CN105038158A - Preparation method of food-grade full-degradable high-temperature-resistant polylactic acid composite material - Google Patents
Preparation method of food-grade full-degradable high-temperature-resistant polylactic acid composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a food-grade full-degradable high-temperature-resistant polylactic acid composite material, and belongs to the field of biodegradable high polymer materials. The composite material comprises, by weight, 100 parts of poly-l-lactic acid (PLLA), 1-10 parts of poly-d-lactic acid (PDLA) and 0.5-1 part of functional additives. Compared with traditional petroleum-based high polymer materials, the composite material has the advantages of being easy to degrade and renewable; compared with common polylactic acid, the composite material has excellent heat resistance. Thus, the polylactic acid composite material can be applied to high-temperature-resistant food packages.
Description
Technical field
The present invention relates to a kind of food grade degradable high temperature resistant type lactic acid composite material and preparation method thereof, belong to biodegradated polymer materal field.
Background technology
Poly(lactic acid) (PLA) is a kind of polymkeric substance of nontoxic, fully biodegradable.It not only has good unreactiveness, workability, but also has good biocompatibility, is one of the most promising biodegradable polymer.Poly(lactic acid) can be divided into Poly-L-lactic acid, dextrorotation poly(lactic acid) and PDLLA.Industry high speed development current, the highlighting of in short supply and environmental problem of petroleum resources makes the demand of people to non-petroleum base plastics and environment-friendly materials become more and more higher.Poly(lactic acid) as a kind of bio-based materials, not only possess can be degradable function, and can carry out forming process more easily on existing equipment, be that a kind of using value is high, the novel material had a bright future.
At normal temperatures, polylactic resin can keep stable performance, under composting conditions, be finally degraded into water and carbonic acid gas, free from environmental pollution; It also has good biocompatibility and Bioabsorbable in addition; And there is good mechanical property, thermoplasticity and fiberizability, oil resistant, flavor barrier performance are also better, the general-purpose equipment of general-purpose plastics can be adopted to carry out extruding, inject, blowing, stretching, the machine-shaping such as spinning, and easy to process.
Because the crystallization velocity of poly(lactic acid) is slow, the shortcomings such as the low and poor heat resistance (heat-drawn wire HDT is only 55 ~ 60 DEG C) of degree of crystallinity constrain the high-temperature field range of application of poly-lactic acid material in industry.Raising PLA molecule chain rigidity, the crystallization rate introducing crosslinking structure or raising PLA and degree of crystallinity all can improve the thermotolerance of PLA.Wherein improve a kind of method that the crystallization rate of PLA and degree of crystallinity are high-efficiency environment friendlies, the poly(lactic acid) of high-crystallinity still has higher mechanical property and thermotolerance more than Tg temperature.In addition, in practical study and application, also mineral filler, glass fibre, plant fibre blending can be used, and the modification way that the macromolecular material of some high glass-transition temperatures is blended, for poly(lactic acid) provides resistance toheat to a certain degree.But the lactic acid composite material prepared by these methods does not often meet the safety requirements of food grade packaging, bring adverse influence also to poly(lactic acid) biological degradability simultaneously.
In Chinese patent CN200910100148.1 heat-resistance polylactic acid composite material and preparation method thereof, disclosing a kind of poly(lactic acid) and biopolymer---starch blending, nucleator improve the crystallization behavior of poly(lactic acid), improve the method for the thermotolerance of lactic acid composite material.The poly(lactic acid) biological degradability of this method modification is excellent, but resistance toheat is general, is difficult to apply to high temperature resistant food packaging applications.
Chinese patent CN200810174648.5 mono-kind has in the poly(lactic acid) of high-melting heat resistance, discloses a kind of by carboxy blocking agent polydactyl acid, improves the method for molten state poly(lactic acid) thermotolerance.This kind of method has certain limitation for the thermotolerance improving poly(lactic acid).
Chinese patent CN200910105326.X heat-resistant halogen-free flame-retardant polylactic acid is how far in matrix material and preparation method thereof, disclose a kind of by aromatic polycarbonate resin and aliphatic polyester resin and polylactic acid blend, and improve the thermotolerance of poly(lactic acid) by the method for crosslinking reaction.The method introduces petroleum base nonrenewable resource in a large number, cannot apply to high temperature resistant food packaging applications, and reduces the biodegradability of poly(lactic acid).
In the preparation method of a Chinese patent CN2005101191118.7 thermal resistant easy processed polylactic, disclose a kind of method being improved matrix material thermotolerance by styrol copolymer heat-proof macromolecule material and polylactic acid blend.The method adopts polystyrene copolymer as blend, greatly reduces poly(lactic acid) biological degradability.
In Chinese patent CN201110110906.5 modified polylactic acid material and preparation method thereof, disclose and the heat resistance modified and toughening modifying of dew for poly(lactic acid) material is synchronously completed, improve the thermotolerance of poly(lactic acid), its Vicat softening point, at about 85 DEG C, cannot apply to high temperature resistant food packaging applications under this vicat softening temperature point.
In Chinese patent CN201310481947.4 high strength, resistant to elevated temperatures fully-degradable polylactic acid sheet material and preparation method thereof, disclose with poly(lactic acid) is matrix resin, interpolation mineral filler is toughener, add the functional additives such as coupling agent, oxidation inhibitor, lubricant, realize the heat-resisting of poly(lactic acid) and toughening modifying, wherein vicat softening temperature can reach 110 DEG C.
Found by above Chinese patent disclosure, while improving the thermotolerance of poly(lactic acid), food packaging applications cannot be applied to, be difficult to the biological degradability taking into account itself uniqueness, if weaken the biological degradability of material self excellence in modifying process, the Biodegradable material for a kind of environmental protection of research is disadvantageous.
The present invention is based on the above defect, utilize PLLA and PDLA by forcing machine melt blending, extruder screw temperature range is 170 ~ 210 DEG C, screw speed is 100 ~ 200rpm, screw slenderness ratio is 15 ~ 48, hybrid element and the weak shear field element of a Strong shear field is loaded respectively at the melt zone of screw rod, homogenizing zone, PDLA is dispersed in PLLA matrix by hybrid element, blend original position nucleation at this stage residence 20 ~ 40s, improve the Stereocomplex body SC crystal grain formed in PLLA/PDLA Blending Processes under the induction in weak shear field.PLLA with this hard SC crystal grain for nucleus, form high-crystallinity, resistant to elevated temperatures lactic acid composite material, raw material used is bio-based materials that is renewable, environmental protection, and based on above advantage, this matrix material is applicable to high temperature resistant food grade wrapping material.
Summary of the invention
The object of the present invention is to provide a kind of food grade degradable high temperature resistant type lactic acid composite material and preparation method thereof, by the mode of PLLA/PDLA melt blending in an extruder, hybrid element and the weak shear field element of a Strong shear field is loaded respectively at the melt zone of screw rod, homogenizing zone, PDLA is dispersed in PLLA matrix by hybrid element, blend original position nucleation at this stage residence 20 ~ 40s, improve the Stereocomplex body SC crystal grain formed in PLLA/PDLA Blending Processes under the induction in weak shear field.The advantages such as lactic acid composite material grain growing prepared by the method is even, degree of crystallinity is high and high temperature resistant.In addition, present method preparation technology is simple, greatly improves the thermotolerance of lactic acid composite material, shortens the production cycle.The main body base material used in the present invention all has excellent biological degradability, meets the requirement of green material, and can apply to high temperature resistant packaging material for food field.
To achieve these goals, technical scheme of the present invention is:
A kind of food grade degradable high temperature resistant type lactic acid composite material, its moiety and weight fraction proportioning are: Poly-L-lactic acid (PLLA) 100 parts,
Dextrorotation poly(lactic acid) (PDLA) 1 ~ 5 part,
Functional additive 0.5 ~ 1 part,
Wherein said Poly-L-lactic acid molecular weight is 15 ~ 300,000, is injection grade or extrusion grade;
Wherein said dextrorotation polylactic acid molecule amount is 5 ~ 100,000, is injection grade or extrusion grade;
Wherein said functional additive is oxidation inhibitor, one or both auxiliary agents in light absorber use with any proportioning, wherein said antioxidant is β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, and wherein said light absorber is salol.
A kind of food grade degradable high temperature resistant type lactic acid composite material preparation method, carries out according to following step:
(1) pre-treatment of raw material: PLLA, PDLA are positioned in vacuum drying oven dry 5 hours for subsequent use.
(2) melt blending of matrix material: by the PLLA in step (1), PDLA and functional additive add melt blending in twin screw extruder simultaneously and extrude, extruder screw temperature range is 170 ~ 210 DEG C, screw speed is 100 ~ 200rpm, screw slenderness ratio is 15 ~ 48, at the melt zone of screw rod, homogenizing zone loads hybrid element and the weak shear field element of a Strong shear field respectively, PDLA is dispersed in PLLA matrix by hybrid element, blend original position nucleation at this stage residence 20 ~ 40s under the induction in weak shear field, improve the Stereocomplex body SC crystal grain formed in PLLA/PDLA Blending Processes, use injection moulding machine that extrudate is prepared into standard batten.
Finally, universal tensile tester and Vicat softening point tester is used to characterize the mechanical property of material, resistance toheat.
Beneficial effect: for forefathers in the modification work improving poly(lactic acid) thermotolerance, traditional method tends in poly(lactic acid), fill organic/inorganic fibre or some self thermotolerances good filler formation matrix material mostly, although improve the thermotolerance of poly(lactic acid) to a certain extent, these weighting materials weaken the biological degradability of poly(lactic acid) uniqueness.In the present invention, adopt the method for PLLA/PDLA melt blending in an extruder, extruder screw temperature range is 170 ~ 210 DEG C, screw speed is 100 ~ 200rpm, screw slenderness ratio is 15 ~ 48, at the melt zone of screw rod, homogenizing zone loads hybrid element and the weak shear field element of a Strong shear field respectively, PDLA is dispersed in PLLA matrix by hybrid element, the contact area increased between the two makes PLLA/PDLA molecular chain with the H key of the formation between methyl and carbonyl for motivating force, in the process of melt blending, blend original position nucleation at this stage residence 20 ~ 40s under the induction in weak shear field, closely piling up between PLLA/PDLA homopolymer molecular chain is made to form the Stereocomplex body SC crystal grain of degree of perfection more.SC crystal grain melt temperature is at about 220 DEG C, higher than poly(lactic acid) processing temperature, therefore in the poly(lactic acid) course of processing, SC crystal grain can keep good integrity, in addition, less by the SC grain-size after improving under the effect of weak shear field, based on above advantage, SC crystal grain can as the nucleus of poly(lactic acid), PLLA for nucleus with this hard SC crystal grain, greatly improves the degree of crystallinity of PLA, thus improves its resistance toheat.In addition, the body material used in the present invention is fully bio-degradable type, and taken into account heat-resisting and biological degradation synchronism, meet the requirement of green material completely, based on above advantage, this matrix material is applicable to high temperature resistant food grade wrapping material.
Embodiment
Described in the present invention, material performance test method is as follows:
Food grade degradable high temperature resistant type lactic acid composite material pellet is injection molded into standard batten in injection moulding machine, the resistance toheat of test sample, reference standard is the vicat softening point temperature that GB/T1633-2000 " mensuration of thermoplastics vicat softening point temperature " tests blend, the mechanical property of test sample, reference standard is GB/T2013525-1992 " plastic tensile method for testing performance " test sample tensile property.
Embodiment 1:
Formula: Poly-L-lactic acid is about 10 kilograms of (molecular weight 150,000, domestic, extrusion grade), dextrorotation poly(lactic acid) 1 kilogram of (molecular weight 50,000, domestic), antioxidant [β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid], light absorber salol is 50g altogether;
PLLA, PDLA are positioned in vacuum drying oven dry 8 hours for subsequent use.By the PLLA in step 1, PDLA and functional additive add melt blending in twin screw extruder simultaneously and extrude, extruder screw temperature range is 170 ~ 210 DEG C, screw speed is 100 ~ 200rpm, screw slenderness ratio is 15 ~ 48, at the melt zone of screw rod, homogenizing zone loads hybrid element and the weak shear field element of a Strong shear field respectively, PDLA is dispersed in PLLA matrix by hybrid element, blend original position nucleation at this stage residence 20 ~ 40s under the induction in weak shear field, improve the Stereocomplex body SC crystal grain formed in PLLA/PDLA Blending Processes, use injection moulding machine that extrudate is prepared into standard batten, finally, use universal tensile tester and Vicat softening point tester to the mechanical property of material, resistance toheat characterizes, test result is as table 1.
Embodiment 2:
Formula: Poly-L-lactic acid is about 10 kilograms of (molecular weight 150,000, domestic, extrusion grade), dextrorotation poly(lactic acid) 5 kilograms of (molecular weight 50,000, domestic), antioxidant [β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid], light absorber salol is 100g altogether;
PLLA, PDLA are positioned in vacuum drying oven dry 8 hours for subsequent use.By the PLLA in step 1, PDLA and functional additive add melt blending in twin screw extruder simultaneously and extrude, extruder screw temperature range is 150 ~ 180 DEG C, screw speed is 100 ~ 200rpm, screw slenderness ratio is 15 ~ 48, at the melt zone of screw rod, homogenizing zone loads hybrid element and the weak shear field element of a Strong shear field respectively, PDLA is dispersed in PLLA matrix by hybrid element, blend original position nucleation at this stage residence 20 ~ 40s under the induction in weak shear field, improve the Stereocomplex body SC crystal grain formed in PLLA/PDLA Blending Processes, use injection moulding machine that extrudate is prepared into standard batten, finally, use universal tensile tester and Vicat softening point tester to the mechanical property of material, resistance toheat characterizes, test result is as table 1.
Comparative example 3:
Formula: Poly-L-lactic acid is about 10 kilograms (molecular weight 150,000, domestic, extrusion grade), antioxidant [β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid], light absorber salol is 45g altogether;
PLLA is positioned in vacuum drying oven dry 5 hours for subsequent use.PLLA in step 1 and functional additive are added melt blending in twin screw extruder simultaneously extrude, extruder screw temperature range is 170 ~ 210 DEG C, screw speed is 100 ~ 200rpm, screw slenderness ratio is 15 ~ 48, use injection moulding machine that extrudate is prepared into standard batten, finally, use universal tensile tester and Vicat softening point tester to characterize the mechanical property of material, resistance toheat, test result is as table 1.
Comparative example 4
[1]:
Formula: poly(lactic acid) 57 parts, PBAT30 part, talcum powder (3000 order) 10 parts, coupling agent (KH570) 1 part, 2 parts, oxidation inhibitor.
By the poly(lactic acid) of above-mentioned raw materials and the PBAT dry 8h of vacuum drying oven at 80 DEG C, talcum powder is at the dry 8h of 100 DEG C of air dry ovens; Then carry out extruding pelletization by twin screw extruder, setting extruder temperature is 160 ~ 200 DEG C, and progressively improve from feed zone to head temperature, feed worm rotating speed is 25rpm, and driving screw rotating speed is 150rpm, and pelletizing length is 2mm; Master batch makes standard batten by injection moulding machine again, and finally, use universal tensile tester and Vicat softening point tester to characterize the mechanical property of material, resistance toheat, test result is as table one.
Comparative example 5
[1]:
Formula: poly(lactic acid) 58 parts, PPC10 part, talcum powder (8000 order) 20 parts, coupling agent (KH570) 0.5 part, 0.5 part, oxidation inhibitor, whiteruss 1 part.
By the poly(lactic acid) of above-mentioned raw materials and the PPC dry 8h of vacuum drying oven at 80 DEG C, talcum powder is at the dry 8h of 100 DEG C of air dry ovens; Then carry out extruding pelletization by twin screw extruder, setting extruder temperature is 160 ~ 200 DEG C, and progressively improve from feed zone to head temperature, feed worm rotating speed is 25rpm, and driving screw rotating speed is 140rpm, and pelletizing length is 2mm; Master batch makes standard batten by injection moulding machine again, and finally, use universal tensile tester and Vicat softening point tester to characterize the mechanical property of material, resistance toheat, test result is as shown in the table.
The vicat softening point temperature of lactic acid composite material and tensile strength Comparative result table under the different embodiment of table 1. and comparative example
| Title | Vicat softening point temperature/DEG C | Tensile strength/MPa |
| Embodiment 1 | 107 | 74 |
| Embodiment 2 | 115 | 79 |
| Comparative example 3 | 65 | 60 |
| Comparative example 4 | 82 | 71 |
| Comparative example 5 | 86 | 86 |
[1] Chinese patent CN201310481947.4
Claims (5)
1. a food grade degradable high temperature resistant type lactic acid composite material, it is characterized in that its component and mass percent as follows:
Poly-L-lactic acid 100 parts;
Dextrorotation poly(lactic acid) 1 ~ 10 part;
Functional additive 0.5 ~ 1 part.
2. a kind of food grade degradable high temperature resistant type lactic acid composite material according to claim 1, is characterized in that wherein said Poly-L-lactic acid molecular weight is 15 ~ 300,000.
3. a kind of food grade degradable high temperature resistant type lactic acid composite material according to claim 1, is characterized in that wherein said dextrorotation polylactic acid molecule amount is 5 ~ 100,000.
4. a kind of food grade degradable high temperature resistant type lactic acid composite material according to claim 1, it is characterized in that wherein said functional additive is oxidation inhibitor, one in light absorber, or two kinds of multiple auxiliary agents use with any proportioning, wherein said antioxidant is β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, wherein said light absorber is salol.
5. a food grade degradable high temperature resistant type lactic acid composite material preparation method, is characterized in that carrying out according to the following step:
(1) pre-treatment of raw material: PLLA, PDLA are positioned in vacuum drying oven dry 8 hours for subsequent use;
(2) melt blending of matrix material: by the PLLA in step 1, PDLA and functional additive add melt blending in twin screw extruder simultaneously and extrude, extruder screw temperature range is 170 ~ 210 DEG C, screw speed is 100 ~ 200rpm, screw slenderness ratio is 15 ~ 48, at the melt zone of screw rod, homogenizing zone loads hybrid element and the weak shear field element of a Strong shear field respectively, PDLA is dispersed in PLLA matrix by the Strong shear field hybrid element of melt zone, blend original position nucleation at this stage residence 20 ~ 40s under the induction in weak shear field, improve the Stereocomplex body SC crystal grain formed in PLLA/PDLA Blending Processes, use injection moulding machine that extrudate is prepared into standard batten, finally, use universal tensile tester and Vicat softening point tester to the mechanical property of material, resistance toheat characterizes.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506776A (en) * | 2016-02-03 | 2016-04-20 | 北京服装学院 | Modified polylactic acid fiber and preparation method thereof |
| CN105936742A (en) * | 2016-06-07 | 2016-09-14 | 常州大学 | Preparation method of low-cost heat-resistant food grade polylactic acid material |
| CN107216627A (en) * | 2017-07-18 | 2017-09-29 | 苏州西脉红枫生物科技有限公司 | A kind of degradation material and preparation method thereof |
| CN109553941A (en) * | 2018-11-16 | 2019-04-02 | 广东众塑降解材料有限公司 | A kind of biology base full degradation chopsticks material and preparation method thereof |
| CN111548615A (en) * | 2020-05-12 | 2020-08-18 | 中国科学院长春应用化学研究所 | Bidirectional stretching stereo composite polylactic acid film and preparation method thereof |
| CN112063140A (en) * | 2020-08-14 | 2020-12-11 | 安徽丰原生物新材料有限公司 | Polylactic acid modified material for injection molding product and preparation method thereof |
| CN112063139A (en) * | 2020-08-14 | 2020-12-11 | 安徽丰原生物新材料有限公司 | Polylactic acid modified material for food contact injection molding product and preparation method thereof |
| CN114031913A (en) * | 2021-12-13 | 2022-02-11 | 杭州卓普新材料科技有限公司 | Anti-aging heat-resistant polylactic acid injection molding material and preparation method thereof |
| CN114103274A (en) * | 2021-10-09 | 2022-03-01 | 杭州同杰诚新材料有限公司 | Biodegradable toughened high-temperature-resistant composite straw |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090186178A1 (en) * | 2006-05-30 | 2009-07-23 | Toyo Seikan Kaisha,Ltd. | Biodegradable stretch mold container having excellent heat resistance |
| CN102164993A (en) * | 2008-09-29 | 2011-08-24 | 帝人株式会社 | Polylactic acid film |
| CN104109363A (en) * | 2014-07-04 | 2014-10-22 | 江南大学 | High-strength high-toughness transparent polylactic acid composition and preparation method thereof |
-
2015
- 2015-07-24 CN CN201510440089.8A patent/CN105038158A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090186178A1 (en) * | 2006-05-30 | 2009-07-23 | Toyo Seikan Kaisha,Ltd. | Biodegradable stretch mold container having excellent heat resistance |
| CN102164993A (en) * | 2008-09-29 | 2011-08-24 | 帝人株式会社 | Polylactic acid film |
| CN104109363A (en) * | 2014-07-04 | 2014-10-22 | 江南大学 | High-strength high-toughness transparent polylactic acid composition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄文娴: "稳态剪切场下PLLA及PLLA/PDLA共混物结晶行为的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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| CN105506776A (en) * | 2016-02-03 | 2016-04-20 | 北京服装学院 | Modified polylactic acid fiber and preparation method thereof |
| CN105506776B (en) * | 2016-02-03 | 2019-01-22 | 北京服装学院 | A kind of modified polylactic acid fiber and preparation method thereof |
| CN105936742A (en) * | 2016-06-07 | 2016-09-14 | 常州大学 | Preparation method of low-cost heat-resistant food grade polylactic acid material |
| CN107216627A (en) * | 2017-07-18 | 2017-09-29 | 苏州西脉红枫生物科技有限公司 | A kind of degradation material and preparation method thereof |
| CN109553941A (en) * | 2018-11-16 | 2019-04-02 | 广东众塑降解材料有限公司 | A kind of biology base full degradation chopsticks material and preparation method thereof |
| CN111548615A (en) * | 2020-05-12 | 2020-08-18 | 中国科学院长春应用化学研究所 | Bidirectional stretching stereo composite polylactic acid film and preparation method thereof |
| CN111548615B (en) * | 2020-05-12 | 2021-11-05 | 中国科学院长春应用化学研究所 | Bidirectional stretching stereo composite polylactic acid film and preparation method thereof |
| CN112063140A (en) * | 2020-08-14 | 2020-12-11 | 安徽丰原生物新材料有限公司 | Polylactic acid modified material for injection molding product and preparation method thereof |
| CN112063139A (en) * | 2020-08-14 | 2020-12-11 | 安徽丰原生物新材料有限公司 | Polylactic acid modified material for food contact injection molding product and preparation method thereof |
| CN114103274A (en) * | 2021-10-09 | 2022-03-01 | 杭州同杰诚新材料有限公司 | Biodegradable toughened high-temperature-resistant composite straw |
| CN114031913A (en) * | 2021-12-13 | 2022-02-11 | 杭州卓普新材料科技有限公司 | Anti-aging heat-resistant polylactic acid injection molding material and preparation method thereof |
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