CN113956634B - Toughened biodegradable composition and application thereof - Google Patents

Toughened biodegradable composition and application thereof Download PDF

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Publication number
CN113956634B
CN113956634B CN202011405625.8A CN202011405625A CN113956634B CN 113956634 B CN113956634 B CN 113956634B CN 202011405625 A CN202011405625 A CN 202011405625A CN 113956634 B CN113956634 B CN 113956634B
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polyester resin
starch
polylactic acid
aliphatic
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CN113956634A (en
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陈伟聪
黄成明
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Dongguan Jinfuliang Plastic And Rubber Technology Co ltd
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Dongguan Jinfuliang Plastic And Rubber Technology Co ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention relates to the field of biodegradable polyester, in particular to a toughened biodegradable composition and application thereof. A toughened biodegradable composition comprises degradable polyester resin, starch, functional additive, filler and auxiliary agent; wherein the degradable polyester resin comprises (a) polylactic acid and (b) aliphatic/aromatic mixed polyester resin, and the content of the degradable polyester resin in the composition is 50-90% by taking the total weight of the composition as a reference. The toughened biodegradable composition provided by the invention has the advantages that the prepared tensile sample strip can still have excellent tensile property and bending property after being stored for a long time, and the composite material still has good toughness after high-content starch is added.

Description

Toughened biodegradable composition and application thereof
Technical Field
The invention relates to the field of biodegradable polyester, in particular to a toughened biodegradable composition and application thereof.
Background
Polylactic acid (PLA) is a novel bio-based and renewable biodegradable material, is derived from starch of green plants (corn and cassava), glucose is obtained by saccharification of raw materials, high-purity monomer lactic acid is prepared by fermentation of the glucose and certain strains, and polylactic acid with certain molecular weight is synthesized by a polymerization or condensation method. It has good biodegradability, and can be effectively decomposed in land landfill, industrial compost or in sea. Finally, carbon dioxide and water are generated, white pollution is not caused, and the method is very favorable for protecting the environment. PLA is high in price, three times of the traditional PE, is in a stock shortage state all the time, and is difficult to popularize in a large area. PLA material has high strength, but also has large brittleness, poor heat resistance, low melt strength and narrow processing temperature window, limits the application range to a certain extent and needs to be used after modification.
PBAT is a copolymer of butanediol adipate and butanediol terephthalate, has the characteristics of PBA and PBT, and has better ductility and elongation at break as well as better heat resistance and impact property; in addition, the biodegradable plastic has excellent biodegradability, and is one of the best degradable materials which are very active in the research of the current biodegradable plastics and are applied in the market.
Due to the characteristics of hydrophilicity and strong polarity of starch, the starch has poor compatibility with polymer matrixes such as rubber, polyester and the like, the dispersion of starch nanocrystals is influenced, and the reinforcing effect is weakened. In addition, starch-based biodegradable plastics often incorporate excessive amounts of polyols to improve their dispersibility, which can easily allow the PLA matrix to degrade or migrate to the surface of the composite, resulting in a significant degradation of the mechanical properties of the composite after storage over time.
Disclosure of Invention
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided herein, the definition of the term provided herein controls.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention. The sources of the components not mentioned in the present invention are all commercially available.
After earnest study to solve the above problems, the inventors of the present invention found that the strength and toughness of the composition can be improved and the composting effect can be very beneficial by introducing a functional additive into a specific degradable polyester resin to achieve a certain degree of crosslinking.
The invention provides a toughening biodegradable composition, which comprises degradable polyester resin, starch, functional additives, fillers and auxiliaries; wherein the degradable polyester resin comprises (a) polylactic acid and (b) aliphatic/aromatic mixed polyester resin, and the content of the degradable polyester resin in the composition is 30-80%, preferably 40-70% by taking the total weight of the composition as a reference.
< degradable polyester resin >
The degradable polyester resin preferably comprises (a) polylactic acid and (b) an aliphatic/aromatic hybrid polyester resin in a mass ratio of (a) =1 to 5, preferably 1.
The polylactic acid (a) may be a single resin or a combination of two or more resins, and may be a homopolymer of L-lactic acid or a homopolymer of D-lactic acid, or a copolymer of L-lactic acid and D-lactic acid. Suitable copolymers of L-lactic acid and D-lactic acid may be, for example, copolymers composed of 20 to 100mol% of L-lactic acid units or D-lactic acid units and 0 to 80mol% of the corresponding enantiomer (optical isomer) units.
Further, the polylactic acid (a) may be a stereocomplex polylactic acid, for example, a mixture of polylactic acid (a) and polylactic acid (B) wherein (a)/(B) (mass ratio) is 10/90 to 90/10, polylactic acid (a) is composed of 90 to 100mol% l-lactic acid units and 0 to 10mol% d-lactic acid units, and polylactic acid (B) is composed of 90 to 100mol% d-lactic acid units and 0 to 10mol% l-lactic acid units. The copolymerization components other than lactic acid in the polylactic acids (a) and (B) constituting the stereocomplex polylactic acid include dicarboxylic acids, polyols, hydroxycarboxylic acids, lactones, and the like having two or more functional groups each capable of forming an ester bond.
As a result of the examination of the polylactic acid (a), the polylactic acid (a) preferably has a weight average molecular weight of more than 50000, and may be a single molecular weight or a mixture of different molecular weights. More preferably, polylactic acid is a biaxially oriented polymer having a weight average molecular weight of greater than 50000, such polylactic acids include NatureWorks6201D, 6202D, 6251D, 3051D, which may be used alone or in combination; among these, 4044D and/or 4043D are particularly preferred, and 4043D is most preferred. 4043D is the density at 1.24g/cm 3 A biaxially oriented polymer having a melt mass flow rate (210 degrees, 2.16 kg) of 6.0g/10 min.
The polymer is generally oriented in both uniaxial and biaxial directions. The uniaxial orientation means that an external force is applied in one axial direction to orient the molecular chain in one direction; correspondingly, biaxial orientation refers to any direction in which the molecular chains are oriented parallel to the plane of the film by applying external forces in two perpendicular directions. The crystallinity of the oriented molecules is improved, for example, the crystallinity of the biaxially oriented polylactic acid is higher than that of the uniaxially oriented polylactic acid, so that the strength of the biaxially oriented polylactic acid is higher in each direction, but the elongation at break is reduced.
In consideration of the difficulty in balancing the elongation at break of the biaxially oriented polylactic acid with the tensile strength thereof in the study, it has been unexpectedly found that an aliphatic/aromatic mixed polyester resin obtained by the mutual synergy with (b) an aliphatic/aromatic mixed polyester resin, particularly preferably an aliphatic diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid as main raw materials, can secure a certain composting effect while maintaining the mechanical properties.
The aliphatic diol herein is preferably an aliphatic diol having 3 to 10 carbon atoms, and particularly preferably an aliphatic diol having 4 to 6 carbon atoms. Specifically, 1, 3-propanediol, 1, 4-butanediol, 1, 4-cyclohexanedimethanol and the like are included, and 1, 4-butanediol is particularly preferable.
The dicarboxylic acid in the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid is preferably a dicarboxylic acid having 3 to 10 carbon atoms. Specifically, succinic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, and the like are included, and among them, succinic acid, adipic acid, and terephthalic acid are particularly preferable, and adipic acid and terephthalic acid are most preferable.
Through the research on the aliphatic/aromatic mixed polyester resin (b), the aliphatic/aromatic mixed polyester resin (b) is a copolymer of butanediol adipate and butanediol terephthalate, and is thermoplastic biodegradable flexible plastic.
In the study of the aliphatic/aromatic mixed polyester resin, the density is preferably 1.25 to 1.35g/cm 3 Aliphatic/aromatic hybrid polyester resins having a melt mass flow rate (210 degrees, 2.16 kg) of 2.0 to 5.0g/10min, including as such resins the THJS series of Xinjiang blue mountain tun river, e.g. THJS-6802、THJS-7801、THJS-8801、THJS-5801、THJS-6801。
The THJS series has proper aliphatic chain and aromatic structure, and the aliphatic chain has structure similar to that of polylactic acid, so that it is added into polylactic acid to promote the migration of polylactic acid chain, to play certain nucleation role and to raise the orientation. During degradation, the THJS series aliphatic/aromatic mixed polyester resin is more difficult to degrade by water molecules due to steric hindrance than ester groups in polylactic acid, so that the degradation is from oriented degradation to non-oriented degradation, the integral degradation rate is balanced, no adverse effect is generated in the whole compost, and the THJS series aliphatic/aromatic mixed polyester resin has a very good composting effect on crops.
< starch >
The starch of the present invention includes all types of starch, such as corn starch, tapioca starch, potato starch, wheat starch, rice starch, sorghum starch, and the like. Modified starches are also included, modified starches being for example non-ionic and/or anionic and/or cationic modified, esterified and/or etherified and/or crosslinked. Preferably degraded native starch or modified starch.
Examples of suitable degraded native starches include upper stem unmodified starches such as corn starch, high amylose starch, wheat starch, rice starch and the like.
Examples of the modified starch include a hydrophobic biodegradable starch ester product obtained by mixing an anhydrous starch having an amylose content of 50% or more with an esterifying agent in an aprotic solvent to allow a reaction between the starch and the esterifying agent; the starch ester modified by adopting vinyl ester as an esterification reagent is prepared by adopting vinyl ester with ester group having 2-18 carbon atoms and reacting the vinyl ester with starch in a non-aqueous organic solvent by using an esterification catalyst; starch grafted with polyvinyl ester while esterifying; the polyester graft polymerization starch alloy is prepared by uniformly mixing polyester graft polymerization starch with a polyester graft chain on a starch molecule, wherein the tail end of the graft chain and part or all of hydroxyl directly connected to the starch are sealed by ester groups, and single polyester with the same composition of the polyester graft chain and part or all of the tail hydroxyl is sealed by ester groups.
The above-mentioned preferred natural starch or modified starch may be used alone or in admixture of plural kinds thereof as long as the selected starches are compatible with each other. Specifically, the starch preferably includes at least one of corn starch, potato starch, wheat starch, starch acetate, hydroxymethyl starch, and hydroxyethyl starch, and most preferably corn starch, wherein the degradable polyester resin is contained in the composition in an amount of 30 to 80%, preferably 40 to 70%, based on the total weight of the composition.
< functional additive >
As the functional additive, epoxy substances containing at least 1 epoxy group are preferred, and by introducing the epoxy group to react with the terminal group of the above preferred polylactic acid, for example, a hydroxyl group or a carboxyl group in the polylactic acid, the linear chain or the branched chain can be extended, thereby improving the dispersibility of the inorganic filler and the mechanical properties of the composition.
Preferably, the epoxy-based material having at least 1 epoxy group is at least one selected from the group consisting of an alkylene oxide, a glycidyl ester and an epoxy-based acrylic copolymer.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 4-dioxane, a diepoxy long-chain alkane compound, and alkylene oxides in which the above-mentioned compounds are substituted with an arbitrary halogen, and examples of the diepoxy long-chain alkane compound include 1, 7-octadiene diepoxy compounds.
Examples of the glycidyl ester include glycidyl neodecanoate, triglycidyl isocyanurate, glycidyl versatate, and diglycidyl hexahydrophthalate, and among them, preferred are glycidyl versatate, and examples thereof include glycidyl pivalate, glycidyl neoheptanoate, glycidyl neononanoate, glycidyl neodecanoate, glycidyl neoundecanoate, and glycidyl neotridecanoate.
The epoxy acrylic copolymer is generally a resin obtained by using a polymerizable vinyl monomer as a reactive diluent in an epoxy acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid. Examples of such epoxy acrylic copolymers include: diglycidyl ether type epoxy resins having a main skeleton of a bisphenol compound represented by bisphenol a, bisphenol F, and brominated bisphenol a; polyglycidyl ether type epoxy resins having as a skeleton a polynuclear phenol compound represented by phenol, cresol novolac, or brominated phenol novolac; polyglycidyl ester type epoxy resins having as a main skeleton organic polybasic acids typified by dimer acid and trimellitic acid; and glycidyl ether type epoxy resins having bisphenol a ethylene oxide, propylene oxide-added ethylene glycol, and a hydrogenated bisphenol a compound as a skeleton. Specifically, epoxy resins TDE-85, E-20, E-44 and E-51 are more preferred, and trifunctional epoxy resins TDE-85 containing both an alicyclic epoxy group and a glycidyl ester group are most preferred.
The functional additives suitable for the present invention preferably include the above-mentioned glycidyl ester and epoxy-based acrylic copolymer; the glycidyl ester as one of the functional additives can be used alone or in combination of two or more, and the epoxy acrylic copolymer as one of the functional additives can be used alone or in combination of two or more, and the total content of the functional additives is preferably 1 to 10wt%, preferably 2 to 8wt%, more preferably 4 to 6wt%, based on the total weight of the composition.
Through the research on the functional additive, the functional additive is further preferably selected from (c) tertiary carboxylic acid glycidyl ester and (d) at least one selected from epoxy resin TDE-85, E-20, E-44 and E-51; particularly preferred are functional additives comprising (c) glycidyl versatate and (d) epoxy resin TDE-85, both of which can be present in relatively wide ranges, preferably (c) =1 to 5, preferably 1 to 3, more preferably 1.
Among the functional additives of the epoxy substances, the epoxy resin TDE-85 has glycidyl ester groups and ester ring epoxy groups, and meanwhile, the two epoxy groups in molecules have different reaction activation energies, the glycidyl ester groups with low activation energies and the glycidyl ester of the tertiary carboxylic acid react with carboxyl and hydroxyl on the polylactic acid and the polyester quickly, the generated hydroxyl is further reacted by the glycidyl ester and then is crosslinked and aggregated in the resin, and the ester ring epoxy groups with higher activation energies are connected with the crosslinked aggregates in the reaction to form a uniformly dispersed core crosslinked structure so as to improve the mechanical property.
The glycidyl ester of the tertiary carboxylic acid has a highly branched long chain structure with large hydrophobicity, and the research finds that the glycidyl ester can be introduced into resin together with epoxy resin, so that the problem of matrix compatibility is solved. Furthermore, the viscosity of the resin matrix can be reduced due to the multi-branched structure of the tertiary carboxylic acid, and the wettability of the inorganic filler is improved, so that the inorganic filler is better dispersed. In particular, the large number of hydroxyl functional groups formed when the reaction is complete can promote crosslinking.
In addition, due to the addition of the starch, the functional additive of the epoxy substance reacts with the terminal hydroxyl and the terminal carboxyl of the (a) polylactic acid and the (b) aliphatic/aromatic mixed polyester resin and the hydroxyl of the starch to generate a ternary block copolymer irregularly crosslinked with the three, and the irregular block copolymer can greatly improve the interface compatibility and improve the comprehensive performance of the composition.
< Filler >
The filler is preferably an inorganic filler, and is filled to improve heat resistance and rigidity. Inorganic fillers include, but are not limited to, talc, calcium carbonate, calcium sulfate, magnesium oxide, calcium stearate, wollastonite, mica, silica, calcium silicate, clay, and carbon black. Among these inorganic fillers, wollastonite and talc are preferable. Talc powder with an average particle size of 0.5 to 10 μm, preferably 5 to 10 μm, is most preferred. Wherein, the content of the filler is 2 to 30 percent, preferably 5 to 20 percent, based on the total weight of the composition; if the content is outside this range, it is difficult to improve heat resistance and rigidity.
< auxiliary agent >
In the research, because the hydrophilicity of the starch and the (b) aliphatic/aromatic mixed polyester resin have poor compatibility, the performance of the finished product is influenced, and the processing performance and the stability of the later-period product can be effectively improved by adding a proper amount of additives in the system.
Auxiliaries include, but are not limited to, coupling agents, lubricants, flame retardants, antioxidants, ultraviolet absorbers, and the like. Preferred adjuvants include coupling agents and lubricants.
Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a borate coupling agent, and it is considered that the silane coupling agent is preferably used. Examples of such silane coupling agents include gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (. Beta. -aminoethyl) -gamma-aminopropylmethyldimethoxysilane, and among these, gamma-aminopropyltriethoxysilane is most preferable, and alpha-D-glucose contained in starch can be reacted with siloxane in gamma-aminopropyltriethoxysilane to crosslink and improve the compatibility of starch in the system, and in the presence of a functional additive, a hydroxyl functional group formed after chemical crosslinking can be further reacted with a silane coupling agent to improve the water-blocking effect of the composition.
In general, when the above-mentioned coupling agent is used, the content of the lubricant is 0.5 to 7%, preferably 1 to 5%, based on the total weight of the composition.
Examples of the lubricant include metal salts of aliphatic carboxylic acids, aliphatic carboxylic acid esters, aliphatic carboxylic acids, hydrocarbon compounds, paraffins, ketone compounds, carboxamides, bisamide compounds, and the like, among which metal salts of aliphatic carboxylic acids, aliphatic carboxylic acid esters, hydrocarbon compounds, and ketone compounds are preferable, and metal salts of aliphatic carboxylic acids and aliphatic carboxylic acid esters are more preferable.
The metal salt of aliphatic carboxylic acid is preferably a metal salt of a higher fatty acid having 16 to 36 carbon atoms, and examples thereof include magnesium stearate, calcium stearate, barium stearate, calcium montanate, sodium montanate, zinc stearate, aluminum stearate, sodium stearate, and lithium stearate.
The aliphatic carboxylic acid ester is a compound formed from an aliphatic carboxylic acid and an alcohol, and examples thereof include beeswax, lanolin, stearic acid ester, behenic acid behenate, behenic acid stearate, glycerol monopalmitate, glycerol monostearate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.
In general, when the above-mentioned lubricant is used, the content of the lubricant is 1 to 10%, preferably 3 to 8%, based on the total weight of the composition.
As the flame retardant, for example, phosphorus-based flame retardants such as phosphoric acid esters, phosphonic acid esters and phosphorus compounds [ e.g., tricresyl phosphate, tris (2, 3-dibromopropyl) phosphate, dimethylmethanephosphonate, polyphosphates and ammonium polyphosphates ], and red phosphorus; halogen-containing flame retardants such as bromine-based flame retardants (organic bromine compounds such as decabromodiphenyl ether and tetrabromobisphenol a), and chlorine-based flame retardants (such as hexachloroendomethylenetetrahydrophthalic acid (HET acid)); metal (hydro) oxides such as antimony trioxide, magnesium hydroxide and aluminum hydroxide; and borate-type flame retardants such as zinc borate and barium metaborate. In general, when the above flame retardant is used, the content of the flame retardant is 1 to 10%, preferably 3 to 8%, based on the total weight of the composition.
As the antioxidant, for example, phenols (hindered phenols) such as 2, 6-di-t-butyl-p-cresol (BHT) and 2,2' -methylenebis (4-methyl-6-t-butylphenol); thios, such as dilauryl 3,3 '-thiodipropionate (DLTDP) and distearyl 3,3' -thiodipropionate (DSTDP); phosphorus species (organic phosphorus compounds optionally having halogen), such as triphenyl phosphide (TPP), triisodecyl phosphide (TDP), and halides thereof; and amines (hindered aromatic amines) such as octyldiphenylamine, N-butyl-p-aminophenol and N, N-diisopropyl-p-phenylenediamine. In general, when the above antioxidant is used, the content of the antioxidant is 1 to 10%, preferably 3 to 8%, based on the total weight of the composition.
As the ultraviolet absorber, for example, benzophenone type such as 2-hydroxybenzophenone and 2, 4-dihydroxybenzophenone; salicylates such as phenyl salicylate and 2, 4-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate; benzotriazoles such as (2 ' -hydroxyphenyl) benzotriazole and (2 ' -hydroxy-5 ' -tolyl) benzotriazole; and acrylic acids such as ethyl-2-cyano-3, 3' -diphenylacrylate and methyl-2-methoxycarbonyl-3- (p-methoxybenzyl) acrylate. In general, when the above ultraviolet absorber is used, the content of the ultraviolet absorber is 1 to 10%, preferably 3 to 8%, based on the total weight of the composition.
The second aspect of the present invention provides the use of the above composition in a color masterbatch, and in general, the composition of the present invention may be used alone to make a color masterbatch, or may be used to combine with other substances having certain functions to make a color masterbatch, for example, a color masterbatch with a specific function may be customized according to the needs of a customer in the actual supply process, where the other components added in the customization may be a toughening substance, a wear-resistant substance, a nutrient substance, and so on.
The preparation process of the coloring master batch can adopt a conventional preparation method, for example, the coloring master batch can be obtained by mixing the materials in proportion, putting the mixture into a double-screw extruder, extruding at 150-190 ℃ and granulating. The size of the master batch can be any size, and can also be adjusted according to actual requirements, and the invention does not limit the size at all. The average particle size of the master batch for obtaining the composting effect can be usually 0.1 to 3mm. The color master batch can be mixed with various plastic matrixes by the addition of 2-5% to obtain blown film pipes, lunch boxes, mulching films and the like.
Has the advantages that: the toughening biodegradable composition disclosed by the invention has the advantages that the prepared stretching sample strip still has excellent stretching performance and bending performance after being stored for a long time, and the composite material still has good toughness after being added with high-content starch, is very suitable for being used as a shopping bag material and a disposable composite material, can be applied to the fields of preparing biodegradable agricultural films, disposable tableware and the like, can be completely decomposed and quickly absorbed by microorganisms in soil after being used for many times, has little environmental pollution, and has good environmental benefits and wide application prospects.
Detailed Description
The present invention is described in detail below with reference to examples, which are provided for the purpose of further illustration only and are not to be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations thereof by those skilled in the art based on the teachings of the present invention will still fall within the scope of the present invention.
Example 1
The composition of toughened biodegradable composition (A1) is given in the following table:
TABLE 1
Name of raw materials Weight (unit: gram)
Polylactic acid (4043D) 34
Corn starch 18
Aliphatic/aromatic mixed polyester resin (THJS-6802) 22
Nonanoic acid glycidyl ester 3.5
Epoxy resin (TDE-85) 2.2
KH550 2.3
Talcum powder 13
Oleic acid amides 2.5
Ethylene bis stearamide 2.5
Example 2
The composition of toughened biodegradable composition (A2) is given in the following table:
TABLE 2
Name of raw materials Weight (unit: gram)
Polylactic acid (4043D) 34
Corn starch 18
Aliphatic/aromatic mixed polyester resin (THJS-6801) 22
Glycidyl pivalate 3.5
Epoxy resin (TDE-85) 2.2
KH550 2.3
Talcum powder 13
Oleic acid amides 2.5
Ethylene bis stearamide 2.5
Example 3
The composition of toughened biodegradable composition (A3) is given in the following table:
TABLE 3
Name of raw materials Weight (unit: gram)
Polylactic acid (4043D) 34
Corn starch 18
Aliphatic/aromatic hybrid polyester resin (THJS-8801) 22
Novel glycidyl heptanoate 3.5
Epoxy resin (TDE-85) 2.2
KH550 2.3
Talcum powder 13
Oleic acid amides 2.5
Ethylene bis stearamide 2.5
Example 4
The composition of toughened biodegradable composition (A4) is given in the following table:
TABLE 4
Name of raw materials Weight (unit: gram)
Polylactic acid (4043D) 34
Corn starch 38
Aliphatic/aromatic mixed polyester resin (THJS-6802) 22
Nonanoic acid glycidyl ester 3.5
Epoxy resin (TDE-85) 2.2
KH550 2.3
Talcum powder 13
Oleic acid amides 2.5
Ethylene bis stearamide 2.5
Example 5
The composition of toughened biodegradable composition (A5) is given in the following table:
TABLE 5
Figure BDA0002814035300000101
Figure BDA0002814035300000111
Example 6
The composition of toughened biodegradable composition (A6) is given in the following table:
TABLE 6
Name of raw materials Weight (unit: gram)
Polylactic acid (4043D) 34
Corn starch 18
Aliphatic/aromatic mixed polyester resin (THJS-6802) 22
Epoxy resin (TDE-85) 5.7
KH550 2.3
Talcum powder 13
Oleic acid amides 2.5
Ethylene bis stearamide 2.5
Example 7
The composition of toughened biodegradable composition (A7) is given in the following table:
TABLE 7
Figure BDA0002814035300000112
Figure BDA0002814035300000121
Example 8
The composition of toughened biodegradable composition (A8) is given in the following table:
TABLE 8
Name of raw materials Weight (unit: gram)
Polylactic acid (4043D) 34
Corn starch 18
Polybutylene terephthalate (Kingfa PBT UTPBT-HB) 22
Nonanoic acid glycidyl ester 3.5
Epoxy resin (TDE-85) 2.2
KH550 2.3
Talcum powder 13
Oleic acid amides 2.5
Ethylene bis stearamide 2.5
Performance testing
According to the formula, the blend is added into a double-screw extruder for extrusion granulation, and the temperature of each section of the extruder is set as (from a feed inlet to a die): 100-140-150-160-153 ℃; the rotating speed of the screw is 100rpm, and the rotating speed of the feeding is 10rpm; the extruded and granulated particles were dried at 80-100 ℃ and then injection molded, and the following tests were carried out after drying at room temperature for one month.
1. Elongation at break: testing according to GB 1040-2006; wherein x represents: more than 80 percent; and O represents: 70-80%, and less than 80%; and delta represents: 50-70% and less than 50%; x represents: less than 50%.
2. Tensile strength: testing according to GB 1040-2006; wherein x represents: over 40MPa; and O represents: between 30 and 40MPa, and less than 40MPa; Δ represents: 20-30 Mpa, and less than 30Mpa; x represents: less than 20MPa.
3. Bending property: testing according to GB/T5054.4; wherein x represents: more than 30 times; and O represents: 20 to 30 times, and less than 30 times; Δ represents: 10 to 20 times, and less than 20 times; x represents: less than 10 times.
TABLE 9
Examples Elongation at break Tensile strength Bendability Percent of pass
A1 ◎ ◎ ◎ Qualified
A2 ◎ ◎ ◎ Qualified
A3 ◎ ◎ ◎ Qualified
A4 △ × × Fail to be qualified
A5 ○ △ △ Fail to be qualified
A6 ◎ ○ △ Fail to be qualified
A7 ○ △ × Fail to be qualified
A8 ○ ○ ○ Fail to be qualified

Claims (5)

1. The toughened biodegradable composition is characterized by comprising degradable polyester resin, starch, a functional additive, a filler and an auxiliary agent; wherein the degradable polyester resin comprises (a) polylactic acid and (b) aliphatic/aromatic mixed polyester resin, and the content of the degradable polyester resin in the composition is 50-90% by taking the total weight of the composition as a reference;
the mass ratio of (a) polylactic acid to (b) aliphatic/aromatic hybrid polyester resin (a) = 1;
the aliphatic/aromatic mixed polyester resin is a copolymer of butanediol adipate and butanediol terephthalate;
the functional additive comprises glycidyl versatate and epoxy resin TDE-85;
the total content of the functional additive accounts for 1-10% of the total weight of the composition;
the auxiliary agent comprises at least one of a coupling agent, a lubricant, a flame retardant, an antioxidant and an ultraviolet absorbent;
the starch is 18% of the total weight of the composition.
2. The composition of claim 1, wherein the polylactic acid has a weight average molecular weight of greater than 50000.
3. The composition of claim 2, wherein the polylactic acid is a biaxially oriented polymer.
4. The composition according to any one of claims 1 to 3, characterized in that the filler has an average particle size of 0.5 to 10 μm.
5. Use of a composition according to any one of claims 1 to 4 in a pigmented masterbatch.
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