CN101319032A - Method for preparing crosslinked polylactic acid - Google Patents
Method for preparing crosslinked polylactic acid Download PDFInfo
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- CN101319032A CN101319032A CNA200810050975XA CN200810050975A CN101319032A CN 101319032 A CN101319032 A CN 101319032A CN A200810050975X A CNA200810050975X A CN A200810050975XA CN 200810050975 A CN200810050975 A CN 200810050975A CN 101319032 A CN101319032 A CN 101319032A
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- lactic acid
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000004626 polylactic acid Substances 0.000 title abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- -1 poly(lactic acid) Polymers 0.000 claims description 52
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- RIVJYLGQARVCBI-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;cumene Chemical compound CC(C)C1=CC=CC=C1.CC(C)(C)OOC(C)(C)C RIVJYLGQARVCBI-UHFFFAOYSA-N 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 10
- 150000002978 peroxides Chemical class 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a crosslinking method for a crosslinked polylactic acid. The crosslinking method comprises the following steps that: 100 portions of polylactic resins, 0.05 to 1 portion of peroxide, 1 to 10 portions of silane coupling agent and 0.01 to 0.3 portion of catalyst are mixed in an internal mixer; the temperature in the internal mixer is between 140 and 200 DEG C, and the blending time is between 3 and 10 minutes; and the resins after blending are crosslinked for 4 to 96 hours in hot water at a temperature of between 30 and 90 DEG C after hot press molding at a temperature of 190 DEG C, and then the crosslinked polylactic acid is prepared. The gel content measured is between 10 and 80 percent; and the range of the mechanical properties is as follows: the tensile strength is between 50 and 60 MPa, and the elongation at break is between 3 and 8 percent. The application scope of the polylactic acid is effectively expanded through crosslinking.
Description
Technical field
The present invention is a kind of preparation method of crosslinked poly(lactic acid), belongs to polymeric material field.
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.
Yet, because the poly(lactic acid) crystallization rate is slow,, after temperature surpasses its second-order transition temperature (60 ℃), beginning distortion by being amorphous material after the melt-processed, this has limited it to a great extent and has been extensive use of.By between molecular chain, introducing chemical bond, it is carried out crosslinked, can effectively overcome above-mentioned deficiency.In addition, the tridimensional network that crosslinked back forms can significantly improve its a lot of key properties, as wearability, chemical-resistant resistance, stress cracking resistance, and ageing resistance and viscous deformation's property etc.Shock strength and tensile strength are improved, and shrinkability descends, and low-temperature performance also improves.
In recent years, poly(lactic acid) is carried out crosslinked a lot of report that has on document, the method for use all is to concentrate on radiation method and superoxide method, causes the free radical that produces by radiation effect or superoxide and interosculates and form crosslinking structure.Adopt the method for radiation crosslinking to realize crosslinked (Mitomo, the H. of PLA as Japanese scholar; Kaneda, A.; Quynh, T.M.; Nagasawa, N.; Yoshii, F.Polymer 2005,46, and 4695.); People such as Pennings A.J. use superoxide that PLA has been carried out chemically crosslinked (Nijenhuis, A.J.; Grijpma, D.W.; Pennings, A.J.Polymer, 1996,37,2783.).
Although can effectively make aliphatic polyester realize crosslinked and improve its correlated performance by superoxide and radiating method, but angle from composition, structure regulating, there is limitation in these two kinds of methods, promptly the network structure of Xing Chenging remains the C-C bond and closes, the single network of similar polymers, structural changes are abundant inadequately.Use superoxide in addition in actual applications, need higher amount of peroxide usually, often be greater than 5%, cross-linking efficiency is very low.If processing temperature is higher than the flash-point of superoxide, the steam of a large amount of superoxide mixes with airborne oxygen and surpasses finite concentration, may cause steam explosion.Use the constraint in method of radiating raying source bigger, no matter be rumbatron or cobalt source, disposable input is all quite big, and the technology that is not easy to is popularized and promoted.
The crosslinked with silicane technology is to grow up in the later stage sixties 20th century, and it is crosslinked to be mainly used in polyolefine.Its ultimate principle be will be polysiloxane grafted under superoxide causes siloxanes is hydration under certain condition to the molecular polyolefin chain, crosslinking reaction is taken place, the formation crosslinking structure.
Compare with radiation crosslinking with the superoxide initiation is crosslinked, crosslinked with silicane has remarkable advantages.At first, the crosslinked with silicane structure is abundant, and alkenylene chain can be selected in the silane, both the kind of may command cross-bridge, the length of may command cross-bridge again.Secondly, the crosslinked with silicane reaction can occur in after the forming process, does not influence forming process, and will help the stress relaxation after the forming process and the crystallization of crystalline polymer.
The purpose of this invention is to provide a kind of crosslinked poly(lactic acid) and preparation method thereof, improving deficiency such as the low and poor mechanical property of polylactic acid melt intensity, thereby enlarge its range of application.
Preparation method of the present invention is as follows:
The poly(lactic acid) weight-average molecular weight of using is 5-20 ten thousand; Shared parts by weight are 100 parts;
The superoxide that uses is benzoyl peroxide (BPO), dicumyl peroxide (DCP), ditertiary butyl peroxide (DTBP), tert-butyl peroxide isopropyl benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, (2,5-dimethyl-2,5 di-t-butyl) the peroxy hexane, (2,5-dimethyl-2,5 di-t-butyls) peroxy hexin or 2, the 4-dichlorobenzoperoxide; Shared parts by weight are 0.05-1 part;
The silane coupling agent that uses is vinyltrimethoxy silane, and is a kind of in vinyltriethoxysilane and vinyl three ('beta '-methoxy oxyethyl group) silane; Shared umber is 1-10 part;
The catalyzer that uses is organometallic compound, two lauric acid dibutylester tin, stannous acetate, two sad dibutylester tin; Shared umber is 0.01-0.3 part;
By proportioning polylactic resin, superoxide, silane coupling agent and catalyzer are mixed at Banbury mixer, the temperature of material in Banbury mixer is between 140-200 ℃, the blend time is 3-10 minute, with the resin after the blend 190 ℃ down hot-forming after, in 30-90 ℃ hot water crosslinked 4-96 hour, obtain a kind of crosslinked poly(lactic acid).
It is as follows that a kind of poly butylene succinate that cross-linking method of the present invention obtains, crosslinked back gel content can reach 80%. mechanical property scopes: tensile strength is 50-60MPa, elongation at break 3-8%.By the crosslinked effective range of application of expanding poly butylene succinate.
Embodiment
It is 100 parts of 50,000 poly(lactic acid) parts by weight that embodiment 1. gets weight-average molecular weight, 0.05 part of benzoyl peroxide (BPO) parts by weight, 1 part of vinyltrimethoxy silane parts by weight, 0.01 part of two lauric acid dibutylester tin parts by weight.Above-mentioned substance is after height stirs machine and stirs, and 140 ℃ of following melt blendings are 3 minutes in Banbury mixer, with the resin after the blend 190 ℃ hot-forming down after, in 30 ℃ hot water crosslinked 4 hours, obtain a kind of crosslinked poly(lactic acid).Measured gel content is 10%, and mechanical property is as follows: tensile strength is 50MPa, elongation at break 3%.
It is 100 parts of 200,000 poly(lactic acid) parts by weight that embodiment 2. gets weight-average molecular weight, 1 part of dicumyl peroxide (DCP) parts by weight, 10 parts of vinyltriethoxysilane parts by weight, 0.3 part of stannous acetate parts by weight.Above-mentioned substance is after height stirs machine and stirs, and 160 ℃ of following melt blendings are 10 minutes in Banbury mixer, with the resin after the blend 190 ℃ hot-forming down after, in 90 ℃ hot water crosslinked 96 hours, obtain a kind of crosslinked poly(lactic acid).Measured gel content is 80%, and mechanical property is as follows: tensile strength is 60MPa, elongation at break 8%.
It is 100 parts of 100,000 poly(lactic acid) parts by weight that embodiment 3. gets weight-average molecular weight, 0.8 part of ditertiary butyl peroxide (DTBP) parts by weight, 5 parts of vinyl three ('beta '-methoxy oxyethyl group) silane parts by weight, 0.2 part of two sad dibutylester tin parts by weight, above-mentioned substance is after height stirs machine and stirs, and 200 ℃ of following melt blendings are 8 minutes in Banbury mixer, with the resin after the blend 190 ℃ hot-forming down after, in 40 ℃ hot water crosslinked 72 hours, obtain a kind of crosslinked poly(lactic acid).Measured gel content is 70%, and mechanical property is as follows: tensile strength is 56Mpa, elongation at break 6%.
It is 100 parts of 150,000 poly(lactic acid) parts by weight that embodiment 4. gets weight-average molecular weight, 0.7 part of tert-butyl peroxide isopropyl benzene parts by weight, 8 parts of vinyltriethoxysilane parts by weight, 0.2 part of sad dibutylester tin parts by weight, above-mentioned substance is after height stirs machine and stirs, and 170 ℃ of following melt blendings are 6 minutes in Banbury mixer, with the resin after the blend 190 ℃ hot-forming down after, in 50 ℃ hot water crosslinked 48 hours, obtain a kind of crosslinked poly(lactic acid).Measured gel content is 60%, and mechanical property is as follows: tensile strength is 55Mpa, elongation at break 6%.
It is 100 parts of 80,000 poly(lactic acid) parts by weight that embodiment 5. gets weight-average molecular weight, 1,1-bis(t-butylperoxy)-3,3,0.7 part of 5-trimethyl-cyclohexane parts by weight, 8 parts of vinyltriethoxysilane parts by weight, 0.1 part of sad dibutylester tin parts by weight, above-mentioned substance is after height stirs machine and stirs, 170 ℃ of following melt blendings are 6 minutes in Banbury mixer, with the resin after the blend 190 ℃ down hot-forming after, in 60 ℃ hot water crosslinked 72 hours, obtain a kind of crosslinked poly(lactic acid).Measured gel content is 53%, and mechanical property is as follows: tensile strength is 53Mpa, elongation at break 4%.
It is 100 parts of 150,000 poly(lactic acid) parts by weight that embodiment 6. gets weight-average molecular weight, (2,5-dimethyl-2,5 di-t-butyl) peroxy hexane parts by weight are 0.7 part, 8 parts of vinyltriethoxysilane parts by weight, 0.1 part of sad dibutylester tin parts by weight, above-mentioned substance is after height stirs machine and stirs, and 170 ℃ of following melt blendings are 6 minutes in Banbury mixer, with the resin after the blend 190 ℃ hot-forming down after, in 70 ℃ hot water crosslinked 72 hours, obtain a kind of crosslinked poly(lactic acid).Measured gel content is 73%, and mechanical property is as follows: tensile strength is 56Mpa, elongation at break 6%.
It is 100 parts of 150,000 poly(lactic acid) parts by weight that embodiment 7. gets weight-average molecular weight, (2,5-dimethyl-2,5 di-t-butyl) peroxy hexin parts by weight are 0.7 part, 5 parts of vinyltriethoxysilane parts by weight, 0.1 part of sad dibutylester tin parts by weight, above-mentioned substance is after height stirs machine and stirs, and 180 ℃ of following melt blendings are 6 minutes in Banbury mixer, with the resin after the blend 190 ℃ hot-forming down after, in 50 ℃ hot water crosslinked 48 hours, obtain a kind of crosslinked poly(lactic acid).Measured gel content is 33%, and mechanical property is as follows: tensile strength is 51Mpa, elongation at break 8%.
It is 100 parts of 150,000 poly(lactic acid) parts by weight that embodiment 8. gets weight-average molecular weight, 2,0.7 part of 4-dichlorobenzoperoxide parts by weight, 5 parts of vinyltriethoxysilane parts by weight, 0.1 part of sad dibutylester tin parts by weight, above-mentioned substance is after height stirs machine and stirs, 180 ℃ of following melt blendings are 6 minutes in Banbury mixer, with the resin after the blend 190 ℃ down hot-forming after, in 50 ℃ hot water crosslinked 48 hours, obtain a kind of crosslinked poly(lactic acid).Measured gel content is 28%, and mechanical property is as follows: tensile strength is 54Mpa, elongation at break 5%.
Claims (1)
1, crosslinked poly(lactic acid) and the cross-linking method thereof of a kind of silicon, it is characterized in that step and condition are as follows: the poly(lactic acid) weight-average molecular weight of using is 5-20 ten thousand; Shared parts by weight are 100 parts;
The superoxide that uses is benzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide isopropyl benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, (2,5-dimethyl-2,5 di-t-butyl) the peroxy hexane, (2,5-dimethyl-2,5 di-t-butyls) peroxy hexin or 2, the 4-dichlorobenzoperoxide; Shared parts by weight are 0.05-1 part;
The silane coupling agent that uses is vinyltrimethoxy silane, and is a kind of in vinyltriethoxysilane and vinyl three ('beta '-methoxy oxyethyl group) silane; Shared umber is 1-10 part;
The catalyzer that uses is two lauric acid dibutylester tin, stannous acetate, two sad dibutylester tin; Shared umber is 0.01-0.3 part;
By proportioning polylactic resin, superoxide, silane coupling agent and catalyzer are mixed at Banbury mixer, the temperature of material in Banbury mixer is between 140-200 ℃, the blend time is 3-10 minute, with the resin after the blend 190 ℃ down hot-forming after, in 30-90 ℃ hot water crosslinked 4-96 hour, obtain a kind of crosslinked poly(lactic acid).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810050975XA CN101319032B (en) | 2008-07-18 | 2008-07-18 | Method for preparing crosslinked polylactic acid |
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| CN200810050975XA CN101319032B (en) | 2008-07-18 | 2008-07-18 | Method for preparing crosslinked polylactic acid |
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| CN101319032A true CN101319032A (en) | 2008-12-10 |
| CN101319032B CN101319032B (en) | 2010-09-08 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399423A (en) * | 2010-09-14 | 2012-04-04 | 允友成有限公司 | Functional resin composition |
| CN102471564A (en) * | 2009-07-10 | 2012-05-23 | 尤尼吉可株式会社 | Polylactic acid-based resin composition and molded article |
| CN104371082A (en) * | 2013-08-14 | 2015-02-25 | 中国石油化工股份有限公司 | Polylactic acid compound preparation method |
| CN112300417A (en) * | 2020-10-30 | 2021-02-02 | 安徽元琛环保科技股份有限公司 | Kettle type synthesis method of polylactic acid with high melting index and prepared modified polylactic acid |
| CN112920565A (en) * | 2021-01-30 | 2021-06-08 | 汕头市三马塑胶制品有限公司 | High-melt-strength biodegradable polyester material and preparation method thereof |
| CN114015185A (en) * | 2021-10-20 | 2022-02-08 | 界首市天鸿新材料股份有限公司 | Biodegradable heat shrinkable film and processing technology thereof |
-
2008
- 2008-07-18 CN CN200810050975XA patent/CN101319032B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471564A (en) * | 2009-07-10 | 2012-05-23 | 尤尼吉可株式会社 | Polylactic acid-based resin composition and molded article |
| CN102399423A (en) * | 2010-09-14 | 2012-04-04 | 允友成有限公司 | Functional resin composition |
| CN102399423B (en) * | 2010-09-14 | 2013-06-12 | 允友成有限公司 | Functional resin composition |
| CN104371082A (en) * | 2013-08-14 | 2015-02-25 | 中国石油化工股份有限公司 | Polylactic acid compound preparation method |
| CN112300417A (en) * | 2020-10-30 | 2021-02-02 | 安徽元琛环保科技股份有限公司 | Kettle type synthesis method of polylactic acid with high melting index and prepared modified polylactic acid |
| CN112300417B (en) * | 2020-10-30 | 2023-07-04 | 安徽元琛环保科技股份有限公司 | Kettle type synthesis method of high-melt-index polylactic acid and prepared modified polylactic acid |
| CN112920565A (en) * | 2021-01-30 | 2021-06-08 | 汕头市三马塑胶制品有限公司 | High-melt-strength biodegradable polyester material and preparation method thereof |
| CN114015185A (en) * | 2021-10-20 | 2022-02-08 | 界首市天鸿新材料股份有限公司 | Biodegradable heat shrinkable film and processing technology thereof |
| CN114015185B (en) * | 2021-10-20 | 2024-01-12 | 界首市天鸿新材料股份有限公司 | Biodegradable heat-shrinkable film and processing technology thereof |
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| CN101319032B (en) | 2010-09-08 |
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