CN115011083A - Fully biodegradable composite material capable of being repeatedly processed and preparation method thereof - Google Patents
Fully biodegradable composite material capable of being repeatedly processed and preparation method thereof Download PDFInfo
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- CN115011083A CN115011083A CN202210723488.5A CN202210723488A CN115011083A CN 115011083 A CN115011083 A CN 115011083A CN 202210723488 A CN202210723488 A CN 202210723488A CN 115011083 A CN115011083 A CN 115011083A
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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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
-
- 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
-
- 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
Abstract
The invention discloses a fully biodegradable composite material capable of being repeatedly processed and a preparation method thereof, and belongs to the technical field of degradable composite materials. The invention takes PBAT and PLA as the matrix and talcum powder as the reinforcing agent, and the material has complete degradability. The introduction of the fine talcum powder effectively improves the mechanical strength of the composite material, the grafting of the maleic anhydride can improve the compatibility of a PBAT/PLA system, the surface treatment can be carried out on the talcum powder by the coupling agent, and the compatibility and the combination degree of the talcum powder and a PBAT/PLA polyester substrate are improved, so that the composite material is endowed with obdurability and easy processability. The addition of the chain extender can promote the recombination of PLA/PBAT molecular chain segments which are broken or hydrolyzed by repeated extrusion, improve the mechanical property of a PLA/PBAT blending system and delay the biodegradation of the blend. The composite material provided by the invention realizes the recovery and reproduction of leftover materials, can be recycled for more than five times at most, effectively reduces the production cost, and saves the raw materials and energy consumption.
Description
Technical Field
The invention relates to a fully biodegradable composite material capable of being repeatedly processed and a preparation method thereof, belonging to the technical field of degradable composite materials.
Background
Plastics pollution control is an important environmental problem which is concerned with all over the world, and is also a worldwide problem. At present, the technical research aiming at the plastic pollution treatment mainly focuses on two fields of research and development of fully biodegradable plastic materials and research and development of plastic treatment technologies, and the development of fully biodegradable plastics not only can reduce or avoid pollution caused by disposable plastic products, but also can assist in realizing carbon peak reaching and carbon neutralization targets.
Since 2020 new edition plastic order, the whole biodegradable material has developed a hot trend nationwide. Degradable plastic products are vigorously promoted and used in various places, but the full-biodegradable materials are easily degraded by environmental factors, and particularly have the characteristics of easy hydrolysis, performance reduction, aging and the like in the repeated processing process of recycling leftover materials. In the industrialization process, the film blowing process can generate about 3% of waste materials (transition materials for debugging film specifications, unqualified products and the like), the edge cutting materials can be generated in the film rolling and bag making process (15% of edge materials are generated at the digging opening of the handle of the vest bag shopping bag, 5% of edge materials are generated in the hand bag), the profit margin of the biodegradation film blowing and bag making industry is small, if the generated edge materials can not be refilled in time according to the proportion, the production cost is inevitably greatly improved, and the enterprise profit is seriously influenced. Therefore, it is necessary to develop a stable and reproducible high-performance fully biodegradable composite material formulation process system.
The prior fully biodegradable composite material adopts a PBAT/PLA/inorganic salt or PBAT/PLA/starch system, and the fully biodegradable composite material obtained by the formula/method has the following problems: 1. PBAT is an ester polymer, hydrolysis is easy to occur under an acidic condition, the process is irreversible, and molecular chains are easy to shear and break in the processing process; 2. in the system, in order to design a physical filling system with hydrolysis resistance, the compatibility between the filler and the PBAT/PLA is generally solved by a coupling agent, but the compatibility problem of the PBAT/PLA is not well solved, and the heat sealing performance of the film is directly influenced.
For example, CN111892794A discloses a PBAT-talc fully biodegradable blend and a preparation method thereof, which improves the compatibility between the filler and the polyester by a grafting reaction of a silane coupling agent and talc to improve the physical and mechanical properties of a talc-filled polyester film, and the graft copolymer provides a film with a tensile strength as high as 6000psi by providing the blend in a one-step extrusion process. However, the film is easy to hydrolyze when exposed to the environment, and the recycled leftover materials generated by end-blown film and bag making have poor repeatable processing performance.
Disclosure of Invention
In order to solve the problems of poor repeated processability and easy aging and hydrolysis of the existing fully degradable material, the invention provides a PBAT/PLA/talcum powder fully biodegradable composite material capable of being repeatedly processed and a preparation method thereof. The invention takes PBAT (polybutylene adipate terephthalate) and PLA (polylactic acid) as substrates, and the material has complete degradability; the introduction of the fine talcum powder effectively improves the mechanical strength of the composite material and reduces the production cost; the maleic anhydride grafting can improve the compatibility of a PBAT/PLA system; the coupling agent can carry out surface treatment on the talcum powder, improve the compatibility and the combination degree of the talcum powder and a PBAT/PLA polyester matrix and endow the composite material with obdurability and easy processability; the addition of the hydrolysis resistant agent inhibits ester bond hydrolysis caused by repeated processing of a polyester matrix, and reduces the reduction of the comprehensive performance of the material; the addition of the chain extender can promote the recombination of PLA/PBAT molecular chain segments which are broken or hydrolyzed by repeated extrusion, improve the mechanical property of a PLA/PBAT blending system and delay the biodegradation of the blend. The PBAT/PLA/talcum powder fully-biodegradable composite material capable of being repeatedly processed is obtained by effectively controlling the types and the types of the components and the adding proportion, the tensile strength of the prepared material can reach 45MPa, and the heat sealing strength can reach 14.2N/15 mm; repeating the processing for more than 3 times, wherein the attenuation rate of the tensile strength is less than or equal to 25 percent. The repeatedly-processable and degradable composite material provided by the invention realizes the recovery and reproduction of leftover materials, can be recycled for more than five times at most, effectively reduces the production cost, and saves the raw materials and energy consumption.
The reworkable full-biodegradable composite material comprises the following components in parts by weight:
in one embodiment, the fully biodegradable composite material is composed of the following components:
in one embodiment, the particle size of the talcum powder particles is 2000-3000 meshes.
In one embodiment, the chain extender is of the acrylic polymer type and the epoxy functional group polymer type. Alternatively, the epoxy functional type chain extender BTCE-9019.
In one embodiment, the coupling agent is one or more of an aluminate coupling agent, a phthalate coupling agent, and a silane coupling agent.
In one embodiment, the coupling agent is epoxysilane KH 560.
In one embodiment, the main component of the hydrolysis resistant agent is one or a combination of two or more of monomer type carbodiimide, polymer type carbodiimide, isocyanate and acrylate. Alternatively, the polymeric carbodiimide BTWR-500.
In one embodiment, the processing aid selected is calcium stearate, zinc stearate, magnesium stearate, stearic acid.
In one embodiment, the preparation of the fully biodegradable composite material comprises the following steps:
the method comprises the following steps: adding 10-20 parts of fine talcum powder and 0.5-1 part of coupling agent into a high-speed mixer, setting the temperature to be 80-100 ℃, rotating the speed to be 400-600 r/min, and stirring for reaction for 10-15min to obtain the activated fine talcum powder.
Step two: adding 50-60 parts of PBAT, 5-10 parts of PLA, activated fine talcum powder, 0.3-0.5 part of maleic anhydride and 1-2 parts of processing aid into a high-speed mixer, setting the temperature to be 100-105 ℃, rotating at the speed of 500-600 revolutions per minute, mixing for 10-15min, adding 0.5-1 part of hydrolysis resistant agent and 0.2-0.3 part of chain extender, and then continuously stirring and mixing for 3-5 min.
Step three: and (4) feeding the mixture prepared in the step two into a double-screw extruder for melt blending and granulation, and drying to obtain the repeatedly processable PBAT/PLA/talcum powder full-biodegradable composite material.
In one embodiment, the melt blending temperature of the double-screw extruder is 140-155 ℃, and the length-diameter ratio of the screw is more than 40; the rotating speed of the screw is 100-130 r/min.
In one embodiment, fine talc refers to 3000 mesh talc having a particle size of 2000-.
It is a second object of the present invention to provide a film or packaging material prepared using the reworkable, degradable composite of the present invention.
Optionally, the composite material produced using the method of the present invention is recycled from scrap produced during further processing (e.g., blown film, bag making).
Optionally, the film or the packaging material is prepared by blending the novel composite material and the leftover material.
Optionally, the blending proportion of the leftover materials is 0-50%. The composite material prepared by the invention can be mixed with leftover granules (prepared by extruding and granulating waste films) generated in the film blowing and bag making processes of the material for use, the mixing proportion can reach more than 40-50 percent, and the tensile property and the heat sealing property are not influenced. The leftover materials are from about 3% of waste materials (transition materials, unqualified products and the like of the debugging film specification) generated in the film blowing process in the industrialized process, and the leftover materials are generated in the film rolling and bag making process (about 15% of leftover materials are generated at the digging opening of the handle of the vest bag shopping bag, and 5% of leftover materials are generated in the handle bag.
In one embodiment, the film or the packaging material is prepared by using the recyclable and degradable composite material or the leftover material produced by processing the composite material, performing extrusion blow molding, traction cooling and rolling to obtain a roll film, and slitting and making bags from the roll film.
A third object of the invention is to provide the use of said reworkable, degradable composite material.
In one embodiment, the application includes application in the fields of biodegradable agricultural mulch films, biodegradable shopping bags, biodegradable garbage bags and the like.
The invention has the advantages and effects that:
the tensile strength of the recyclable all-biodegradable composite material can reach more than 40MPa, the heat sealing strength can reach more than 12N/15mm, and the tensile strength attenuation rate of the recyclable all-biodegradable composite material is less than or equal to 25 percent (namely the retention rate is more than 75 percent) after the recyclable all-biodegradable composite material is repeatedly processed for more than 3 times. The composite material provided by the invention realizes the recovery and reproduction of leftover materials, can be recycled for more than five times at most, effectively reduces the production cost, and saves the raw materials and energy consumption.
Detailed description of the preferred embodiments
The present invention will be described in detail below.
And (3) testing tensile property: determination of tensile Properties of plastics according to GB/T1040.3-2006 part 3: test conditions for thin plastics and sheets
Sealing strength performance test: QB/T2358-1998 plastic film packaging bag heat seal strength test method
Determination of repeatable processability: and (3) repeatedly extruding the composite material obtained in the third step of the example 1 for three times by using a double-screw extrusion granulator (by adopting the process parameters of the third step), respectively testing the longitudinal tensile strength of the film after the three times of extrusion, comparing the longitudinal tensile strength with the tensile strength of the composite material obtained in the third step, and calculating the strength attenuation rate/strength retention rate.
Example 1 preparation of a reworkable PBAT/PLA/Talc fully biodegradable composite
The full-biodegradable composite material comprises the following components in parts by mass:
wherein the particle size of the talcum powder particles is 2000-3000 meshes.
The chain extender is an epoxy functional group type chain extender BTCE-9019 which is purchased from Nanjing Baitong New Material Co.
The coupling agent is a silane coupling agent, namely epoxy silane KH 560.
The main component of the hydrolysis resistant agent is polymeric carbodiimide BTWR-500 which is purchased from BTWR-500 model products of new materials Co.
The processing aid is calcium stearate.
The preparation method comprises the following steps:
the method comprises the following steps: adding the fine talcum powder and the coupling agent into a high-speed mixing M machine, setting the temperature at 90 ℃ and the rotating speed at 500 r/min, and stirring for reaction for 12min to obtain the activated fine talcum powder.
Step two: adding PBAT, PLA, activated fine talcum powder, maleic anhydride and processing aid into a high-speed mixer, setting the temperature at 100 ℃ and the rotating speed at 500 r/min, mixing for 12min, adding an anti-hydrolysis agent and a chain extender, and continuously stirring and mixing for 5 min.
Step three: and (3) feeding the mixture prepared in the step two into a double-screw extruder for melt blending and granulation, wherein the melt blending temperature of the double-screw extruder is 150 ℃, the length-diameter ratio of screws is 48: 1. the screw rotation speed is 120 r/min. Drying to obtain the PBAT/PLA/talcum powder fully biodegradable composite material which can be repeatedly processed.
Example 2 preparation of a reprocessable PBAT/PLA/Talc fully biodegradable composite
Compared with the example 1, the fully biodegradable composite material is prepared by only adjusting the component content of the fully biodegradable composite material and the other steps and methods are the same. The content of the specific components is as follows:
the full-biodegradable composite material comprises the following components in parts by mass:
example 3 preparation of a reworkable PBAT/PLA/Talc fully biodegradable composite
Compared with the example 1, the fully biodegradable composite material is prepared by only adjusting the component content of the fully biodegradable composite material and the other steps and methods are the same. The content of the specific components is as follows:
the full-biodegradable composite material comprises the following components in parts by weight:
comparative example 1
Compared with the embodiment 1, the fully biodegradable composite material is prepared by only removing the maleic anhydride in the components of the fully biodegradable composite material, and the components, the content and the preparation method of other substances are the same.
Comparative example 2
Compared with the embodiment 1, the fully biodegradable composite material is prepared by only removing the chain extender in the components of the fully biodegradable composite material, and the components, the content and the preparation method of other substances are the same.
Comparative example 3
Compared with the example 1, the fully biodegradable composite material is prepared by only removing the hydrolysis resistant agent from the components of the fully biodegradable composite material, and the components, the content and the preparation method of other substances are the same.
Comparative example 4
Compared with the embodiment 1, the full biodegradable composite material is prepared by adjusting the adding amount of the chain extender substance in the components to 0.4 part and the components, the content and the preparation method of other substances are the same.
Comparative example 5
Compared with the example 1, the addition amount of the hydrolysis resistant agent substance in the components is adjusted to 0.4 part, and the components, the content and the preparation method of other substances are the same, so that the fully biodegradable composite material is prepared.
The fully biodegradable composite materials prepared in examples 1 to 3 and comparative examples 1 to 5 were subjected to performance tests, and the results are shown in table 1.
TABLE 1
Example 4: use of composite materials
The composite material prepared in the embodiment 1-3 can be used for obtaining biodegradable agricultural mulching films, biodegradable shopping bags, biodegradable garbage bags and the like through blow molding, cooling, rolling, slitting and bag making.
The prepared product has high tensile strength, good repeatable processing performance, good weather resistance and difficult aging.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The fully biodegradable composite material capable of being repeatedly processed is characterized by comprising the following components in parts by mass:
2. the fully biodegradable composite according to claim 1, characterized by consisting of:
3. the fully biodegradable composite material according to claim 1, wherein the particle size of the talc powder is 2000-3000 mesh.
4. The fully biodegradable composite according to claim 1, characterized in that said chain extender is of acrylic polymer type and epoxy functional group polymer type.
5. The fully biodegradable composite according to claim 1, wherein said coupling agent is one or more of aluminate coupling agent, phthalate coupling agent, and silane coupling agent.
6. The fully biodegradable composite according to claim 1, wherein the hydrolysis resistant agent comprises one or a combination of two or more of monomeric carbodiimide, polymeric carbodiimide, isocyanate and acrylate as a main component.
7. The method for preparing the fully biodegradable composite material according to any one of claims 1 to 6, wherein the preparation of the fully biodegradable composite material comprises the following steps:
the method comprises the following steps: adding 10-20 parts of fine talcum powder and 0.5-1 part of coupling agent into a high-speed mixer, setting the temperature to be 80-100 ℃, rotating the speed to be 400-600 r/min, and stirring for reaction for 10-15min to obtain the activated fine talcum powder.
Step two: adding 50-60 parts of PBAT, 5-10 parts of PLA, activated fine talcum powder, 0.3-0.5 part of maleic anhydride and 1-2 parts of processing aid into a high-speed mixer, setting the temperature to be 100-105 ℃, rotating speed to be 500-600 r/min, mixing for 10-15min, adding 0.5-1 part of hydrolysis resistant agent and 0.2-0.3 part of chain extender, and then continuously stirring and mixing for 3-5 min.
Step three: and (4) feeding the mixture prepared in the step two into a double-screw extruder for melt blending and granulation, and drying to obtain the repeatedly processable PBAT/PLA/talcum powder full-biodegradable composite material.
8. A film or packaging material prepared from the reworkable, degradable composite material of any one of claims 1-6.
9. The method for producing a film or a packaging material according to claim 8, wherein the degradable packaging bag is produced by extrusion blow molding, drawing cooling, winding the recyclable and degradable composite material according to any one of claims 1 to 6 or the scrap thereof, and slitting and bagging the wound film.
10. Use of the reworkable, degradable composite material of any one of claims 1 to 6.
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| CN202210723488.5A CN115011083A (en) | 2022-06-23 | 2022-06-23 | Fully biodegradable composite material capable of being repeatedly processed and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115466491A (en) * | 2022-10-09 | 2022-12-13 | 合肥工业大学 | High-modulus degradable PBAT/PLA compound and preparation method thereof |
| CN116606538A (en) * | 2023-06-26 | 2023-08-18 | 苏州优矿塑新材料股份有限公司 | Degradable composite material based on reaction compatibilization, environment-friendly straw and preparation method thereof |
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| CN109810476A (en) * | 2017-11-20 | 2019-05-28 | 武汉华丽生物股份有限公司 | Fully biodegradable film bag material and film bag preparation method |
| CN111484709A (en) * | 2019-12-31 | 2020-08-04 | 南通龙达生物新材料科技有限公司 | Talcum powder filled full-biodegradation special film blowing material and preparation method thereof |
| CN113956623A (en) * | 2021-09-29 | 2022-01-21 | 佛山粤晟达新材料有限公司 | Full-biodegradable plastic composite modified material suitable for film bag and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109810476A (en) * | 2017-11-20 | 2019-05-28 | 武汉华丽生物股份有限公司 | Fully biodegradable film bag material and film bag preparation method |
| CN111484709A (en) * | 2019-12-31 | 2020-08-04 | 南通龙达生物新材料科技有限公司 | Talcum powder filled full-biodegradation special film blowing material and preparation method thereof |
| CN113956623A (en) * | 2021-09-29 | 2022-01-21 | 佛山粤晟达新材料有限公司 | Full-biodegradable plastic composite modified material suitable for film bag and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115466491A (en) * | 2022-10-09 | 2022-12-13 | 合肥工业大学 | High-modulus degradable PBAT/PLA compound and preparation method thereof |
| CN116606538A (en) * | 2023-06-26 | 2023-08-18 | 苏州优矿塑新材料股份有限公司 | Degradable composite material based on reaction compatibilization, environment-friendly straw and preparation method thereof |
| CN116606538B (en) * | 2023-06-26 | 2024-01-19 | 苏州优矿塑新材料股份有限公司 | Degradable composite material based on reaction compatibilization, environment-friendly straw and preparation method thereof |
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