CN104448674A - Fiber reinforced PMMA (polymethyl methacrylate) / ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof - Google Patents
Fiber reinforced PMMA (polymethyl methacrylate) / ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof Download PDFInfo
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- CN104448674A CN104448674A CN201310414889.3A CN201310414889A CN104448674A CN 104448674 A CN104448674 A CN 104448674A CN 201310414889 A CN201310414889 A CN 201310414889A CN 104448674 A CN104448674 A CN 104448674A
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Abstract
The invention discloses a fiber reinforced PMMA (polymethyl methacrylate) / ABS (acrylonitrile butadiene styrene) composite material and a preparation method thereof. The fiber reinforced PMMA / ABS composite material comprises the following components by weight: 15% - 71% of ABS resin, 5% - 20% of PMMA resin, 3 - 10% of a compatible agent, 10% - 20% of PLA resin, 0 - 10% of an anti-impact modifier, 10% - 20% of reinforced fiber and 1 - 5% of an assistant agent. The glass fiber reinforced PMMA/ABS alloy material with the advantages of high rigidity, high strength, low carbon environmental protection, high gloss and good comprehensive performance can be prepared by reasonable selection of the components for matching and using of characteristics of two materials for making up for deficiencies of other material in performance according to the basic principle of compatibility of polymer materials, is applicable to home appliance, consumer electronic and other product appearance injection molded parts and other product injection molded parts which have high requirements of strength and rigidity, high surface gloss and are prepared by non-mark injection molding, and can meet application in the fields of home appliance casings, sport equipment parts, 3C (China Compulsory Certification) product casings, and the like.
Description
[technical field]
The present invention relates to technical field of polymer materials, particularly relate to a kind of fiber reinforcement PMMA/ABS matrix material and preparation method thereof.
[background technology]
Along with the progress of society, people are to the requirement of environment also along with raising, and the coordinated development of macromolecular material and environment protection becomes more and more urgent.Meanwhile, that lives sample along with people improving constantly, and the outward appearance device of elegant, steady air also more and more becomes the important selection of human consumer, thus product design is had higher requirement to injection moulding macromolecular material.Macromolecular material just develops rapidly towards the direction of environmental friendliness, through engineering approaches, functionalization, low cost.In order to fall the cost of macromolecular material, improving and improving the property of its some aspect, expanding its range of application, develop eco-friendly macromolecular material, people more and more pay close attention to and pay attention to study on the modification and the application of material.
PMMA/ABS alloy is a kind of high-gloss scraping-resistant resin not needing application.It has outstanding shock strength, glossiness, mechanical property and pencil hardness (F-2H), the appearance component field extensive application in the industries such as household electrical appliance.Adopt high gloss to exempt from spray material and not only can save fixed investment, save labor cost and paint cost, and operation can be reduced and be conducive to environmental protection.Along with continuing to bring out of new product designs theory, people have higher requirement to performances such as the strength and stiffness of plastic, take material modification technology, the PMMA/ABS alloy material of exploitation glass fiber reinforcement, and reach the target reducing material cost and meet injection molding process requirement, become the focus that people pay close attention to.
Poly(lactic acid) (PLA) material is a kind of broad-spectrum biodegradated polymer materal, has become one of the most valued material in bio-medical material.Poly(lactic acid), also referred to as polylactide, belongs to polyester family.Poly(lactic acid) is that main raw material is polymerized the polymkeric substance obtained with lactic acid, and raw material sources are abundant and can regenerate.The production process of poly(lactic acid) is pollution-free, and product can biological degradation, and realizing the circulation at occurring in nature, is therefore desirable Green Polymer Material.
Poly(lactic acid) has the general feature of general plastic, and as higher rigidity and intensity, easy machine-shaping, is applicable to multiple fabrication process condition.But poly(lactic acid) is a kind of hard brittle material at normal temperatures, and its heat resisting temperature is lower, and its crystal habit can affect its transparency.With the general plastic of routine as compared with PP, ABS, PC etc., its above-mentioned performance all needs to improve, and is strengthened to make its usability.
Along with the development of industrial design, new design philosophy continues to bring out, the performances such as the strength and stiffness of material are had higher requirement, stricter requirement be it is also proposed to environmental protection aspect, adopt the fiberglass reinforced PMMA/ABS alloy material of material modification technological development low-carbon environment-friendly, and reach the requirement reducing costs and meet industrial design, become a kind of trend.But this investigation of materials is scarcely out of swaddling-clothes, disclosed achievement in research and patent actually rare.
[summary of the invention]
The technical problem to be solved in the present invention is to provide the fiber reinforcement PMMA/ABS matrix material of a kind of good mechanical property, low-carbon environment-friendly.
Another technical problem that will solve of the present invention is to provide a kind of preparation method of above-mentioned fiber reinforcement PMMA/ABS matrix material.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is, a kind of fiber reinforcement PMMA/ABS matrix material, composed of the following components by weight percentage:
ABS resin 15%-71%;
PMMA resin 5%-20%;
Compatilizer 3-10%;
PLA resin 10%-20%;
Impact modifier 0-10%;
Fortifying fibre 10%-20%;
Auxiliary agent 1-5%.
Above-described fiber reinforcement PMMA/ABS matrix material, described ABS resin is ABS and/or MABS.
Above-described fiber reinforcement PMMA/ABS matrix material, described PMMA resin is polymethylmethacrylate, its average weight-average molecular weight is between 8-30 ten thousand, and wherein the mass percentage content of polymethylmethacrylate is 98-100%, and pencil hardness is at 2H/500G.
Above-described fiber reinforcement PMMA/ABS matrix material, described compatilizer is SMA, AS, AS grafted maleic anhydride, or their mixture.
Above-described fiber reinforcement PMMA/ABS matrix material, described PLA resin is heat-resistant type polylactic resin, and weight-average molecular weight is 100000-250000.
Above-described fiber reinforcement PMMA/ABS matrix material, described impact modifier adopts nucleocapsid structure impact modifier, and wherein stratum nucleare is acrylic rubber, organo-silicone rubber or both mixtures; Shell is butyl methacrylate and cinnamic multipolymer, and surface grafting has glycidyl acryiate polymer.
Above-described fiber reinforcement PMMA/ABS matrix material, described fortifying fibre is glass fibre or carbon fiber, and glass fibre is the alkali free glass fibre of surface through silane coupling agent process; Described carbon fiber is PAN-based carbon fiber, tensile strength > 500kg/mm2, tensile modulus > 250GPa.
Above-described fiber reinforcement PMMA/ABS matrix material, described auxiliary agent is oxidation inhibitor, photostabilizer, UV light absorber, lubricant or their mixture.
A preparation method for above-mentioned fiber reinforcement PMMA/ABS matrix material, comprises the following steps:
1) ABS resin, PMMA resin, compatilizer, PLA resin, impact modifier, fortifying fibre, auxiliary agent are mixed in high-speed mixer;
2) the good raw material of mixing is placed in twin screw extruder, fortifying fibre in this way long fibre is added by venting hole, and fortifying fibre in this way short fiber is added by side feeding, and extrusion temperature is 150-220 DEG C.
Fiber reinforcement PMMA/ABS matrix material of the present invention, realize the abundant plasticizing of different components in multicomponent system and improve its blended characteristic, obtaining the fiberglass reinforced PMMA/ABS alloy material of a kind of high rigidity, high-strength, low-carbon environment-friendly, high gloss, good combination property.Can be used for the household electrical appliances such as switch panel, sanitary ware, household appliances shell.Consumption electronic product.Biological degradation high gloss reinforced PMMA/ABS composite material preparation method of the present invention, simple to operate, with low cost, be suitable for suitability for industrialized production.
[embodiment]
Below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The object of the invention is to comprehensive PMMA, ABS, PLA tri-kinds of material advantages, improve the defect that three exists, reach a kind of ideal over-all properties, especially PMMA, ABS mechanical property, solvent resistance is improved, PLA resistance toheat, PMMA and PLA resistance to impact shock and shortening shaping cooling and shaping time, reduce material carbon emission, save petroleum resources, reduce PMMA, PLA cost, expand PLA Application Areas.Material surface glossiness provided by the invention is good, and low surface precipitations, high rigidity, height are heat-resisting, are applicable to intensity and the product that rigid requirements is higher, surface gloss is high and non-trace injection molding.
Following examples of the present invention provide biodegradable high gloss fiber reinforcement PMMA/ABS matrix material its preparation method, composed of the following components by weight percentage:
ABS resin 15%-71%;
PMMA resin 5%-20%;
Compatilizer 3-10%;
PLA resin 10%-20%;
Impact modifier 0-10%;
Fortifying fibre 10%-20%;
Auxiliary agent 1-5%.
Particularly, ABS resin is that rubber grain sees the ABS that particle diameter is less or transparent ABS, as strange beautiful 757,757K, 758; The 121H of LG, bright and beautiful lake 750; The MABS920 etc. that east is beautiful;
PMMA is polymethylmethacrylate, and its average weight-average molecular weight is between 8-30 ten thousand, and wherein the mass percentage content of MMA is 98-100%, and pencil hardness is at 2H/500G.PMMA resin can adopt IH830, IG840, IF850 etc. of LG.
Compatilizer is SMA, AS, AS grafted maleic anhydride, or their mixture.As SMASZ26080, the strange beautiful AS80HF of POLYSCOPE.
AS grafted maleic anhydride is made by oneself, method is as follows: by AS resin, maleic anhydride (MAH), dicumyl peroxide (DCP) (analytical pure) by weight weighing, AS resin: maleic anhydride (MAH): dicumyl peroxide (DCP)=90-110:2-8:0.2-0.6; Be preferably AS resin: maleic anhydride (MAH): dicumyl peroxide (DCP)=100:2:0.2, then mix in high-speed mixer, then in twin screw extruder, reactive extrusion is carried out, chemical reaction is carried out in extrusion, be added to forcing machine extruding pelletization, and vacuum exhaust in extrusion.
PLA resin is the HI high impact heat-resistant type polylactic resin of high transmission rate, and its weight-average molecular weight is 100000-250000;
Described impact modifier adopts nucleocapsid structure impact modifier, and wherein stratum nucleare is acrylic rubber, organo-silicone rubber or both mixtures; Shell is butyl methacrylate and cinnamic multipolymer, and surface grafting has glycidyl acryiate polymer.(as LG:EM500A, the C-223A of Mitsubishi)
Described fortifying fibre is glass fibre or carbon fiber, glass fibre is the alkali free glass fibre of surface through silane coupling agent process, described carbon fiber is PAN-based carbon fiber, its tensile strength > 500kg/mm2, tensile modulus > 250GPa.
Auxiliary agent is auxiliary agent or their mixtures such as oxidation inhibitor, photostabilizer, UV light absorber, lubricant.
The preparation method of biological degradation high gloss reinforced PMMA/ABS composite material, comprises the following steps:
1) ABS resin, PMMA resin, compatilizer, PLA resin, impact modifier, fortifying fibre, auxiliary agent are mixed in high-speed mixer;
2) the good raw material of mixing is placed in twin screw extruder, fiber in this way long fibre is added by venting hole, and short fiber is added by side feeding in this way, and extrusion temperature is extrude in the twin screw of 150-220 DEG C, tie rod.The finished product are obtained after cooling, pelletizing, drying.
Below in conjunction with specific embodiment, above-mentioned biological degradation high gloss reinforced PMMA/ABS composite material preparation method is described in detail.
Embodiment 1
Embodiment of the present invention biological degradation high gloss reinforced PMMA/ABS composite material preparation method, comprises the steps:
Take raw material as following weight percent:
ABS resin 12170%;
PMMA resin IG8405%;
Compatilizer AS80HF4%;
PLA resin 10%%;
Enhanced short fiber 10%;
Auxiliary agent 1%.
1) ABS resin, PMMA resin, compatilizer, PLA resin, fortifying fibre, auxiliary agent are mixed in high-speed mixer;
2) the good raw material of mixing is placed in twin screw extruder, short fiber is added by side feeding, and extrusion temperature is extrude in the twin screw of 150-220 DEG C, tie rod.The finished product are obtained after cooling, pelletizing, drying.
Embodiment 2
Embodiment of the present invention biological degradation high gloss reinforced PMMA/ABS composite material preparation method, comprises the steps:
Take raw material as following weight percent:
ABS resin 12165%;
PMMA resin IG8405%;
Compatilizer AS80HF4%;
PLA resin 10%;
Enhanced short fiber 15%;
Auxiliary agent 1%;
1) ABS resin, PMMA resin, compatilizer, PLA resin, fortifying fibre, auxiliary agent are mixed in high-speed mixer;
2) the good raw material of mixing is placed in twin screw extruder, short fiber is added by side feeding, and extrusion temperature is extrude in the twin screw of 150-220 DEG C, tie rod.The finished product are obtained after cooling, pelletizing, drying.
Embodiment 3
Embodiment of the present invention biological degradation high gloss reinforced PMMA/ABS composite material preparation method, comprises the steps:
Take raw material as following weight percent:
ABS resin 12160%;
PMMA resin IG8405%;
Compatilizer AS80HF4%;
PLA resin 10%;
Enhanced short fiber 20%;
Auxiliary agent 1%;
1) ABS resin, PMMA resin, compatilizer, PLA resin, fortifying fibre, auxiliary agent are mixed in high-speed mixer;
2) the good raw material of mixing is placed in twin screw extruder, short fiber is added by side feeding, and extrusion temperature is extrude in the twin screw of 150-220 DEG C, tie rod.The finished product are obtained after cooling, pelletizing, drying.
Embodiment 4
Embodiment of the present invention biological degradation high gloss reinforced PMMA/ABS composite material preparation method, comprises the steps:
Take raw material as following weight percent:
ABS resin 12155%;
PMMA resin IG8405%;
Compatilizer AS80HF4%;
PLA resin 20%;
Enhanced short fiber 15%;
Auxiliary agent 1%;
1) ABS resin, PMMA resin, compatilizer, PLA resin, fortifying fibre, auxiliary agent are mixed in high-speed mixer;
2) the good raw material of mixing is placed in twin screw extruder, short fiber is added by side feeding, and extrusion temperature is extrude in the twin screw of 150-220 DEG C, tie rod.The finished product are obtained after cooling, pelletizing, drying.
Embodiment 5
Embodiment of the present invention biological degradation high gloss reinforced PMMA/ABS composite material preparation method, comprises the steps:
Take raw material as following weight percent:
ABS resin 12150%;
PMMA resin IG84020%;
Compatilizer AS80HF4%;
PLA resin 10%;
Enhanced short fiber 15%;
Auxiliary agent 1%;
1) ABS resin, PMMA resin, compatilizer, PLA resin, fortifying fibre, auxiliary agent are mixed in high-speed mixer;
2) the good raw material of mixing is placed in twin screw extruder, short fiber is added by side feeding, and extrusion temperature is extrude in the twin screw of 150-220 DEG C, tie rod.The finished product are obtained after cooling, pelletizing, drying.
Embodiment 6
Embodiment of the present invention biological degradation high gloss reinforced PMMA/ABS composite material preparation method, comprises the steps:
Take raw material as following weight percent:
ABS resin 12146%;
PMMA resin IG84020%;
Compatilizer AS80HF4%;
PLA resin 10%;
Impact modifier 4%
Enhanced short fiber 15%;
Auxiliary agent 1%;
1) ABS resin, PMMA resin, compatilizer, PLA resin, impact modifier, fortifying fibre, auxiliary agent are mixed in high-speed mixer;
2) the good raw material of mixing is placed in twin screw extruder, short fiber is added by side feeding, and extrusion temperature is extrude in the twin screw of 150-220 DEG C, tie rod.The finished product are obtained after cooling, pelletizing, drying.
Embodiment 7
Embodiment of the present invention biological degradation high gloss reinforced PMMA/ABS composite material preparation method, comprises the steps:
Take raw material as following weight percent:
ABS resin 12142%;
PMMA resin IG84020%;
Compatilizer AS80HF4%;
PLA resin 10%;
Impact modifier 8%
Enhanced short fiber 15%;
Auxiliary agent 1%;
1) ABS resin, PMMA resin, compatilizer, PLA resin, impact modifier, fortifying fibre, auxiliary agent are mixed in high-speed mixer;
2) the good raw material of mixing is placed in twin screw extruder, short fiber is added by side feeding, and extrusion temperature is extrude in the twin screw of 150-220 DEG C, tie rod.The finished product are obtained after cooling, pelletizing, drying.
Comparative example: by weight percentages of components PMMACM21130%, ABS12169%, EBS1% mixing, through extruding pelletization, obtain comparative example product.
Performance test:
Testing standard is USS.Tensile strength standard: ASTMD638, specimen types is I type, and batten is of a size of 57mm*13mm*3.2mm (effective dimensions), and draw speed is 50mm/min; Flexural strength standard: ASTMD790, batten is of a size of 128mm*13mm*3.2mm, and rate of bending is 20mm/min; Chalpy impact standard: ASTMD256, batten is of a size of 63.5mm*12.7mm*3.2mm; Breach residue 10.16mm.
Table 1: the performance test table of embodiment and comparative example
| Performance | Testing standard | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Proportion | ASTM D792 | 1.08 | 1.15 | 1.20 | 1.25 |
| Tensile strength (MPa) | ASTM D638 | 50 | 60 | 65 | 80 |
| Melting index (230 DEG C/5KG) | ASTM D1238 | 15 | 25 | 20 | 18 |
| S flexural strength (MPa) | ASTM D790 | 90 | 95 | 100 | 110 |
| Notched Izod impact strength (J/m) | ASTM D256 | 120 | 90 | 100 | 110 |
| Flame retardant properties | UL94(1.6mm) | HB | HB | HB | HB |
| Blackness | / | Dazzle black | Dazzle black | Dazzle black | Dazzle black |
Continued 1:
| Performance | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Proportion | 1.22 | 1.24 | 1.24 | 1.24 |
| Tensile strength (MPa) | 68 | 70 | 68 | 65 |
| Melting index (230 DEG C/5KG) | 15 | 13 | 12 | 12 |
| S flexural strength (MPa) | 105 | 108 | 105 | 100 |
| Notched Izod impact strength (J/m) | 95 | 90 | 98 | 102 |
| Flame retardant properties | HB | HB | HB | HB |
| Blackness | Dazzle black | Dazzle black | Dazzle black | Dazzle black |
Biological degradation high gloss reinforced PMMA/ABS composite material of the present invention comprehensive PMMA, ABS, PLA tri-kinds of material advantages, improve PMMA, ABS mechanical property, solvent resistance, surface gloss is good, low surface precipitations, high rigidity, height heat-resisting, be applicable to intensity and the product that rigid requirements is higher, surface gloss is high and non-trace injection molding, as household electrical appliances.The outward appearance moulding of the products such as consumer electronics and other product mouldings.The application for fields such as casing of domestic electrical equipment, sports equipment component, 3C Product shells can be met.
PMMA has the excellent transparency, and optical good, surface gloss is good, and hardness is high, wear-resisting, and tinctorial property waits a little well, but property is crisp, and viscosity is high, not easily processes, and does not have low-carbon environment-friendly feature; ABS belongs to a kind of strong and unyielding material, good toughness, and processing fluidity is good, and surface gloss is higher, and a little, rigidity can not show a candle to PC and PLA to the low grade of cost, not solvent resistant, does not have low-carbon environment-friendly feature; The defects such as PLA is a kind of bio-based Low-carbon environment-friendlymaterial material, have the features such as biodegradable performance, intensity is good, high-modulus, high transparency, solvent resistance are excellent, but property is crisp, and heatproof, processibility are not bad, and cooling time is long.
Polyblend of the present invention, has had the feature of PMMA, PLA, ABS concurrently:
(1) the present invention utilizes ABS shock strength high, and utilizes toughner to improve the shock strength of PMMA, PLA, improves the processing characteristics of PMMA, PLA, shortens the machine-shaping time, reduces cost simultaneously;
(2) improved the phase interface bonding strength of PMMA, PLA, ABS by compatilizer technology, increase the consistency of three kinds of materials, put forward heavy alloyed mechanical property further, improve the interfacial combined function of glass and resin, improve the strength rigid of alloy material;
(3) PLA is a kind of low-carbon environment-friendly, degradable material, makes this alloy become a kind of Low-carbon environment-friendlymaterial material;
(4) meet the demand of the industrial designs such as ultra-thin, narrow limit at present, under the cooperation of seamless Shooting Technique, ensure with PMMA/ABS equity outward appearance while, improve rigidity, reduce degree of deformation;
(5) the reasonable offer product utilizing the present invention to prepare is nontoxic, pollution-free, low-carbon environment-friendly, and cost is lower, excellent combination property, has higher economic worth and wide market outlook;
(6) the present invention is realized by physical blending, can realize industrialization scale operation on existing equipment basis.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a fiber reinforcement PMMA/ABS matrix material, is characterized in that, composed of the following components by weight percentage:
ABS resin 15%-71%;
PMMA resin 5%-20%;
Compatilizer 3-10%;
PLA resin 10%-20%;
Impact modifier 0-10%;
Fortifying fibre 10%-20%;
Auxiliary agent 1-5%.
2. fiber reinforcement PMMA/ABS matrix material according to claim 1, is characterized in that, described ABS resin is ABS and/or MABS.
3. fiber reinforcement PMMA/ABS matrix material according to claim 1, it is characterized in that, described PMMA resin is polymethylmethacrylate, its average weight-average molecular weight is between 8-30 ten thousand, wherein the mass percentage content of polymethylmethacrylate is 98-100%, and pencil hardness is at 2H/500G.
4. fiber reinforcement PMMA/ABS matrix material according to claim 1, is characterized in that, described compatilizer is SMA, AS, AS grafted maleic anhydride, or their mixture.
5. fiber reinforcement PMMA/ABS matrix material according to claim 1, is characterized in that, described PLA resin is heat-resistant type polylactic resin, and weight-average molecular weight is 100000-250000.
6. fiber reinforcement PMMA/ABS matrix material according to claim 1, is characterized in that, described impact modifier adopts nucleocapsid structure impact modifier, and wherein stratum nucleare is acrylic rubber, organo-silicone rubber or both mixtures; Shell is butyl methacrylate and cinnamic multipolymer, and surface grafting has glycidyl acryiate polymer.
7. fiber reinforcement PMMA/ABS matrix material according to claim 1, is characterized in that, described fortifying fibre is glass fibre or carbon fiber, and glass fibre is the alkali free glass fibre of surface through silane coupling agent process; Described carbon fiber is PAN-based carbon fiber, tensile strength > 500kg/mm
2, tensile modulus > 250GPa.
8. fiber reinforcement PMMA/ABS matrix material according to claim 1, is characterized in that, described auxiliary agent is oxidation inhibitor, photostabilizer, UV light absorber, lubricant or their mixture.
9. a preparation method for fiber reinforcement PMMA/ABS matrix material according to claim 1, is characterized in that, comprise the following steps:
1) ABS resin, PMMA resin, compatilizer, PLA resin, impact modifier, fortifying fibre, auxiliary agent are mixed in high-speed mixer;
2) the good raw material of mixing is placed in twin screw extruder, fortifying fibre in this way long fibre is added by venting hole, and fortifying fibre in this way short fiber is added by side feeding, and extrusion temperature is 150-220 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310414889.3A CN104448674A (en) | 2013-09-12 | 2013-09-12 | Fiber reinforced PMMA (polymethyl methacrylate) / ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310414889.3A CN104448674A (en) | 2013-09-12 | 2013-09-12 | Fiber reinforced PMMA (polymethyl methacrylate) / ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
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| CN111138800A (en) * | 2019-12-31 | 2020-05-12 | 金发科技股份有限公司 | ABS/polyester alloy composition and preparation method thereof |
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Application publication date: 20150325 |