ES共聚酯(重均分子量为200,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为18摩尔％)；聚酯B为BT-ES共聚酯(重均分子量为200,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)。得到聚酯组合物VII-A7和无纺布VII-B7。
实施例VII-8
按照实施例VII-1的方法进行，不同的是，聚酯A为BT-BO共聚酯(重均分子量为500,000，其中，以BT重复单元和BO重复单元的总摩尔数为基准，BT重复单元的含量为18摩尔％)；聚酯B为BT-ES共聚酯(重均分子量为500,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为50摩尔％)。得到聚酯组合物VII-A8和无纺布VII-B8。
实施例VII-9
按照实施例VII-1的方法进行，不同的是，使用相同重量的0.25kg二氧化钛代替实施例VII-1中使用的0.25kg抗氧化剂300。得到聚酯组合物VII-A9和无纺布VII-B9。
实施例VII-10
按照实施例VII-1的方法进行，不同的是，未加入0.25kg抗氧化剂300。得到聚酯组合物VII-A10和热收缩薄膜VII-B10。
对比例VII-1
按照实施例VII-1的方法进行，不同的是，将实施例VII-1中的聚酯A直接制成无纺布VII-DB1，而不包括实施例VII-1中与聚酯B的共混过程。
对比例VII-2
按照实施例VII-1的方法进行，不同的是，将实施例VII-1中的聚酯B直接制成无纺布VII-DB2，而不包括实施例VII-1中与聚酯A的共混过程。
对比例VII-3
按照实施例VII-1的方法进行，不同的是，使用相同重量的PBT(购自杜邦公司，牌号为Crastin SC164 NC010，下同)代替实施例VII-1中使用的聚酯A，制得无纺布VII-DB3。
对比例VII-4
按照实施例VII-1的方法进行，不同的是，使用相同重量的PBT代替实施例VII-1中使用的聚酯B，制得无纺布VII-DB4。
对比例VII-5
按照实施例VII-1的方法进行，不同的是，使用相同重量的PBS(购自巴斯夫公司，牌号为1111HTA4，下同)代替实施例VII-1中使用的聚酯A，制得无纺布VII-DB5。
对比例VII-6
按照实施例VII-1的方法进行，不同的是，使用相同重量的PBS代替实施例VII-1中使用的聚酯B，制得无纺布VII-DB6。
对比例VII-7
按照实施例VII-1的方法进行，不同的是，聚酯A的用量为2kg，聚 酯B的用量为3kg，制得无纺布VII-DB7。
对比例VII-8
按照实施例VII-1的方法进行，不同的是，聚酯A的用量为2.5kg，聚酯B的用量为2.5kg，制得薄膜VII-DB8。
对比例VII-9
按照实施例VII-1的方法进行，不同的是，将PBT直接制成无纺布VII-DB9。
对比例VII-10
按照实施例VII-1的方法进行，不同的是，将PBS直接制成无纺布VII-DB10。
测试例VII-1至VII-20
吸水性测试采用两种方法验证，分别是无纺布滴水实验，以及材料本身对水的接触角实验。具体测试过程如下所示。
滴水实验：用滴管将一滴去离子水滴在制得的无纺布表面，如果水滴自由渗透过无纺布，则结果标记为“渗”；如果水滴浮在表面并保持良好形状，类似于荷叶表面的水滴存在形状，则结果标记为“滴”。
接触角实验：将每一个实施例或对比例中得到的组合物，在170℃，4000kgs的压力下，压制成70mm×70mm×1mm的片。随后，用移液枪小心地将一滴去离子水滴在压片的表面上，然后用相机的微距模式在侧面拍摄水滴的形状，从图片中读取水滴与材料表面的接触角。如果接触角小于90°，结果标记为“亲水”；如果接触角大于90°，结果标记为“疏水”。
透气性实验：使用一个气球捆扎在一个内直径约1mm的细管上，充入气体使之达到相同的大小。气球通过细管自由放气，时间计为t1。随后将一小块实施例或对比例中的无纺布蒙在细管口，然后测试排空的时间，记为t2。如果t2小于2×t1，结果标记为“透气”，否则标记为“不透气”。
耐乙醇实验：耐乙醇实验用于说明无纺布在进行乙醇灭菌过程中是否会与乙醇发生反应，或溶解于乙醇，以反映无纺布的易灭菌性。具体地，将2g无纺布试样置于75体积％乙醇中，室温放置24h，之后晾干，观察无纺布试样的表面并对其进行称重。如果试样同时满足(1)外观无明显变化，(2)重量不低于原重量的99％，则结果标记为“可”，否则标记为“否”。
热收缩性实验：将一块10cm×10cm的无纺布分别置于(80℃，90℃，95℃)的热水中10s，然后取出，测量其尺寸，然后算出缩小部分的无纺布面积占初始面积的百分比。
以上滴水实验、接触角实验、透气性实验、耐乙醇实验和热收缩性实验的结果如表7-1和表7-2所示。
表7-1
  无纺布 滴水实验 接触角实验 透气性实验 耐乙醇实验
测试例VII-1 VII-B1 渗 亲水 透气 可
测试例VII-2 VII-B2 渗 亲水 透气 可
测试例VII-3 VII-B3 渗 亲水 透气 可
测试例VII-4 VII-B4 渗 亲水 透气 可
测试例VII-5 VII-B5 渗 亲水 透气 可
测试例VII-6 VII-B6 渗 亲水 透气 可
测试例VII-7 VII-B7 渗 亲水 透气 可
测试例VII-8 VII-B8 渗 亲水 透气 可
测试例VII-9 VII-B9 渗 亲水 透气 可
测试例VII-10 VII-B10 渗 亲水 透气 可
测试例VII-11 VII-DB1a 渗 亲水 透气 可
测试例VII-12 VII-DB2 渗 亲水 透气 可
测试例VII-13 VII-DB3a 渗 亲水 透气 可
测试例VII-14 VII-DB4b - - - -
测试例VII-15 VII-DB5a 渗 亲水 透气 可
测试例VII-16 VII-DB6a 渗 亲水 透气 可
测试例VII-17 VII-DB7 渗 亲水 透气 可
测试例VII-18 VII-DB8 渗 亲水 透气 可
测试例VII-19 VII-DB9b - - - -
测试例VII-20 VII-DB10a 渗 亲水 透气 可
注：“a”表示加工形成的无纺布良品率很低，易破损；
“b”表示无法得到无纺布；
“-”表示无法测出。
表7-2
  无纺布 80℃ 90℃ 95℃
测试例VII-1 VII-B1 31 63 70
测试例VII-2 VII-B2 12 36 49
测试例VII-3 VII-B3 28 51 62
测试例VII-4 VII-B4 2 19 31
测试例VII-5 VII-B5 8 21 28
测试例VII-6 VII-B6 30 32 32
测试例VII-7 VII-B7 27 42 50
测试例VII-8 VII-B8 27 41 48
测试例VII-9 VII-B9 27 61 68
测试例VII-10 VII-B10 30 63 69
测试例VII-11 VII-DB1 0 2 10
测试例VII-12 VII-DB2 0 1 12
测试例VII-13 VII-DB3 0 0 0
测试例VII-14 VII-DB4 0 0 0
测试例VII-15 VII-DB5 0 0 0
测试例VII-16 VII-DB6 0 0 0
测试例VII-17 VII-DB7 2 7 15
测试例VII-18 VII-DB8 5 11 18
测试例VII-19 VII-DB9 0 0 0
测试例VII-20 VII-DB10 0 0 0
测试实施例VII-1至VII-20
分别将实施例VII-1至VII-10和对比例VII-1至VII-10制得的无纺布制成一次性手术服，临床使用后，将废弃的一次性手术服浸泡在沸水中消毒。
结果发现，由实施例VII-1至VII-10得到的无纺布VII-B1至VII-B10制成的一次性手术服在沸水中大幅度收缩，体积明显减小，便于回收。并且，将回收的材料作为制备无纺布的原料重新加入纺粘机中，按照实施例VII-1中的纺粘法条件，重新制得无纺布。同时发现，重新制得的无纺布与上述实施例VII-1至VII-10中制备的无纺布VII-B1至VII-B10具有相似的性能，适于继续作为一次性医用纺织制品的原材料，从而实现了材料的回收利用。
而由对比例VII-1至VII-10得到的无纺布VII-DB1至VII-DB10制成的一次性手术服在沸水中体积几乎没有变化，这将使回收工作十分繁琐。并且，将回收的材料作为制备无纺布的原料重新加入纺粘机中，按照实施例VII-1中的纺粘法条件，重新制得无纺布。结果发现，有些无法良好成型，而其它则不具备良好的热收缩性能，不适于继续作为一次性医用纺织制品的原材料。
通过以上测试例VII-1至VII-20和测试实施例VII-1至VII-20的结果可以看出，本发明通过将特定的共聚物(聚酯A和聚酯B)按照特定的配比(聚酯A的含量为51-99重量％，聚酯B的含量为1-49重量％)进行共混，得到的无纺布具有良好的吸水性、透气性和易灭菌性，特别是，本发明的无纺布可以在热水(如100℃)中消毒并大幅度收缩，因此很容易被压缩至很小的体积，方便材料(特别是一次性材料)的回收以及再生产，并且，重新生产制得的无纺布与首次使用的无纺布具有相似的性能，适于继续作为一次性无纺布制品(特别是一次性医用纺织制品)的原材料，从而很好地解决了材料的再回收利用问题。
弹性纤维
实施例VIII-1
(1)聚酯组合物的制备
在搅拌的条件下(搅拌的速率为10r/min，时间为10min)，将150g BT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)颗粒、30g BT-BS共聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)颗粒、20g BT-BA共聚酯C(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，其中，BT重复单元的含量为60摩尔％)颗粒、10g二氧化钛混合并以10r/min的速度搅拌10min，然后加入双螺杆挤出机中，在220℃温度下熔融挤出并造粒，得到聚酯组合物VIII-A1。
(2)弹性纤维的制备
将以上聚酯聚合物VIII-A1在170℃下通过熔体纺丝法纺成纤度为72dtex的纤维。将这些纤维在40℃下放置60min，然后升温至70℃并拉伸至原长的4倍。冷却后即得到弹性纤维VIII-B1。
实施例VIII-2
(1)聚酯组合物的制备
在搅拌的条件下(搅拌的速率为10r/min，时间为10min)，将186g BT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)颗粒、12g BT-BS共聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)颗粒、4g BT-BA共聚酯C(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，其中，BT重复单元的含量为60摩尔％)颗粒、10g二氧化钛混合并以10r/min的速度搅拌10min，然后加入双螺杆 挤出机中，在220℃温度下熔融挤出并造粒，得到聚酯组合物VIII-A2。
(2)弹性纤维的制备
将以上聚酯聚合物VIII-A2在170℃下通过熔体纺丝法纺成纤度为72dtex的纤维。将这些纤维在40℃下放置60min，然后升温至70℃并拉伸至原长的4倍。冷却后即得到弹性纤维VIII-B2。
实施例VIII-3
(1)聚酯组合物的制备
在搅拌的条件下(搅拌的速率为10r/min，时间为10min)，将120g BT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为40摩尔％)颗粒、40g BT-BS共聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为17摩尔％)颗粒、40g BT-BA共聚酯C(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，其中，BT重复单元的含量为85摩尔％)颗粒、10g二氧化钛混合并以10r/min的速度搅拌10min，然后加入双螺杆挤出机中，在220℃温度下熔融挤出并造粒，得到聚酯组合物VIII-A3。
(2)弹性纤维的制备
将以上聚酯聚合物VIII-A3在170℃下通过熔体纺丝法纺成纤度为72dtex的纤维。将这些纤维在40℃下放置60min，然后升温至70℃并拉伸至原长的4倍。冷却后即得到弹性纤维VIII-B3。
实施例VIII-4
(1)聚酯组合物的制备
在搅拌的条件下(搅拌的速率为10r/min，时间为10min)，将120g BT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为25摩尔％)颗粒、70g BT-BS共聚酯B(重均分子量为100,000，其中，以BT重复单元和BS 重复单元的总摩尔数为基准，BT重复单元的含量为5摩尔％)颗粒、10g BT-BA共聚酯C(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，其中，BT重复单元的含量为55摩尔％)颗粒、10g二氧化钛混合并以10r/min的速度搅拌10min，然后加入双螺杆挤出机中，在220℃温度下熔融挤出并造粒，得到聚酯组合物VIII-A4。
(2)弹性纤维的制备
将以上聚酯聚合物VIII-A4在170℃下通过熔体纺丝法纺成纤度为72dtex的纤维。将这些纤维在40℃下放置60min，然后升温至70℃并拉伸至原长的4倍。冷却后即得到弹性纤维VIII-B4。
实施例VIII-5
(1)聚酯组合物的制备
在搅拌的条件下(搅拌的速率为10r/min，时间为10min)，将60g BT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为49摩尔％)颗粒、138g BT-BS共聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为19摩尔％)颗粒、2g PBT(购自杜邦公司，牌号为Crastin SC164 NC010)颗粒、10g二氧化钛混合并以10r/min的速度搅拌10min，然后加入双螺杆挤出机中，在220℃温度下熔融挤出并造粒，得到聚酯组合物VIII-A5。
(2)弹性纤维的制备
将以上聚酯聚合物VIII-A5在170℃下通过熔体纺丝法纺成纤度为72dtex的纤维。将这些纤维在40℃下放置60min，然后升温至70℃并拉伸至原长的4倍。冷却后即得到弹性纤维VIII-B5。
实施例VIII-6
(1)聚酯组合物的制备
在搅拌的条件下(搅拌的速率为10r/min，时间为10min)，将60g  BT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为20摩尔％)颗粒、2g BT-BS共聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为1摩尔％)颗粒、138g BT-BA共聚酯C(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，其中，BT重复单元的含量为51摩尔％)颗粒、10g二氧化钛混合并以10r/min的速度搅拌10min，然后加入双螺杆挤出机中，在220℃温度下熔融挤出并造粒，得到聚酯组合物VIII-A6。
(2)弹性纤维的制备
将以上聚酯聚合物VIII-A6在170℃下通过熔体纺丝法纺成纤度为72dtex的纤维。将这些纤维在40℃下放置60min，然后升温至70℃并拉伸至原长的4倍。冷却后即得到弹性纤维VIII-B6。
实施例VIII-7
(1)聚酯组合物的制备
在搅拌的条件下(搅拌的速率为10r/min，时间为10min)，将196g BT-BS共聚酯A(重均分子量为130,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)颗粒、2g BT-BS共聚酯B(重均分子量为100,000，其中，以BT重复单元和BS重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)颗粒、2g BT-BA共聚酯C(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，其中，BT重复单元的含量为60摩尔％)颗粒、10g二氧化钛混合并以10r/min的速度搅拌10min，然后加入双螺杆挤出机中，在220℃温度下熔融挤出并造粒，得到聚酯组合物VIII-A7。
(2)弹性纤维的制备
将以上聚酯聚合物A7在170℃下通过熔体纺丝法纺成纤度为72dtex的纤维。将这些纤维在40℃下放置60min，然后升温至70℃并拉伸至原 长的4倍。冷却后即得到弹性纤维VIII-B7。
实施例VIII-8
按照实施例VIII-1的方法进行，不同的是，聚酯A为BT-BA共聚酯(重均分子量为130,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)；聚酯B为BT-ES酯(重均分子量为100,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)；聚酯C为BT-ES酯(重均分子量为100,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为60摩尔％)。得到聚酯组合物VIII-A8和弹性纤维VIII-B8。
实施例VIII-9
按照实施例VIII-1的方法进行，不同的是，聚酯A为BT-ES共聚酯(重均分子量为130,000，其中，以BT重复单元和ES重复单元的总摩尔数为基准，BT重复单元的含量为30摩尔％)；聚酯B为BT-BA酯(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为10摩尔％)；聚酯C为BT-BA酯(重均分子量为100,000，其中，以BT重复单元和BA重复单元的总摩尔数为基准，BT重复单元的含量为60摩尔％)。得到聚酯组合物VIII-A9和弹性纤维VIII-B9。
实施例VIII-10
按照实施例VIII-1的方法进行，不同的是，使用相同重量碳酸钙代替实施例VIII-1中的二氧化钛。得到聚酯组合物VIII-A10和弹性纤维VIII-B10。
实施例VIII-11
按照实施例VIII-1的方法进行，不同的是，未加入10g二氧化钛。得到聚酯组合物VIII-A11和弹性纤维VIII-B11。
实施例VIII-12
(1)聚酯组合物的制备
按照实施例VIII-1的方法进行，得到聚酯组合物VIII-A1。
(2)弹性纤维的制备
将以上聚酯聚合物VIII-A1在170℃下通过熔体纺丝法纺成纤度为72dtex的纤维。将这些纤维在55℃下放置120min，然后升温至110℃并拉伸至原长的10倍。冷却后即得到弹性纤维VIII-B12。
实施例VIII-13
(1)聚酯组合物的制备
按照实施例VIII-1的方法进行，得到聚酯组合物VIII-A1。
(2)弹性纤维的制备
将以上聚酯聚合物VIII-A1在170℃下通过熔体纺丝法纺成纤度为72dtex的纤维。将这些纤维在20℃下放置2min，然后升温至56℃并拉伸至原长的1.2倍。冷却后即得到弹性纤维VIII-B13。
实施例VIII-14
(1)聚酯组合物的制备
按照实施例VIII-1的方法进行，得到聚酯组合物VIII-A1。
(2)弹性纤维的制备
将以上聚酯聚合物VIII-A1在170℃下通过熔体纺丝法纺成纤度为72dtex的纤维。然后直接降温至70℃并拉伸至原长的4倍，而不包括实施例VIII-1中的在40℃下放置的过程。冷却后即得到弹性纤维VIII-B14。
对比例VIII-1
按照实施例VIII-1的方法进行，不同的是，在步骤(1)中，将150g实施例VIII-1使用的聚酯A、50g实施例VIII-1使用的聚酯B和10g二氧化钛混合，而不加入实施例VIII-1使用的聚酯C。得到聚酯组合物VIII-DA1和弹性纤维VIII-DB1。
对比例VIII-2
按照实施例VIII-1的方法进行，不同的是，在步骤(1)中，将150g实施例VIII-1使用的聚酯A、50g实施例VIII-1使用的聚酯C和10g二氧化钛混合，而不加入实施例VIII-1使用的聚酯B。得到聚酯组合物VIII-DA2和弹性纤维VIII-DB2。
对比例VIII-3
按照实施例VIII-1的方法进行，不同的是，在步骤(1)中，将120g实施例VIII-1使用的聚酯B、80g实施例VIII-1使用的聚酯C和10g二氧化钛混合，而不加入实施例VIII-1使用的聚酯A。得到聚酯组合物VIII-DA3和弹性纤维VIII-DB3。
对比例VIII-4
按照实施例VIII-1的方法进行，不同的是，在步骤(1)中，将20g实施例VIII-1使用的聚酯A、160g实施例VIII-1使用的聚酯B、20g实施例VIII-1使用的聚酯C和10g二氧化钛混合。得到聚酯组合物VIII-DA4和弹性纤维VIII-DB4。
对比例VIII-5
按照实施例VIII-1的方法进行，不同的是，在步骤(1)中，使用相同重量的PBS(购自巴斯夫公司，牌号为1111HTA4)代替实施例VIII-1中使用的聚酯A。得到聚酯组合物VIII-DA5和弹性纤维VIII-DB5。
对比例VIII-6
按照实施例VIII-1的方法进行，不同的是，在步骤(1)中，使用相同重量的PBS(购自巴斯夫公司，牌号为1111HTA4)代替实施例VIII-1中使用的聚酯B。得到聚酯组合物VIII-DA6和弹性纤维VIII-DB6。
对比例VIII-7
按照实施例VIII-1的方法进行，不同的是，在步骤(1)中，使用相同重量的PBA代替实施例VIII-1中使用的聚酯C，其中，PBA的制备方 法包括以下步骤：在氮气气氛中，将己二酸和丁二醇在钛酸四丁酯和乙酰丙酮镧共同存在下，与240℃下搅拌，进行反应；己二酸、丁二醇、钛酸四丁酯和乙酰丙酮镧的比例VIII-为1800：2000：1：1。反应2小时后，对体系抽真空，直至压力稳定在100Pa，持续半小时。体系中剩余物质即为产物。得到聚酯组合物VIII-DA7和弹性纤维VIII-DB7。
对比例VIII-8
按照实施例VIII-1的方法进行，不同的是，在步骤(1)中，将200g实施例VIII-1使用的聚酯A和10g二氧化钛混合。得到聚酯组合物VIII-DA8和弹性纤维VIII-DB8。
对比例VIII-9
按照实施例VIII-1的方法进行，不同的是，在步骤(1)中，将200g实施例VIII-1使用的聚酯B和10g二氧化钛混合。得到聚酯组合物VIII-DA9和弹性纤维VIII-DB9。
对比例VIII-10
按照实施例VIII-1的方法进行，不同的是，在步骤(1)中，将200g实施例VIII-1使用的聚酯C和10g二氧化钛混合。得到聚酯组合物VIII-DA10和弹性纤维VIII-DB10。
测试例VIII-1至VIII-24
按照以下方法分别评价实施例VIII-1至VIII-14和对比例VIII-1至VIII-10得到的弹性纤维的断裂强度、断裂伸长率、应力松弛和永久应变率。结果如表8所示。
具体地，将长度为2cm(L1)的试样，在Instron 5965拉伸仪上，以50mm/min的速度，拉伸至2倍原长(应变为100％)，此时的应力记为E1。然后保持该长度20s后，此时的应力记为E2。然后将应变减小，直至应力为0，此时试样的长度为L2。然后，将试样以50mm/min的速度 拉伸直至断裂，断裂时的试样长度为L3，应力值为E3。上述各参数的计算公式如下：
断裂强度＝E3
断裂伸长率％＝100％×(L3-L1)/L1
应力松弛率％＝100％×(E1-E2)/E1
永久应变率％＝100％×(L2-L1)/L1
表8
Figure PCTCN2017107106-appb-000048
注：“a”表示无法生产出完好的纤维；
“b”表示生产出的纤维断丝很多，且均匀性也较差；
“-”表示无法测出。
由以上表8的结果可以看出，本发明通过将特定的聚酯A、聚酯B和聚酯C按照特定的配比(30-98重量％的聚酯A，1-69重量％的聚酯B，1-69重量％的聚酯C)进行共混后得到聚酯组合物，使用该聚酯组合物制成的弹性纤维的弹性性能良好，断裂强度≥1cN/dtex，且通过配方和分子结构的调节能够在较大范围内改变，最大断裂强度接近20cN/dtex；并且，本发明提供的弹性纤维的断裂伸长率高达130％以上，应力松弛和永久应变率均可以≤12％，这说明本发明提供的弹性纤维兼具适中的弹性和强度，且性能可调节性范围广，因此其具有良好的应用前景。
另外，通过将实施例VIII-1与实施例VIII-12至VIII-14的结果相比较可知，本发明特别采用高温成丝-低温放置-高温拉伸的方法和条件制备得到弹性纤维，该方法可以进一步提高弹性纤维的断裂强度，扩大性能可调节范围，降低弹性纤维的应力松弛和永久应变率。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (48)

  1. 聚酯组合物，包含：
    (1)第一聚酯，该第一聚酯的量为基于第一聚酯和第二聚酯的总重量计50重量％至100重量％，优选51重量％至99重量％，该第一聚酯选自脂肪族-芳香族共聚酯中的一种或多种，该脂肪族-芳香族共聚酯为含有式(I)所示的重复单元A和式(II)所示的重复单元B的共聚物，
    Figure PCTCN2017107106-appb-100001
    其中以所述脂肪族-芳香族共聚酯中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为51-95摩尔％，所述重复单元B的含量为5-49摩尔％，优选所述重复单元A的含量为55-80摩尔％和所述重复单元B的含量为20-45摩尔％；m为2-10、优选2-6、更优选2-4的整数和n为2-8、优选2-4的整数；p为2-10，优选2-4的整数；且m、n和p彼此相同或不同；
    (2)任选的第二聚酯，该第二聚酯的量基于第一聚酯和第二聚酯的总重量计最多50重量％，优选1重量％至49重量％，该第二聚酯选自脂肪族聚酯、芳香族聚酯和不同于第一聚酯的脂肪族-芳香族共聚酯中的一种或多种；
    其中所述聚酯组合物包含至少两种聚酯。
  2. 根据权利要求1所述的聚酯组合物，其特征在于，作为第二聚酯的所述脂肪族聚酯含有式(I”’)所示的重复单元D，
    Figure PCTCN2017107106-appb-100002
    其中m3与权利要求1中m的定义相同，n3与权利要求1中n的定义相同，且m3和n3彼此相同或不同，所述脂肪族聚酯的重均分子量为50,000-900,000，优选100,000-500,000，该重均分子量根据GPC测得。
  3. 根据权利要求1所述的聚酯组合物，其特征在于，作为第二聚酯的所述芳香族聚酯由式(II)所示的重复单元B组成。
  4. 根据权利要求1所述的聚酯组合物，其特征在于，作为第二聚酯的所述不同于第一聚酯的脂肪族-芳香族共聚酯为含有式(I)所示的重复单元A和式(II)所示的重复单元B的共聚物。
  5. 根据权利要求1或4所述的聚酯组合物，其特征在于，作为第一聚酯或第二聚酯的含有式(I)所示的重复单元A和式(II)所示的重复单元B的脂肪族-芳香族共聚酯的重均分子量为50,000-900,000，优选100,000-500,000，该重均分子量根据GPC测得；优选分子量分布为1.2-3，由GPC测得。
  6. 根据权利要求1所述的聚酯组合物，其特征在于，作为第一聚酯的所述脂肪族-芳香族共聚酯是无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种；作为第二聚酯的所述脂肪族-芳香族共聚酯是无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种。
  7. 根据权利要求1所述的聚酯组合物，其特征在于，所述聚酯组合物另外包含一种或多种选自以下的添加剂：成核剂，纤维填料，和具有加速组合物熔体固化、调节组合物力学强度、调节组合物颜色和光泽、改善组合物的阻燃性、抗氧化性的作用的辅助填料，以及芥酸酰胺和/或白油。
  8. 根据权利要求7所述的聚酯组合物，其特征在于，所述辅助填料选自碳酸盐类、硅酸盐类、硫酸盐类、无机质中空微球、金属粉、炭黑、 滑石粉、芥酸酰胺、二氧化钛、氧化铁、羧酸金属盐、磷酸金属盐、四溴双酚A、十溴二苯醚、六溴环十二烷、低密度聚乙烯、多聚磷酸酯或盐、亚磷酸酯、受阻酚、受阻胺、二苄山梨醇及其衍生物、超支化聚酰胺、乙烯-甲基丙烯酸离聚物、乙撑双硬脂酰胺、硅酮粉和季戊四醇硬脂酸酯中的至少一种，优选至少两种；优选为碳酸钙、无水硫酸钙、铜粉、氧化铁、炭黑、二氧化钛、磷酸三(2,3-二溴丙基)酯、低密度聚乙烯、超支化聚酰胺、乙撑双硬脂酰胺和芥酸酰胺中的至少一种，优选至少两种，优选以所述聚酯组合物的总重量为基准，所述辅助填料的含量为0.1-60重量％，优选0.1-50重量％，更优选为1-25重量％，更优选1-20重量％，更优选2-10重量％。
  9. 根据权利要求7所述的聚酯组合物，其特征在于，所述成核剂选自滑石粉、氧化钙、炭黑、碳酸钙、无机颜料、高岭土、羧酸金属盐、磷酸金属盐、二苄山梨醇及其衍生物、聚乙烯基环己烷、聚乙烯基环戊烷、低密度聚乙烯、超支化聚酰胺和乙烯-甲基丙烯酸离聚物中的一种或几种；优选为碳酸钙、低密度聚乙烯、二苄山梨醇及其衍生物和超支化聚酰胺中的一种或几种，优选以所述聚酯组合物的总重量为基准，所述成核剂的含量为0.01-20重量％，优选为0.2-5重量％。
  10. 根据权利要求7所述的聚酯组合物，其特征在于，所述纤维填料为碳纤维、玻璃纤维、玄武岩纤维、芳纶纤维和PET纤维中的一种或几种，优选为玻璃纤维、碳纤维和玄武岩纤维中的一种或几种；优选地，所述纤维填料的长度为0.1-10mm，优选为0.5-2mm。
  11. 根据权利要求1-10中任一项所述的聚酯组合物，其特征在于，所述聚酯组合物包含
    (1)聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，
    Figure PCTCN2017107106-appb-100003
    (2)聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，
    Figure PCTCN2017107106-appb-100004
    (3)脂肪族聚酯，
    其中，m1和m2彼此独立地与权利要求1中对m的定义相同，n1和n2彼此独立地与权利要求1中对n的定义相同，且m1和n1彼此相同或不同，m2和n2彼此相同或不同，并且n1小于n2；
    以所述聚酯A、所述聚酯B和所述脂肪族聚酯的总摩尔数为基准，所述重复单元B的含量为5-49摩尔％，优选10-45摩尔％，更优选20-40摩尔％。
  12. 根据权利要求11所述的聚酯组合物，其特征在于，以所述聚酯A中重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为51-90摩尔％；所述重复单元B的含量为10-49摩尔％；
    以所述聚酯B中重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为40-95摩尔％，优选为50-90摩尔％；所述重复单元B的含量为5-60摩尔％，优选为10-50摩尔％。
  13. 根据权利要求11或12所述的聚酯组合物，其特征在于，所述聚酯A、所述聚酯B与所述脂肪族聚酯的摩尔比为20-90：1-90：1-20；优选为20-90：1-70：1-20。
  14. 根据权利要求1-10中任一项所述的聚酯组合物，其特征在于，以各组分的总重量为基准，该聚酯组合物含有以下组分：
    (1)51-98重量％的聚酯A，所述聚酯A为含有式(I-1)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为56-80摩尔％，优选为60-75摩尔％；所述重复单元B的含量为20-44摩尔％，优选为25-40摩尔％；
    Figure PCTCN2017107106-appb-100005
    (2)1-48重量％的聚酯B，所述聚酯B为含有式(I’)所示的重复单元C和式(IV’)所示的重复单元D的共聚物，且以所述聚酯B中的重复单元C和重复单元D的总摩尔数为基准，所述重复单元C的含量为81-99摩尔％，优选为85-95摩尔％，所述重复单元D的含量为1-19摩尔％，优选为5-15摩尔％，
    Figure PCTCN2017107106-appb-100006
    其中，m1与权利要求1中对m的定义相同，n1与权利要求1中对n的定义相同，且m1和n1彼此相同或不同；a1与权利要求1中p的定义相同，且a1与m1彼此相同或不同；
    (3)1-48重量％的聚酯C，所述聚酯C为含有式(I”)所示的重复单元E和式(IV”)所示的重复单元F的共聚物，且以所述聚酯C中的重复单元E和重复单元F的总摩尔数为基准，所述重复单元E的含量为0-55摩尔％，优选为15-50摩尔％，所述重复单元F的含量为45-100摩尔％，优选为50-85摩尔％，
    Figure PCTCN2017107106-appb-100007
    其中，m2与权利要求1中对m的定义相同，n2与权利要求1中对n的定义相同，且m2和n2彼此相同或不同；a2与权利要求1中p的定义相同，且a2与m2彼此相同或不同。
  15. 根据权利要求14所述的聚酯组合物，其特征在于，所述聚酯组合物含有70-94重量％的聚酯A、3-25重量％的聚酯B和3-20重量％的聚酯C。
  16. 根据权利要求1-10中任一项的聚酯组合物，其特征在于，以各组分的总重量为基准，该聚酯组合物含有以下组分：
    (1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为51-70摩尔％，优选为55-68摩尔％，所述重复单元B的含量为30-49摩尔％，优选为32-45摩尔％，
    Figure PCTCN2017107106-appb-100008
    其中，m1与权利要求1中对m的定义相同，n1与权利要求1中对n的定义相同，且m1和n1相同或不同；优选，m1为2-4的整数，n1为2-4的整数，优选2；
    (2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的 重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为1-50摩尔％，优选为20-45摩尔％，所述重复单元B的含量为50-99摩尔％，优选为55-80摩尔％，
    Figure PCTCN2017107106-appb-100009
    其中，m2与权利要求1中对m的定义相同，n2与权利要求1中对n的定义相同，且m2和n2相同或不同；优选，m2为2-4的整数，n2为2-4的整数，优选2。
  17. 根据权利要求16所述的聚酯组合物，其特征在于，所述聚酯组合物含有80-95重量％的聚酯A和5-20重量％的聚酯B。
  18. 根据权利要求1-10中任一项的聚酯组合物，其特征在于，以各组分的总重量为基准，该聚酯组合物含有以下组分：
    (1)50-98重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为55-79摩尔％，优选为60-77摩尔％，所述重复单元B的含量为21-45摩尔％，优选为23-40摩尔％，
    Figure PCTCN2017107106-appb-100010
    其中，m1与权利要求1中对m的定义相同，n1与权利要求1中对n的定义相同，且m1和n1彼此相同或不同；优选，m1为2-4的整数，n1为2-4的整数，优选4；
    (2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的 重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为80-100摩尔％，优选为85-95摩尔％，所述重复单元B的含量为0-20摩尔％，优选为5-15摩尔％，
    Figure PCTCN2017107106-appb-100011
    其中，m2与权利要求1中对m的定义相同，n2与权利要求1中对n的定义相同，且m2和n2彼此相同或不同；优选，m2为2-4的整数，n2为2-4的整数，优选2；
    (3)1-49重量％的纤维填料。
  19. 根据权利要求18所述的聚酯组合物，其特征在于，所述聚酯组合物含有60-90重量％的聚酯A、5-30重量％的聚酯B和5-30重量％的纤维填料。
  20. 根据权利要求1-10中任一项的聚酯组合物，其特征在于，以各组分的总重量为基准，该聚酯组合物含有以下组分：
    (1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为60-80摩尔％，优选为62-78摩尔％，所述重复单元B的含量为20-40摩尔％，优选为22-38摩尔％，
    Figure PCTCN2017107106-appb-100012
    其中，m1与权利要求1中对m的定义相同，n1与权利要求1中对n的定义相同，且m1和n1彼此相同或不同；优选m1为2-4的整数，n1为2-4的整数，优选n1为2；
    (2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为20-59摩尔％，优选为30-55摩尔％，所述重复单元B的含量为41-80摩尔％，优选为45-70摩尔％，
    Figure PCTCN2017107106-appb-100013
    其中，m2与权利要求1中对m的定义相同，n2与权利要求1中对n的定义相同，且m2和n2彼此相同或不同；优选，m2为2-4的整数，n2为2-4的整数，优选n2为2。
  21. 根据权利要求20所述的聚酯组合物，其特征在于，所述聚酯组合物含有70-90重量％的聚酯A和10-30重量％的聚酯B。
  22. 根据权利要求1-10中任一项所述的聚酯组合物，其特征在于，以各组分的总重量为基准，该聚酯组合物含有以下组分：
    (1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为60-80摩尔％，优选为62-72摩尔％，所述重复单元B的含量为20-40摩尔％，优选为28-38摩尔％，
    Figure PCTCN2017107106-appb-100014
    其中，m1与权利要求1中对m的定义相同，n1与权利要求1中对n的定义相同，且m1和n1彼此相同或不同；优选，m1为2-4的整数，n1为2-4的整数；优选n1为2；
    (2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为81-99摩尔％，优选为85-97摩尔％，所述重复单元B的含量为1-19摩尔％，优选为3-15摩尔％，
    Figure PCTCN2017107106-appb-100015
    其中，m2与权利要求1中对m的定义相同，n2与权利要求1中对n的定义相同，且m2和n2彼此相同或不同；优选，m2为2-4的整数，n2为2-4的整数，优选n2为2。
  23. 根据权利要求22所述的聚酯组合物，其特征在于，所述聚酯组合物含有60-90重量％的聚酯A和10-40重量％的聚酯B。
  24. 根据权利要1-10中任一项的聚酯组合物，其特征在于，以各组分的总重量为基准，该聚酯组合物含有以下组分：
    (1)51-99重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为75-95摩尔％，优选为81-95摩尔％，所述重复单元B的含量为5-25摩尔％，优选为5-19摩尔％，
    Figure PCTCN2017107106-appb-100016
    其中，m1与权利要求1中对m的定义相同，n1与权利要求1中对n的定义相同，且m1和n1彼此相同或不同；优选，m1为2-4的整数，n1为2-4的整数；优选n1为2；
    (2)1-49重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为20-74摩尔％，优选为40-70摩尔％，所述重复单元B的含量为26-80摩尔％，优选为30-60摩尔％，
    Figure PCTCN2017107106-appb-100017
    其中，m2与权利要求1中对m的定义相同，n2与权利要求1中对n的定义相同，且m2和n2彼此相同或不同；优选，m2为2-4的整数，n2为2-4的整数，优选n2为2。
  25. 根据权利要求24所述的聚酯组合物，其特征在于，所述聚酯组合物含有55-70重量％的聚酯A和30-45重量％的聚酯B。
  26. 根据权利要求1-10中任一项所述的聚酯组合物，其特征在于，以各组分的总重量为基准，该聚酯组合物含有以下组分：
    (1)30-98重量％的聚酯A，所述聚酯A为含有式(I’)所示的重复单元A和式(II-1)所示的重复单元B的共聚物，且以所述聚酯A中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为51-80摩尔％，优选为60-75摩尔％；所述重复单元B的含量为20-49摩尔％，优选为25-40摩尔％，
    Figure PCTCN2017107106-appb-100018
    其中，m1与权利要求1中对m的定义相同，n1与权利要求1中对n的定义相同，且m1和n1彼此相同或不同；优选，m1为2-8的整数和n1为2-6的整数，更优选m1为2-4的整数和n1为2-4的整数；
    (2)1-69重量％的聚酯B，所述聚酯B为含有式(I”)所示的重复单元C和式(II-1)所示的重复单元B的共聚物，且以所述聚酯B中的重复单元C和重复单元B的总摩尔数为基准，所述重复单元C的含量为81-99摩尔％，优选为83-95摩尔％，所述重复单元B的含量为1-19摩尔％，优选为5-17摩尔％，
    Figure PCTCN2017107106-appb-100019
    其中，m2与权利要求1中对m的定义相同，n2与权利要求1中对n的定义相同，且m2和n2彼此相同或不同；优选，m2为2-8的整数，n2为2-6的整数；更优选，m2为2-4的整数，n2为2-4的整数；
    (3)1-69重量％的聚酯C，所述聚酯C为含有式(I”’)所示的重复单元D和式(II-1)所示的重复单元B的共聚物，且以所述聚酯C中的重复单元D和重复单元B的总摩尔数为基准，所述重复单元D的含量为0-49摩尔％，优选为15-45摩尔％，所述重复单元B的含量为51-100摩尔％，优选为55-85摩尔％，
    Figure PCTCN2017107106-appb-100020
    其中，m3与权利要求1中对m的定义相同，n3与权利要求1中对n的定义相同，且m3和n3彼此相同或不同；优选，m3为2-8的整数，n3为2-6的整数；更优选，m3为2-4的整数，n3为2-4的整数。
  27. 根据权利要求26所述的聚酯组合物，其特征在于，所述聚酯组合物含有60-93重量％的聚酯A、5-38重量％的聚酯B和1-20重量％的聚酯C。
  28. 制备根据权利要求1-27中任一项的聚酯组合物的方法，包括将包括第一聚酯和第二聚酯在内的所有组分共混，并将得到的混合物进行挤出造粒，以得到聚酯组合物，优选所述共混的过程不加入相容剂。
  29. 根据权利要求28所述的方法，其特征在于，所述共混在搅拌的条件下进行。
  30. 根据权利要求28所述的方法，其特征在于，所述挤出造粒在双螺杆挤出机中进行；优选地，在温度为80-270℃，优选为110-220℃；螺杆转速为10-70rpm，扭矩为2-80N*m下进行。
  31. 根据权利要求1-27中任一项所述的聚酯组合物用于以下方面中一个或多个方面中的用途：形状记忆材料、3D打印线材、热收缩套管、功能层(例如用于运动护具的功能层)、运动护具(例如牙齿护具、四肢关节护具、身体大面积护具和头部护具)、医用肢体固定支架、热收缩薄膜、无纺布和无纺布制品(尤其是一次性无纺布制品，更优选一次性医用无纺布制品)。
  32. 形状记忆材料，其包含根据权利要求11-13中任一项所述的聚酯组合物。
  33. 3D打印线材，其包含根据权利要求14或15所述的聚酯组合物，优选所述3D打印线材的直径为0.1-10mm，优选为1-4mm。
  34. 制备根据权利要求33的3D打印线材的方法，包括将聚酯组合物依次经过挤出和冷却，以得到3D打印线材；优选，挤出的温度为90-260℃，冷却的温度为0-60℃。
  35. 热收缩套管，包含根据权利要求16或17所述的聚酯组合物。
  36. 制备根据权利要求35所述的热收缩套管的方法，包括将聚酯组合物依次经过挤出、牵引、冷却和定型，以得到热收缩套管；优选，挤出的温度为90-240℃，优选为120-180℃；并且冷却的温度为0-60℃，优选为20-40℃。
  37. 根据权利要求36所述的方法，其中所述方法还包括将冷却后的管材依次进行加热、扩径、二次冷却和定型；优选地，所述加热的温度为65-120℃，优选为70-90℃；优选地，所述扩径的倍率为原尺寸的1.5-5 倍，优选为3-5倍；优选地，所述二次冷却的温度为0-60℃，优选为20-40℃。
  38. 功能层，包含根据权利要求18或19所述的聚酯组合物，优选用于运动护具的功能层。
  39. 制备根据权利要求38所述的功能层的方法，包括将聚酯组合物成型，其中成型的方式优选为挤出或注塑；优选地，所述注塑的温度为140-270℃，优选为170-185℃。
  40. 医用肢体固定支架，包含根据权利要求20或21所述的聚酯组合物；优选，所述医用肢体固定支架的厚度为0.2-10mm，优选为1-3mm；优选地，所述医用肢体固定支架具有和/或不具有孔结构，优选为具有孔结构；更优选地，所述孔结构的孔径为1-10mm，优选为1-5mm。
  41. 制备根据权利要求40所述的医用肢体固定支架的方法，包括将聚酯组合物依次经过挤出、成型和可选的打孔，以得到医用肢体固定支架；优选，所述挤出的温度为90-230℃，优选为110-170℃；优选地，所述成型的方式为注塑和/或压塑；优选地，所述成型使得所述医用肢体固定支架的厚度为0.2-10mm，优选为1-3mm；优选地，所述打孔使用的打孔器的直径为1-10mm，优选为1-5mm。
  42. 热收缩薄膜，包含根据权利要求22或23所述的聚酯组合物。
  43. 制备根据权利要求42所述的热收缩薄膜的方法，包括将聚酯组合物依次经过流延成膜、静置和拉伸，以得到热收缩薄膜；优选，所述流延成膜的温度为80-220℃，优选为110-180℃；优选地，所述静置的时间为30分钟-20天，优选为4-24小时；优选地，所述拉伸为单向拉伸或双向拉伸；优选地，所述拉伸的温度为40-150℃，优选为60-120℃。
  44. 无纺布，包含根据权利要求24或25所述的聚酯组合物。
  45. 制备根据权利要求44所述的无纺布的方法，包括将聚酯组合物通过纺粘法制得无纺布；优选，所述纺粘法包括挤出、纺丝、成网和加 固的过程；优选地，所述挤出的过程包括三个温区，第一温区的温度为140-250℃，第二温区的温度为150-260℃，第三温区的温度为170-260℃；优选地，所述纺丝的温度为150-240℃，所述纺丝的速率为10-40r/min；优选地，所述成网的速率为5-30r/min；优选地，所述加固采用热轧的方式，所述热轧的温度为80-170℃。
  46. 弹性纤维，包含根据权利要求26或27所述的聚酯组合物；优选，所述弹性纤维的纤度为5-500dtex；根据标准GB/T 14337-2008的断裂强度为3-19cN/dtex；根据标准GB/T 14337-2008的断裂伸长率为130-620％；根据标准GB/T 14337-2008的应力松弛率1-12％；根据标准GB/T 14337-2008的永久应变率为1-11％。
  47. 制备根据权利要求46所述的弹性纤维的方法，包括将聚酯组合物依次经过成丝、低温放置和拉伸，以得到弹性纤维；优选，所述成丝的方式为熔体纺丝；优选地，所述成丝的温度为120-270℃，优选为150-220℃；优选地，所述低温放置的条件包括：温度为20-55℃，优选为25-45℃；时间为2-120min，优选为15-60min；优选地，所述拉伸的条件包括：温度为56-110℃，优选为60-90℃；拉伸的倍率为1.2-10倍，优选为2-5倍。
  48. 如权利要求1-27中任一项中限定的作为第一聚酯的脂肪族-芳香族共聚酯用于以下方面中一个或多个方面中的用途：形状记忆材料、3D打印线材、热收缩套管、功能层(例如用于运动护具的功能层)、运动护具(例如牙齿护具、四肢关节护具、身体大面积护具和头部护具)、医用肢体固定支架、热收缩薄膜、无纺布和无纺布制品(尤其是一次性无纺布制品，更优选一次性医用无纺布制品)。
PCT/CN2017/107106 2016-10-21 2017-10-20 聚酯组合物及其制备方法和应用 Ceased WO2018072746A1 (zh)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2019520899A JP7584219B2 (ja) 2016-10-21 2017-10-20 ポリエステル組成物、その製造方法およびその応用
CA3040988A CA3040988A1 (en) 2016-10-21 2017-10-20 Polyester composition, preparation method therefor and application thereof
EP17862862.4A EP3530694A4 (en) 2016-10-21 2017-10-20 Polyester composition, preparation method therefor and application thereof
US16/343,711 US11466151B2 (en) 2016-10-21 2017-10-20 Polyester composition, preparation method therefor and application thereof
JP2024130717A JP2024155925A (ja) 2016-10-21 2024-08-07 ポリエステル組成物、その製造方法およびその応用

Applications Claiming Priority (16)

Application Number Priority Date Filing Date Title
CN201610922101.3 2016-10-21
CN201610922101.3A CN107974052B (zh) 2016-10-21 2016-10-21 一种聚酯组合物及其制备方法和应用
CN201710702760.0A CN109401211B (zh) 2017-08-16 2017-08-16 聚酯组合物和医用肢体固定支架及其制备方法
CN201710703774.4 2017-08-16
CN201710703232.7A CN109401212B (zh) 2017-08-16 2017-08-16 聚酯组合物和热收缩薄膜及其制备方法
CN201710703232.7 2017-08-16
CN201710703617.3A CN109401214B (zh) 2017-08-16 2017-08-16 聚酯组合物和弹性纤维及其制备方法
CN201710703875.1 2017-08-16
CN201710703435.6 2017-08-16
CN201710703875.1A CN109401216B (zh) 2017-08-16 2017-08-16 聚酯组合物和功能层及其制备方法和应用
CN201710703617.3 2017-08-16
CN201710703435.6A CN109401213B (zh) 2017-08-16 2017-08-16 聚酯组合物和3d打印线材及其制备方法
CN201710703901.0A CN109401217B (zh) 2017-08-16 2017-08-16 聚酯组合物和热收缩套管及其制备方法
CN201710703774.4A CN109401215B (zh) 2017-08-16 2017-08-16 聚酯组合物和无纺布及其制备方法和应用
CN201710702760.0 2017-08-16
CN201710703901.0 2017-08-16

Publications (1)

Publication Number Publication Date
WO2018072746A1 true WO2018072746A1 (zh) 2018-04-26

Family

ID=62018235

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/107106 Ceased WO2018072746A1 (zh) 2016-10-21 2017-10-20 聚酯组合物及其制备方法和应用

Country Status (5)

Country Link
US (1) US11466151B2 (zh)
EP (1) EP3530694A4 (zh)
JP (2) JP7584219B2 (zh)
CA (1) CA3040988A1 (zh)
WO (1) WO2018072746A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957946A (zh) * 2022-06-09 2022-08-30 吉林建筑大学 一种改性聚乳酸基材料及其应用
EP4575053A3 (en) * 2023-12-01 2025-09-24 SK leaveo Co., Ltd. Biodegradable resin composition and biodegradable molded article including the same

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110731335B (zh) * 2019-07-01 2022-01-11 湖南农业大学 一种荷叶护绿和保鲜的方法
WO2022019876A1 (en) * 2020-07-20 2022-01-27 Hewlett-Packard Development Company, L.P. Three-dimensional printing
WO2023229214A1 (ko) * 2022-05-21 2023-11-30 에코밴스 주식회사 생분해성 폴리에스테르 수지 조성물 및 이를 포함하는 생분해성 성형품
WO2023229215A1 (ko) 2022-05-21 2023-11-30 에코밴스 주식회사 생분해성 폴리에스테르 수지 조성물, 이를 포함하는 생분해성 폴리에스테르 필름 및 이를 포함하는 생분해성 성형품
KR102945831B1 (ko) * 2022-06-08 2026-03-27 에스케이리비오 주식회사 생분해성 폴리에스테르 수지 조성물, 이를 포함하는 생분해성 폴리에스테르 필름 및 이를 포함하는 생분해성 성형품
WO2023229213A1 (ko) * 2022-05-21 2023-11-30 에코밴스 주식회사 생분해성 성형품 및 생분해성 폴리에스테르 수지 조성물 및 생분해성 폴리에스테르 필름
US20230399529A1 (en) * 2022-06-13 2023-12-14 Dequn Pan Carbon fiber blended modified 3d printing consumables and method for manufacturing carbon fiber blended modified 3d printing consumables

Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US157083A (en) 1874-11-24 Improvement in fire-proof paints
US4376438A (en) 1976-11-09 1983-03-15 Bayer Aktiengesellschaft Method of producing a supporting bandage and bandaging material suitable for this purpose
US5339832A (en) 1993-05-24 1994-08-23 E-Z Gard Industries, Inc. Thermoplastic mouthguard with integral shock absorbing framework
CN1541252A (zh) * 2001-07-18 2004-10-27 �Ϻ���ͨ��ѧ 聚酯共混物及由其制造的热收缩薄膜
CN1580092A (zh) 2004-05-18 2005-02-16 南亚塑胶工业股份有限公司 一种共聚酯及使用这种共聚酯制成热收缩套管的方法
CN101049729A (zh) 2007-04-30 2007-10-10 周亚平 Pet热缩套管的制备方法
CN100429256C (zh) 2004-12-30 2008-10-29 中国石油化工股份有限公司 可生物降解的线性无规共聚酯及其制备方法和应用
CN101374892A (zh) * 2006-01-27 2009-02-25 可隆株式会社 热收缩性聚酯膜
US20090157020A1 (en) * 2007-12-14 2009-06-18 Kimberly-Clark Worldwide, Inc. Film Formed from a Blend of Biodegradable Aliphatic-Aromatic Copolyesters
CN101508830A (zh) * 2009-03-18 2009-08-19 马世金 一种生物可降解共聚酯组合物
CN102206402A (zh) * 2010-03-30 2011-10-05 富士化工株式会社 管状成型品
CN102397133A (zh) 2011-11-15 2012-04-04 大连壹灏医疗用品有限公司 医用聚氨酯高分子绷带
CN103160948A (zh) 2013-04-07 2013-06-19 苏州聚复高分子材料有限公司 快速成型形状记忆高分子材料及其制备方法和应用
CN103171219A (zh) * 2011-12-20 2013-06-26 东丽纤维研究所（中国）有限公司 一种由内层和外层结构组成的薄膜
CN103333402A (zh) 2013-06-14 2013-10-02 长园集团股份有限公司 一种无卤无红磷阻燃热缩管及其制备方法
CN103483789A (zh) 2013-09-29 2014-01-01 太仓市鸿运包装材料有限公司 一种生物可降解的热收缩膜及其制备方法
CN103625061A (zh) 2013-11-29 2014-03-12 卫辉市银金达薄膜有限公司 一种流延加工成型的环保型可降解热收缩膜及其制造方法
CN103649167A (zh) * 2011-07-15 2014-03-19 沙特基础工业公司 颜色稳定的生物可降解的脂肪族-芳香族共聚酯、其制造方法和制品
CN104004377A (zh) 2014-06-10 2014-08-27 广州市傲趣电子科技有限公司 一种软性弹性3d打印橡胶耗材及其制备方法
CN104039865A (zh) 2011-12-13 2014-09-10 伍德依万特-费休股份有限公司 用于制备脂肪族聚酯的方法
CN204317582U (zh) 2015-01-03 2015-05-13 欧阳昆 一种环保手术衣
CN204398434U (zh) 2015-01-03 2015-06-17 欧阳昆 一种用于制作手术衣的复合材料
CN104845353A (zh) 2015-05-27 2015-08-19 上海材料研究所 用于fdm 3d打印的热塑性聚氨酯改性复合材料及其制备方法
CN105015128A (zh) 2015-08-06 2015-11-04 海宁市美迪康非织造新材料有限公司 一次性使用手术衣加强片材料及其制备方法
CN105054444A (zh) 2015-08-14 2015-11-18 昆山洁宏无纺布制品有限公司 可降解、阻燃、抗静电型手术衣用无纺布及其制造方法
CN105504474A (zh) 2016-01-08 2016-04-20 同济大学 一种形状记忆高分子复合材料及其制备方法
CN205800418U (zh) 2016-07-21 2016-12-14 湖州欧丽卫生材料有限公司 一种医用抗菌pp木浆复合水刺非织造布
CN106519400A (zh) 2016-11-28 2017-03-22 山东中塑泰富科技有限公司 一种可降解聚烯烃热收缩膜材料及其制备方法

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0118796D0 (en) 2001-08-01 2001-09-26 Dupont Teijin Films Us Ltd Par Copolyester film
MX282711B (es) 2003-12-22 2011-01-10 Eastman Chem Co Mezclas de polimeros con resistencia de impacto muescado mejorada.
KR101153669B1 (ko) 2004-04-26 2012-06-18 도호 가가꾸 고오교 가부시키가이샤 생분해성 수지 조성물
US7332562B2 (en) 2004-12-23 2008-02-19 China Petroleum & Chemical Corporation Biodegradable linear random copolyester and process for preparing it and use of the same
CN101098932B (zh) 2005-01-12 2011-08-17 巴斯福股份公司 可生物降解聚酯混合物
US7557167B2 (en) 2006-09-28 2009-07-07 Gore Enterprise Holdings, Inc. Polyester compositions, methods of manufacturing said compositions, and articles made therefrom
JP5164197B2 (ja) * 2006-12-25 2013-03-13 旭化成ケミカルズ株式会社 熱可塑性組成物からなる射出成形品
JP2008189764A (ja) * 2007-02-02 2008-08-21 Mitsubishi Engineering Plastics Corp 黒色のレーザー溶着用ポリエステル樹脂組成物およびこれを用いた成形品
CN101126180A (zh) 2007-07-26 2008-02-20 浙江恒逸集团有限公司 一种弹性聚酯纤维及其制备方法
IT1396597B1 (it) 2009-11-05 2012-12-14 Novamont Spa Miscele di poliesteri biodegradabili
EP2550329B1 (de) 2010-03-24 2014-03-19 Basf Se Verfahren zur folienherstellung
KR20130010080A (ko) 2010-03-24 2013-01-25 바스프 에스이 클링필름의 제조 방법
US8739316B1 (en) 2010-06-09 2014-06-03 No Problem, Inc. Protective headgear and inserts
CN102408688A (zh) * 2010-09-26 2012-04-11 比亚迪股份有限公司 一种聚乳酸复合材料及其制备方法
JP5925994B2 (ja) 2011-03-30 2016-05-25 シーアイ化成株式会社 生分解性マルチフィルム
CN102838856B (zh) * 2011-06-23 2015-06-17 中国石油化工股份有限公司 一种生物可降解的复合物及其制备方法和一次性用品
CN102838854B (zh) 2011-06-23 2014-12-03 中国石油化工股份有限公司 一种生物可降解的复合物及其制备方法和一次性用品
US9056979B2 (en) 2012-11-15 2015-06-16 Basf Se Biodegradable polyester mixture
WO2014075998A1 (de) 2012-11-15 2014-05-22 Basf Se Biologisch abbaubare polyestermischung
KR20150040673A (ko) 2013-10-07 2015-04-15 삼성정밀화학 주식회사 생분해성 수지 컴파운드 및 생분해성 포장재
CN105566616B (zh) 2014-10-15 2018-09-21 中国石油化工股份有限公司 一种共聚酯制备方法及所得共聚酯在3d打印中的应用
CN107974052B (zh) 2016-10-21 2019-07-19 中国石油化工股份有限公司 一种聚酯组合物及其制备方法和应用

Patent Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US157083A (en) 1874-11-24 Improvement in fire-proof paints
US4376438A (en) 1976-11-09 1983-03-15 Bayer Aktiengesellschaft Method of producing a supporting bandage and bandaging material suitable for this purpose
US5339832A (en) 1993-05-24 1994-08-23 E-Z Gard Industries, Inc. Thermoplastic mouthguard with integral shock absorbing framework
CN1541252A (zh) * 2001-07-18 2004-10-27 �Ϻ���ͨ��ѧ 聚酯共混物及由其制造的热收缩薄膜
CN1580092A (zh) 2004-05-18 2005-02-16 南亚塑胶工业股份有限公司 一种共聚酯及使用这种共聚酯制成热收缩套管的方法
CN100429256C (zh) 2004-12-30 2008-10-29 中国石油化工股份有限公司 可生物降解的线性无规共聚酯及其制备方法和应用
CN101374892A (zh) * 2006-01-27 2009-02-25 可隆株式会社 热收缩性聚酯膜
CN101049729A (zh) 2007-04-30 2007-10-10 周亚平 Pet热缩套管的制备方法
US20090157020A1 (en) * 2007-12-14 2009-06-18 Kimberly-Clark Worldwide, Inc. Film Formed from a Blend of Biodegradable Aliphatic-Aromatic Copolyesters
CN101508830A (zh) * 2009-03-18 2009-08-19 马世金 一种生物可降解共聚酯组合物
CN102206402A (zh) * 2010-03-30 2011-10-05 富士化工株式会社 管状成型品
CN103649167A (zh) * 2011-07-15 2014-03-19 沙特基础工业公司 颜色稳定的生物可降解的脂肪族-芳香族共聚酯、其制造方法和制品
CN102397133A (zh) 2011-11-15 2012-04-04 大连壹灏医疗用品有限公司 医用聚氨酯高分子绷带
CN104039865A (zh) 2011-12-13 2014-09-10 伍德依万特-费休股份有限公司 用于制备脂肪族聚酯的方法
CN103171219A (zh) * 2011-12-20 2013-06-26 东丽纤维研究所（中国）有限公司 一种由内层和外层结构组成的薄膜
CN103160948A (zh) 2013-04-07 2013-06-19 苏州聚复高分子材料有限公司 快速成型形状记忆高分子材料及其制备方法和应用
CN103333402A (zh) 2013-06-14 2013-10-02 长园集团股份有限公司 一种无卤无红磷阻燃热缩管及其制备方法
CN103483789A (zh) 2013-09-29 2014-01-01 太仓市鸿运包装材料有限公司 一种生物可降解的热收缩膜及其制备方法
CN103625061A (zh) 2013-11-29 2014-03-12 卫辉市银金达薄膜有限公司 一种流延加工成型的环保型可降解热收缩膜及其制造方法
CN104004377A (zh) 2014-06-10 2014-08-27 广州市傲趣电子科技有限公司 一种软性弹性3d打印橡胶耗材及其制备方法
CN204317582U (zh) 2015-01-03 2015-05-13 欧阳昆 一种环保手术衣
CN204398434U (zh) 2015-01-03 2015-06-17 欧阳昆 一种用于制作手术衣的复合材料
CN104845353A (zh) 2015-05-27 2015-08-19 上海材料研究所 用于fdm 3d打印的热塑性聚氨酯改性复合材料及其制备方法
CN105015128A (zh) 2015-08-06 2015-11-04 海宁市美迪康非织造新材料有限公司 一次性使用手术衣加强片材料及其制备方法
CN105054444A (zh) 2015-08-14 2015-11-18 昆山洁宏无纺布制品有限公司 可降解、阻燃、抗静电型手术衣用无纺布及其制造方法
CN105504474A (zh) 2016-01-08 2016-04-20 同济大学 一种形状记忆高分子复合材料及其制备方法
CN205800418U (zh) 2016-07-21 2016-12-14 湖州欧丽卫生材料有限公司 一种医用抗菌pp木浆复合水刺非织造布
CN106519400A (zh) 2016-11-28 2017-03-22 山东中塑泰富科技有限公司 一种可降解聚烯烃热收缩膜材料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3530694A4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957946A (zh) * 2022-06-09 2022-08-30 吉林建筑大学 一种改性聚乳酸基材料及其应用
CN114957946B (zh) * 2022-06-09 2024-01-30 吉林建筑大学 一种改性聚乳酸基材料及其应用
EP4575053A3 (en) * 2023-12-01 2025-09-24 SK leaveo Co., Ltd. Biodegradable resin composition and biodegradable molded article including the same

Also Published As

Publication number Publication date
EP3530694A4 (en) 2020-06-10
JP2024155925A (ja) 2024-10-31
US11466151B2 (en) 2022-10-11
EP3530694A1 (en) 2019-08-28
CA3040988A1 (en) 2018-04-26
JP7584219B2 (ja) 2024-11-15
US20190270882A1 (en) 2019-09-05
JP2020502288A (ja) 2020-01-23

Similar Documents

Publication Publication Date Title
JP7584219B2 (ja) ポリエステル組成物、その製造方法およびその応用
CN112812261B (zh) 一种水性聚氨酯乳液、丁腈橡胶-聚氨酯复合手套及其制备方法
US8518315B2 (en) Plasticizer for thermoplastic materials
CN105907061A (zh) Pbs/pla/pha生物降解复合材料及其制备方法
KR102418918B1 (ko) 가요성 및 연성이 개선된 생분해성 부직포, 이의 제조 방법 및 이를 사용한 생분해성 마스크
US12214041B2 (en) Polyurethane excipient
US9827442B2 (en) Thermoplastic sheet, a radiation mask of thermoplastic sheet and method for providing said sheet and said mask
CN108779279A (zh) 拉伸多孔性膜及其制造方法
TW200418896A (en) Monolithic thermoplastic ether polyurethane having high water vapor transmission
CN112778603A (zh) 一种抗蠕变性透气膜组合物及其制备方法
US8628710B2 (en) Plasticizer for thermoplastic polymer materials
JP2002302825A (ja) 高耐熱性ポリプロピレン繊維
CN106620808A (zh) 一种医用固定形状记忆高分子复合材料及其制备方法
KR102805788B1 (ko) 생분해성 수지 조성물, 이를 포함하는 의료용 부목 및 이의 제조 방법
CN109401211B (zh) 聚酯组合物和医用肢体固定支架及其制备方法
US11944507B2 (en) Immobilisation device
EP2358814B1 (en) Plasticizer for thermoplastic polymer materials
US20210260240A1 (en) Bendable splint and molding method thereof
CN110804292B (zh) 一种纤维增强聚己内酯复合材料及其制备方法和应用
TW202337976A (zh) 延伸多孔性薄膜及其製造方法
CN108641316A (zh) 一种高分子复合材料、制备及应用
Ibebunjo Shape memory respirator mask for Covid-19
JPH1135666A (ja) ポリエステル系樹脂組成物およびその用途
CN122060299A (zh) 一种高分子多层网格结构体及其制备方法和在支撑防护中的应用
JPS62214920A (ja) ホ−ス製造用マンドレル

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17862862

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3040988

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2019520899

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2017862862

Country of ref document: EP

Effective date: 20190521