CN1544525A - Method for preparing biodegradable poly-lactic acid foam plastic - Google Patents
Method for preparing biodegradable poly-lactic acid foam plastic Download PDFInfo
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- CN1544525A CN1544525A CNA2003101158264A CN200310115826A CN1544525A CN 1544525 A CN1544525 A CN 1544525A CN A2003101158264 A CNA2003101158264 A CN A2003101158264A CN 200310115826 A CN200310115826 A CN 200310115826A CN 1544525 A CN1544525 A CN 1544525A
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Abstract
The invention provides a hyperoxide cross-linked biodegradable polylactic acid aerated plastics comprises by weight percent of, 60-97% of polylactic acid, 1-10% hydroperoxide, 1-20% of foaming agent, and 1-5% of core forming agent, the preparation comprises the steps of mixing the raw material uniformly, blending 5 minutes in closed-smelting machine at 90 deg C. to 120 deg C, crosslink foaming 2-5 minutes in oil bath or on vulcanizing press at 130 deg C. -190 deg C.
Description
Technical field
The present invention relates to the method that a kind of peroxide crosslinking technology prepares biodegradable polylactic acid foam plastic.
Background technology
The initial raw material of synthesizing polylactic acid is a starch, and starch is converted into lactic acid through biological fermentation process, and lactic acid is through polycondensation or ring-opening polymerization obtains poly(lactic acid) through rac-Lactide again.This shows that one of essence of poly(lactic acid) difference and other general-purpose plastics is the plant resources that it has utilized recyclability.Yet the identical performance of poly(lactic acid) tool and general-purpose plastics is as workability.But poly(lactic acid) also has unique biological consistency and biological degradability.Therefore, in the last few years, poly(lactic acid) is the concern of the academic boundary of polymer and industrial community extremely, became 21 century hot research object.
No matter be with polyethylene, polystyrene, should be that porous plastics that raw material makes has all that light weight, material-saving, thermal conductivity are low with urethane, heat-proof quality, absorb performances such as shock load, sound-proofing properties are good, specific tenacity height, bring into play enormous function at packaging industry.Yet after these porous plastics were used, very difficult recycling recycled once more, was discarded in the environment, can not assimilate with environment, and environment is caused significant damage.As swim in the ocean and swallowed by marine organisms, cause marine organisms death.
Poly(lactic acid) is prepared into porous plastics, makes it both to have the characteristic of porous plastics, have biodegradation character again, after its goods consumption, in physical environment, be easy to be degraded by microorganisms, generate carbonic acid gas and water, with the environment complete assimilation.
People such as Sterzel adopt the method sneak into pneumatogen in poly(lactic acid) to prepare poly(lactic acid) structural foam (United States Patent (USP) 5348983,1994), still, could foam after making the less particle of particle diameter to poly(lactic acid).People such as Kameoka adopt and to sneak into the method that chemical foaming agent and pneumatogen directly extrude and prepare polylactic acid foam plastic (United States Patent (USP) 5763098,1998), the porous plastics density that adopts the method gained of chemical foaming agent be 0.5g cm
3, and adopt the porous plastics density of the method gained of pneumatogen be 0.10g cm
3In our last work, consider that the melt viscosity and the intensity that improve poly(lactic acid) help expanded polylactic acid, in the course of processing, add chainextender, effectively alleviate because the reduction of the polylactic acid molecule amount that processing causes, adopt the chemical foaming method to make polylactic acid foam plastic, its density be 0.5g cm
3
Summary of the invention
The purpose of this invention is to provide a kind of biodegradable polylactic acid foam plastic preparation method.
Provide a kind of peroxide crosslinking to prepare the method for biodegradable polylactic acid foam plastic at the deficiencies in the prior art.Promptly adding superoxide in the course of processing, to cause poly(lactic acid) crosslinked, by the chemical foaming method, obtains even, the fine and closely woven biodegradable foam plastic of abscess after making poly(lactic acid) crosslinked.Up to now, domestic and foreign literature and patent are not seen the report that adopts peroxide crosslinking to prepare biodegradable polylactic acid foam plastic as yet.
Biodegradable polylactic acid foam plastic provided by the invention, wherein:
The poly(lactic acid) second-order transition temperature is 40-60 ℃, and the weight percentage of adding is 60-97%.
Superoxide is benzoyl peroxide (BPO), t-butyl peroxy benzoate, dicumyl peroxide (DCP), tertiary butyl cumyl peroxide, ditertiary butyl peroxide, (2,5-dimethyl-2,5 di-t-butyls) peroxy hexane, (2,5-dimethyl-2,5 di-t-butyls) peroxy hexin, 2,4-dichlorobenzoperoxide, di-t-butyl peroxy diisopropylbenzene(DIPB) or 1,1-bis(t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane; The weight percentage that adds is 1-10%.
Whipping agent is a Cellmic C 121 (AC), 2,2 '-Diisopropyl azodicarboxylate (AZDN), diisopropyl azodiformate (DIPA), two azoanilines (DAB), N, N-dinitroso five methyne tetramines, N, N-dimethyl-N, N '-dinitroso is to benzene, benzol sulfohydrazide (BSH), 4,4 '-OBSH (OBSH), 3,3 '-disulfonyl hydrazide sulfobenzide, 1, the mixture of 3 '-benzene disulfohydrazide, diazobenzeneanilide, oxaluria, nitro urine, yellow soda ash and citric acid or the mixture of lime carbonate and citric acid, the weight percentage of adding is 1-20%.
Polyfunctional monomer is acrylate, trimethylolpropane trimethacrylate, season amylalcohol tetramethyl-acrylate, Viscoat 295 or the trimethylolpropane trimethacrylate of triallyl cyanurate, triallyl benzenetricarboxylic acid ester, diallyl phthalic ester, season amylalcohol, and the weight percentage of adding is 0%-5%.
Nucleator is zinc oxide, calcium oxide, silicon-dioxide, aluminum oxide, talcum powder or lime carbonate, and the weight percentage of adding is 1-5%.
The melt blending process: starting material are mixed in container in proportion in advance, mixing 5 minutes in 90-120 ℃ in Banbury mixer or mill then.
With gained material 120 ℃ of die formings on thermocompressor, after crosslinked in oil bath, in the baking oven or on the thermocompressor 130-190 ℃ foamed 2-5 minute.
Below will come further detailed explanation the present invention by representing example of the present invention.In example, mark and per-cent are all by weight except as otherwise noted.But the present invention is not limited to these examples.
Embodiment
Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to foregoing.
Embodiment 1. poly(lactic acid), benzoyl peroxide, AC whipping agent, talcum powder were by following proportioning 97: 1: 1: 1 in Banbury mixer 110 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ be pressed into sheet material after, 180 ℃ were carried out crosslinked foaming 2 minutes in oil bath.The density of the porous plastics that obtains is 0.60g/cm
3Mechanical property: Young's modulus is 321MPa, and tensile strength is 4.50MPa, and elongation at break is 4.3%.The biological degradation experiment can be degraded fully.
Embodiment 2. poly(lactic acid), t-butyl peroxy benzoate, N, N-dinitroso five methyne tetramines, talcum powder, urea were by following proportioning 95: 2: 2: 0.5: 0.5 in mill 110 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ be pressed into sheet material after, carried out crosslinked foaming 3 minutes in 180 ℃ of baking ovens.The density of the porous plastics that obtains is 0.35g/cm
3Mechanical property: Young's modulus is 293MPa, and tensile strength is 3.94MPa, and elongation at break is 4.0%.The biological degradation experiment can be degraded fully.
Embodiment 3. poly(lactic acid), 2,4-dichlorobenzoperoxide, 4,4 '-OBSH, silicon-dioxide, urea were by following proportioning 94: 3: 2: 0.5: 0.5 in mill 110 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, carried out crosslinked foaming 5 minutes on 140 ℃ of thermocompressores.The density of the porous plastics that obtains is 0.40g/cm
3Mechanical property: Young's modulus is 303MPa, and tensile strength is 3.88MPa, and elongation at break is 4.5%.The biological degradation experiment can be degraded fully.
Embodiment 4. poly(lactic acid), dicumyl peroxide, diisopropyl azodiformate, lime carbonate were by following proportioning 94.5: 3: 2: 0.5 in mill 110 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, carried out crosslinked foaming 4 minutes on 170 ℃ of thermocompressores.The density of the porous plastics that obtains is 0.24g/cm
3Mechanical property: Young's modulus is 261MPa, and tensile strength is 2.88MPa, and elongation at break is 4.2%.The biological degradation experiment can be degraded fully.
Embodiment 5. poly(lactic acid), ditertiary butyl peroxide, diisopropyl azodiformate, silicon-dioxide were by following proportioning 94.5: 3: 2: 0.5 in mill 110 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, carried out crosslinked foaming 4 minutes on 180 ℃ of thermocompressores.The density of the porous plastics that obtains is 0.28g/cm
3Mechanical property: Young's modulus is 277MPa, and tensile strength is 2.96MPa, and elongation at break is 4.0%.The biological degradation experiment can be degraded fully.
Embodiment 6. poly(lactic acid), tertiary butyl cumyl peroxide, diisopropyl azodiformate, silicon-dioxide were by following proportioning 94.5: 3: 2: 0.5 in mill 110 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, carried out crosslinked foaming 4 minutes on 176 ℃ of thermocompressores.The density of the porous plastics that obtains is 0.30g/cm
3Mechanical property: Young's modulus is 280MPa, and tensile strength is 2.99MPa, and elongation at break is 4.4%.The biological degradation experiment can be degraded fully.
Embodiment 7. poly(lactic acid), (2,5-dimethyl-2,5 di-t-butyl) peroxy hexane, diisopropyl azodiformate, calcium oxide were by following proportioning 94.5: 3: 2: 0.5 in mill 110 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, carried out crosslinked foaming 3 minutes on 180 ℃ of thermocompressores.The density of the porous plastics that obtains is 0.30g/cm
3Mechanical property: Young's modulus is 280MPa, and tensile strength is 2.99MPa, and elongation at break is 4.4%.The biological degradation experiment can be degraded fully.
Embodiment 8. poly(lactic acid), (2,5-dimethyl-2,5 di-t-butyl) peroxy hexin, diisopropyl azodiformate, silicon-dioxide were by following proportioning 94.5: 3: 2: 0.5 in mill 110 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, on 190 ℃ of thermocompressores, carried out crosslinked foaming 4 minutes.The density of the porous plastics that obtains is 0.36g/cm
3Mechanical property: Young's modulus is 295MPa, and tensile strength is 3.21MPa, and elongation at break is 4.8%.The biological degradation experiment can be degraded fully.
Embodiment 9. poly(lactic acid), di-t-butyl peroxy diisopropylbenzene(DIPB), diisopropyl azodiformate, silicon-dioxide were by following proportioning 94.5: 3: 2: 0.5 in mill 110 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, on 180 ℃ of thermocompressores, carried out crosslinked foaming 5 minutes.The density of the porous plastics that obtains is 0.29g/cm
3Mechanical property: Young's modulus is 300MPa, and tensile strength is 3.51MPa, and elongation at break is 4.5%.The biological degradation experiment can be degraded fully.
Embodiment 10. poly(lactic acid), 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, 3,3 '-disulfonyl hydrazide sulfobenzide, silicon-dioxide were by following proportioning 94.5: 3: 2: 0.5 in mill 110 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, on 150 ℃ of thermocompressores, carried out crosslinked foaming 5 minutes.The density of the porous plastics that obtains is 0.20g/cm
3Mechanical property: Young's modulus is 264MPa, and tensile strength is 3.21MPa, and elongation at break is 4.8%.The biological degradation experiment can be degraded fully.
Embodiment 11. poly(lactic acid), benzoyl peroxide, 2,2 '-Diisopropyl azodicarboxylate, silicon-dioxide were by following proportioning 94.5: 3: 2: 0.5 in mill 90 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, on 135 ℃ of thermocompressores, carried out crosslinked foaming 5 minutes.The density of the porous plastics that obtains is 0.50g/cm
3Mechanical property: Young's modulus is 321MPa, and tensile strength is 4.23MPa, and elongation at break is 4.0%.The biological degradation experiment can be degraded fully.
Embodiment 12. poly(lactic acid), benzoyl peroxide, two azoanilines, silicon-dioxide were by following proportioning 94.5: 3: 2: 0.5 in mill 90 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, on 135 ℃ of thermocompressores, carried out crosslinked foaming 4 minutes.The density of the porous plastics that obtains is 0.60g/cm
3Mechanical property: Young's modulus is 345MPa, and tensile strength is 5.13MPa, and elongation at break is 4.0%.The biological degradation experiment can be degraded fully.
Embodiment 13. poly(lactic acid), benzoyl peroxide, N, N-dimethyl-N, N '-dinitroso to benzene, silicon-dioxide, trimethylolpropane trimethacrylate by following proportioning 93.5: 3: 2: 0.5: 1 in mill 90 ℃ mixing 5 minutes down.The mixture that obtains under 120 ℃ after being pressed into sheet material on the vulcanizing press, on 130 ℃ of thermocompressor upper flat plate vulcanizers, carried out crosslinked foaming 3 minutes.The density of the porous plastics that obtains is 0.55g/cm
3Mechanical property: Young's modulus is 350MPa, and tensile strength is 5.05MPa, and elongation at break is 4.7%.The biological degradation experiment can be degraded fully.
Embodiment 14. poly(lactic acid), benzoyl peroxide, benzol sulfohydrazide, silicon-dioxide, Viscoat 295 were by following proportioning 93.5: 3: 2: 0.5: 1 in mill 90 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, on 135 ℃ of thermocompressores, carried out crosslinked foaming 5 minutes.The density of the porous plastics that obtains is 0.61g/cm
3Mechanical property: Young's modulus is 359MPa, and tensile strength is 5.12MPa, and elongation at break is 4.5%.The biological degradation experiment can be degraded fully.
Embodiment 15. poly(lactic acid), benzoyl peroxide, oxaluria, silicon-dioxide, season, amylalcohol tetramethyl-acrylate was by following proportioning 93.5: 3: 2: 0.5: 1 in mill 90 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, on 150 ℃ of thermocompressores, carried out crosslinked foaming 4 minutes.The density of the porous plastics that obtains is 0.42g/cm
3Mechanical property: Young's modulus is 333MPa, and tensile strength is 4.42MPa, and elongation at break is 4.0%.The biological degradation experiment can be degraded fully.
Embodiment 16. poly(lactic acid), benzoyl peroxide, 1,3 '-benzene disulfohydrazide, calcium oxide, trimethylolpropane trimethacrylate were by following proportioning 93.5: 3: 2: 0.5: 1 in mill 100 ℃ mixing 5 minutes down.The mixture that obtains 120 ℃ depress to sheet material after, on 140 ℃ of thermocompressores, carried out crosslinked foaming 4 minutes.The density of the porous plastics that obtains is 0.44g/cm
3Mechanical property: Young's modulus is 365MPa, and tensile strength is 4.76MPa, and elongation at break is 4.7%.The biological degradation experiment can be degraded fully.
Embodiment 17. poly(lactic acid), benzoyl peroxide, diazobenzeneanilide, silicon-dioxide, season amylalcohol acrylate by following proportioning 93.5: 3: 2: 0.5: 1 in mill 100 ℃ mixing 5 minutes down.The mixture that obtains 100 ℃ depress to sheet material after, on 130 ℃ of thermocompressores, carried out crosslinked foaming 3 minutes.The density of the porous plastics that obtains is 0.60g/cm
3Mechanical property: Young's modulus is 375MPa, and tensile strength is 4.85MPa, and elongation at break is 4.0%.The biological degradation experiment can be degraded fully.
Embodiment 18. poly(lactic acid), benzoyl peroxide, nitro urine, silicon-dioxide, diallyl phthalic ester were by following proportioning 89.5: 3: 2: 0.5: 5 in mill 100 ℃ mixing 5 minutes down.The mixture that obtains 100 ℃ depress to sheet material after, on 150 ℃ of thermocompressores, carried out crosslinked foaming 2 minutes.The density of the porous plastics that obtains is 0.50g/cm
3Mechanical property: Young's modulus is 335MPa, and tensile strength is 3.85MPa, and elongation at break is 4.3%.The biological degradation experiment can be degraded fully.
The mixture of embodiment 19. poly(lactic acid), benzoyl peroxide, yellow soda ash and citric acid, aluminum oxide, triallyl cyanurate were by following proportioning 94.5: 2: 2: 0.5: 1 in mill 90 ℃ mixing 5 minutes down.The mixture that obtains 100 ℃ depress to sheet material after, on 135 ℃ of thermocompressores, carried out crosslinked foaming 3 minutes.The density of the porous plastics that obtains is 0.55g/cm
3Mechanical property: Young's modulus is 321MPa, and tensile strength is 3.55MPa, and elongation at break is 3.9%.The biological degradation experiment can be degraded fully.
The mixture of embodiment 20. poly(lactic acid), benzoyl peroxide, lime carbonate and citric acid, silicon-dioxide, triallyl benzenetricarboxylic acid ester were by following proportioning 60: 10: 20: 5: 5 in mill 90 ℃ mixing 5 minutes down.The mixture that obtains 100 ℃ depress to sheet material after, on 135 ℃ of thermocompressores, carried out crosslinked foaming 5 minutes.The density of the porous plastics that obtains is 0.54g/cm
3Mechanical property: Young's modulus is 311MPa, and tensile strength is 3.70MPa, and elongation at break is 4.2%.The biological degradation experiment can be degraded fully.
Claims (3)
1. biodegradable polylactic acid foam plastic, the percentage ratio meter is made up of the poly(lactic acid) of 60-97%, the superoxide of 1-10%, the whipping agent of 1-20% and the nucleator of 1-5% by weight, wherein:
Used poly(lactic acid) second-order transition temperature is 40-60 ℃;
Used superoxide is: benzoyl peroxide, t-butyl peroxy benzoate, dicumyl peroxide, tertiary butyl cumyl peroxide, ditertiary butyl peroxide, (2,5-dimethyl-2,5 di-t-butyls) peroxy hexane, (2,5-dimethyl-2,5 di-t-butyls) peroxy hexin, 2,4-dichlorobenzoperoxide, di-t-butyl peroxy diisopropylbenzene(DIPB) or 1,1-bis(t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane;
Used whipping agent is: Cellmic C 121,2,2 '-Diisopropyl azodicarboxylate, diisopropyl azodiformate, two azoanilines, N, N-dinitroso five methyne tetramines, N, N-dimethyl-N, N '-dinitroso is to benzene, benzol sulfohydrazide, 4,4 '-OBSH, 3,3 '-disulfonyl hydrazide sulfobenzide, 1, the mixture of 3 '-benzene disulfohydrazide, diazobenzeneanilide, oxaluria, nitro urine, yellow soda ash and citric acid or the mixture of lime carbonate and citric acid;
Used nucleator is: zinc oxide, calcium oxide, silicon-dioxide, aluminum oxide, talcum powder or lime carbonate.
2. polylactic acid foam plastic according to claim 1, it is characterized in that adding the polyfunctional monomer that weight percentage is 0-5%, this polyfunctional monomer is: triallyl cyanurate, triallyl benzenetricarboxylic acid ester, diallyl phthalic ester, season amylalcohol acrylate, trimethylolpropane trimethacrylate, season amylalcohol tetramethyl-acrylate, Viscoat 295 or trimethylolpropane trimethacrylate.
3. method for preparing the described polylactic acid foam plastic of claim 1, starting material are mixed in proportion, mixing 5 minutes in 90-120 ℃ in Banbury mixer or mill, the gained material is 120 ℃ of die formings on thermocompressor, after crosslinked in oil bath, in the baking oven or on the thermocompressor 130-190 ℃ foamed 2-5 minute.
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| CNA2003101158264A CN1544525A (en) | 2003-11-27 | 2003-11-27 | Method for preparing biodegradable poly-lactic acid foam plastic |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891941A (en) * | 2010-07-23 | 2010-11-24 | 西安工程大学 | Biodegradable composite foamed plastic and preparation method |
| CN1810877B (en) * | 2005-01-25 | 2010-12-01 | 株式会社Jsp | Expandable polylactic acid resin particles, expanded polylactic acid resin beads and molded article obtained from expanded polylactic acid resin beads |
| CN102241831A (en) * | 2011-04-28 | 2011-11-16 | 中国科学院宁波材料技术与工程研究所 | Preparation method of molded bodies of biodegradable polymer foamed particles |
| CN101831080B (en) * | 2009-03-10 | 2011-12-28 | 广州市波斯塑胶颜料有限公司 | Endotherm-exotherm equilibrious foaming agent |
| CN102321269A (en) * | 2011-09-26 | 2012-01-18 | 浙江工业大学 | Method for preparing meso-porous silica/polylactic acid foamed material by supercritical CO2 foaming |
| CN101838449B (en) * | 2009-03-16 | 2012-05-30 | 伟盟工业股份有限公司 | Poly lactic acid foaming composition |
| CN102639619A (en) * | 2009-11-19 | 2012-08-15 | 株式会社钟化 | Interconnected cell porous body and manufacturing method thereof |
| CN101362833B (en) * | 2008-09-25 | 2012-08-22 | 上海交通大学 | Method for preparing polylactic acid foam material |
| CN101293973B (en) * | 2007-04-24 | 2012-09-05 | 日东电工株式会社 | Filling foam composition, foam filling member, and filling foam |
| CN103772878A (en) * | 2014-01-13 | 2014-05-07 | 杭州伊贝实业有限公司 | Completely biodegradable material and preparation method thereof and cosmetics container |
| CN107459799A (en) * | 2017-08-02 | 2017-12-12 | 北京汽车股份有限公司 | Composite foam material and preparation method thereof, part and automobile |
| CN115122563A (en) * | 2022-08-22 | 2022-09-30 | 深圳市绿自然生物降解科技有限公司 | Special equipment and process for biodegradation micro-crosslinking foaming |
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2003
- 2003-11-27 CN CNA2003101158264A patent/CN1544525A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810877B (en) * | 2005-01-25 | 2010-12-01 | 株式会社Jsp | Expandable polylactic acid resin particles, expanded polylactic acid resin beads and molded article obtained from expanded polylactic acid resin beads |
| CN101293973B (en) * | 2007-04-24 | 2012-09-05 | 日东电工株式会社 | Filling foam composition, foam filling member, and filling foam |
| CN101362833B (en) * | 2008-09-25 | 2012-08-22 | 上海交通大学 | Method for preparing polylactic acid foam material |
| CN101831080B (en) * | 2009-03-10 | 2011-12-28 | 广州市波斯塑胶颜料有限公司 | Endotherm-exotherm equilibrious foaming agent |
| CN101838449B (en) * | 2009-03-16 | 2012-05-30 | 伟盟工业股份有限公司 | Poly lactic acid foaming composition |
| CN102639619A (en) * | 2009-11-19 | 2012-08-15 | 株式会社钟化 | Interconnected cell porous body and manufacturing method thereof |
| CN101891941A (en) * | 2010-07-23 | 2010-11-24 | 西安工程大学 | Biodegradable composite foamed plastic and preparation method |
| CN101891941B (en) * | 2010-07-23 | 2012-07-18 | 西安工程大学 | Biodegradable composite foamed plastic and preparation method |
| CN102241831B (en) * | 2011-04-28 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Preparation method of molded bodies of biodegradable polymer foamed particles |
| CN102241831A (en) * | 2011-04-28 | 2011-11-16 | 中国科学院宁波材料技术与工程研究所 | Preparation method of molded bodies of biodegradable polymer foamed particles |
| CN102321269A (en) * | 2011-09-26 | 2012-01-18 | 浙江工业大学 | Method for preparing meso-porous silica/polylactic acid foamed material by supercritical CO2 foaming |
| CN102321269B (en) * | 2011-09-26 | 2013-07-31 | 浙江工业大学 | Method for preparing meso-porous silica/polylactic acid foamed material by supercritical CO2 foaming |
| CN103772878A (en) * | 2014-01-13 | 2014-05-07 | 杭州伊贝实业有限公司 | Completely biodegradable material and preparation method thereof and cosmetics container |
| CN103772878B (en) * | 2014-01-13 | 2016-08-17 | 杭州伊贝实业有限公司 | Biodegradable Materials and preparation method thereof and cosmetic packaging box |
| CN107459799A (en) * | 2017-08-02 | 2017-12-12 | 北京汽车股份有限公司 | Composite foam material and preparation method thereof, part and automobile |
| CN115122563A (en) * | 2022-08-22 | 2022-09-30 | 深圳市绿自然生物降解科技有限公司 | Special equipment and process for biodegradation micro-crosslinking foaming |
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