CN102875920A - High-gloss scratch-resistant ABS/PVC (acrylonitrile-butadiene-styrene/polyvinyl chloride) alloy and preparation method thereof - Google Patents
High-gloss scratch-resistant ABS/PVC (acrylonitrile-butadiene-styrene/polyvinyl chloride) alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-gloss scratch-resistant ABS/PVC (acrylonitrile-butadiene-styrene/polyvinyl chloride) alloy and a preparation method thereof. The alloy comprises ABS, PVC, PMMA (polymethyl methacrylate), toughening agent, assistant, stabilizer, lubricant and antioxidant. The ABS/PVC alloy is balance in mechanical property, excellent in flame retardancy, easy to machine, low in cost, easy to color, scratch-resistant, high in surface hardness, and is applicable to high-gloss and scratch-resistant products such as electronic appliances, automobiles and machinery.
Description
Technical field
The invention belongs to macromolecule modified field, particularly a kind of ABS/PVC Alloy And Preparation Method.
Background technology
Acrylonitrile-butadiene-styrene terpolymer (ABS) and polyvinyl chloride (PVC) are present most widely used general-purpose plastics in the world, and wherein the PVC consumption comes the second in the world, and ABS is number five.PVC has good physicals and chemical property, have excellent chemical stability, flame retardant resistance and electrical insulating property, but its processing characteristics is relatively poor; ABS then has excellent over-all properties and toughness, easy coloring, easily processing, but flame retardant properties is relatively poor.ABS and PVC is compound, and both comprehensive both over-all propertieies have remedied again both weakness.
The ABS/PVC alloy is because its outstanding over-all properties and flame retardant properties, electrical insulating property, and cost is lower, be widely used at present the industries such as household electrical appliances, electronic apparatus, automobile, machinery, be used for substituted flame-proof ABS, flame-retarding HIPS (high-impact polystyrene), fire retardation PC (polycarbonate), PC/ABS alloy, PPO/PS(polyphenyl ether/styrene) engineering plastics of the contour performance of alloy.But the surface gloss of ABS/PVC alloy is lower, still can't substitute flame-proof ABS or the PC/ABS alloy of high gloss in the product that effects on surface is had relatively high expectations.Therefore, the ABS/PVC alloy of developing a kind of high gloss is for expanding its Application Areas, improving the scope of application very important meaning is arranged.Patent CN101475727 discloses a kind of production method that is prepared high-light ABS by PMMA blending and modifying ABS; Patent CN102311590 also discloses a kind of method for preparing high light flame-proof ABS with the PMMA blend, all less than open the ABS/PVC alloy is carried out the report that modification improves its glossiness and scraping and wiping resistance performance.
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Summary of the invention
The purpose of this invention is to provide a kind of Gao Guang, scrape resistant, ABS/PVC alloy that cost is low, the product of the high glossiness such as its alternative flame-proof ABS, flame-retarding HIPS, PC/ABS; Another object of the present invention provides the preparation method of this ABS/PVC alloy.
In order to achieve the above object, the present invention realizes by following technical proposal:
A kind of high smooth scrape resistant ABS/PVC alloy material is comprised of by its parts by weight following component:
ABS:200-400 part,
PVC:400-650 part,
PMMA:50-200 part,
Toughner: 0-50 part,
Oxidation inhibitor: 2-5 part,
Auxiliary agent: the ratio of weight and number of itself and PVC is 2-5:100,
Thermo-stabilizer: the ratio of weight and number of itself and PVC is 4-7:100,
Lubricant: the ratio of weight and number of itself and PVC is 0.5-1:100.
The preferred version of such scheme is comprised of by its parts by weight following component:
ABS:250-350 part,
PVC:500-600 part,
PMMA:100-150 part,
Toughner: 0-50 part,
Oxidation inhibitor: 2-5 part,
Auxiliary agent: the ratio of weight and number of itself and PVC is 2-5:100,
Thermo-stabilizer: the ratio of weight and number of itself and PVC is 4-7:100,
Lubricant: the ratio of weight and number of itself and PVC is 0.5-1:100.
Wherein said ABS is the acrylonitrile-butadiene-styrene copolymer that emulsion method is produced, and wherein acrylonitrile content is 25-35%, and butadiene content is 25-35%.
Described PVC is that the polymerization degree is the polyvinyl chloride of the suspension method production of 650-850.
Described PMMA is that molecular weight is the polymethylmethacrylate of 5-30 ten thousand.
Described auxiliary agent is hud typed acrylate copolymer (ACR).
Described toughner is MBS (MBS).
Described thermo-stabilizer is the mixture that organic tin stablizer and hydrotalcite, Zinic stearas, calcium stearate, epoxy soybean oil form, and contains respectively organotin 1.5-3 part, hydrotalcite 0.5-1 part, Zinic stearas 0.3-0.7 part, calcium stearate 0.6-1.2 part, epoxy soybean oil 0.8-1.3 part among per 100 parts of PVC.
Described lubricant is polyethylene wax or oxidized polyethlene wax.
Described oxidation inhibitor is selected from β-(3,5-di-t-butyl hydroxy phenyl) vinylformic acid ten caprylates (antioxidant 1076), three-(2, the 4-tert-butyl-phenyl) one or more in phosphorous acid ester (irgasfos 168), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), the two lauryl alcohol esters (oxidation inhibitor DLTDP) of thio-2 acid.
A kind of method for preparing high light scrape resistant ABS/PVC alloy material, to mix in PVC, processing aid, stablizer, oxidation inhibitor and the lubricant adding high mixer, behind 70-90 ℃ of lower mixing 5-10min, in high mixer, continue to add ABS, PMMA, toughner, remix 5-10min; Then the material that mixes is sent into extruding pelletization in the conical double screw extruder by pay-off, material the shearing of screw rod, mixing and carry under fully fusion, extrude finally by crossing, to make product behind the tie rod, cooling, each zone temperatures of forcing machine is set as 140-185 ℃.
High-light ABS provided by the present invention/PVC alloy has the following advantages:
1, among the present invention because PVC has excellent chemical stability, flame retardant resistance, and ABS has excellent toughness, easy coloring processing, so ABS/PVC alloy of the present invention have balanced mechanical property easily process, painted, and flame retardant properties is excellent, and with low cost.
2, the present invention carries out modification to the ABS/PVC alloy to improve its glossiness and scraping and wiping resistance performance, make its processing finished surface light, hardness is high and scrape resistant, and surface gloss is higher than flame-proof ABS, flame-retarding HIPS.
3, the suitable ABS/PVC alloy of the present invention is applicable to require the product casing that high photoresistance combustion, surface gloss are good, the fields such as household electrical appliances that scrape resistant requires, automobile, machinery are arranged.
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Embodiment
The invention will be further described below in conjunction with embodiment, and its purpose only is better to understand the object of the invention, and unrestricted protection scope of the present invention.All substances all are known commercially available prod in the embodiment of the invention, and its unit is weight part.
Embodiment 1
ABS(Zhenjiang is very beautiful, PA757): 350 parts
The PVC(Qilu Petrochemical, S700, polymerization degree 650-750): 600 parts
PMMA(Zhenjiang is very beautiful, CM211): 50 parts
ACR:25 part
Organotin: 15 parts
Hydrotalcite: 5.4 parts
Zinic stearas: 3 parts
Calcium stearate: 7.2 parts
Epoxy soybean oil: 7.2 parts
Oxidized polyethlene wax: 3 parts
Antioxidant 1076: 1 part
Irgasfos 168: 2 parts
Load weighted PVC, ACR, organotin, hydrotalcite, Zinic stearas, calcium stearate, epoxy soybean oil, oxidation inhibitor, oxidized polyethlene wax are added in the high mixer at 80 ℃ of lower 5-10min of mixing with antioxidant 1076,168, then continue to add ABS and PMMA remix 5-10min, at last the material that mixes is sent into extruding pelletization in the conical double screw extruder by the pay-off of delicate metering, each zone temperatures of forcing machine is set as 140-185 ℃.Material the shearing of screw rod, mixing and carry under fully fusion, extrude finally by crossing, make product behind the tie rod, cooling.
Embodiment 2
The ABS(platform, AG12A1): 370 parts
The PVC(Qilu Petrochemical, S700, polymerization degree 650-750): 500 parts
PMMA(Zhenjiang is very beautiful, CM211): 100 parts
MBS:30 part
ACR:15 part
Organotin: 11 parts
Hydrotalcite: 4 parts
Zinic stearas: 2.5 parts
Calcium stearate: 5 parts
Epoxy soybean oil: 5 parts
Polyethylene wax: 3.7 parts
Antioxidant 1076: 2 parts
Irgasfos 168: 3 parts
Load weighted PVC, ACR, thermo-stabilizer, oxidation inhibitor and lubricant are added in the high mixer at 80 ℃ of lower 5-10min of mixing, then continue to add ABS, PMMA and MBS remix 5-10min, then the material that mixes is sent into extruding pelletization in the conical double screw extruder by the pay-off of delicate metering, each zone temperatures of forcing machine is set as 140-185 ℃.Material the shearing of screw rod, mixing and carry under fully fusion, extrude finally by crossing, make product behind the tie rod, cooling.
Embodiment 3
ABS(Zhenjiang is very beautiful, PA757): 250 parts
The PVC(Qilu Petrochemical, S700, polymerization degree 650-750): 650 parts
PMMA(Zhenjiang is very beautiful, CM211): 50 parts
MBS:50 part
ACR:30 part
Organotin: 19.5 parts
Hydrotalcite: 6.5 parts
Zinic stearas: 3.2 parts
Calcium stearate: 7.8 parts
Epoxy soybean oil: 8.5 parts
Oxidized polyethlene wax: 3.9 parts
Antioxidant 1010: 1 part
Irgasfos 168: 2 parts
Load weighted PVC, ACR, thermo-stabilizer, oxidation inhibitor and lubricant are added in the high mixer at 80 ℃ of lower 5-10min of mixing, then continue to add ABS, PMMA and MBS remix 5-10min, then the material that mixes is sent into extruding pelletization in the conical double screw extruder by the pay-off of delicate metering, each zone temperatures of forcing machine is set as 145-175 ℃.Material the shearing of screw rod, mixing and carry under fully fusion, extrude finally by crossing, make product behind the tie rod, cooling.
Embodiment 4
ABS(Zhenjiang is very beautiful, PA757): 200 parts
The PVC(Qilu Petrochemical, S700, polymerization degree 650-750): 550 parts
PMMA(Zhenjiang is very beautiful, CM211): 200 parts
MBS:50 part
ACR:22 part
Organotin: 13.2 parts
Hydrotalcite: 4.4 parts
Zinic stearas: 2.2 parts
Calcium stearate: 6.6 parts
Epoxy soybean oil: 6.6 parts
Polyethylene wax: 5.5 parts
Antioxidant 1010: 1 part
Oxidation inhibitor DLTDP:1.5 part
Load weighted PVC, ACR, thermo-stabilizer, oxidation inhibitor and lubricant are added in the high mixer at 70 ℃ of lower 5-10min of mixing, then continue to add ABS, PMMA and MBS remix 5-10min, then the material that mixes is sent into extruding pelletization in the conical double screw extruder by the pay-off of delicate metering, each zone temperatures of forcing machine is set as 140-185 ℃.Material the shearing of screw rod, mixing and carry under fully fusion, extrude finally by crossing, make product behind the tie rod, cooling.
Embodiment 5
ABS(Jin Hu, 750N): 320 parts
The PVC(Qilu Petrochemical, S700, polymerization degree 650-750): 500 parts
PMMA(Zhenjiang is very beautiful, CM211): 150 parts
MBS:30 part
ACR:18 part
Organotin: 11 parts
Hydrotalcite: 3.5 parts
Zinic stearas: 1.5 parts
Calcium stearate: 5 parts
Epoxy soybean oil: 5 parts
Oxidized polyethlene wax: 3 parts
Antioxidant 1010: 1 part
Oxidation inhibitor DLTDP:3 part
Load weighted PVC, ACR, thermo-stabilizer, oxidation inhibitor and lubricant are added in the high mixer at 90 ℃ of lower 5-10min of mixing, then continue to add ABS, PMMA and MBS remix 5-10min, then the material that mixes is sent into extruding pelletization in the conical double screw extruder by the pay-off of delicate metering, each zone temperatures of forcing machine is set as 140-185 ℃.Material the shearing of screw rod, mixing and carry under fully fusion, extrude finally by crossing, make product behind the tie rod, cooling.
Embodiment 6
ABS(Zhenjiang is very beautiful, PA757): 350 parts
Peak, PVC(upper chlorine Shen, WS800, polymerization degree 750-850): 450 parts
PMMA(Zhenjiang is very beautiful, CM211): 150 parts
MBS:50 part
ACR:13.5 part
Organotin: 9 parts
Hydrotalcite: 2.7 parts
Zinic stearas: 1.4 parts
Calcium stearate: 2.6 parts
Epoxy soybean oil: 3.6 parts
Polyethylene wax: 4 parts
Antioxidant 1010: 1.5 parts
Oxidation inhibitor DLTDP:2.5 part
Load weighted PVC, ACR, thermo-stabilizer, oxidation inhibitor and lubricant are added in the high mixer at 80 ℃ of lower 5-10min of mixing, then continue to add ABS, PMMA and MBS remix 5-10min, then the material that mixes is sent into extruding pelletization in the conical double screw extruder by the pay-off of delicate metering, each zone temperatures of forcing machine is set as 140-185 ℃.Material the shearing of screw rod, mixing and carry under fully fusion, extrude finally by crossing, make product behind the tie rod, cooling.
Embodiment 7
The ABS(platform, AG12A1): 400 parts
Peak, PVC(upper chlorine Shen, WS800, polymerization degree 750-850): 400 parts
PMMA(Zhenjiang is very beautiful, CM211): 170 parts
MBS:30 part
ACR:8 part
Organotin: 6 parts
Hydrotalcite: 2 parts
Zinic stearas: 1.2 parts
Calcium stearate: 2.8 parts
Epoxy soybean oil: 4 parts
Polyethylene wax: 3 parts
Antioxidant 1010: 2 parts
Oxidation inhibitor DLTDP:3 part
Load weighted PVC, ACR, thermo-stabilizer, oxidation inhibitor and lubricant are added in the high mixer at 90 ℃ of lower 5-10min of mixing, then continue to add ABS, PMMA and MBS remix 5-10min, then the material that mixes is sent into extruding pelletization in the conical double screw extruder by the pay-off of delicate metering, each zone temperatures of forcing machine is set as 140-185 ℃.Material the shearing of screw rod, mixing and carry under fully fusion, extrude finally by crossing, make product behind the tie rod, cooling.
Embodiment 8
ABS(Jin Hu, 750N): 300 parts
Peak, PVC(upper chlorine Shen, WS800, polymerization degree 750-850): 600 parts
PMMA(Zhenjiang is very beautiful, CM211): 80 parts
MBS:20 part
ACR:30 part
Organotin: 15 parts
Hydrotalcite: 4.8 parts
Zinic stearas: 4.2 parts
Calcium stearate: 7.2 parts
Epoxy soybean oil: 7.2 parts
Polyethylene wax: 6 parts
Antioxidant 1076: 1 part
Irgasfos 168: 1.5 parts
Load weighted PVC, ACR, thermo-stabilizer, oxidation inhibitor and lubricant are added in the high mixer at 70 ℃ of lower 5-10min of mixing, then continue to add ABS and MBS remix 5-10min, then the material that mixes is sent into extruding pelletization in the conical double screw extruder by the pay-off of delicate metering, each zone temperatures of forcing machine is set as 140-185 ℃.Material the shearing of screw rod, mixing and carry under fully fusion, extrude finally by crossing, make product behind the tie rod, cooling.
Form and preparation method thereof according to the prior art formula of ABS/PVC alloy and to prepare three ABS/PVC alloy contrast product, it forms component and mainly is comprised of ABS and PVC, other components are prepared with reference to the component that provides among the present invention, its preparation method is also with preparation method of the present invention, through mixing, granulation, extrude, become product.Concrete component and content thereof are as follows:
Comparative Examples 1:
The ABS(platform, AG12A1): 550 parts
The PVC(Qilu Petrochemical, S700, polymerization degree 650-750): 450 parts,
ACR:15 part
Organotin: 10 parts
Hydrotalcite: 3 parts
Zinic stearas: 1.5 parts
Calcium stearate: 2.5 parts
Epoxy soybean oil: 4.5 parts
Polyethylene wax: 4.5 parts
Antioxidant 1076: 1 part
Irgasfos 168: 3 parts.
Comparative Examples 2
ABS(Jin Hu, 750N): 370 parts
The PVC(Qilu Petrochemical, S700, polymerization degree 650-750): 600 parts
MBS:30 part
ACR:20 part
Organotin: 15 parts
Hydrotalcite: 5 parts
Zinic stearas: 3 parts
Calcium stearate: 7 parts
Epoxy soybean oil: 6 parts
Oxidized polyethlene wax: 3 parts
Antioxidant 1076: 1 part
Irgasfos 168: 2 parts.
Comparative Examples 3
The ABS(platform, AG12A1): 500 parts
The PVC(Qilu Petrochemical, S700, polymerization degree 650-750): 500 parts
ACR:15 part
Organotin: 12 parts
Hydrotalcite: 4 parts
Zinic stearas: 2 parts
Calcium stearate: 8 parts
Epoxy soybean oil: 5 parts
Oxidized polyethlene wax: 2.5 parts
Antioxidant 1076: 2 parts
Irgasfos 168: 3 parts.
The sample that makes among above-described embodiment 1-8 and the Comparative Examples 1-3 is injection molded into the laggard row test of standard batten according to unified technique, characterizes according to GB and test, wherein:
The simply supported beam notched Izod impact strength is undertaken by GB GB/T 1043, the toughness of exosyndrome material;
Flame retardant resistance is undertaken by GB GB/T2408, the flame retardant resistance of exosyndrome material;
Pencil hardness is undertaken by GB/T 13448-2006, the resistance to scratch performance of exosyndrome material, and its characterization result is recorded as 6B, 5B, 4B, 3B, 2B, 1B, F, HB, 1H, 2H, 3H, 4H, 5H, 6H, and record value is approximately better by rear resistance to scratch performance;
Glossiness is undertaken by ASTM D523, the surface gloss of exosyndrome material, and the higher presentation surface glossiness of record value is higher.
And their test result compared, its test data is as shown in table 1 below:
Table 1 embodiment the performance test results
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| The simply supported beam notched Izod impact strength | 15 | 36 | 30 | 28 | 25 | 58 | 48 | 28 | 30 | 48 | 40 |
| Flame retardant resistance | V0 | V1 | V0 | V0 | V0 | V1 | HB | V0 | HB | V0 | V1 |
| Pencil hardness | 2H | 3H | 2H | 4H | 3H | 3H | 3H | 2H | 1H | 1H | 1H |
| Glossiness | 90 | 88 | 88 | 98 | 95 | 92 | 90 | 90 | 75 | 78 | 72 |
By the result of upper table 1 as can be known existing ABS/PVC alloy material glossiness generally about 70-80, pencil hardness is 1H; And add in the present invention after an amount of PMMA carries out modification to it, with the increase of PMMA content, the glossiness of ABS/PVC alloy also increases thereupon, is up to 98, pencil hardness is up to 4H.
Come again comparison Comparative Examples 1 and embodiment 6, Comparative Examples 2 and embodiment 1 and 8, Comparative Examples 3 and embodiment 5, can find out, under the condition that ABS, PVC ratio approach, part ABS is replaced to PMMA, the pencil hardness of material has then improved 1H-2H, glossiness has been brought up to more than 90, and the flame retardant properties of alloy material of the present invention does not significantly reduce, illustrate to add that glossiness and the resistance to scratch performance of ABS/PVC alloy is significantly improved behind the PMMA, and obviously do not have influence on the key propertys such as its toughness, flame retardant resistance.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (11)
1. one kind high smooth scrape resistant ABS/PVC alloy is characterized in that: be comprised of by its weight part following component:
ABS:200-400 part,
PVC:400-650 part,
PMMA:50-200 part,
Toughner: 0-50 part,
Oxidation inhibitor: 2-5 part,
Auxiliary agent: the ratio of weight and number of itself and PVC is 2-5:100,
Thermo-stabilizer: the ratio of weight and number of itself and PVC is 4-7:100,
Lubricant: the ratio of weight and number of itself and PVC is 0.5-1:100.
2. a kind of high smooth scrape resistant ABS/PVC alloy according to claim 1 is characterized in that: be comprised of by its parts by weight following component:
ABS:250-350 part,
PVC:500-600 part,
PMMA:100-150 part,
Toughner: 0-50 part,
Oxidation inhibitor: 2-5 part,
Auxiliary agent: the ratio of weight and number of itself and PVC is 2-5:100,
Thermo-stabilizer: the ratio of weight and number of itself and PVC is 4-7:100,
Lubricant: the ratio of weight and number of itself and PVC is 0.5-1:100.
3. a kind of high smooth scrape resistant ABS/PVC alloy according to claim 1 is characterized in that: described ABS is the acrylonitrile-butadiene-styrene copolymer that emulsion method is produced, and wherein acrylonitrile content is 25-35%, and butadiene content is 25-35%.
4. a kind of high smooth scrape resistant ABS/PVC alloy material according to claim 1 is characterized in that: described PVC is that the polymerization degree is the polyvinyl chloride that the suspension method of 650-850 is produced.
5. a kind of high smooth scrape resistant ABS/PVC alloy according to claim 1, it is characterized in that: described PMMA is that molecular weight is the polymethylmethacrylate of 5-30 ten thousand.
6. a kind of high smooth scrape resistant ABS/PVC alloy according to claim 1, it is characterized in that: described auxiliary agent is hud typed acrylate copolymer.
7. a kind of high smooth scrape resistant ABS/PVC alloy material according to claim 1, it is characterized in that: described toughner is MBS.
8. a kind of high smooth scrape resistant ABS/PVC alloy according to claim 1, it is characterized in that: described thermo-stabilizer is the mixture that organic tin stablizer and hydrotalcite, Zinic stearas, calcium stearate, epoxy soybean oil form, and contains respectively organotin 1.5-3 part, hydrotalcite 0.5-1 part, Zinic stearas 0.3-0.7 part, calcium stearate 0.6-1.2 part, epoxy soybean oil 0.8-1.3 part among per 100 parts of PVC.
9. a kind of high smooth scrape resistant ABS/PVC alloy according to claim 1, it is characterized in that: described lubricant is polyethylene wax or oxidized polyethlene wax.
10. a kind of high smooth scrape resistant ABS/PVC alloy described in according to claim 1, it is characterized in that: described oxidation inhibitor is selected from β-(3,5-di-t-butyl hydroxy phenyl) vinylformic acid ten caprylates (antioxidant 1076), three-(2, the 4-tert-butyl-phenyl) one or more in phosphorous acid ester (irgasfos 168), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), the two lauryl alcohol esters (oxidation inhibitor DLTDP) of thio-2 acid.
11. method for preparing a kind of high smooth scrape resistant ABS/PVC alloy as claimed in claim 1, it is characterized in that: PVC, auxiliary agent, stablizer, oxidation inhibitor and lubricant are added in the high mixer mix, behind 70-90 ℃ of lower mixing 5-10min, in high mixer, continue to add ABS, PMMA, toughner, remix 5-10min; Then the material that mixes is sent into extruding pelletization in the conical double screw extruder by pay-off, each zone temperatures of forcing machine is set as 140-185 ℃.
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| CN105462138A (en) * | 2016-01-06 | 2016-04-06 | 金发科技股份有限公司 | PMMA/PVC alloy material and preparation method thereof |
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