CN108559238B - Biodegradable polyhydroxycarboxylic acid alloy material and preparation method and application thereof - Google Patents
Biodegradable polyhydroxycarboxylic acid alloy material and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a biodegradable polyhydroxycarboxylic acid alloy material, which comprises, by mass, 50-75% of polylactic acid, 15-45% of polyhydroxycarboxylic acid except polylactic acid, 0.5-10% of a first copolymer and 0.1-1% of a second copolymer different from the first copolymer; the monomers of the first copolymer include a first monomer having a functional group reactive with an end group of polylactic acid and/or an end group of polyhydroxycarboxylic acid other than polylactic acid and a second monomer having a double bond; the second copolymer polymer is a copolymer of methyl acrylate and glycidyl methacrylate; preparation: weighing raw materials according to a formula, drying the weighed polyhydroxycarboxylic acid, mixing the dried polyhydroxycarboxylic acid with the rest raw materials, and extruding; and the application in producing cold drink cup covers; the invention realizes the effect of better mechanical property at lower temperature, and the like, and is biodegradable and quick in crystallization and forming.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a biodegradable polyhydroxycarboxylic acid alloy material and a preparation method and application thereof.
Background
Global supply of petroleum resources is becoming more and more intense, and under the condition that environmental problems caused by synthetic plastics using petroleum as a main raw material are becoming more and more prominent, the low-carbon industry is taken as another main way for protecting environmental climate and promoting economic development, the low-carbon industry is more and more emphasized by developed countries and main developing countries, and the low-carbon economy is becoming a world trend. Under the guidance of low-carbon economy, the development and application of biodegradable plastics have been promoted worldwide, and the development and application of biodegradable plastics must play an important role in treating environmental climate problems caused by waste plastics (white pollution) and promoting the development of social economy, for example, the traditional plastic cup cover has nondegradable property and is one of important sources of 'white pollution'.
The biodegradable high molecular material produced by biological resources through a biological industrial technology replaces the traditional high molecular material which takes petroleum as a raw material and is chemically synthesized, and the net emission of carbon dioxide which can reduce hundreds of millions of tons can be realized every year. At present, biodegradable plastics are one of hot spots of new materials in the world, and have huge growth potential, according to Research reports issued by Occams Research, the yield of bio-based chemicals and high polymer materials in the world is about 5000 ten thousand tons at present, and the yield value can reach 100-150 hundred million dollars in 2021 year. Determinants for promoting the development of the biodegradable plastic industry are being formed, such as national policy support, vigorous customer demand (for example, the demand of cup covers is reported by Freedonia group of Cleveland market research company, the cup cover demand rises by 4.7% of annual growth rate, and the current market value is estimated to reach billions of dollars), the oil price is rising continuously, and the like, particularly, the rise of low-carbon economy brings a wider market for the development of the biodegradable plastic and provides a better development blueprint.
The developed countries and parts of developing countries have successive legislation to support the use of biodegradable plastics in human life and production, such as the U.S. plan for preferred procurement of bio-based products, the japanese plan for bio-based materials 2020, the australian plan for sustainable packaging, etc. It is expected that with the development of legislation in various countries, biodegradable plastics will be popularized in the field of novel packaging materials first.
Biodegradable materials can be divided into fully biodegradable materials and destructively biodegradable materials. In a strict sense, a destructive biodegradable material does not belong to the category of biodegradable plastics, such as polyolefin/starch composites, wood-plastic composites, non-degradable plastic/degradable plastic composites, and the like. In the case of composite materials using starch and wood chips as raw materials, although the starch, wood chips and the like are derived from renewable natural resources, when the starch, wood chips and the like are degraded, polyolefin remaining in soil is even more difficult to treat than residues of pure plastic products and cannot be recycled, incineration is the best mode for treating destructive biodegradable plastics, and post-treatment of full biodegradable plastics does not have the problem of destructive biodegradable plastics.
The primary raw material source of the full-biodegradable plastic has two ways: natural resources and oil/gas. Wherein, the polyhydroxy carboxylic acid (polyhydroxyalkanoate, PHA) is a polymer material which exists as a carbon source of some microorganisms in nature, is a polyester polymer material which is synthesized by taking corn starch as a raw material, can be used as the carbon source of the microorganisms in severe environment, can be finally degraded into water and carbon dioxide in natural environment by the enzyme action generated by the microorganisms, simultaneously, the consumption amount of the carbon dioxide is larger than the discharge amount in the whole PHA synthesis, application and degradation period, and the PHA is a polymer material which has excellent performance and is environment-friendly, such as a degradable polymer material derived from renewable resources, has higher use temperature than other types of biodegradable plastics, has good biocompatibility and gas barrier property, thereby having wide market prospect, but PHA has low crystallization speed, The disadvantages of serious post-crystallization, large brittleness of the product, poor processing rheological property, low thermal decomposition temperature, difficult processing, serious performance reduction in a lower temperature environment and the like cause the product to be greatly limited in the practical application process, so that the technical personnel in the field need to find a material which can meet the requirements of biodegradation and excellent performances of various molded properties such as toughness, processing performance, product dimensional stability, application performance at a lower temperature and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a polyhydroxycarboxylic acid alloy material which not only has the characteristic of biodegradability, but also can improve the processing rheological property and the toughness of the material, solves the problem of poor dimensional stability of a product, and simultaneously improves the performance stability of the material in a low-temperature environment, so that the polyhydroxycarboxylic acid alloy material can be applied in a lower-temperature environment.
The invention also provides a preparation method of the polyhydroxycarboxylic acid alloy material.
The invention also provides the application of the polyhydroxycarboxylic acid alloy material in producing cold drink cup covers.
In order to solve the technical problems, the invention adopts a technical scheme as follows:
a polyhydroxycarboxylic acid alloy material, its raw materials include polyhydroxycarboxylic acid, said polyhydroxycarboxylic acid includes polylactic acid and other polyhydroxycarboxylic acid except polylactic acid; the feedstock further comprises a first copolymeric polymer, a second copolymeric polymer different from the first copolymeric polymer;
the polylactic acid, the polyhydroxycarboxylic acid except the polylactic acid, the first copolymer polymer and the second copolymer polymer respectively account for 50-75% by mass, 15-45% by mass, 0.5-10% by mass and 0.1-1% by mass of the raw materials;
wherein the monomers of the first copolymer polymer include a first monomer having a functional group reactive with an end group of the polylactic acid and/or an end group of the polyhydroxycarboxylic acid other than the polylactic acid, and a second monomer having a double bond; the second copolymer polymer is a copolymer of methyl acrylate and glycidyl methacrylate.
According to some preferred aspects of the present invention, the first monomer is a combination of one or more selected from the group consisting of maleic anhydride, glycidyl methacrylate, acrylate compounds, oxazole compounds and isocyanate compounds.
According to some preferred aspects of the invention, the second monomer is a combination of one or more selected from the group consisting of ethylene, styrene, propylene, non-conjugated dienes, butadiene, pentene, hexene, heptene and octene.
According to some specific and preferred aspects of the present invention, the first copolymer is a combination of one or more selected from the group consisting of ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-maleic anhydride copolymer, ethylene-methyl acrylate-maleic anhydride copolymer, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted ethylene propylene diene monomer, and maleic anhydride grafted hydrogenated butadiene-styrene copolymer.
According to some specific and preferred aspects of the present invention, the other polyhydroxycarboxylic acid other than polylactic acid is a combination of one or more selected from the group consisting of poly 3-hydroxybutyrate, poly 4-hydroxybutyrate, poly 3-hydroxyvalerate, poly (3-hydroxybutyrate-4-hydroxybutyrate) copolyester, poly (3-hydroxybutyrate-3-hydroxyvalerate) copolyester, and poly (4-hydroxybutyrate-3-hydroxyvalerate) copolyester.
According to some preferred aspects of the present invention, the epoxy group content of the second copolymer is 1 to 10% by mass. More preferably, the epoxy group content in the second copolymer is 4 to 8% by mass. According to a specific aspect of the present invention, the content of the epoxy group in the second copolymer polymer is 6.5% by mass.
According to the present invention, the weight-average molecular weight of the second copolymer polymer is 5000-. More preferably, the weight-average molecular weight of the second copolymer is 8000-12000. According to a particular aspect of the invention, the second copolymeric polymer has a weight average molecular weight of about 10000.
According to some preferred aspects of the present invention, the polylactic acid, the polyhydroxycarboxylic acid other than polylactic acid, the first copolymer polymer and the second copolymer polymer are present in an amount of 55 to 70%, 22 to 40%, 2 to 8% and 0.1 to 0.8% by mass, respectively, based on the raw material.
According to the invention, the weight average molecular weight of the polylactic acid is 5-10 ten thousand. According to the present invention, the polyhydroxycarboxylic acid other than polylactic acid has a weight average molecular weight of 10 to 60 ten thousand. Preferably, the polyhydroxycarboxylic acid other than the polylactic acid has a weight average molecular weight of 25 to 35 ten thousand.
In the present invention, the polylactic acid and the polyhydroxycarboxylic acid other than the polylactic acid each have a biomass origin of 100% according to ASTM6866 determination method.
According to some specific and preferred aspects of the present invention, the raw material further includes a lubricant in an amount of 0.1 to 1% by mass of the raw material.
According to some specific aspects of the present invention, the lubricant is a combination of one or more selected from the group consisting of calcium stearate, zinc stearate, sodium stearate, barium stearate, oxidized polyethylene wax, polyethylene-vinyl acetate wax, N-ethylene bis stearamide, pentaerythritol stearate, montanate, and silicone powder.
According to some specific and preferred aspects of the present invention, the raw material further includes a nucleating agent in an amount of 0.1 to 1% by mass of the raw material.
According to some specific aspects of the invention, the nucleating agent is a combination of one or more selected from the group consisting of sodium montmorillonite, talc, mica, zeolite, vermiculite, wollastonite, sepiolite, alumina, magnesia, zinc oxide, aluminum nitride, boron nitride, silicon carbide, calcium carbonate, barium sulfate.
According to some specific and preferred aspects of the present invention, the raw material further comprises an antioxidant in an amount of 0.1 to 1% by mass based on the raw material.
According to some specific aspects of the invention, the antioxidant is one or more selected from the group consisting of pentaerythritol tetrakis [ methylene β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), tris (2, 4-di-tert-butylphenyl) phosphite, 2, 6-di-tert-butyl-p-potassium phenol, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite (antioxidant 626) and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098).
The invention provides another technical scheme that: a preparation method of the polyhydroxycarboxylic acid alloy material comprises the following steps: weighing the raw materials according to a formula ratio, drying the weighed polyhydroxycarboxylic acid, mixing the dried polyhydroxycarboxylic acid with the rest raw materials, and performing extrusion molding to prepare the polyhydroxycarboxylic acid alloy material.
The invention provides another technical scheme that: the application of the polyhydroxycarboxylic acid alloy material in producing cold drink cup covers.
In the invention, the term "biodegradable" means that the primary raw materials of polylactic acid and polyhydroxycarboxylic acid are derived from starch, but not from petroleum-based chemicals, and the biodegradation rate of the alloy material is more than 90%.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
on the basis of blending modification of polylactic acid and other polyhydroxycarboxylic acids except polylactic acid, the specific synergistic effect of the first copolymer and the second copolymer is combined, so that mechanical properties such as toughness of the polyhydroxycarboxylic acid alloy material can have a good effect within the range of-25-60 ℃, the problem that the use temperature range of a biodegradable material in the prior art is too narrow is solved, the stability of various properties of the material at a low temperature is improved, and meanwhile, the modified material disclosed by the invention not only has the biodegradable characteristic, is environment-friendly, and is high in crystallization speed and easier to process.
Detailed Description
In the prior art, the biodegradable material has a narrow use temperature range, and particularly has poor performances such as toughness at lower temperature, so that better application is difficult to realize. At present, the biodegradability of polyhydroxycarboxylic acid (polyhydroxyalkanoate, PHA) is more and more widely concerned and applied, wherein polylactic acid (PLA) is one kind of polyhydroxycarboxylic acid, and is also a polyester-based polymer material derived from corn starch, which can be completely biodegraded, and is decomposed into water and carbon dioxide under natural conditions by the action of microbial enzymes, and the polylactic acid has excellent mechanical properties and processing rheological properties, and has been applied to human social practice to a certain extent, such as the medical field and the 3D printing field, but the characteristics of slow crystallization speed, high shrinkage rate of finished products, poor dimensional stability, brittle nature, poor processing stability, low glass transition temperature, poor durability and the like severely limit the application of the polylactic acid in various fields.
In practice, the applicant finds that when polylactic acid and other polyhydroxycarboxylic acid except polylactic acid are used for blending modification, the synergistic effect of the specific first copolymer polymer and the specific second copolymer polymer are combined, and the content of each copolymer polymer is controlled, the problem of high brittleness of products when polylactic acid or other polyhydroxycarboxylic acid except polylactic acid is used alone can be greatly improved, the modified material can be suitable for a wider temperature range, and particularly, the effect of keeping various properties of the material such as toughness at a lower temperature is excellent, so that the modified material can be suitable for producing cold drink cup covers.
Based on the above, the invention provides a polyhydroxycarboxylic acid alloy material, the raw material of which comprises polyhydroxycarboxylic acid, the polyhydroxycarboxylic acid comprises polylactic acid and other polyhydroxycarboxylic acid except the polylactic acid; the feedstock further comprises a first copolymeric polymer, a second copolymeric polymer different from the first copolymeric polymer; the polylactic acid, the polyhydroxycarboxylic acid except the polylactic acid, the first copolymer polymer and the second copolymer polymer respectively account for 50-75% by mass, 15-45% by mass, 0.5-10% by mass and 0.1-1% by mass of the raw materials; wherein the monomers of the first copolymer polymer include a first monomer having a functional group that reacts with an end group of the polylactic acid and/or an end group of the polyhydroxycarboxylic acid other than the polylactic acid, and a second monomer having a double bond; the second copolymer polymer is a copolymer of methyl acrylate and glycidyl methacrylate.
The invention also provides a method for preparing the polyhydroxycarboxylic acid alloy material, which comprises the following steps of; weighing the raw materials according to a formula ratio, drying the weighed polyhydroxycarboxylic acid, mixing the dried polyhydroxycarboxylic acid with the rest raw materials, and performing extrusion molding to prepare the polyhydroxycarboxylic acid alloy material. Wherein, during extrusion molding, a double-screw extruder can be used for extrusion molding, and the processing temperature of the double-screw extruder is controlled to be 80-200 ℃. Preferably, the processing temperature of the twin-screw extruder is controlled to be 120-200 ℃. More preferably, the processing temperature of the twin-screw extruder is controlled to 150-. The rotation speed of the main screw is controlled to be 200-500 r/min, preferably 250-350 r/min. After extrusion molding to obtain the polyhydroxycarboxylic acid alloy material, injection molding is preferably carried out at 160-200 ℃, and more preferably at 160-180 ℃.
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the basic principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not specified are generally the conditions in routine experiments.
In the following, all starting materials are either commercially available or prepared by conventional methods in the art, unless otherwise specified.
The performance test methods are basically as follows: bending property: ISO 178:2001 plastic bending property test;
notched izod impact strength: ISO 180:2001 plastic Izod impact performance.
Heat distortion temperature: ISO 75-1 plastics-determination of temperature without load-part 1: the general experimental method.
In the following, the second copolymer polymer was a copolymer of methyl acrylate and glycidyl methacrylate, in which the content of the epoxy group in the second copolymer polymer was 6.5% (by mass content) and the weight average molecular weight was about 10000.
PHBV: a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, available from Ningbo Tianan biomaterials Limited, having a 3% content of 3-hydroxyvaleric acid and a viscosity average molecular weight of about 45 million. The weight average molecular weight of the polylactic acid is 6-8 ten thousand.
Example 1
Accurately weighed were 2.781 kg of PHBV, 6.489 kg of PLA, 0.6 kg of ethylene-methyl acrylate copolymer (available from Arkema Lotryl 29MA03, France), 0.03 kg of antioxidant 1010, 0.04 kg of calcium stearate, 0.03 kg of talc and 0.03 kg of the second copolymer.
The preparation method comprises the following steps: firstly, carrying out vacuum drying on PLA and PHBV for 24 hours at the temperature of 60 ℃, then uniformly mixing the PLA and the PHBV with the rest raw materials, then extruding (the extrusion temperature is 160 +/-5 ℃), granulating and drying to obtain the polyhydroxycarboxylic acid alloy material.
The extruded samples were injection molded into test specimens according to ASTM standards (injection temperature 170. + -. 5 ℃ C.), and the resulting products had a 23 ℃ unnotched impact strength of 199J/m, a 23 ℃ unnotched impact strength of 157J/m, a flexural modulus of 2800MPa, and a heat distortion temperature of 54 ℃ at 0.455 MPa.
Example 2
2.781 kg of PHBV, 6.489 kg of PLA, 0.6 kg of ethylene-methyl acrylate-glycidyl methacrylate copolymer (available from Arkema Lotader 8900, France), 0.03 kg of antioxidant 626, 0.04 kg of N, N-diethenylstearic acid, 0.03 kg of boron nitride and 0.03 kg of the second copolymer were weighed out accurately.
The preparation method comprises the following steps: firstly, carrying out vacuum drying on PLA and PHBV for 24 hours at the temperature of 60 ℃, then uniformly mixing the PLA and the PHBV with the rest raw materials, then extruding (the extrusion temperature is 160 +/-5 ℃), granulating and drying to obtain the polyhydroxycarboxylic acid alloy material.
The extruded samples were injection molded into test specimens according to ASTM standards (injection temperature 170. + -. 5 ℃ C.), giving a product having an unnotched impact strength at 23 ℃ of 209J/m, an unnotched impact strength at 23 ℃ of 162J/m, a flexural modulus of 2800MPa and a heat distortion temperature at 0.455MPa of 56 ℃.
Example 3
3.708 kg of PHBV, 5.562 kg of PLA, 0.6 kg of ethylene-maleic anhydride copolymer (from Arkema Lotryl 4700, France), 0.03 kg of antioxidant 1098, 0.04 kg of pentaerythritol stearate, 0.03 kg of sodium montmorillonite and 0.03 kg of a second copolymer polymer were weighed out accurately.
The preparation method comprises the following steps: firstly, carrying out vacuum drying on PLA and PHBV for 24 hours at the temperature of 60 ℃, then uniformly mixing the PLA and the PHBV with the rest raw materials, then extruding (the extrusion temperature is 160 +/-5 ℃), granulating and drying to obtain the polyhydroxycarboxylic acid alloy material.
The extruded samples were injection molded into test specimens according to ASTM standards (injection temperature 170. + -. 5 ℃ C.), and the products obtained had an unnotched impact strength at 23 ℃ of 165J/m, an unnotched impact strength at 23 ℃ of 133J/m, a flexural modulus of 2900MPa, and a heat distortion temperature at 0.455MPa of 56 ℃.
Example 4
3.708 kg of PHBV, 5.562 kg of PLA, 0.6 kg of maleic anhydride grafted polyolefin elastomer (from DuPont) were weighed out accurately
493d) 0.03 kg of antioxidant 1076, 0.04 kg of pentaerythritol stearate, 0.03 kg of boron nitride, 0.03 kg of second copolymeric polymer.
The preparation method comprises the following steps: firstly, carrying out vacuum drying on PLA and PHBV for 24 hours at the temperature of 60 ℃, then uniformly mixing the PLA and the PHBV with the rest raw materials, then extruding (the extrusion temperature is 160 +/-5 ℃), granulating and drying to obtain the polyhydroxycarboxylic acid alloy material.
The extruded samples were injection molded into test specimens according to ASTM standards (injection temperature 170. + -. 5 ℃ C.), and the products obtained had an unnotched impact strength at 23 ℃ of 172J/m, an unnotched impact strength at 23 ℃ of 141J/m, a flexural modulus of 2900MPa, and a heat distortion temperature at 0.455MPa of 57 ℃.
Example 5
3.245 kg of PHBV, 6.0255 kg of PLA, 0.6 kg of maleic anhydride grafted polyolefin elastomer (from DuPont) were weighed out accurately
493d) 0.03 kg of antioxidant 1076, 0.04 kg of pentaerythritol stearate, 0.03 kg of boron nitride, 0.03 kg of second copolymeric polymer.
The preparation method comprises the following steps: firstly, carrying out vacuum drying on PLA and PHBV for 24 hours at the temperature of 60 ℃, then uniformly mixing the PLA and the PHBV with the rest raw materials, then extruding (the extrusion temperature is 160 +/-5 ℃), granulating and drying to obtain the polyhydroxycarboxylic acid alloy material.
The extruded samples were injection molded into test specimens according to ASTM standards (injection temperature 170. + -. 5 ℃ C.), and the products obtained had an unnotched impact strength at 23 ℃ of 183J/m, an unnotched impact strength at 23 ℃ of 139J/m, a flexural modulus of 2900MPa, and a heat distortion temperature at 0.455MPa of 54 ℃.
Comparative example 1
The difference is essentially the same as in example 1, except that no PHBV is added and the amount of PLA added is adjusted to 9.27 kg accordingly.
The extruded samples were injection molded into test specimens according to ASTM standards (injection temperature 170. + -. 5 ℃ C.), and the products obtained had a 23 ℃ unnotched impact strength of 116.0J/m, a 23 ℃ unnotched impact strength of 108.3J/m, a bending modulus of 2800MPa, and a heat distortion temperature of 58 ℃ at 0.455 MPa.
Comparative example 2
The difference is essentially the same as example 1, except that no PLA is added and the amount of PHBV added is adjusted to 9.27 kg accordingly.
The extruded samples were injection molded into test specimens according to ASTM standards (injection temperature 170. + -. 5 ℃ C.), and the products obtained had an unnotched impact strength at 23 ℃ of 56.4J/m, an unnotched impact strength at 23 ℃ of 52.1J/m, a flexural modulus of 3050MPa, and a heat distortion temperature at 0.455MPa of 140.0 ℃.
Comparative example 3
The procedure is essentially the same as in example 1, except that the ethylene-methyl acrylate copolymer is not added, and the amount of PHBV added is accordingly adjusted to 3.381 kg.
The extruded samples were injection molded into test specimens according to ASTM standards (injection temperature 170. + -. 5 ℃ C.), and the products obtained had a 23 ℃ unnotched impact strength of 43.2J/m, a 23 ℃ unnotched impact strength of 41.7J/m, a flexural modulus of 2950MPa, and a heat distortion temperature of 118.3 ℃ at 0.455 MPa.
Comparative example 4
The same as example 1 except that no second copolymer was added, and the amount of PHBV added was 2.811 kg.
The extruded sample was injection molded into a test sample according to ASTM standards (injection temperature 170. + -. 5 ℃ C.), and the product obtained had an unnotched impact strength at 23 ℃ of 37.8J/m, an unnotched impact strength at 23 ℃ of 35.5J/m, a flexural modulus of 3000MPa, and a heat distortion temperature at 0.455MPa of 123.1 ℃.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (5)
1. A polyhydroxycarboxylic acid alloy material, the raw material of which comprises polyhydroxycarboxylic acid, is characterized in that the polyhydroxycarboxylic acid comprises polylactic acid and other polyhydroxycarboxylic acid except the polylactic acid; the feedstock further comprises a first copolymeric polymer, a second copolymeric polymer different from the first copolymeric polymer;
the polylactic acid, the polyhydroxycarboxylic acid except the polylactic acid, the first copolymer polymer and the second copolymer polymer respectively account for 50-75% by mass, 15-45% by mass, 6-10% by mass and 0.1-1% by mass of the raw materials;
wherein the other polyhydroxycarboxylic acid except the polylactic acid is poly (3-hydroxybutyrate-3-hydroxyvalerate);
the first copolymer is one or more of ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-maleic anhydride copolymer, ethylene-methyl acrylate-maleic anhydride copolymer, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted ethylene propylene diene monomer and maleic anhydride grafted hydrogenated butadiene-styrene copolymer;
the second copolymer is a copolymer of methyl acrylate and glycidyl methacrylate, and the mass percentage of epoxy groups in the second copolymer is 1-10%.
2. The polyhydroxycarboxylic acid alloy material according to claim 1, wherein the mass percentages of the polylactic acid, the polyhydroxycarboxylic acid other than polylactic acid, the first copolymer and the second copolymer in the raw materials are 55-70%, 22-40%, 6-8% and 0.1-0.8%, respectively.
3. The polyhydroxycarboxylic acid alloy material according to claim 1, wherein the raw material further comprises a lubricant in an amount of 0.1 to 1% by mass based on the raw material; the raw materials also selectively comprise a nucleating agent and an antioxidant which respectively account for 0.1-1% of the raw materials by mass.
4. A method for preparing the polyhydroxycarboxylic acid alloy material according to any one of claims 1 to 3, wherein the method comprises: weighing the raw materials according to a formula ratio, drying the weighed polyhydroxycarboxylic acid, mixing the dried polyhydroxycarboxylic acid with the rest raw materials, and performing extrusion molding to prepare the polyhydroxycarboxylic acid alloy material.
5. Use of the polyhydroxycarboxylic acid alloy material as claimed in any one of claims 1 to 3 in the manufacture of cold drink cup lids.
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