CN113150520A - Biodegradable plastic for disposable spoon - Google Patents
Biodegradable plastic for disposable spoon Download PDFInfo
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- CN113150520A CN113150520A CN202110456480.2A CN202110456480A CN113150520A CN 113150520 A CN113150520 A CN 113150520A CN 202110456480 A CN202110456480 A CN 202110456480A CN 113150520 A CN113150520 A CN 113150520A
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- bamboo powder
- polylactic acid
- pbat
- composite material
- parts
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- 229920000704 biodegradable plastic Polymers 0.000 title claims abstract description 8
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 39
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 39
- 241001330002 Bambuseae Species 0.000 claims abstract description 39
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 39
- 239000011425 bamboo Substances 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000004626 polylactic acid Substances 0.000 claims abstract description 35
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 34
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 15
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 14
- 239000003549 soybean oil Substances 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229920001896 polybutyrate Polymers 0.000 claims abstract 5
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 235000013305 food Nutrition 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims 1
- 239000004033 plastic Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 8
- 238000001746 injection moulding Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 23
- 239000000155 melt Substances 0.000 description 5
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004609 Impact Modifier Substances 0.000 description 2
- -1 Polybutylene terephthalate-adipate Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 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
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G21/00—Table-ware
- A47G21/04—Spoons; Pastry servers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses biodegradable plastic for a disposable spoon, and belongs to the field of bio-based high polymer materials. The invention adopts a one-step method to compound six components of polylactic acid, PBAT, bamboo powder, a chain extender, epoxidized soybean oil and sebacic acid to prepare the high-toughness biodegradable material. The method has the advantages that the conversion of the composite material from brittleness to toughness is realized by simply regulating and controlling the content of PBAT, and the problems of poor compatibility, low impact strength, poor processing flowability and the like of the polylactic acid/bamboo powder composite material are solvedThe problem is that the high impact polylactic acid/bamboo powder composite material can be prepared, and the material has the tensile strength of 20-38 MPa, the elongation at break of 2-20 percent and the impact strength of 10-20 KJ/m2Compared with the unmodified polylactic acid/bamboo powder composite material, the impact strength is improved by 3 times after modification. In addition, due to the improvement of processing fluidity, the spoon formed by injection molding of the added formula does not have the defects of cavities, bubbles and the like.
Description
Technical Field
The invention discloses a preparation method of biodegradable plastic for a disposable spoon, and belongs to the field of green biodegradable materials.
Background
Polylactic acid is a thermoplastic bio-based polymer material synthesized from renewable resources, has excellent biocompatibility and compost degradability, and is widely applied to packaging materials and biomedical materials. However, the problems of low heat distortion temperature, high brittleness, high cost and insufficient impact strength of polylactic acid limit the large-scale industrial application thereof. Research on high-performance and low-cost polylactic acid materials has received much attention. Polybutylene terephthalate-adipate (PBAT) 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 for active research and market application of biodegradable plastics. The bamboo material belongs to fast growing wood, and the bamboo fiber powder film obtained from the bamboo material has the advantages of high strength, narrow included angle of superfine fibers, low cost and the like. Therefore, the bamboo powder can be used as the reinforcing fiber of the polylactic acid, so that the impact strength and the heat distortion temperature of the polylactic acid are improved, and the material cost is reduced to a certain extent. However, the bamboo powder contains a large amount of hydrophilic groups such as alcoholic hydroxyl and phenolic hydroxyl on the surface, so that the polarity and the hydrophilicity of the bamboo powder are high, and when the bamboo powder is compounded with non-polar polylactic acid, the bamboo powder is gathered together and is difficult to uniformly disperse in a polylactic acid matrix. In addition, the unmodified bamboo powder particles have large frictional resistance, so that the melt flowability is poor, and the processing and the forming are difficult. Therefore, the difficulty in developing a high-performance polylactic acid/bamboo powder composite material is to improve the interface compatibility between the polylactic acid matrix and the bamboo powder so as to obtain a product with excellent comprehensive performance.
Methods to improve interfacial compatibility include bamboo powder surface pretreatment (physical or chemical modification) and addition of compatibilizers (reactive and non-reactive). The surface pretreatment of the bamboo powder can change the surface morphology of the fiber and remove components (such as pectin, hemicellulose, lignin, parenchyma cells and the like) which have negative influence on the interface bonding strength. The addition of the compatibilizer can improve the interfacial bonding force among the components and improve the compatibility of the components. At present, the most common method for the surface pretreatment of bamboo powder is alkali treatment. Although the contact area between the blast furnace and the polylactic acid matrix can be effectively improved, more hydrophilic groups can be generated by alkaline hydrolysis, the operation process is time-consuming and complicated, and a large amount of waste liquid can be generated, so that certain pollution is caused to the environment. The addition of the compatibilizer (including reactive and non-reactive compatibilizers) can reduce the processing flow, and is simple and efficient. Therefore, the addition of proper types and dosage of the compatibilizer is the main research and development direction for improving the performance of the polylactic acid/bamboo powder composite material.
The vegetable oil is a green raw material with rich source and low price, the compatibility of the material obtained by directly blending the epoxidized soybean oil and the polylactic acid/bamboo powder is improved to a certain extent, but small molecules of the epoxidized soybean oil can migrate to the surface of the material along with the prolonging of time to cause the phenomena of stickiness and the like on the surface of a product, and the long-term use of the product is not facilitated. Sebacic acid is a long-chain fatty acid, is obtained by catalytic hydrolysis of castor oil, is a bio-based monomer derived from renewable resources, like epoxidized soybean oil. The epoxidized soybean oil, the sebacic acid and the polylactic acid are simultaneously added into an internal mixer for mixing, and the tensile property of the obtained polylactic acid material is greatly improved.
Disclosure of Invention
Based on the reasons, the invention adopts a one-step method to mix six components of PLA, PBAT, bamboo powder (BF), a chain extender (ADR), Epoxidized Soybean Oil (ESO) and Sebacic Acid (SA) to prepare the high-toughness biodegradable composite material. The method has the advantages that the conversion of the composite material from brittleness to toughness is realized by simply regulating and controlling the content of PBAT, so that the composite material suitable for injection molding of the disposable spoon can be obtained.
A fully-degradable composite material for a disposable spoon is composed of the following raw materials in percentage by weight:
polylactic acid: 40-80 parts;
bamboo powder: 10-50 parts;
PBAT: 10-40 parts;
chain extender: 0-2 parts of a solvent;
epoxidized soybean oil: 0-5 parts;
sebacic acid: 0 to 2 parts.
Wherein the sum of the weight of the polylactic acid, the bamboo powder and the PBAT is 100 parts.
The preparation process of the fully-degradable composite material for the disposable spoon comprises the following steps: firstly, adding polylactic acid (PLA), polybutylene terephthalate (PBAT), bamboo powder, a chain extender (ADR), epoxidized soybean oil and sebacic acid into a high-speed mixer, uniformly mixing at normal temperature, adding into a double-screw extruder, and performing melt extrusion, bracing, air cooling and granulation to obtain the fully biodegradable composite material.
The temperature of the double-screw extruder is controlled to be 180-190 ℃, and the rotating speed is controlled to be 80-150 rpm; the length-diameter ratio of the screw is 32: 1-45: 1.
The fully-degradable composite material for the disposable spoon has excellent mechanical property and processing property, and can be used in the field of food contact materials such as knife, fork and spoon due to the renewable and degradable raw materials and the characteristics of no toxicity and greenness.
Compared with the prior art, the fully-degradable composite material for the disposable spoon has the following outstanding advantages: all the raw materials used in the invention have biodegradability, have the characteristics of environmental protection and degradability after being discarded, and have positive promotion significance for sustainable development of environment and society. The epoxidized soybean oil-graft-sebacic acid oligomer formed by the epoxidized soybean oil and the sebacic acid in the double-screw extrusion process has the functions of a toughening agent, a compatilizer and an impact modifier, so that the compatibility of PLA and PBAT with bamboo powder is increased; the addition of the chain extender can effectively solve the compatibility of PLA and PBAT. The invention simply and efficiently solves the problems of poor compatibility between PLA and PBAT and between the PLA and PBAT and bamboo powder, low impact strength, poor processing fluidity and the like.
The material has the tensile strength of 20-38 MPa, the elongation at break of 2-20 percent and the impact strength of 10-20 KJ/m2Compared with the unmodified polylactic acid/bamboo powder composite material, the impact strength is improved by 3 times after modification. In addition, due to the improvement of processing fluidity, the spoon formed by injection molding of the added formula does not have the defects of cavities, bubbles and the like.
Detailed Description
Comparative examples and preferred examples of the present invention will be described in detail below.
TABLE 1 proportions of the components of the present invention
Comparative example 1
Comparative example 1 is a polylactic acid/bamboo powder composite system without PBAT, epoxidized soybean oil, sebacic acid, and a chain extender. The preparation method comprises the following steps: adding polylactic acid and bamboo powder into a double-screw extruder according to the weight ratio of 70:30, carrying out melt extrusion, bracing, air cooling and granulation to obtain the polylactic acid/bamboo powder composite material, wherein the temperature of the double-screw extruder is controlled to be 180-190 ℃. Comparative example 1 had a tensile strength of 38.32MPa, an elongation at break of 1.65%, and an unnotched impact strength of 5.8KJ/m for a simply supported beam2. It can be seen that the polylactic acid/bamboo powder composite material before modification has large brittleness and low impact strength, and is not suitable for production of injection molding parts.
The following examples are to improve the toughness and impact resistance of the polylactic acid/bamboo powder composite material by adding different components of PBAT, while adding 0.7 part of chain extender, 2.7 parts of epoxidized soybean oil and 0.3 part of sebacic acid as compatilizers.
Example 1
PLA, bamboo powder, PBAT, ADR, ESO and SA are mixed according to the weight ratio of 60:10:30:0.7:2.7:0.3, then double screws are added for melt extrusion, bracing, air cooling and granulation, and the fully degradable composite material is obtained, wherein the temperature of a double screw extruder is controlled to be 180-190 ℃. Example 1 had a modulus of 3746.4MPa, a tensile strength of 37.45MPa, an elongation at break of 9.83%, and an unnotched impact strength of 10.91KJ/m for a simply supported beam2。
Example 2
PLA, bamboo powder, PBAT, ADR, ESO and SA are mixed according to the weight ratio of 50:20:30:0.7:2.7:0.3, then double screws are added for melt extrusion, bracing, air cooling and granulation, and the fully degradable composite material is obtained, wherein the temperature of a double screw extruder is controlled to be 180-190 ℃. Example 2 had a modulus of 3012.6MPa, a tensile strength of 31.25MPa, an elongation at break of 13.62%, and an unnotched impact strength of 12.31KJ/m for a simply supported beam2。
Example 3
PLA, bamboo powder, PBAT, ADR, ESO and SA are mixed according to the weight ratio of 50:20:30:0.7:2.7:0.3, then double screws are added for melt extrusion, bracing, air cooling and granulation, and the fully degradable composite material is obtained, wherein the temperature of a double screw extruder is controlled to be 180-190 ℃. Example 3 had a modulus of 1940.8MPa, a tensile strength of 24.21MPa, an elongation at break of 19.06%, and an unnotched impact strength of 18.55KJ/m for a simply supported beam2。
All the mechanical property data of examples 1 to 3 are shown in table 2. From the results, it can be seen that as the content of PBAT increases, the tensile modulus and tensile strength of the composite gradually decrease, and the elongation at break and impact strength gradually increase. Table 2 shows the melt indexes of examples 1 to 3, wherein the higher the melt index is, the better the melt fluidity during injection molding is, and the processing fluidity does not change much with the increase of PBAT content in the examples, but the melt indexes of all the composite materials added with PBAT are larger than those of the composite materials not added with PBAT. The addition of the PBAT can ensure that injection molding parts can not have defects of cavities, bubbles and the like. Therefore, the addition of PBAT, epoxidized soybean oil, sebacic acid and a chain extender obviously improves the interfacial compatibility of the polylactic acid/bamboo powder system and simultaneously plays a role of a toughening agent, a compatilizer and an impact modifier.
TABLE 2 mechanical Properties of composites of different formulations
TABLE 3 melt index for composite materials of different formulations
Finally, it is noted that the above-mentioned preferred examples are merely intended to illustrate rather than to limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, those skilled in the art will understand that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110456480.2A CN113150520B (en) | 2021-04-26 | 2021-04-26 | Biodegradable plastic for disposable spoon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110456480.2A CN113150520B (en) | 2021-04-26 | 2021-04-26 | Biodegradable plastic for disposable spoon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113150520A true CN113150520A (en) | 2021-07-23 |
| CN113150520B CN113150520B (en) | 2022-08-16 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110456480.2A Active CN113150520B (en) | 2021-04-26 | 2021-04-26 | Biodegradable plastic for disposable spoon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113150520B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115354446A (en) * | 2022-08-19 | 2022-11-18 | 吉祥三宝高科纺织有限公司 | Polylactic acid thermal insulating flocculus with high fluffiness and high resilience and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130303653A1 (en) * | 2011-01-24 | 2013-11-14 | Arkema Inc. | Epoxidized fatty acid alkyl esters as flexibilizers for poly(lactic acid) |
| CN106336636A (en) * | 2016-10-14 | 2017-01-18 | 西南大学 | Preparation method of polylactic acid/epoxy soybean oil resin alloy and product |
| US20200283622A1 (en) * | 2016-03-24 | 2020-09-10 | Sk Chemicals Co., Ltd. | Poly(lactic acid) resin composition and molded product comprising same |
| 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 |
-
2021
- 2021-04-26 CN CN202110456480.2A patent/CN113150520B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130303653A1 (en) * | 2011-01-24 | 2013-11-14 | Arkema Inc. | Epoxidized fatty acid alkyl esters as flexibilizers for poly(lactic acid) |
| US20200283622A1 (en) * | 2016-03-24 | 2020-09-10 | Sk Chemicals Co., Ltd. | Poly(lactic acid) resin composition and molded product comprising same |
| CN106336636A (en) * | 2016-10-14 | 2017-01-18 | 西南大学 | Preparation method of polylactic acid/epoxy soybean oil resin alloy and product |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115354446A (en) * | 2022-08-19 | 2022-11-18 | 吉祥三宝高科纺织有限公司 | Polylactic acid thermal insulating flocculus with high fluffiness and high resilience and preparation method thereof |
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