WO2020119158A1 - 一种可生物降解制品及其制备方法 - Google Patents

一种可生物降解制品及其制备方法 Download PDF

Info

Publication number
WO2020119158A1
WO2020119158A1 PCT/CN2019/100438 CN2019100438W WO2020119158A1 WO 2020119158 A1 WO2020119158 A1 WO 2020119158A1 CN 2019100438 W CN2019100438 W CN 2019100438W WO 2020119158 A1 WO2020119158 A1 WO 2020119158A1
Authority
WO
WIPO (PCT)
Prior art keywords
parts
biodegradable
biodegradable product
starch
product according
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/CN2019/100438
Other languages
English (en)
French (fr)
Inventor
施晓旦
郝鲁峰
郑璐
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.)
Shanghai Changfa New Materials Co Ltd
Original Assignee
Shanghai Changfa New Materials Co Ltd
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
Application filed by Shanghai Changfa New Materials Co Ltd filed Critical Shanghai Changfa New Materials Co Ltd
Priority to EP19896390.2A priority Critical patent/EP3998311A4/en
Publication of WO2020119158A1 publication Critical patent/WO2020119158A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/826—Apparatus therefor
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B29B7/92—Wood chips or wood fibres
    • 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
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B29B9/16—Auxiliary treatment of granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • 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
    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
    • B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • 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
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the technical field of degradable composite materials, in particular to a biodegradable product and a preparation method thereof.
  • the pulp and paper industry separates about 140 million tons of cellulose from plants every year, and at the same time obtains a large amount of papermaking waste by-products, but so far, more than 95% of papermaking waste is still directly discharged into rivers or concentrated and burned. Less effective use.
  • the invention patent CN106317941A discloses a fully biodegradable garbage bag, which includes 35-55 parts PBAT, 45-65 parts PLA, 0.3-0.8 parts antioxidant and 0.5-2 parts dibenzoyl peroxide by weight.
  • the cost of biodegradable garbage bags is high and difficult to promote.
  • the purpose of the present invention is to provide a biodegradable product and its preparation method in view of the deficiencies in the prior art.
  • a biodegradable product the composition of which is as follows in parts by weight:
  • the components of the biodegradable product are as follows:
  • the components of the biodegradable product are as follows:
  • the biodegradable resin is one of polybutylene succinate, polybutylene terephthalate/butylene adipate, polylactic acid, polyhydroxy fatty acid ester, and polymethyl ethylene carbonate. One or more mixtures.
  • the papermaking waste is one or more mixtures of putty, pulp residue, veneer, pulping waste liquid extract, and silicon-containing white mud.
  • the particle size of the papermaking waste is 50-5000 mesh.
  • the particle size of the papermaking waste is 200-3000 mesh.
  • the particle size of the papermaking waste is 500-2000 mesh.
  • the starch is a mixture of one or more of tapioca starch, corn starch, potato starch, cationic modified starch and anionic modified starch.
  • the inorganic mineral is a mixture of one or more of calcium carbonate, kaolin, talc, and diatomaceous earth.
  • composition of the auxiliary agent in terms of parts by weight is as follows:
  • Lubricants 0.5 to 5 parts.
  • composition of the auxiliary agent in terms of parts by weight is as follows:
  • composition of the auxiliary agent in terms of parts by weight is as follows:
  • the cross-linking agent is a mixture of one or more of dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5 di-tert-butyl peroxide ;
  • the plasticizer is a mixture of one or more of butyl citrate, acetyl tri-n-butyl citrate, glycerin, and epoxy soybean oil;
  • the lubricant is calcium stearate.
  • the invention also provides a method for preparing a biodegradable product, which includes the following steps:
  • Step 1 Add biodegradable resin, paper-making waste, starch, inorganic minerals, and additives to the high-speed mixer in proportion to mix, to obtain the primary mixing material;
  • Step 2 Add the primary mixed material to the twin-screw extruder for extrusion and granulation to obtain a biodegradable product master batch;
  • Step 3 Film forming the masterbatch of the biodegradable product to obtain a biodegradable product.
  • the biodegradable resin, paper-making waste, starch, inorganic minerals, and additives are added in proportion to the high-speed mixer and mixed for 5min-1000min, and the temperature is raised to 10-150°C, and the rotation speed is 10- 5000rpm.
  • mixing is performed for 30-500 minutes.
  • mixing is performed for 60 to 300 minutes.
  • the temperature is raised to 20 to 130°C.
  • the temperature is raised to 50-80°C.
  • the rotation speed is 100-3000 rpm.
  • the rotation speed is 200-2000 rpm.
  • the temperature in the first to sixth zones of the twin-screw extruder is 80-240°C
  • the head temperature of the twin-screw extruder is 80-240°C
  • the rotation speed is 30-600 rpm.
  • the temperature in the first to sixth zones of the twin-screw extruder is 100-220°C.
  • the temperature in the first to sixth zones of the twin-screw extruder is 110-200°C.
  • the head temperature of the twin screw extruder is 100-220°C.
  • the head temperature of the twin screw extruder is 110-200°C.
  • the rotation speed is 60-450 rpm.
  • the rotation speed is 120-300 rpm.
  • the conditions for blown film forming are: the temperature is 80-240°C.
  • the present invention adopts the above technical solutions, and compared with the prior art, has the following technical effects:
  • biodegradable product and its preparation method of the present invention combine papermaking waste, starch, inorganic minerals and biodegradable resin, greatly reducing the cost of biodegradable products; effectively using papermaking waste and reducing the environment pressure.
  • Polyadipate/butylene terephthalate (poly(butyleneadipate-co-terephthalate), PBAT) 60 parts, polylactic acid (PLA) 10 parts, papermaking waste 15 parts, corn starch 12 parts, carbonic acid 3 parts of calcium, 1 part of dicumyl peroxide (DCP), 6 parts of epoxy soybean oil, and 1 part of calcium stearate.
  • PVA polylactic acid
  • DCP dicumyl peroxide
  • epoxy soybean oil 1 part of calcium stearate.
  • Step 1 Dry, crush and sieve papermaking waste to obtain 500-2000 mesh papermaking waste;
  • Step 2 Add the initial mixture to the twin-screw extruder for extrusion and granulation.
  • the temperatures in the first to sixth zones of the twin-screw extruder are 180°C, 185°C, 190°C, 195°C, 195°C, At 195°C, the head temperature of the twin-screw extruder is 190°C, and the rotation speed is 300rpm to obtain the masterbatch of biodegradable products;
  • Step 3 The masterbatch of the biodegradable product is transferred to the film blowing machine, and the film is blown and formed under the condition of a temperature of 130°C to obtain the biodegradable product.
  • the biodegradable product may be a biodegradable film or a biodegradable bag.
  • PBAT polyadipate/butylene terephthalate
  • PVA polylactic acid
  • DCP dicumyl peroxide
  • cyclic Oxygenated soybean oil 6 parts, calcium stearate 1 part.
  • Step 1 Dry, crush and sieve papermaking waste to obtain 50-5000 mesh papermaking waste
  • Step 2 Add the initial mixture to the twin-screw extruder for extrusion and granulation.
  • the temperatures in the first to sixth zones of the twin-screw extruder are 130°C, 135°C, 140°C, 145°C, and 145°C, respectively.
  • the head temperature of the twin screw extruder is 150°C, and the rotation speed is 200rpm, to obtain the masterbatch of biodegradable products;
  • Step 3 The masterbatch of the biodegradable product is transferred to the film blowing machine, and the film is blown and formed under the condition of a temperature of 140°C to obtain the biodegradable product.
  • the biodegradable product may be a biodegradable film or a biodegradable bag.
  • PBAT polyadipate/butylene terephthalate
  • PVA polylactic acid
  • DCP dicumyl peroxide
  • glycerin 6 servings 1 serving of calcium stearate.
  • Step 1 Dry, crush and sieve papermaking waste to obtain 50-5000 mesh papermaking waste
  • Step 2 Add the initial mixture to the twin-screw extruder for extrusion and granulation.
  • the temperatures in the first to sixth zones of the twin-screw extruder are 160°C, 165°C, 170°C, 175°C, and 175°C, respectively.
  • the head temperature of the twin screw extruder is 170°C, and the rotation speed is 150 rpm to obtain the masterbatch of biodegradable products;
  • Step 3 The masterbatch of the biodegradable product is transferred to the film blowing machine, and the film is blown and formed under the condition of a temperature of 135°C to obtain the biodegradable product.
  • the biodegradable product may be a biodegradable film or a biodegradable bag.
  • PBAT polyadipate/butylene terephthalate
  • BPO benzoyl peroxide
  • TBC citric acid Tributyl ester
  • Step 1 Dry, crush and sieve papermaking waste to obtain 200-300 mesh papermaking waste;
  • Step 2 Add the initial mixture to the twin-screw extruder for extrusion and granulation.
  • the temperatures in the first to sixth zones of the twin-screw extruder are 150°C, 155°C, 160°C, 165°C, and 165°C, respectively.
  • the head temperature of the twin-screw extruder is 160°C, and the rotation speed is 250rpm to obtain the masterbatch of biodegradable products;
  • Step 3 The masterbatch of the biodegradable product is transferred to the film blowing machine, and the film is blown and formed under the condition of a temperature of 140°C to obtain the biodegradable product.
  • the biodegradable product may be a biodegradable film or a biodegradable bag.
  • PBAT polyadipate/butylene terephthalate
  • PPC polymethylpropylene carbonate
  • BPO benzoyl peroxide
  • Step 1 Dry, crush and sieve papermaking waste to obtain 50-5000 mesh papermaking waste
  • Step 2 Add the initial mixture to the twin-screw extruder for extrusion and granulation.
  • the temperatures in the first to sixth zones of the twin-screw extruder are 140°C, 145°C, 150°C, 155°C, and 155°C, respectively.
  • the head temperature of the twin screw extruder is 150°C, and the rotation speed is 200rpm, to obtain the masterbatch of biodegradable products;
  • Step 3 The masterbatch of the biodegradable product is transferred to the film blowing machine, and the film is blown and formed under the condition of a temperature of 145°C to obtain the biodegradable product.
  • the biodegradable product may be a biodegradable film or a biodegradable bag.
  • poly(butylene succinate) 55 parts poly(butylene succinate), 15 parts polylactic acid (PLA), 10 parts paper waste, 18 parts potato starch, 3 parts diatomaceous earth, diisopropyl peroxide Benzene (DCP) 1 part, glycerin 5 parts, calcium stearate 1 part.
  • PHA polylactic acid
  • DCP diisopropyl peroxide Benzene
  • Step 1 Dry, crush and sieve papermaking waste to obtain 500-2000 mesh papermaking waste;
  • Step 2 Add the initial mixture to the twin-screw extruder for extrusion and granulation.
  • the temperatures in the first to sixth zones of the twin-screw extruder are 180°C, 185°C, 190°C, 195°C, 195°C, At 195°C, the head temperature of the twin-screw extruder is 190°C, and the rotation speed is 300rpm to obtain the masterbatch of biodegradable products;
  • Step 3 The masterbatch of the biodegradable product is transferred to the film blowing machine, and the film is blown and formed under the condition of a temperature of 130°C to obtain the biodegradable product.
  • the biodegradable product may be a biodegradable film or a biodegradable bag.
  • This comparative example is a conventional biodegradable product, consisting of the following parts by weight of raw materials:
  • PBAT polyadipate/butylene terephthalate
  • PVA polylactic acid
  • DCP dicumyl peroxide
  • epoxy soybean oil 6 servings 1 serving of calcium stearate.
  • Step 1 Add 70 parts of PBAT, 15 parts of PLA, 15 parts of corn starch, 1 part of DCP, 6 parts of epoxy soybean oil and 1 part of calcium stearate to the high-speed blender at a temperature of 60°C and a speed of 200 rpm Under conditions, mix for 100min to obtain the initial mixture;
  • Step 2 Add the initial mixture to the twin-screw extruder for extrusion and granulation.
  • the temperatures in the first to sixth zones of the twin-screw extruder are 180°C, 185°C, 190°C, 195°C, 195°C, At 195°C, the head temperature of the twin-screw extruder is 190°C, and the rotation speed is 200rpm to obtain the masterbatch of conventional biodegradable products;
  • Step 3 Send the masterbatch of conventional biodegradable products to a film blowing machine, and blow the film under the condition of a temperature of 140°C to obtain conventional biodegradable products.
  • the conventional biodegradable product may be a conventional biodegradable film or a conventional biodegradable bag.
  • This comparative example is a conventional biodegradable product, consisting of the following parts by weight of raw materials:
  • PBAT polyadipate/butylene terephthalate
  • PBS polybutylene succinate
  • DCP dicumyl peroxide
  • Step 1 Add 65 parts of PBAT, 20 parts of PBS, 13 parts of tapioca starch, 13 parts of calcium carbonate, 1 part of DCP, 6 parts of glycerin and 1 part of calcium stearate to the high-speed blender at a temperature of 350°C, Under the condition of rotating speed 100rpm, mix for 70min to obtain the initial mixture;
  • Step 2 Add the initial mixture to the twin-screw extruder for extrusion and granulation.
  • the temperatures in the first to sixth zones of the twin-screw extruder are 150°C, 155°C, 160°C, 165°C, and 165°C, respectively.
  • the head temperature of the twin-screw extruder is 160°C and the rotation speed is 130 rpm, to obtain the masterbatch of conventional biodegradable products;
  • Step 3 Transfer the masterbatch of conventional biodegradable products to a film blowing machine, and blow the film under the condition of 145°C to obtain conventional biodegradable products.
  • the conventional biodegradable product may be a conventional biodegradable film or a conventional biodegradable bag.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

一种可生物降解制品及其制备方法，其组成成分按重量份数如下：生物降解树脂40～90份；造纸废弃物5～50份；淀粉0～40份；无机矿物质0～5份；助剂2～15份。

Description

一种可生物降解制品及其制备方法 技术领域
本发明涉及可降解复合材料技术领域，尤其涉及一种可生物降解制品及其制备方法。
背景技术
由于环境的急剧恶化，廉价、无环境污染的高性能可降解材料取代石油基的传统塑料成为了研究的热点。因生物降解树脂较高的成本，限制了其合理的商业用途。
制浆造纸工业每年要从植物中分离出大约1.4亿吨纤维素，同时得到大量的造纸废弃物副产品，但迄今为止，超过95％的造纸废弃物仍直接排入江河或浓缩后烧掉，很少得到有效利用。
发明专利CN106317941A公开了一种全生物降解垃圾袋，以重量计，包括35-55份PBAT、45-65份PLA、0.3-0.8份抗氧化剂和0.5-2份过氧化二苯甲酰，该全生物降解垃圾袋成本较高，难以推广。
因此，亟需一种成本较低且可降解，能够复合造纸废弃物的复合材料。
发明内容
本发明的目的是针对现有技术中的不足，提供一种可生物降解制品及其制备方法。
为实现上述目的，本发明采取的技术方案是：
一种可生物降解制品，其组成成分按重量份数如下：
生物降解树脂 40～90份
造纸废弃物 5～50份
淀粉 0～40份
无机矿物质 0～5份
助剂 2～15份。
优选地，所述可生物降解制品，其组成成分按重量份数如下：
生物降解树脂 50～80份
造纸废弃物 10～40份
淀粉 5～25份
无机矿物质 1～4份
助剂 3～12份。
优选地，所述可生物降解制品，其组成成分按重量份数如下：
生物降解树脂 55～75份
造纸废弃物 15～35份
淀粉 10～20份
无机矿物质 2～3份
助剂 4～10份。
优选地，所述生物降解树脂为聚丁二酸丁二醇酯、聚对苯二甲酸/己二酸丁二醇酯、聚乳酸、聚羟基脂肪酸酯、聚甲基乙撑碳酸酯中的一种或多种的混合物。
优选地，所述造纸废弃物为腐浆、浆渣、木皮、制浆废液提取物、含硅白泥的一种或多种的混合物。
优选地，所述造纸废弃物的粒径为50～5000目。
优选地，所述造纸废弃物的粒径为200～3000目。
优选地，所述造纸废弃物的粒径为500～2000目。
优选地，所述淀粉为木薯淀粉、玉米淀粉、马铃薯淀粉、阳离子改性淀粉、阴离子改性淀粉中的一种或多种的混合物。
优选地，所述无机矿物质为碳酸钙、高岭土、滑石粉、硅藻土中的一种或多种的混合物。
优选地，所述助剂的组成成分按重量份数计如下：
交联剂 0.5～2份
增塑剂剂 1～10份
润滑剂 0.5～5份。
优选地，所述助剂的组成成分按重量份数计如下：
交联剂 0.7～1.5份
增塑剂剂 2～9份
润滑剂 1～4份。
优选地，所述助剂的组成成分按重量份数计如下：
交联剂 0.8～1.2份
增塑剂剂 3～8份
润滑剂 1.5～3.5份。
优选地，所述交联剂为过氧化二异丙苯、过氧化苯甲酰、2,5-二甲基-2,5二叔丁基过氧化己烷中的一种或多种的混合物；
所述增塑剂为柠檬酸丁酯、乙酰柠檬酸三正丁酯、甘油、环氧大豆油中的一种或多种的混合物；
所述润滑剂为硬脂酸钙。
本发明还提供一种可生物降解制品的制备方法，包括以下步骤：
步骤1，将生物降解树脂、造纸废弃物、淀粉、无机矿物质、助剂按比例加入高速混合机中混合，得到初混物料；
步骤2、将所述初混物料加入双螺杆挤出机中挤出造粒，得到可生物降解制品母粒；
步骤3、将所述到可生物降解制品母粒吹膜成型，得到可生物降解制品。
优选地，在所述步骤1中，将生物降解树脂、造纸废弃物、淀粉、无机矿物质、助剂按比例加入高速混合机中混合5min-1000min，升温至10～150℃，转速为10-5000rpm。
优选地，在所述步骤1中，混合30-500min。
优选地，在所述步骤1中，混合60～300min。
优选地，在所述步骤1中，升温至20～130℃。
优选地，在所述步骤1中，升温至50～80℃。
优选地，在所述步骤1中，转速为100-3000rpm。
优选地，在所述步骤1中，转速为200-2000rpm。
优选地，在所述步骤2中，双螺杆挤出机的一区至六区温度为80～240℃，双螺杆挤出机的机头温度为80～240℃，转速为30～600rpm。
优选地，在所述步骤2中，双螺杆挤出机的一区至六区温度为100～220℃。
优选地，在所述步骤2中，双螺杆挤出机的一区至六区温度为110～200℃。
优选地，在所述步骤2中，双螺杆挤出机的机头温度100～220℃。
优选地，在所述步骤2中，双螺杆挤出机的机头温度110～200℃。
优选地，在所述步骤2中，转速为60～450rpm。
优选地，在所述步骤2中，转速为120～300rpm。
优选地，在所述步骤3中，吹膜成型的条件为：温度为80～240℃。
本发明采用以上技术方案，与现有技术相比，具有如下技术效果：
本发明的一种可生物降解制品及其制备方法，将造纸废弃物、淀粉、无机矿物质与生物降解树脂进行复合，大幅度降低了可生物降解制品的成本；有效利用造纸废弃物，降低环境压力。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
下面结合具体实施例对本发明作进一步说明，但不作为本发明的限定。
实施例1
本实施例的一种可生物降解制品，由以下重量份数的原料组成：
聚己二酸/对苯二甲酸丁二酯(poly(butyleneadipate-co-terephthalate)，PBAT)60份、聚乳酸(polylactic acid，PLA)10份、造纸废弃物15份、玉米淀粉12份、碳酸钙3份、过氧化二异丙苯(dicumyl peroxide，DCP)1份、环氧大豆油6份、硬脂酸钙1份。
本实施例的可生物降解制品的制备方法如下：
步骤1、将造纸废弃物干燥、粉碎、过筛，得到500～2000目的造纸废弃物；
将60份PBAT、10份PLA、15份造纸废弃物、12份玉米淀粉、3份碳酸钙、 1份DCP、6份环氧大豆油和1份硬脂酸钙比例加入高速共混机中，在温度为100℃、转速500rpm的条件下，混合100min，得到初混物；
步骤2、将初混物加入到双螺杆挤出机中挤出造粒，双螺杆挤出机的一区至六区的温度分别为180℃、185℃、190℃、195℃、195℃、195℃，双螺杆挤出机的机头温度为190℃，转速为300rpm，得到可生物降解制品母粒；
步骤3、将可生物降解制品母粒输送至吹膜机中，在温度为130℃的条件下吹膜成型，得到可生物降解制品。
其中，可生物降解制品可以是可生物降解膜或可生物降解袋。
实施例2
本实施例的一种可生物降解制品，由以下重量份数的原料组成：
聚己二酸/对苯二甲酸丁二酯(PBAT)60份、聚乳酸(PLA)10份、造纸废弃物15份、玉米淀粉15份、过氧化二异丙苯(DCP)1份、环氧大豆油6份、硬脂酸钙1份。
本实施例的可生物降解制品的制备方法如下：
步骤1、将造纸废弃物干燥、粉碎、过筛，得到50～5000目的造纸废弃物；
将60份PBAT、10份PLA、15份造纸废弃物、15份玉米淀粉、1份DCP、6份环氧大豆油和1份硬脂酸钙比例加入高速共混机中，在温度为120℃、转速600rpm的条件下，混合300min，得到初混物；
步骤2、将初混物加入到双螺杆挤出机中挤出造粒，双螺杆挤出机的一区至六区的温度分别为130℃，135℃，140℃，145℃，145℃，145℃，双螺杆挤出机的机头温度为150℃，转速为200rpm，得到可生物降解制品母粒；
步骤3、将可生物降解制品母粒输送至吹膜机中，在温度为140℃的条件下吹膜成型，得到可生物降解制品。
其中，可生物降解制品可以是可生物降解膜或可生物降解袋。
实施例3
本实施例的一种可生物降解制品，由以下重量份数的原料组成：
聚己二酸/对苯二甲酸丁二酯(PBAT)60份、聚乳酸(PLA)10份、造纸废弃物27份、滑石粉3份、过氧化二异丙苯(DCP)1份、甘油6份、硬脂酸钙1份。
本实施例的可生物降解制品的制备方法如下：
步骤1、将造纸废弃物干燥、粉碎、过筛，得到50～5000目的造纸废弃物；
将60份PBAT、10份PLA、27份造纸废弃物、3份滑石粉、1份DCP、6份甘油和1份硬脂酸钙比例加入高速共混机中，在温度为50℃、转速200rpm的条件下，混合30min，得到初混物；
步骤2、将初混物加入到双螺杆挤出机中挤出造粒，双螺杆挤出机的一区至六区的温度分别为160℃，165℃，170℃，175℃，175℃，175℃，双螺杆挤出机的机头温度为170℃，转速为150rpm，得到可生物降解制品母粒；
步骤3、将可生物降解制品母粒输送至吹膜机中，在温度为135℃的条件下吹膜成型，得到可生物降解制品。
其中，可生物降解制品可以是可生物降解膜或可生物降解袋。
实施例4
本实施例的一种可生物降解制品，由以下重量份数的原料组成：
聚己二酸/对苯二甲酸丁二酯(PBAT)70份、造纸废弃物15份、木薯淀粉12份、碳酸钙3份、过氧化苯甲酰(benzoyl peroxide，BPO)1份、柠檬酸三丁酯(Tributyl Citrate，TBC)6份、硬脂酸钙1份。
本实施例的可生物降解制品的制备方法如下：
步骤1、将造纸废弃物干燥、粉碎、过筛，得到200～300目的造纸废弃物；
将70份PBAT、15份造纸废弃物、12份木薯淀粉、3份碳酸钙、1份BPO、6份TBC和1份硬脂酸钙比例加入高速共混机中，在温度为30℃、转速150rpm的条件下，混合1000min，得到初混物；
步骤2、将初混物加入到双螺杆挤出机中挤出造粒，双螺杆挤出机的一区至六区的温度分别为150℃，155℃，160℃，165℃，165℃，165℃，双螺杆挤出机的机头温度为160℃，转速为250rpm，得到可生物降解制品母粒；
步骤3、将可生物降解制品母粒输送至吹膜机中，在温度为140℃的条件下吹膜成型，得到可生物降解制品。
其中，可生物降解制品可以是可生物降解膜或可生物降解袋。
实施例5
本实施例的一种可生物降解制品，由以下重量份数的原料组成：
聚己二酸/对苯二甲酸丁二酯(PBAT)65份、聚甲基乙撑碳酸酯(poly propylene carbonate，PPC)5份、造纸废弃物20份、玉米淀粉8份、高岭土2份、过氧化苯甲酰(BPO)1份、环氧大豆油8份、硬脂酸钙1份。
本实施例的可生物降解制品的制备方法如下：
步骤1、将造纸废弃物干燥、粉碎、过筛，得到50～5000目的造纸废弃物；
将65份PBAT、5份PPC、20份造纸废弃物、8份玉米淀粉、2份高岭土、1份BPO、8份环氧大豆油和1份硬脂酸钙比例加入高速共混机中，在温度为40℃、转速400rpm的条件下，混合300min，得到初混物；
步骤2、将初混物加入到双螺杆挤出机中挤出造粒，双螺杆挤出机的一区至六区的温度分别为140℃，145℃，150℃，155℃，155℃，155℃，双螺杆挤出机的机头温度为150℃，转速为200rpm，得到可生物降解制品母粒；
步骤3、将可生物降解制品母粒输送至吹膜机中，在温度为145℃的条件下吹膜成型，得到可生物降解制品。
其中，可生物降解制品可以是可生物降解膜或可生物降解袋。
实施例6
本实施例的一种可生物降解制品，由以下重量份数的原料组成：
聚丁二酸丁二醇酯(poly(butylene succinate)，PBS)55份、聚乳酸(PLA)15份、造纸废弃物10份、马铃薯淀粉18份、硅藻土3份、过氧化二异丙苯(DCP)1份、甘油5份、硬脂酸钙1份。
本实施例的可生物降解制品的制备方法如下：
步骤1、将造纸废弃物干燥、粉碎、过筛，得到500～2000目的造纸废弃物；
将55份PBS、15份PLA、10份造纸废弃物、18份马铃薯淀粉、3份硅藻土、1份DCP、5份甘油和1份硬脂酸钙比例加入高速共混机中，在温度为60℃、转速300rpm的条件下，混合200min，得到初混物；
步骤2、将初混物加入到双螺杆挤出机中挤出造粒，双螺杆挤出机的一区至六区的温度分别为180℃、185℃、190℃、195℃、195℃、195℃，双螺杆挤出机的机头温度为190℃，转速为300rpm，得到可生物降解制品母粒；
步骤3、将可生物降解制品母粒输送至吹膜机中，在温度为130℃的条件下吹膜成型，得到可生物降解制品。
其中，可生物降解制品可以是可生物降解膜或可生物降解袋。
对比例1
本对比例为常规可生物降解制品，由以下重量份数的原料组成：
聚己二酸/对苯二甲酸丁二酯(PBAT)70份、聚乳酸(polylactic acid，PLA)15份、玉米淀粉15份、过氧化二异丙苯(DCP)1份、环氧大豆油6份、硬脂酸钙1份。
本实施例的常规可生物降解制品的制备方法如下：
步骤1、将70份PBAT、15份PLA、15份玉米淀粉、1份DCP、6份环氧大豆油和1份硬脂酸钙比例加入高速共混机中，在温度为60℃、转速200rpm的条件下，混合100min，得到初混物；
步骤2、将初混物加入到双螺杆挤出机中挤出造粒，双螺杆挤出机的一区至六区的温度分别为180℃、185℃、190℃、195℃、195℃、195℃，双螺杆挤出机的机头温度为190℃，转速为200rpm，得到常规可生物降解制品母粒；
步骤3、将常规可生物降解制品母粒输送至吹膜机中，在温度为140℃的条件下吹膜成型，得到常规可生物降解制品。
其中，常规可生物降解制品可以是常规可生物降解膜或常规可生物降解袋。
对比例2
本对比例为常规可生物降解制品，由以下重量份数的原料组成：
聚己二酸/对苯二甲酸丁二酯(PBAT)65份、聚丁二酸丁二醇酯(PBS)20份、木薯淀粉13份、碳酸钙13份、过氧化二异丙苯(DCP)1份、甘油6份、硬脂酸钙1份。
本实施例的常规可生物降解制品的制备方法如下：
步骤1、将65份PBAT、20份PBS、13份木薯淀粉、13份碳酸钙、1份DCP、6份甘油和1份硬脂酸钙比例加入高速共混机中，在温度为350℃、转速100rpm的条件下，混合70min，得到初混物；
步骤2、将初混物加入到双螺杆挤出机中挤出造粒，双螺杆挤出机的一区至六区的温度分别为150℃，155℃，160℃，165℃，165℃，165℃，双螺杆挤出机的机头温度为160℃，转速为130rpm，得到常规可生物降解制品母粒；
步骤3、将常规可生物降解制品母粒输送至吹膜机中，在温度为145℃的条 件下吹膜成型，得到常规可生物降解制品。
其中，常规可生物降解制品可以是常规可生物降解膜或常规可生物降解袋。
根据GB/T1040.2-2006《塑料拉伸性能的测定》对实施例1～6与对比例1～2进行检测，其性能如下表所示。
  拉伸强度(MPa) 断裂伸长率(％)
实施例1 22.3 255.6
实施例2 23.5 244.2
实施例3 21.9 271.3
实施例4 22.6 261.5
实施例5 23.1 234.3
实施例6 22.7 253.1
对比例1 21.4 258.7
对比例2 20.3 243.1
由上表可知，引入造纸废弃物后，对可生物降解制品的各项力学性能影响不大，能够满足正常使用要求。
以上所述仅为本发明较佳的实施例，并非因此限制本发明的实施方式及保护范围，对于本领域技术人员而言，应当能够意识到凡运用本发明说明书内容所作出的等同替换和显而易见的变化所得到的方案，均应当包含在本发明的保护范围内。

Claims (11)

  1. 一种可生物降解制品，其特征在于，其组成成分按重量份数如下：
    生物降解树脂40～90份
    造纸废弃物5～50份
    淀粉0～40份
    无机矿物质0～5份
    助剂2～15份。
  2. 根据权利要求1所述的可生物降解制品，其特征在于，所述生物降解树脂为聚丁二酸丁二醇酯、聚对苯二甲酸/己二酸丁二醇酯、聚乳酸、聚羟基脂肪酸酯、聚甲基乙撑碳酸酯中的一种或多种的混合物。
  3. 根据权利要求1所述的可生物降解制品，其特征在于，所述造纸废弃物为腐浆、浆渣、木皮、制浆废液提取物、含硅白泥的一种或多种的混合物，所述造纸废弃物的粒径为50～5000目。
  4. 根据权利要求1所述的可生物降解制品，其特征在于，所述淀粉为木薯淀粉、玉米淀粉、马铃薯淀粉、阳离子改性淀粉、阴离子改性淀粉中的一种或多种的混合物。
  5. 根据权利要求1所述的可生物降解制品，其特征在于，所述无机矿物质为碳酸钙、高岭土、滑石粉、硅藻土中的一种或多种的混合物。
  6. 根据权利要求1所述的可生物降解制品，其特征在于，所述助剂的组成成分按重量份数计如下：
    交联剂0.5～2份
    增塑剂剂1～10份
    润滑剂0.5～5份。
  7. 根据权利要求6所述的可生物降解制品，其特征在于，所述交联剂为过氧化二异丙苯、过氧化苯甲酰、2,5-二甲基-2,5二叔丁基过氧化己烷中的一种或多种的混合物；
    所述增塑剂为柠檬酸丁酯、乙酰柠檬酸三正丁酯、甘油、环氧大豆油中的一种或多种的混合物；
    所述润滑剂为硬脂酸钙。
  8. 一种可生物降解制品的制备方法，其特征在于，包括以下步骤：
    步骤1，将生物降解树脂、造纸废弃物、淀粉、无机矿物质、助剂按比例加入高速混合机中混合，得到初混物料；
    步骤2、将所述初混物料加入双螺杆挤出机中挤出造粒，得到可生物降解制品母粒；
    步骤3、将所述到可生物降解制品母粒吹膜成型，得到可生物降解制品。
  9. 根据权利要求8所述的可生物降解制品的制备方法，其特征在于，在所述步骤1中，将生物降解树脂、造纸废弃物、淀粉、无机矿物质、助剂按比例加入高速混合机中混合5min-1000min，升温至10～150℃，转速为10-5000rpm。
  10. 根据权利要求8所述的可生物降解制品的制备方法，其特征在于，在所述步骤2中，挤出造粒的条件为：温度为80～240℃，转速为30～600rpm。
  11. 根据权利要求8所述的可生物降解制品的制备方法，去特征在于，子啊所述步骤3中，吹膜成型的条件为：温度为80～240℃。
PCT/CN2019/100438 2019-07-12 2019-08-13 一种可生物降解制品及其制备方法 Ceased WO2020119158A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19896390.2A EP3998311A4 (en) 2019-07-12 2019-08-13 Biodegradable product and preparation method therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910631478.7 2019-07-12
CN201910631478.7A CN110396283A (zh) 2019-07-12 2019-07-12 一种可生物降解制品及其制备方法

Publications (1)

Publication Number Publication Date
WO2020119158A1 true WO2020119158A1 (zh) 2020-06-18

Family

ID=68325469

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/100438 Ceased WO2020119158A1 (zh) 2019-07-12 2019-08-13 一种可生物降解制品及其制备方法

Country Status (3)

Country Link
EP (1) EP3998311A4 (zh)
CN (1) CN110396283A (zh)
WO (1) WO2020119158A1 (zh)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113429751A (zh) * 2021-06-16 2021-09-24 山西兰花华明纳米材料股份有限公司 一种生物降解功能粒料及其制备方法
CN114085497A (zh) * 2021-10-29 2022-02-25 苏州星火丰盈环保包装有限公司 一种生物基全降解薄膜及其制备方法
CN114163770A (zh) * 2021-12-24 2022-03-11 河源新昊塑胶制品有限公司 一种耐水易降解塑料玩具制备方法
CN114276585A (zh) * 2022-02-14 2022-04-05 天津农学院 一种可降解塑料及其制备方法
CN115160740A (zh) * 2022-06-10 2022-10-11 上海昶法新材料有限公司 一种生物基全降解可控农用膜及其制备方法
CN115725143A (zh) * 2022-12-20 2023-03-03 福州大学 一种可降解高强度耐磨pvc发泡材料及其制备方法
CN115958865A (zh) * 2023-01-03 2023-04-14 上海昶法新材料有限公司 一种水稻专用全生物降解双层地膜及其制备方法
CN116285260A (zh) * 2023-02-08 2023-06-23 珠海格莱利摩擦材料股份有限公司 一种可生物降解的摩擦粒子母粒、摩擦材料及其制备方法和应用
CN117070053A (zh) * 2022-05-09 2023-11-17 山东羽时生物科技有限公司 一种提高干淀粉制备生物降解塑料母料过程中分散性的方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111109220A (zh) * 2019-12-25 2020-05-08 上海昶法新材料有限公司 一种生物基诱虫板及其制备方法
CN111087775A (zh) * 2019-12-25 2020-05-01 上海昶法新材料有限公司 一种可生物降解复合材料、制备方法及可生物降解集装箱底板
CN111100368A (zh) * 2019-12-25 2020-05-05 上海昶法新材料有限公司 一种造纸废弃物改性塑料膜快递袋及其制备方法
CN111117177A (zh) * 2019-12-27 2020-05-08 上海昶法新材料有限公司 一种可生物降解小便池香盒漏斗及其制备方法
CN111073228A (zh) * 2019-12-27 2020-04-28 上海昶法新材料有限公司 一种可生物降解的垃圾袋及其制备方法
CN111234037A (zh) * 2020-02-12 2020-06-05 上海昶法新材料有限公司 生物降解母粒、型材、原料及其制备方法
CN111234477A (zh) * 2020-02-12 2020-06-05 上海昶法新材料有限公司 一种原料组合物在制备生物降解诱虫板中的应用
EP4133005A4 (en) * 2020-04-09 2024-04-24 Arkema, Inc. ORGANIC PEROXIDE FORMULATIONS FOR THE MODIFICATION OF BIOSOURCED AND BIODEGRADABLE POLYMERS
CN111909426A (zh) * 2020-08-13 2020-11-10 寿光金远东变性淀粉有限公司 一种全生物降解塑料垃圾袋材料的制备方法
CN115401977B (zh) * 2022-09-16 2023-10-13 厦门艾美森新材料科技股份有限公司 一种可降解纸打包带及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993558A (zh) * 2009-08-09 2011-03-30 陈天云 用淀粉纤维废塑料生产薄膜
CN106317941A (zh) 2016-08-15 2017-01-11 安徽明诚塑业有限公司 一种抗菌抗撕裂的可降解垃圾袋及其制备方法
CN109694557A (zh) * 2018-12-20 2019-04-30 上海昶法新材料有限公司 一种用于垃圾填埋场的可降解覆盖膜及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6758996B2 (en) * 2001-07-13 2004-07-06 Kadant Composites Inc. Cellulose-reinforced thermoplastic composite and methods of making same
CN101768300A (zh) * 2008-12-30 2010-07-07 沈阳市新北塑编包装材料工程技术研究中心 一种可降解塑编材料及其制备方法
CN108456407A (zh) * 2018-02-08 2018-08-28 合肥达户电线电缆科技有限公司 一种可降解包装材料及其制备方法
CN109694556A (zh) * 2018-12-20 2019-04-30 上海昶法新材料有限公司 一种除草可生物降解农膜用母粒及其制备方法
CN113524829A (zh) * 2021-03-29 2021-10-22 上海昶法新材料有限公司 一种全降解除草地膜及其制备方法
CN113265134A (zh) * 2021-06-23 2021-08-17 吉林省中亿医药包装有限公司 一种与垒土基质相融的生物降解聚酯材料的制备装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993558A (zh) * 2009-08-09 2011-03-30 陈天云 用淀粉纤维废塑料生产薄膜
CN106317941A (zh) 2016-08-15 2017-01-11 安徽明诚塑业有限公司 一种抗菌抗撕裂的可降解垃圾袋及其制备方法
CN109694557A (zh) * 2018-12-20 2019-04-30 上海昶法新材料有限公司 一种用于垃圾填埋场的可降解覆盖膜及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3998311A4

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113429751A (zh) * 2021-06-16 2021-09-24 山西兰花华明纳米材料股份有限公司 一种生物降解功能粒料及其制备方法
CN114085497A (zh) * 2021-10-29 2022-02-25 苏州星火丰盈环保包装有限公司 一种生物基全降解薄膜及其制备方法
CN114163770A (zh) * 2021-12-24 2022-03-11 河源新昊塑胶制品有限公司 一种耐水易降解塑料玩具制备方法
CN114276585A (zh) * 2022-02-14 2022-04-05 天津农学院 一种可降解塑料及其制备方法
CN117070053A (zh) * 2022-05-09 2023-11-17 山东羽时生物科技有限公司 一种提高干淀粉制备生物降解塑料母料过程中分散性的方法
CN115160740A (zh) * 2022-06-10 2022-10-11 上海昶法新材料有限公司 一种生物基全降解可控农用膜及其制备方法
CN115725143A (zh) * 2022-12-20 2023-03-03 福州大学 一种可降解高强度耐磨pvc发泡材料及其制备方法
CN115725143B (zh) * 2022-12-20 2023-09-29 福州大学 一种可降解高强度耐磨pvc发泡材料及其制备方法
CN115958865A (zh) * 2023-01-03 2023-04-14 上海昶法新材料有限公司 一种水稻专用全生物降解双层地膜及其制备方法
CN116285260A (zh) * 2023-02-08 2023-06-23 珠海格莱利摩擦材料股份有限公司 一种可生物降解的摩擦粒子母粒、摩擦材料及其制备方法和应用

Also Published As

Publication number Publication date
EP3998311A1 (en) 2022-05-18
CN110396283A (zh) 2019-11-01
EP3998311A4 (en) 2023-07-19

Similar Documents

Publication Publication Date Title
WO2020119158A1 (zh) 一种可生物降解制品及其制备方法
CN111154243B (zh) 一种生物基可堆肥降解耐热型薄膜复合材料及其制备方法
CN103435981A (zh) 一种全生物降解薄膜的制备方法
KR102305683B1 (ko) 발효 왕겨를 포함하고 있는 인조잔디용 충진재
CN111621239B (zh) 一种全生物降解胶带及其制备方法
CN109762307A (zh) 一种可生物降解垃圾袋专用抗菌母粒及其制备方法
CN103044716A (zh) 生物降解材料及其制备方法
CN106893273A (zh) 一种用作购物袋的碳酸钙高填充生物降解塑料薄膜材料及其制备方法
WO2022142240A1 (zh) 生物降解材料、其原料组合物及其制备方法和应用
CN104693710A (zh) 一种可生物降解石头纸及其制备方法
CN111087775A (zh) 一种可生物降解复合材料、制备方法及可生物降解集装箱底板
CN111073228A (zh) 一种可生物降解的垃圾袋及其制备方法
CN111100368A (zh) 一种造纸废弃物改性塑料膜快递袋及其制备方法
CN113583405A (zh) 一种高性能全降解复合材料及其制备方法
CN113248875A (zh) 一种全降解购物袋膜及其制备方法
CN116478512A (zh) 生物降解生物质热塑共混复合材料、制品及其制备方法
CN113337088B (zh) 注塑用复合降解塑料材料的制备方法
CN119119693A (zh) 一种可生物降解纸塑复合材料及其制备方法
CN101376726B (zh) 具有自润滑作用的可生物降解塑料电子钟壳及其制备方法
CN111087673A (zh) 一种改性塑料膜快递袋及其制备方法
CN113429636B (zh) 一种全生物降解型秸秆增强淀粉材料及其制备方法
KR102732765B1 (ko) 재생 생분해성 수지 조성물, 이의 제조방법 및 이의 용도
CN110894344A (zh) 一种造纸废弃物改性的抗菌可降解垃圾袋及其制备方法
CN115160740A (zh) 一种生物基全降解可控农用膜及其制备方法
CN111234037A (zh) 生物降解母粒、型材、原料及其制备方法

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: 19896390

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2019896390

Country of ref document: EP

Effective date: 20220214