CN113801445A - High-toughness heat-resistant degradable PLA material and preparation method thereof - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 19
- 229920002472 Starch Polymers 0.000 claims abstract description 17
- 239000008107 starch Substances 0.000 claims abstract description 17
- 235000019698 starch Nutrition 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000012745 toughening agent Substances 0.000 claims abstract description 10
- 239000011256 inorganic filler Substances 0.000 claims abstract description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 239000004626 polylactic acid Substances 0.000 claims description 42
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 41
- 238000001746 injection moulding Methods 0.000 claims description 21
- -1 polyethylene Polymers 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 14
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 229920003054 adipate polyester Polymers 0.000 claims description 6
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 6
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 229960002622 triacetin Drugs 0.000 claims description 6
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 5
- 229920002961 polybutylene succinate Polymers 0.000 claims description 5
- 239000004631 polybutylene succinate Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229940022769 d- lactic acid Drugs 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960000448 lactic acid Drugs 0.000 claims description 2
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002562 thickening agent Substances 0.000 abstract description 3
- 235000006708 antioxidants Nutrition 0.000 description 11
- 238000005457 optimization Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000009044 synergistic interaction Effects 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100001223 noncarcinogenic Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- 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)
Abstract
The invention discloses a high-toughness heat-resistant degradable PLA material and a preparation method thereof, wherein the high-toughness heat-resistant degradable PLA material comprises 60-80 parts of PLA, 20-30 parts of starch, 10-15 parts of inorganic filler, 8-12 parts of high-molecular copolymer, 1-3 parts of chain extender, 0.5-2 parts of compatibilizer, 1-3 parts of plasticizer, 1-2 parts of toughening agent and 0.5-2 parts of antioxidant. According to the invention, the high molecular compound, the toughening agent, the thickening agent and the antioxidant are added into the raw materials, so that the raw materials can be synergized, the toughness and the heat resistance of the product are improved, and the material has excellent heat resistance, mechanical strength and toughness, chemical resistance, impact resistance and stable size; meanwhile, because the raw materials are added with the bio-based starch and the inorganic filler, the degradability of the product is improved.
Description
Technical Field
The invention relates to the technical field of PLA material processing, in particular to a high-toughness heat-resistant degradable PLA material and a preparation method thereof.
Background
Polylactic acid (PLA) is one of the most widely used environment-friendly materials at present, has good biocompatibility and biodegradability, can be completely degraded into water and carbon dioxide under the action of microorganisms and enzymes, and is widely applied to a plurality of fields such as packaging, medical use, 3D printing and the like.
PLA is nontoxic, non-carcinogenic, easily degradable and has good biocompatibility, so that the PLA is popular, but the P material LA has poor toughness and poor temperature resistance, and the common PLA material has poor tensile property and impact resistance, so that further popularization of the PLA is seriously hindered.
Disclosure of Invention
The invention aims to provide a high-toughness heat-resistant degradable PLA material and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention adopts the technical scheme that: a high-toughness heat-resistant degradable PLA material comprises the following components in parts by weight,
| PLA | 60 to 80 portions of | |
| Starch | 20-30 parts of | |
| Inorganic filler | 10-15 parts of | |
| High molecular copolymer | 8 to 12 portions of | |
| Chain extender | 1-3 parts of | |
| Compatibilizer | 0.5 to 2 portions of | |
| Plasticizer | 1-3 parts of | |
| Toughening agent | 1-2 parts of | |
| Antioxidant agent | 0.5 to 2 portions of |
As a further optimization, the PLA is one or more of poly-L-lactic acid, poly-D-lactic acid and poly-DL-lactic acid, wherein the weight average molecular weight of the PLA is 100000-300000, the molecular weight distribution is 1.5-2.0, and the crystallinity is 40-60%.
As a further optimization, the inorganic filler is one or more of kaolin, calcium carbonate, talcum powder, mica powder, silicon dioxide and carbon black.
As a further optimization, the high molecular copolymer is one or more of polyethylene, polycarbonate and ABS.
As a further optimization, the chain extender is chain extender PCD or chain extender BDE.
As a further optimization, the compatibilizer is one or more of maleic acid, isocyanate, and epoxy resin.
As a further optimization, the plasticizer is one or more of acetyl tributyl citrate, tricresyl phosphate, glycerol triacetate and propylene glycol adipate polyester.
As further optimization, the toughening agent is one or two of polybutylene succinate, polyethylene succinate, polycaprolactone and polybutylene adipate.
As a further optimization, the antioxidant is 1010 or 168.
The invention also provides a preparation method of the high-toughness heat-resistant degradable PLA material, which comprises the following steps:
s1) accurately weighing each component;
s2) uniformly mixing PLA, the high-molecular copolymer, the chain extender, the compatibilizer, the plasticizer and the toughening agent; continuously adding starch, inorganic filler and antioxidant, and mixing;
s3) adding the mixture into a double-screw extruder, and extruding and granulating at the extrusion temperature of 180-200 ℃;
s4) placing the material particles in an injection molding machine for injection molding to obtain the product, wherein the injection molding temperature is 180-200 ℃.
Compared with the prior art, the invention has the beneficial effects that:
by adding the macromolecular compound, the toughening agent, the thickening agent and the antioxidant into the raw materials, the raw materials have synergistic interaction, the toughness and the heat resistance of the product are improved, and the material has excellent heat resistance, mechanical strength, chemical resistance, impact resistance and dimensional stability; meanwhile, because the raw materials are added with the bio-based starch and the inorganic filler, the degradability of the product is improved.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
75 parts of PLA, 25 parts of starch, 11 parts of kaolin, 12 parts of polyethylene, 2 parts of chain extender PCD, 1 part of maleic acid, 2 parts of tricresyl phosphate, 2 parts of polybutylene succinate and 10102 parts of antioxidant.
The preparation method comprises the following steps: s1) accurately weighing each component; s2) uniformly mixing PLA, polyethylene, a chain extender PCD, maleic acid, tricresyl phosphate and polybutylene succinate; continuously adding starch, kaolin and antioxidant 1010, and uniformly mixing; s3) adding the mixture into a double-screw extruder, and extruding and granulating at the extrusion temperature of 180-200 ℃; s4) placing the material particles in an injection molding machine for injection molding to obtain the product, wherein the injection molding temperature is 180-200 ℃.
Example 2
A high-toughness heat-resistant degradable PLA material comprises, by weight, 63 parts of PLA, 30 parts of starch, 13 parts of talcum powder, 9 parts of polycarbonate, 1 part of chain extender PCD, 2 parts of maleic acid, 2 parts of glycerol triacetate, 2 parts of polyethylene glycol succinate and 1681 part of antioxidant.
The preparation method comprises the following steps: s1) accurately weighing each component; s2) uniformly mixing PLA, high polycarbonate, a chain extender PCD, maleic acid, glycerol triacetate and polyethylene glycol succinate; continuously adding starch, talcum powder and antioxidant 168, and mixing; s3) adding the mixture into a double-screw extruder, and extruding and granulating at the extrusion temperature of 180-200 ℃; s4) placing the material particles in an injection molding machine for injection molding to obtain the product, wherein the injection molding temperature is 180-200 ℃.
Example 3
A high-toughness heat-resistant degradable PLA material comprises, by weight, 78 parts of PLA, 22 parts of starch, 12 parts of mica powder, 10 parts of polyethylene, 2 parts of a chain extender BDE, 2 parts of epoxy resin, 1 part of propylene glycol adipate polyester, 2 parts of polyethylene glycol succinate and 1681 part of an antioxidant.
The preparation method comprises the following steps: s1) accurately weighing each component; s2) uniformly mixing PLA, polyethylene, a chain extender BDE, epoxy resin, propylene glycol adipate polyester and polyethylene glycol succinate; continuously adding starch, mica powder and antioxidant 168, and mixing; s3) adding the mixture into a double-screw extruder, and extruding and granulating at the extrusion temperature of 180-200 ℃; s4) placing the material particles in an injection molding machine for injection molding to obtain the product, wherein the injection molding temperature is 180-200 ℃.
Example 4
The high-toughness heat-resistant degradable PLA material comprises, by weight, 72 parts of PLA, 26 parts of starch, 13 parts of silicon dioxide, 11 parts of polycarbonate, 3 parts of a chain extender BDE, 2 parts of epoxy resin, 2 parts of propylene glycol adipate polyester, 1 part of polycaprolactone and 10102 parts of an antioxidant.
The preparation method comprises the following steps: s1) accurately weighing each component; s2) uniformly mixing PLA, polycarbonate, a chain extender BDE, epoxy resin, propylene glycol adipate polyester and polycaprolactone; continuously adding starch, silicon dioxide and antioxidant 1010, and uniformly mixing; s3) adding the mixture into a double-screw extruder, and extruding and granulating at the extrusion temperature of 180-200 ℃; s4) placing the material particles in an injection molding machine for injection molding to obtain the product, wherein the injection molding temperature is 180-200 ℃.
Example 5
The high-toughness heat-resistant degradable PLA material comprises, by weight, 66 parts of PLA, 28 parts of starch, 15 parts of carbon black, 9 parts of ABS, 1 part of chain extender PCD, 1 part of maleic acid, 3 parts of glycerol triacetate, 1 part of polybutylene adipate and 10102 parts of antioxidant.
The preparation method comprises the following steps: s1) accurately weighing each component; s2) uniformly mixing PLA, ABS, chain extender PCD, maleic acid, glycerol triacetate and polybutylene adipate; continuously adding starch, carbon black and an antioxidant 1010, and uniformly mixing; s3) adding the mixture into a double-screw extruder, and extruding and granulating at the extrusion temperature of 180-200 ℃; s4) placing the material particles in an injection molding machine for injection molding to obtain the product, wherein the injection molding temperature is 180-200 ℃.
Comparative example 1
In this comparative example, tricresyl phosphate and polybutylene succinate were not added, compared to example 1.
Comparative example 2
In this comparative example, no polyethylene was added compared to example 1.
Comparative example 3
In this comparative example, 1010 antioxidant and polyethylene were not added, compared to example 1.
Application examples
The high toughness, heat resistant, degradable PLA materials prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to a performance test,
according to the data, when no macromolecular compound is added into the raw materials, the tensile strength, the elongation at break and the like of the finished product are reduced, and when no toughening agent and no plasticizer are added into the raw materials, the elongation at break and the bending strength of the finished product can be reduced, so that the toughness of the product is influenced; when the antioxidant and the high molecular compound are not added into the raw materials, the heat distortion temperature of the product is reduced, and the heat resistance of the product is influenced.
In conclusion, by adding the high molecular compound, the toughening agent, the thickening agent and the antioxidant into the raw materials, the raw materials have synergistic interaction, the toughness and the heat resistance of the product are improved, and the material has excellent heat resistance, high mechanical property, chemical resistance, impact resistance and stable size; meanwhile, because the raw materials are added with the bio-based starch and the inorganic filler, the degradability of the product is improved.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A high-toughness heat-resistant degradable PLA material is characterized by comprising the following components in parts by weight,
2. the high toughness, heat resistant, degradable PLA material of claim 1 wherein the PLA is one or more of poly-L-lactic acid, poly-D-lactic acid and poly-DL-lactic acid.
3. The high toughness, heat resistant, degradable PLA material of claim 1 wherein the inorganic filler is one or more of kaolin, calcium carbonate, talc, mica powder, silica and carbon black.
4. The high toughness heat resistant degradable PLA material of claim 1 wherein the high molecular copolymer is one or more of polyethylene, polycarbonate and ABS.
5. The high toughness, heat resistant, degradable PLA material of claim 1 wherein the chain extender is chain extender PCD or BDE.
6. The high toughness, heat resistant, degradable PLA material of claim 1 wherein the compatibilizer is one or more of maleic acid, isocyanate and epoxy.
7. The high toughness, heat resistant, degradable PLA material of claim 1 wherein the plasticizer is one or more of tributyl acetylcitrate, tricresyl phosphate, glycerol triacetate, and propylene glycol adipate polyester.
8. The high toughness heat resistant degradable PLA material of claim 1 wherein the toughening agent is one or two of polybutylene succinate, polyethylene succinate, polycaprolactone and polybutylene adipate.
9. The high toughness heat resistant degradable PLA material of claim 1 wherein the antioxidant is the antioxidant 1010 or antioxidant 168.
10. The preparation method of the high toughness heat resistant degradable PLA material according to any one of the claims 1 to 9, characterized by comprising the following steps:
s1) accurately weighing each component;
s2) uniformly mixing PLA, the high-molecular copolymer, the chain extender, the compatibilizer, the plasticizer and the toughening agent; continuously adding starch, inorganic filler and antioxidant, and mixing;
s3) adding the mixture into a double-screw extruder, and extruding and granulating at the extrusion temperature of 180-200 ℃;
s4) placing the material particles in an injection molding machine for injection molding to obtain the product, wherein the injection molding temperature is 180-200 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114874599A (en) * | 2022-05-31 | 2022-08-09 | 东莞市惠国新材科技有限公司 | Polymer material and preparation method and application thereof |
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| CN112210196A (en) * | 2020-10-10 | 2021-01-12 | 莱涤新材料(宁波)有限公司 | Biodegradable polylactic acid product and preparation method thereof |
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| CN113045872A (en) * | 2021-03-01 | 2021-06-29 | 温州大学新材料与产业技术研究院 | High-heat-resistance and high-toughness biodegradable PLA modified material and preparation method thereof |
| CN112961481A (en) * | 2021-03-16 | 2021-06-15 | 深圳金大全科技有限公司 | Formula and preparation method of full-biodegradable heat-resistant super-tough high-gloss low-temperature-resistant PLA material |
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