CN103642185B - Polylactic acid foam material and preparation method thereof - Google Patents
Polylactic acid foam material and preparation method thereof Download PDFInfo
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- CN103642185B CN103642185B CN201310606455.3A CN201310606455A CN103642185B CN 103642185 B CN103642185 B CN 103642185B CN 201310606455 A CN201310606455 A CN 201310606455A CN 103642185 B CN103642185 B CN 103642185B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
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- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Biological Depolymerization Polymers (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a kind of Polylactic acid foam material, it is obtained through foaming by mixture, described mixture includes the polylactic acid of 100 weight portions, the water of 0.5～15 weight portion, the carrier of 1～90 weight portion, the plasticizer of 0～20 weight portion, the nucleator of 0～15 weight portion, the hydrolysis-resisting agent of 0～3 weight portion, the chain extender of 0～5 weight portion.The Polylactic acid foam material of the application is using water as foaming agent, and it being provided without organic foaming agent, the foaming making polylactic acid is safety and environmental protection, and the matrix that the application adopts polylactic acid to be foamed materials, it has good biological degradability, therefore makes Polylactic acid foam material can realize biodegradation.The preparation method that present invention also provides described Polylactic acid foam material.
Description
Technical field
The present invention relates to foam technology field, particularly relate to a kind of Polylactic acid foam material and preparation method thereof.
Background technology
Foam plastics is a kind of new material, and it is with plastics for solvent, containing a large amount of bubbles, the composite that therefore it is filler with gas that foam plastics may also be.Due to foam plastics there is light weight, thermal conductivity is low, heat-proof quality good, can absorb the valuable performances such as shock loading, shock-absorbing capacity is excellent, sound insulation value good, specific strength is high, extensive use in family's articles for daily use, the vehicles, insulant, packaging material, electrical equipment, sports facility, electronic product and chemistry and the industry such as weaving.
At present most expanded materials, such as polystyrene foamed material, polyethylene foam material and polypropylene foam etc., due to the poor operability recycled and the aspect such as price is low, the overwhelming majority is taken as garbage after using and throws away.But foamed materials light weight, volume are big and are difficult to degraded of rotting, and bring serious impact to environment, cause " white pollution ".The effective way solving the problems referred to above is that by foaming, Biodegradable material is obtained foamed materials, to adapt to the needs in market and application.Therefore, develop and use biodegradable expanded material to be increasingly becoming the important development trend of foam material field.
Most of expanded materials are to be prepared from by gas foaming within the scope of specific polymerization system viscosity.Foaming agent adds in polymeric matrix, by heat resolve, or is directly injected into offer gas, makes polymer can form the assistant types of foam structure at the process conditions.Therefore, foaming agent is the important processing aid that expanded material is indispensable.Different according to the mode producing gas in foaming process, foaming agent is generally divided into physical blowing agent and the big class of CBA two.Physical blowing agent includes inertia compression gas and the low-boiling point liquid dissolving in resin.Inertia compression gas mainly includes air, nitrogen and carbon dioxide etc.；Low-boiling point liquid is mainly aliphatic hydrocarbon or halogenated hydrocarbons, such as pentane, hexane or Chlorofluorocarbons (CFCs) etc..Environment is easily produced to pollute by low-boiling point liquid, and owing to it is inflammable, brings very big potential safety hazard to producing.CBA is often referred to the heat decomposition type CBA with powdery feature, and it can be scattered in plastics and rubber uniformly, decomposes rapidly at processing temperatures, produces a large amount of gas, so that resin expanded.In CBA, azodicarbonamide is main force's kind, and its consumption accounts for first of CBA.But, environment and operator are produced great harm by the carbon monoxide, the harmful gas such as ammonia that contain in the gas composition that CBA decomposes, and residue after decomposition and unreacted CBA such as can pollute at the problem.
The foaming agent preparing the use of degradable polylactic acid foam plastic at present mainly comprises above-mentioned physical blowing agent or CBA.If application number is that 201010290724 Chinese invention patents disclose a kind of Plant fiber and strengthen Polylactic acid foam material, this material is prepared from by following component: polylactic acid 20%～95%, plant fiber powder 1%～60%, foaming agent 1%～5%, nucleator 1%～5%, antioxidant 1%～5%, bulking agent 1%～5%.It is low, biodegradable that the expanded material of this patent has apparent density, TPO expanded material can be replaced to be widely used in thermal insulation, buffering and packaging field and preparation technology is simple, production efficiency is high.But, the foaming agent of use is CBA, such as azodiisobutyronitrile, azodicarbonamide and Barium azodicarboxylate etc..For another example application number is that 200510104903 Chinese invention patents provide a kind of Biodegradable composition and contain starch, polylactic acid, polyhydric alcohol and foaming agent, wherein, described starch is substitution value be 0.1～3 esterification starch and/or etherification starch.The foamed product that the compositions provided in this patent obtains has good expansion ratio and compressive strength, but also has higher biological degradation rate and mycete degraded level.But, the foaming agent of use is N-nitroso compound foaming agent, azo foaming agent and hydrazides class CBA, and it will also result in the pollution of environment after decomposing.
Summary of the invention
Present invention solves the technical problem that and be in that to provide a kind of non-environmental-pollution and biodegradable Polylactic acid foam material and preparation method thereof.
In view of this, this application provides a kind of Polylactic acid foam material, mixture obtain through foaming, described mixture includes:
Preferably, described Polylactic acid foam material does not include organic foaming agent.
Preferably, described carrier is one or more in montmorillonite, kieselguhr, cellulose, polyacrylamide and starch.
Preferably, described plasticizer is one or more in o-phthalic acid dibutyl ester, tributyl citrate, acetylation tributyl citrate, epoxy soybean oil and glycerol.
Preferably, described nucleator is one or more in zinc oxide, calcium carbonate, azodicarbonamide, Pulvis Talci and silicon dioxide.
Preferably, described hydrolysis-resisting agent is one or both in carbodiimides and polycarbodiimide.
Preferably, described chain extender is one or more in toluene di-isocyanate(TDI), hexamethylene-diisocyanate, poly methylene poly phenyl poly isocyanate and methyl diphenylene diisocyanate.
Preferably, the weight average molecular weight of described polylactic acid is 5～200,000.
The preparation method that present invention also offers described Polylactic acid foam material, including:
By extrusion foaming after following raw material stirring, obtain Polylactic acid foam material；
Preferably, the temperature range of described extrusion foaming is:
One district's temperature is 50～90 DEG C, and two district's temperature are 50～100 DEG C, and three district's temperature are 100～160 DEG C, and four district's temperature are 120～190 DEG C, and five district's temperature are 130～190 DEG C, and six district's temperature are 130～180 DEG C, and seven district's temperature are 120～150 DEG C.
The invention provides a kind of Polylactic acid foam material, described Polylactic acid foam material is obtained by mixture foaming, described mixture includes: polylactic acid, water, carrier, plasticizer, nucleator, hydrolysis-resisting agent and chain extender, the Polylactic acid foam material of the application is using water as foaming agent, and it is provided without organic foaming agent, avoid in the process preparing foamed materials and decomposite pollution gas, thus making the preparation process of Polylactic acid foam material is safety and environmental protection, and the matrix that the application adopts polylactic acid to be foamed materials, it has good biological degradability, therefore Polylactic acid foam material can realize biodegradation.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but it is to be understood that these describe simply as further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The embodiment of the invention discloses a kind of Polylactic acid foam material, following mixture obtain through foaming, described mixture includes:
Polylactic acid foam material of the present invention is obtained through foaming by raw material, and expanded material is that polymeric matrix is prepared from by gas foaming.At normal atmospheric pressure, the boiling point of water is 100 DEG C, and gasification latent heat is 40.8 kj/mol, and 1 gram of water can produce 1.24 liters of steam after being gasified totally, compared with other material such as carbon dioxide, the gas production of water is very big.The present invention, using water as the foaming agent of polylactic acid, has advantages such as being easy to get, cheap, free from environmental pollution, human body is non-stimulated, quantity of steam is big, thus solving the problems that existing physically or chemically foaming agent brings.
According to the present invention, described polylactic acid is resin material well known to those skilled in the art, and it has biological degradability, therefore makes foamed materials also have biological degradability.The weight average molecular weight of described polylactic acid is preferably 50,000～200,000, it is preferred to 80,000～150,000.If the weight average molecular weight of described polylactic acid is lower than 50,000, then the Polylactic acid foam material prepared is too crisp cannot be used.
The present invention is with water for foaming agent, and it can produce substantial amounts of steam in case of heating, so that polylactic acid forms foam structure, obtains foamed materials.The content of described water is 0.5 weight portion～15 weight portion, it is preferred to 1 weight portion～12 weight portion, more preferably 5 weight portion～10 weight portions.Herein described polylactic acid foam plastic does not include organic foaming agent.
According to the present invention, the raw material of described Polylactic acid foam material includes carrier, and described carrier is preferably one or more in montmorillonite, kieselguhr, cellulose, polyacrylamide and starch.The content of described carrier is 1～90 weight portion, it is preferred to 5～80 weight portions, more preferably 10～60 weight portions.
In order to the performance making Polylactic acid foam material is better, also including plasticizer in herein described Polylactic acid foam material, described plasticizer can be effectively improved Polylactic acid foam material mechanical property.Described plasticizer is preferably one or more in o-phthalic acid dibutyl ester, tributyl citrate, acetylation tributyl citrate, epoxy soybean oil and glycerol, and the content of described plasticizer is 0～20 weight portion, it is preferred to 5～15 weight portions.
Also including nucleator in the raw material of Polylactic acid foam material of the present invention, described nucleator can reduce the abscess-size of expanded material.Described nucleator is preferably one or more in zinc oxide, calcium carbonate, azodicarbonamide, Pulvis Talci and silicon dioxide.The content of described nucleator is 0～15 weight portion, it is preferred to 2～10 weight portions, more preferably 5～8 weight portions.
According to the present invention, described hydrolysis-resisting agent and described chain extender all can reduce polylactic acid hydrolysis in preparing foamed materials process.Described hydrolysis-resisting agent is preferably one or both in carbodiimides and polycarbodiimide, and the content of described hydrolysis-resisting agent is 0～3 weight portion, it is preferred to 1～2 weight portion.Described chain extender is preferably one or more in toluene di-isocyanate(TDI), hexamethylene-diisocyanate, poly methylene poly phenyl poly isocyanate and methyl diphenylene diisocyanate.The content of described chain extender is 0～5 weight portion, it is preferred to 2～4 weight portions.
The invention provides a kind of Polylactic acid foam material, it is obtained through foaming by mixture, and described mixture includes polylactic acid, water, carrier, plasticizer, nucleator, hydrolysis-resisting agent and chain extender.The application uses water as foaming agent by adopting, and it can form substantial amounts of bubble in heating process, makes expanded polylactic acid, thus obtaining Polylactic acid foam material；Replace organic foaming agent with water, make the safe preparation process of Polylactic acid foam material, environmental protection；The application is using polylactic acid as foaming raw material simultaneously, and it has biological degradability, therefore makes the foamed materials of preparation also have biological degradability.
The preparation method that present invention also offers described Polylactic acid foam material, including:
By extrusion foaming after following raw material stirring, obtain Polylactic acid foam material；
According to the present invention, described Polylactic acid foam material adopts the method for directly extrusion directly to prepare.In the process preparing polylactic acid foam, stirring after first polylactic acid, water, carrier, plasticizer, nucleator, hydrolysis-resisting agent being mixed with chain extender, the time of described stirring is preferably 3～5min, enables above-mentioned raw materials mix homogeneously.
After above-mentioned material stirring is completed, the direct extrusion foaming of mixture that will obtain, obtain Polylactic acid foam material.The application is preferably in extrusion foaming in double screw extruder.In the process of described extrusion foaming, the heating system of double screw extruder is divided into different regions, so that better performances after expanded material extrusion.According to the present invention, the temperature range of described extrusion foaming is preferably divided into seven regions, the temperature in one district is preferably 50 DEG C～90 DEG C, the temperature in 2nd district is preferably 50 DEG C～100 DEG C, the temperature in 3rd district is preferably 100 DEG C～160 DEG C, and the temperature in 4th district is preferably 120 DEG C～190 DEG C, and the temperature in 5th district is preferably 130 DEG C～190 DEG C, the temperature in 6th district is preferably 130 DEG C～180 DEG C, and the temperature in 7th district is preferably 120 DEG C～150 DEG C.In above-mentioned zone, front trizonal basal temperature is relatively low, it is possible to effectively prevent foaming agent watery vomiting stream, and then four regional temperatures are high, makes foaming agent water be in superheat state, it is possible to meet the needs of foaming.
The preparation method that this application provides a kind of Polylactic acid foam material, in the process of preparation Polylactic acid foam material, using polylactic acid as the raw material of expanded material, water is as foaming agent, the method adopting directly extrusion prepares Polylactic acid foam material, makes safe preparation process environmental protection.It addition, the application in the process of extrusion foaming also by control extrusion foaming temperature range, make the Polylactic acid foam material of preparation have good compressive strength and expansion ratio.Test result indicate that, the expansion ratio of Polylactic acid foam material prepared by the application is 1～40 times, and compressive strength is 0.05MPa～10MPa.
In order to be further appreciated by the present invention, below in conjunction with embodiment, Polylactic acid foam material provided by the invention and preparation method thereof being described in detail, protection scope of the present invention is not limited by the following examples.
The raw material adopted in following example is commercially available prod, the TE-35 type double screw extruder that the equipment double screw extruder adopted provides for Nanjing Ke Ya plastic apparatus company limited.
Embodiment 1
Pressing row parts by weight and weigh each component: weight average molecular weight is the polylactic acid 100 parts of 50,000,0.5 part of water, starch 1 part, after above-mentioned each component is stirred 3 minutes in mixer, on twin screw, direct extrusion foaming, obtains polylactic acid foam plastic；The temperature range of extrusion foaming system is: a district: 50 DEG C, 2nd district: 50 DEG C, 3rd district: 100 DEG C, 4th district: 120 DEG C, 5th district: 130 DEG C, 6th district: 130 DEG C, 7th district: 120 DEG C, and the temperature of die head is 100 DEG C.The expansion ratio of polylactic acid foam plastic prepared by the present embodiment is 1 times, and compressive strength is 10MPa.
Embodiment 2
Press row parts by weight and weigh each component: weight average molecular weight is the polylactic acid 100 parts of 200,000,15 parts of water, starch 90 parts, dioctyl phthalate 20 parts, zinc oxide 15 parts, carbodiimides 3 parts, toluene di-isocyanate(TDI) 5 parts.After above-mentioned each component is stirred 3 minutes in mixer, on twin screw, direct extrusion foaming, obtains polylactic acid foam plastic；The temperature range of extrusion foaming system is: a district: 90 DEG C, 2nd district: 100 DEG C, 3rd district: 160 DEG C, 4th district: 190 DEG C, 5th district: 190 DEG C, 6th district: 180 DEG C, 7th district: 150 DEG C, and die head temperature is 150 DEG C.The expansion ratio of Polylactic acid foam material prepared by the present embodiment is 40 times, and compressive strength is 0.05MPa.
Embodiment 3
Press row parts by weight and weigh each component: weight average molecular weight is the polylactic acid 100 parts of 80,000,10 parts of water, montmorillonite 20 parts, tributyl citrate 10 parts, calcium carbonate 2 parts, carbodiimides 1 part, toluene di-isocyanate(TDI) 2 parts.After above-mentioned each component is stirred 3 minutes in mixer, on twin screw, direct extrusion foaming, obtains polylactic acid foam plastic；The temperature range of extrusion foaming system is: a district: 90 DEG C, 2nd district: 100 DEG C, 3rd district: 150 DEG C, 4th district: 160 DEG C, 5th district: 160 DEG C, 6th district: 150 DEG C, 7th district: 140 DEG C, die head temperature is the expansion ratio of polylactic acid foam plastic prepared by 130 DEG C of the present embodiment is 30 times, and compressive strength is 0.08MPa.
Embodiment 4
Press row parts by weight and weigh each component: weight average molecular weight is the polylactic acid 100 parts of 150,000,5 parts of water, 10 parts of silicon bath soil, Pulvis Talci 5 parts, carbodiimides 2 parts, hexamethylene-diisocyanate 2 parts.After above-mentioned each component is stirred 3 minutes in mixer, on twin screw, direct extrusion foaming, obtains polylactic acid foam plastic；Extrusion foaming system temperature interval is: a district: 90 DEG C, 2nd district: 100 DEG C, 3rd district: 150 DEG C, 4th district: 160 DEG C, 5th district: 160 DEG C, 6th district: 150 DEG C, 7th district: 140 DEG C, and the temperature of die head is 130 DEG C.The expansion ratio of polylactic acid foam plastic prepared by the present embodiment is 16 times, and compressive strength is 1MPa.
Embodiment 5
Press row parts by weight and weigh each component: weight average molecular weight is the polylactic acid 100 parts of 150,000,5 parts of water, cellulose 10 parts, epoxy soybean oil 10 parts, azodicarbonamide 5 parts, carbodiimides 2 parts, poly methylene poly phenyl poly isocyanate 2 parts.After above-mentioned each component is stirred 3 minutes in mixer, on twin screw, direct extrusion foaming, obtains polylactic acid foam plastic；Extrusion foaming system temperature interval is: a district: 90 DEG C, 2nd district: 100 DEG C, 3rd district: 140 DEG C, 4th district: 150 DEG C, 5th district: 150 DEG C, 6th district: 140 DEG C, 7th district: 140 DEG C, and the temperature of die head is 130 DEG C.The expansion ratio of polylactic acid foam plastic prepared by the present embodiment is 14 times, and compressive strength is 1.2MPa.
Embodiment 6
Press row parts by weight and weigh each component: weight average molecular weight is the polylactic acid 100 parts of 100,000,7 parts of water, polyacrylamide 10 parts, glycerol 10 parts, silica 10 part, carbodiimides 2 parts, methyl diphenylene diisocyanate 2 parts.After above-mentioned each component is stirred 3 minutes in mixer, on twin screw, direct extrusion foaming, obtains polylactic acid foam plastic；Extrusion foaming system temperature interval is: a district: 90 DEG C, 2nd district: 100 DEG C, 3rd district: 140 DEG C, 4th district: 150 DEG C, 5th district: 150 DEG C, 6th district: 140 DEG C, 7th district: 140 DEG C, and the temperature of die head is 130 DEG C.The expansion ratio of foam plastics prepared by the present embodiment is 25 times of compressive strengths is 0.9MPa.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention.The multiple amendment of these embodiments be will be apparent from for those skilled in the art, and generic principles defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention is not intended to be limited to the embodiments shown herein, and is to fit to the widest scope consistent with principles disclosed herein and features of novelty.
Claims (8)
1. a Polylactic acid foam material, is obtained through foaming by mixture, and described mixture includes:
Described hydrolysis-resisting agent is carbodiimides；Described chain extender is one or more in toluene di-isocyanate(TDI), hexamethylene-diisocyanate, poly methylene poly phenyl poly isocyanate and methyl diphenylene diisocyanate.
2. Polylactic acid foam material according to claim 1, it is characterised in that described Polylactic acid foam material does not include organic foaming agent.
3. Polylactic acid foam material according to claim 1, it is characterised in that described carrier is one or more in montmorillonite, kieselguhr, cellulose, polyacrylamide and starch.
4. Polylactic acid foam material according to claim 1, it is characterised in that described plasticizer is one or more in o-phthalic acid dibutyl ester, tributyl citrate, acetylation tributyl citrate, epoxy soybean oil and glycerol.
5. Polylactic acid foam material according to claim 1, it is characterised in that described nucleator is one or more in zinc oxide, calcium carbonate, azodicarbonamide, Pulvis Talci and silicon dioxide.
6. Polylactic acid foam material according to claim 1, it is characterised in that the weight average molecular weight of described polylactic acid is 5～200,000.
7. the preparation method of Polylactic acid foam material described in any one of claim 1～6, including:
By extrusion foaming after following raw material stirring, obtain Polylactic acid foam material；
Described hydrolysis-resisting agent is carbodiimides；Described chain extender is one or more in toluene di-isocyanate(TDI), hexamethylene-diisocyanate, poly methylene poly phenyl poly isocyanate and methyl diphenylene diisocyanate.
8. preparation method according to claim 7, it is characterised in that the temperature range of described extrusion foaming is:
One district's temperature is 50～90 DEG C, and two district's temperature are 50～100 DEG C, and three district's temperature are 100～160 DEG C, and four district's temperature are 120～190 DEG C, and five district's temperature are 130～190 DEG C, and six district's temperature are 130～180 DEG C, and seven district's temperature are 120～150 DEG C.
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| CN105542222B (en) * | 2015-12-30 | 2018-07-27 | 江阴市长泾花园毛纺织有限公司 | A kind of preparation method of polylactic acid gel toughening sponge |
| CN106189146A (en) * | 2016-08-29 | 2016-12-07 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of polylactic acid antibacterial matrices |
| CN106589468B (en) * | 2016-10-21 | 2018-11-27 | 广西师范学院 | Controlled degradation cultivates basin and preparation method thereof |
| CN108948466A (en) * | 2018-07-13 | 2018-12-07 | 湖州市道场乡资产经营有限公司 | A kind of low resilience high resiliency SBR foam sponge |
| CN111040397B (en) * | 2019-08-22 | 2021-09-24 | 广州绿徽新材料研究院有限公司 | Preparation method of heat-resistant flame-retardant modified material and product of combined foamed polylactic acid |
| CN111168803A (en) * | 2019-12-31 | 2020-05-19 | 嘉兴市集美新材料科技有限公司 | Environment-friendly waterproof high-strength artificial board and manufacturing method thereof |
| CN112266590B (en) * | 2020-09-19 | 2023-02-28 | 恒天生物基材料工程技术（宁波）有限公司 | Polylactic acid/microcrystalline cellulose composite foamed sheet and preparation method thereof |
| CN112544695B (en) * | 2020-10-16 | 2022-09-13 | 浙江杭化新材料科技有限公司 | Interlayer paper for fruit and vegetable fresh-keeping |
| US20220162415A1 (en) * | 2020-11-24 | 2022-05-26 | Ricoh Company, Ltd. | Foam sheet, product, formed product, and method for producing foam sheet |
| CN112812515A (en) * | 2020-12-31 | 2021-05-18 | 浙江工业大学 | Degradable foaming material and preparation method thereof |
| CN112920572A (en) * | 2021-01-29 | 2021-06-08 | 大连盈诺环保科技有限公司 | High-temperature-resistant polylactic resin and modified production process thereof |
| CN113105731A (en) * | 2021-04-15 | 2021-07-13 | 山东道恩高分子材料股份有限公司 | Biodegradable foamed sheet |
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| CN102796361A (en) * | 2012-08-10 | 2012-11-28 | 中国科学院长春应用化学研究所 | Biodegradable carbon dioxide-epoxypropane copolymer foamed plastic and preparation method thereof |
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| CN102796361A (en) * | 2012-08-10 | 2012-11-28 | 中国科学院长春应用化学研究所 | Biodegradable carbon dioxide-epoxypropane copolymer foamed plastic and preparation method thereof |
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