CN102040814A - Special black master batch for polylactic acid based degradable plastics and preparation method thereof - Google Patents
Special black master batch for polylactic acid based degradable plastics and preparation method thereof Download PDFInfo
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- CN102040814A CN102040814A CN 201010611390 CN201010611390A CN102040814A CN 102040814 A CN102040814 A CN 102040814A CN 201010611390 CN201010611390 CN 201010611390 CN 201010611390 A CN201010611390 A CN 201010611390A CN 102040814 A CN102040814 A CN 102040814A
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- polylactic acid
- acid based
- degradable plastics
- based degradable
- exclusively used
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 71
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 54
- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004594 Masterbatch (MB) Substances 0.000 title abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- -1 poly(lactic acid) Polymers 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 8
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 20
- 239000004033 plastic Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 10
- 239000006229 carbon black Substances 0.000 abstract description 7
- 238000001125 extrusion Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract 2
- 230000006399 behavior Effects 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000001993 wax Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000004746 geotextile Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a special black master batch for polylactic acid based degradable plastics and a preparation method thereof. The special black master batch for polylactic acid based degradable plastics comprises the following components in percentage by weight: 20-40% of pigment carbon black, 15-30% of dispersing lubricant and 40-65% of carrier resin, wherein the carrier resin adopts polylactic acid. In the special black master batch for polylactic acid based degradable plastics, the polylactic acid carrier resin is taken as a basic component, and interacted with the pigment carbon black, the dispersing lubricant and the like in the extrusion process, thus special black master batch for polylactic acid based degradable plastics has the advantages of good compatibility and easy dispersing. In the process of preparing the plastics by using the special black master batch for polylactic acid based degradable plastics, the black master batch is used a little, the prepared plastic is good in mechanical behaviors, easy in degradation, and economic and environmentally friendly. In the preparation method, the process is simple, and the cost is low; and the preparation method is suitable for industrialized production.
Description
Technical field
The invention belongs to chemical technology field, particularly a kind of black agglomerate that is exclusively used in polylactic acid based degradable plastics and preparation method thereof.
Background technology
Poly(lactic acid) (PLA) is a kind of novel biodegradable material, and the starch material that uses reproducible plant resources (as corn) to be proposed is made.Starch material is made lactic acid via fermenting process, converts poly(lactic acid) to by chemosynthesis again.It has good biodegradability, can be degraded fully by the occurring in nature microorganism after the use, finally generates carbonic acid gas and water, and is free from environmental pollution, and this is highly beneficial to the protection environment, is the environment-friendly material of generally acknowledging.Poly(lactic acid) is applicable to various working methods such as blowing, thermoplastic, and is easy to process, uses very extensive.Can be used for processing from industry to civilian various plastics, wrap food, fast food lunch-box, non-woven fabrics, industry and civilian cloth.And then being processed into geotextile, health care fabric, rag, sanitary product, outdoor antiultraviolet fabric, tent cloth, ground cushion face or the like, market outlook are very good.The solid support material of existing black agglomerate and the consistency of poly(lactic acid) are not very desirable, have influence on the mechanical property of polylactic acid based degradable plastics and the dispersiveness of carbon black.
Summary of the invention
The purpose of the embodiment of the invention is to overcome the above-mentioned deficiency of prior art, and a kind of easy dispersion is provided, and addition is few, and does not influence the black agglomerate that is exclusively used in polylactic acid based degradable plastics of the mechanical property of plastics after adding.
And, the above-mentioned preparation method who is exclusively used in the black agglomerate of polylactic acid based degradable plastics.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of black agglomerate that is exclusively used in polylactic acid based degradable plastics comprises the recipe ingredient of following weight percent:
Colour black 20～40%
Dispersed lubricant 15～30%
Vector resin 40～65%,
Wherein, described vector resin is a poly(lactic acid).
And the above-mentioned black agglomerate preparation method who is exclusively used in polylactic acid based degradable plastics comprises the steps:
Take by weighing each component according to the above-mentioned prescription that is exclusively used in the black agglomerate of polylactic acid based degradable plastics, and carry out pre-mixing;
The formed mixture of pre-mixing is carried out banburying;
Mixture after the banburying is carried out extruding pelletization, obtain the described black agglomerate that is exclusively used in polylactic acid based degradable plastics.
Colour black component in the above-mentioned black agglomerate that is exclusively used in polylactic acid based degradable plastics except that as dyeing with, can make the plastics that contain this black agglomerate effectively prevent, thereby improve the quality and the work-ing life of plastics because of solar radiation produces photo-oxidative degradation.The dispersed lubricant component is attached on other component surfaces in extrusion, make this black agglomerate obtain preliminary preferably gelation and dispersion effect.The vector resin component that with the composition is poly(lactic acid) makes the plastics that contain this black agglomerate easily degrade economic environmental protection.This black agglomerate that is exclusively used in polylactic acid based degradable plastics is a basic components with the poly(lactic acid) vector resin, and in extrusion, interact with components such as colour black, dispersed lubricants, it is good to make that the black agglomerate that is exclusively used in the polylactic acid based degradable plastics of preparation has good consistency, easily disperses.The black agglomerate that is exclusively used in polylactic acid based degradable plastics in utilization prepares in the process of plastics, and this black agglomerate not only consumption is few, and the plastics that make have good mechanical property, easily is degraded economic environmental protection.This black agglomerate preparation method who is exclusively used in polylactic acid based degradable plastics only needs by prescription each component to be carried out pre-mixing, and banburying is extruded and can be obtained product, and its preparation method technology is simple, and cost is low, is suitable for suitability for industrialized production.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is exclusively used in the black agglomerate preparation method's of polylactic acid based degradable plastics process flow diagram for the present invention.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The embodiment of the invention provides a kind of easy dispersion, and addition is few, and does not influence the black agglomerate that is exclusively used in polylactic acid based degradable plastics of the mechanical property of plastics after adding.This black agglomerate that is exclusively used in polylactic acid based degradable plastics comprises the recipe ingredient of following weight percent:
Colour black 20～40%
Dispersed lubricant 15～30%
Vector resin 40～65%,
Wherein, described vector resin is a poly(lactic acid).
Particularly, the existence of above-mentioned colour black component, its effect is except that using as dyeing, can also bring into play the effect of UV light stabilizing agent, can prevent effectively that the plastics that contain embodiment of the invention black agglomerate from producing photo-oxidative degradation because of being subjected to solar radiation, thereby improve the quality and the work-ing life of plastics.Wherein, the particle diameter of this colour black is preferably 10～30nm.
Above-mentioned dispersed lubricant component is preferably one or more in polyethylene wax, ethylene-vinyl acetate wax (EVA wax), ethylene bis stearic acid amide (EBS), the stearic acid series dispersion agent.Wherein, polyethylene wax is preferably just, and fusing point is 100～106 ℃, molecular weight is 3000～5000 polyethylene wax, ethylene-vinyl acetate wax is preferably just, and fusing point is 100～110 ℃, molecular weight is 2500～4000 ethylene-vinyl acetate wax, and fusing point was 140～150 ℃ a ethylene bis stearic acid amide at the beginning of ethylene bis stearic acid amide was preferably.This dispersed lubricant component is attached on other component surfaces in extrusion, under the high speed shear effect in extrusion, make this black agglomerate obtain preliminary preferably gelation and dispersion effect.
The composition of above-mentioned vector resin component is a poly(lactic acid), this poly(lactic acid) makes this be exclusively used in the black agglomerate of polylactic acid based degradable plastics and relevant plastics can be degraded, economic environmental protection, and can also make the plastics that contain this black agglomerate have the favorable mechanical performance.
The above-mentioned black agglomerate that is exclusively used in polylactic acid based degradable plastics is a basic components with the poly(lactic acid) vector resin, and in extrusion, interact with components such as colour black, dispersed lubricants, it is good to make that the black agglomerate that is exclusively used in the polylactic acid based degradable plastics of preparation has good consistency, easily disperses.The black agglomerate that is exclusively used in polylactic acid based degradable plastics in utilization prepares in the process of plastics, and this black agglomerate not only consumption is few, and the plastics that make have good mechanical property, easily is degraded economic environmental protection.
The embodiment of the invention also provides the above-mentioned black agglomerate preparation method who is exclusively used in polylactic acid based degradable plastics, and its technical process as shown in Figure 1.This method comprises the steps:
S1: take by weighing each component according to the above-mentioned prescription that is exclusively used in the black agglomerate of polylactic acid based degradable plastics, and carry out pre-mixing;
S2: the formed mixture of pre-mixing is carried out banburying;
S3: the mixture after the banburying is carried out extruding pelletization, obtain the described black agglomerate that is exclusively used in polylactic acid based degradable plastics.
Particularly, in the above-mentioned black agglomerate preparation method's who is exclusively used in polylactic acid based degradable plastics the S1 step, this pre-mixing is that each component that will take by weighing by prescription was preferably mixed under 800～2000 rev/mins rotating speed 5～30 minutes, makes each component mix, and forms mixture.
In the above-mentioned black agglomerate preparation method's who is exclusively used in polylactic acid based degradable plastics the S2 step, banburying preferably will be through the formed mixture of pre-mixing Banbury mixer banburying 3～20 minutes, make each component in the mixture further mix, reach uniform admixture.
In the above-mentioned black agglomerate preparation method's who is exclusively used in polylactic acid based degradable plastics the S3 step, mixture after banburying preferably adds to be extruded in the forcing machine and granulation, this is extruded is to adopt twin screw extruder to extrude, the temperature of described mixture each section in described twin screw extruder is respectively: 180～220 ℃ of one section temperature, 180～220 ℃ of two sections temperature, 180～220 ℃ of three sections temperature, four sections temperature 180～200, five sections temperature 170～190, six sections temperature 170～190, seven sections temperature 170～190, eight sections temperature 170～190, die head temperature 190～210.
The above-mentioned black agglomerate preparation method who is exclusively used in polylactic acid based degradable plastics only needs by prescription each component to be carried out pre-mixing, and banburying is extruded and can be obtained product, and its preparation method technology is simple, and cost is low, is suitable for suitability for industrialized production.In the extruding pelletization process, the intermolecular interaction under the high speed shear effect of extruding of each component, thus the black agglomerate that makes the embodiment of the invention be exclusively used in polylactic acid based degradable plastics has above-mentioned excellent properties.
Be example now, the present invention is further elaborated with black agglomerate prescription and the preparation method who specifically is exclusively used in polylactic acid based degradable plastics.
Embodiment 1
Be exclusively used in the black agglomerate prescription of polylactic acid based degradable plastics:
PLA plastics 40%, particle diameter are colour carbon black 40%, the dispersed lubricant 20% of 30nm
Wherein, dispersion agent consists of: incipient melting is that 100 ℃, molecular weight are 5000 polyethylene waxs 10%, and incipient melting is 140 ℃ EBS 10%.
Its preparation method: earlier each component is carried out pre-mixing at high-speed mixer in proportion, rotating speed is 2000 rev/mins, mixing time 5 minutes, then in Banbury mixer, carry out banburying, 5 minutes banburying time, then the compound after the banburying is joined in the twin screw extruder and extrude, through cooling, dry, pelletizing obtains required black masterbatch, and this mixture temperature of each section in twin screw extruder is respectively: 200 ℃ of one section temperature, 220 ℃ of two sections temperature, 210 ℃ of three sections temperature, four sections temperature 180, five sections temperature 190, six sections temperature 180, seven sections temperature 190, eight sections temperature 190, die head temperature 190.
Embodiment 2
Be exclusively used in the black agglomerate prescription of polylactic acid based degradable plastics:
PLA plastics 65%, particle diameter are colour carbon black 20%, the dispersed lubricant 15% of 10nm.
Wherein, dispersion agent consists of: incipient melting is that 106 ℃, molecular weight are 3000 polyethylene waxs 5%, and incipient melting is 150 ℃ EBS 10%.
Its preparation method: earlier each component is carried out pre-mixing at high-speed mixer in proportion, rotating speed is 800 rev/mins, mixing time 30 minutes, then in Banbury mixer, carry out banburying, 8 minutes banburying time, then the compound after the banburying is added in the twin screw extruder and extrude, through cooling, dry, pelletizing obtains required black masterbatch, this mixture temperature of each section in twin screw extruder is respectively: 180 ℃ of one section temperature, 180 ℃ of two sections temperature, 220 ℃ of three sections temperature, four sections temperature 200, five sections temperature 170, six sections temperature 170, seven sections temperature 170, eight sections temperature 170, die head temperature 210.
Embodiment 3
Be exclusively used in the black agglomerate prescription of polylactic acid based degradable plastics:
PLA plastics 50% particle diameter is colour carbon black 30% dispersed lubricant 20% of 20nm
Wherein, dispersion agent consists of: incipient melting is that 102 ℃, molecular weight are 4000 polyethylene waxs 5%, and incipient melting is 145 ℃ EBS 10%, and incipient melting is that 110 ℃, molecular weight are 4000 ethylene-vinyl acetate waxes 5%.
Its preparation method: earlier each component is carried out pre-mixing at high-speed mixer in proportion, rotating speed is 800 rev/mins, mixing time 10 minutes, then in Banbury mixer, carry out banburying, 20 minutes banburying time, then the compound after the banburying is added in the twin screw extruder and extrude, through cooling, dry, pelletizing obtains required black masterbatch, and this mixture temperature of each section in twin screw extruder is respectively: 180 ℃ of one section temperature, 210 ℃ of two sections temperature, 185 ℃ of three sections temperature, four sections temperature 190, five sections temperature 185, six sections temperature 180, seven sections temperature 180, eight sections temperature 180, die head temperature 200.
Embodiment 4
Be exclusively used in the black agglomerate prescription of polylactic acid based degradable plastics:
PLA plastics 40%, particle diameter are colour carbon black 40%, the dispersed lubricant 20% of 15nm.
Wherein, dispersion agent consists of: incipient melting is that 105 ℃, molecular weight are 3500 polyethylene waxs 5%, and incipient melting is 148 ℃ EBS 5%, and incipient melting is that 100 ℃, molecular weight are 2500 ethylene-vinyl acetate waxes 5%, Zinic stearas 5%.
Its preparation method: earlier each component is carried out pre-mixing at high-speed mixer in proportion, rotating speed is 800 rev/mins, mixing time 10 minutes, then in Banbury mixer, carry out banburying, 3 minutes banburying time, then the compound after the banburying is added in the twin screw extruder and extrude, through cooling, dry, pelletizing obtains required black masterbatch, this mixture temperature of each section in twin screw extruder is respectively: 205 ℃ of one section temperature, 200 ℃ of two sections temperature, 200 ℃ of three sections temperature, four sections temperature 180, five sections temperature 175, six sections temperature 185, seven sections temperature 180, eight sections temperature 190, die head temperature 205.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. black agglomerate that is exclusively used in polylactic acid based degradable plastics is characterized in that: the recipe ingredient that comprises following weight percent:
Colour black 20～40%
Dispersed lubricant 15～30%
Vector resin 40～65%,
Wherein, described vector resin is a poly(lactic acid).
2. the black agglomerate that is exclusively used in polylactic acid based degradable plastics according to claim 1 is characterized in that: the particle diameter of described colour black is 10～30nm.
3. the black agglomerate that is exclusively used in polylactic acid based degradable plastics according to claim 1 is characterized in that: described dispersed lubricant is one or more in polyethylene wax, ethylene-vinyl acetate wax, ethylene bis stearic acid amide, the stearic acid series dispersion agent.
4. the black agglomerate that is exclusively used in polylactic acid based degradable plastics according to claim 3 is characterized in that: the first fusing point of described polyethylene wax is 100～106 ℃, and molecular weight is 3000～5000.
5. the black agglomerate that is exclusively used in polylactic acid based degradable plastics according to claim 3 is characterized in that: the first fusing point of described ethylene-vinyl acetate wax is 100～110 ℃, and molecular weight is 2500～4000.
6. the black agglomerate that is exclusively used in polylactic acid based degradable plastics according to claim 3 is characterized in that: the first fusing point of described ethylene bis stearic acid amide is 140～150 ℃.
7. a black agglomerate preparation method who is exclusively used in polylactic acid based degradable plastics comprises the steps:
Take by weighing each component according to the arbitrary described prescription that is exclusively used in the black agglomerate of polylactic acid based degradable plastics of claim 1～6, and carry out pre-mixing;
The formed mixture of pre-mixing is carried out banburying;
Mixture after the banburying is carried out extruding pelletization, obtain the described black agglomerate that is exclusively used in polylactic acid based degradable plastics.
8. the black agglomerate preparation method who is exclusively used in polylactic acid based degradable plastics according to claim 7 is characterized in that: described pre-mixing is that each component that will take by weighing by prescription was mixed under 800～2000 rev/mins rotating speed 5～30 minutes.
9. the black agglomerate preparation method who is exclusively used in polylactic acid based degradable plastics according to claim 7 is characterized in that: the described banburying time is 3～20 minutes.
10. the black agglomerate preparation method who is exclusively used in polylactic acid based degradable plastics according to claim 7, it is characterized in that: described extruding is to adopt twin screw extruder to extrude, the temperature of described mixture each section in described twin screw extruder is respectively: 180～220 ℃ of 180～220 ℃, three sections temperature of 180～220 ℃, two sections temperature of one section temperature, four sections temperature 180～200, five sections temperature 170～190, six sections temperature 170～190, seven sections temperature 170～190, eight sections temperature 170～190, die head temperature 190～210.
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| CN101475695A (en) * | 2008-12-29 | 2009-07-08 | 王文广 | Wholly-degradable primary color master batch and preparation thereof |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644794A (en) * | 2004-12-17 | 2005-07-27 | 中国科学院长春应用化学研究所 | Completely biological degradable polylactic coating materials |
| CN101475695A (en) * | 2008-12-29 | 2009-07-08 | 王文广 | Wholly-degradable primary color master batch and preparation thereof |
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| CN102391626B (en) * | 2011-07-29 | 2012-12-12 | 广东美联新材料科技有限公司 | Non-petroleum base complete degradation master batch and preparation method thereof |
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| CN103122498A (en) * | 2013-03-19 | 2013-05-29 | 东华大学 | Preparation method of halogen-free flame-retardant polylactic acid fiber |
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| CN113637189B (en) * | 2021-08-18 | 2024-07-02 | 江苏集萃先进纤维材料研究所有限公司 | Preparation method of polylactic acid plant dye masterbatch |
| CN113980445A (en) * | 2021-12-09 | 2022-01-28 | 王玲芝 | Special biomass color master batch for degradable plastics and preparation method thereof |
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