CN102311589A - Transparent K-resin/GPPS (general purpose polystyrene) alloy material and preparation method thereof - Google Patents
Transparent K-resin/GPPS (general purpose polystyrene) alloy material and preparation method thereof Download PDFInfo
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- CN102311589A CN102311589A CN201010598555A CN201010598555A CN102311589A CN 102311589 A CN102311589 A CN 102311589A CN 201010598555 A CN201010598555 A CN 201010598555A CN 201010598555 A CN201010598555 A CN 201010598555A CN 102311589 A CN102311589 A CN 102311589A
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- 239000000956 alloy Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011347 resin Substances 0.000 title abstract description 19
- 229920005989 resin Polymers 0.000 title abstract description 19
- 239000004793 Polystyrene Substances 0.000 title abstract description 3
- 229920002223 polystyrene Polymers 0.000 title abstract description 3
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000003292 glue Substances 0.000 claims description 39
- 239000003112 inhibitor Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- -1 pentaerythritol ester Chemical class 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004605 External Lubricant Substances 0.000 claims description 3
- 239000004610 Internal Lubricant Substances 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 14
- 238000002834 transmittance Methods 0.000 abstract description 6
- 238000002464 physical blending Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
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- B29C47/92—
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a transparent K-resin/GPPS (general purpose polystyrene) alloy material and a preparation method thereof. The transparent K-resin/GPPS alloy material consists of the following components in percentage by weight: 69 to 80 percent of K-resin, 19 to 30 percent of GPPS, 0.5 to 1 percent of lubricant and 0.2 to 0.6 percent of antioxidant. In the transparent K-resin/GPPS alloy material, the K-resin and the GPPS which have the basically same refractive indexes are used; a highly transparent K-resin/GPPS alloy is prepared by physical blending extrusion; the alloy has the advantages of the K-resin and the GPPS resin and has high toughness, high light transmittance and small internal stress; a plurality of defects of common transparent resin in the market are overcome; and the transparent K-resin/GPPS alloy material has wide application prospect.
Description
[technical field]
The present invention relates to technical field of polymer materials, relate in particular to a kind of transparent K glue/GPPS alloy material and preparation method thereof.
[background technology]
K glue is commonly called as K resin, the transparent anti-impact resin of butylbenzene, is divinyl and cinnamic amorphous polymer, has higher transparence, and transparence is 80～90%, and is as clear as crystal as glass.K glue proportion is lower, is merely 1.01g/cm
3, have good anti-punching performance, but chemical resistance is poor, performance can have decline in oil, acid, alkali and active strong organic solvent.
GPPS is a general purpose polystyrene, has higher transparence, and transparence is 88～92%, and is mobile higher, but impact resistance is relatively poor, is prone to take place brittle rupture, serious limit its widespread use.
Prepare high transparent alloy material; At least will satisfy in following two conditions: 1) the substance particle diameter is enough little; If the particle diameter of substance is less than light wavelength, the material of that interpolation can be counted as the suspended particulates in the light wave, and does not influence passing through of light.2) material that adds and starting material are compatible and refractive index is close generally is transparent after this two material blend.
There are some shortcomings in traditional transparent resin, like the relatively poor weathering resistance of transparent ABS (acrylonitrile-butadiene-styrene copolymer); The stress cracking resistance of transparent PC (polycarbonate) difference; The fragility of PMMA (polymethylmethacrylate) and AS (acrylonitritrile-styrene resin); Higher because of pure GPPS resin transparent degree, in order to improve the transparency of alloy, need to increase the content of GPPS resin in the alloy, and this simple way is only understood the shock strength of sacrificial alloy.So existing K glue/GPPS alloy can not have high transparent and impact simultaneously, this has just limited their application.
[summary of the invention]
The technical problem that the present invention will solve provides transparent K glue/GPPS material of a kind of high transparent, high-impact, good fluidity and preparation method thereof.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is, a kind of transparent K glue/GPPS alloy material is composed of the following components by weight percentage:
K glue 69-80%;
GPPS 19-30％；
Lubricant 0.5-1%;
Oxidation inhibitor 0.2-0.6%.
Described K glue is under 200 degree, 5 kilograms test condition, and melting index is greater than 10g/10min, and transparence is between 80～90%.
Described GPPS is under 200 degree, 5 kilograms test condition, and melting index is greater than 10g/10min, and transparence is between 88～92%.
Said lubricant is interior lubricated and outer lubricated compound system, and internal lubricant is a calcium stearate, and external lubricant is PE wax or OP wax.
Said oxidation inhibitor is composite antioxidant, and primary antioxidant is four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester).
The above transparent K glue/GPPS material, preferably composed of the following components by weight percentage:
K glue 76-78%;
GPPS 21-23％；
Lubricant 0.5-0.7%;
Oxidation inhibitor 0.3-0.5%.
The technical scheme of more than one said transparent K glue/GPPS material preparation methods may further comprise the steps:
A: take by weighing raw material and mix by above-mentioned weight percent;
B: mixed raw materials among the step a is put into the loading hopper of twin screw extruder, through melt extruding granulation; Complete processing is following: twin screw extruder one district temperature 190-200 ℃, two district temperature 210-220 ℃, three district temperature 220-225 ℃, four district temperature 210-220 ℃, head 200-205 ℃, the residence time 1～2min, pressure are 10-20MPa.
The transparent K glue of the present invention/GPPS alloy material is selected essentially identical K glue of refractive index and GPPS for use; Extrude through physical blending and to have prepared high transparent K glue/GPPS alloy, this alloy has the advantage of K glue and two kinds of resins of GPPS, good toughness simultaneously; Transmittance is high; Internal stress is little, has overcome some shortcomings of universal transparent resin on the market, and this alloy has a good application prospect.
[embodiment]
For ease of the present invention is further understood, combine specific embodiment to describe the present invention at present:
In the material prescription of the following example, used K glue is the strange beautiful PB-5903 in Taiwan, and GPPS is the 666H of LG-DOW; Oxidation inhibitor is that four [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2,4-di-t-butyl phenyl ester); Select for use Ciba company to produce, trade names are respectively Irganox1010 and Irganox168.Lubricant is interior lubricated and outer lubricated compound system, and internal lubricant is a calcium stearate, and external lubricant is PE wax or OP wax
Embodiment 1:
With K glue 70% (following all be weight percentage), GPPS 29%, lubricant 0.8%, and oxidation inhibitor 0.2% mixes, and the material that mixes is joined in the hopper of twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, screw rod is respectively distinguished the temperature setting and is respectively: twin screw extruder one district temperature 190-200 ℃, two district temperature 210-220 ℃, three district temperature 220-225 ℃, four district temperature 210-220 ℃, head 200-205 ℃, the residence time 1～2min, pressure are 10-20MPa.
Embodiment 2:
With K glue 72% (following all be weight percentage), GPPS 27%, lubricant 0.7%, and oxidation inhibitor 0.3% mixes, and the material that mixes is joined in the hopper of twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, screw rod is respectively distinguished the temperature setting and is respectively: twin screw extruder one district temperature 190-200 ℃, two district temperature 210-220 ℃, three district temperature 220-225 ℃, four district temperature 210-220 ℃, head 200-205 ℃, the residence time 1～2min, pressure are 10-20MPa.
Embodiment 3:
With K glue 75% (following all be weight percentage), GPPS 24%, lubricant 0.5%, and oxidation inhibitor 0.5% mixes, and the material that mixes is joined in the hopper of twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, screw rod is respectively distinguished the temperature setting and is respectively: twin screw extruder one district temperature 190-200 ℃, two district temperature 210-220 ℃, three district temperature 220-225 ℃, four district temperature 210-220 ℃, head 200-205 ℃, the residence time 1～2min, pressure are 10-20MPa.
Embodiment 4:
With K glue 77% (following all be weight percentage), GPPS 22%, lubricant 0.6%, and oxidation inhibitor 0.4% mixes, and the material that mixes is joined in the hopper of twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, screw rod is respectively distinguished the temperature setting and is respectively: twin screw extruder one district temperature 190-200 ℃, two district temperature 210-220 ℃, three district temperature 220-225 ℃, four district temperature 210-220 ℃, head 200-205 ℃, the residence time 1～2min, pressure are 10-20MPa.
Embodiment 5:
With K glue 79% (following all be weight percentage), GPPS 20%, lubricant 0.6%, and oxidation inhibitor 0.4% mixes, and the material that mixes is joined in the hopper of twin screw extruder, and through melt blending, extruding pelletization becomes alloy material.Wherein, screw rod is respectively distinguished the temperature setting and is respectively: twin screw extruder one district temperature 190-200 ℃, two district temperature 210-220 ℃, three district temperature 220-225 ℃, four district temperature 210-220 ℃, head 200-205 ℃, the residence time 1～2min, pressure are 10-20MPa.
Performance test:
Tensile strength is tested by ASTM D-638 standard.Specimen types is the I type, batten size (mm): (176 ± 2) (length) * (12.6 ± 0.2) (end width) * (3.05 ± 0.2) (thickness), and draw speed is 50mm/min;
Flexural strength and modulus in flexure are tested by ASTM D-790 standard.Specimen types is specimen size (mm): (128 ± 2) * (12.67 ± 0.2) * (3.11 ± 0.2), rate of bending are 20mm/min;
The socle girder notched Izod impact strength is tested by ASTM D-256 standard.Specimen types is the I type, specimen size (mm): (63 ± 2) * (12.45 ± 0.2) * (3.1 ± 0.2); The breach type is a category-A, and the breach residual thickness is 1.9mm;
Melting index is tested by ASTM D-1238, and probe temperature is 200 ℃, and load is 5 kilograms, and be 5min warm up time;
Heat-drawn wire is tested by ASTM D-648, specimen size (mm): (128 ± 2) * (12.45 ± 0.2) * (3.1 ± 0.2), load are 1.82MPa;
Flame retardant properties is tested by UL94, test size (mm): (128 ± 2) * (12.67 ± 0.2) * (3.11 ± 0.2), flame height 20mm.
ASTM D 1003-2000 is pressed in the transparence test, test size (mm): (80 ± 2) * (40 ± 0.2) * (3 ± 0.2),
Embodiment 1-5 prescription and material property see the following form:
Can find out that by last table K glue/GPPS alloy of above embodiment has the good transparency, has the excellent properties of K glue and two kinds of bed materials of GPPS simultaneously concurrently, has further expanded the Application Areas of K glue and GPPS.
Various embodiments of the present invention are selected refractive index close K glue and GPPS for use, can not reduce the transmittance of alloy because of a large amount of addings of the lower K glue of transmittance.Simultaneously, used auxiliary agent particle diameter is enough little, is lower than light wavelength, thereby the alloy of preparation has high transmittance and shock strength concurrently.
Among the above embodiment, the adding proportion of K glue is higher, and is the highest near 80%, guaranteed the alloy high impulse strength, thereby overcome this product transmittance height on the market and the shortcoming of shock strength difference.
Each embodiment contrast shows that GPPS content is high more, and the transparence of alloy is high more, and intensity is high more, but toughness decreases.Over-all properties and cost consideration, the over-all properties of embodiment 4 is best.
More than a kind of transparent K glue provided by the present invention/GPPS material and preparation method thereof has been carried out detailed introduction; Used concrete example among this paper principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that on embodiment and range of application, all can change, in sum, this description should not be construed as limitation of the present invention.
Claims (7)
1. transparent K glue/GPPS alloy material is characterized in that, and is composed of the following components by weight percentage:
K glue 69-80%;
GPPS 19-30％；
Lubricant 0.5-1%;
Oxidation inhibitor 0.2-0.6%.
2. transparent K glue according to claim 1/GPPS alloy material is characterized in that, described K glue is under 200 degree, 5 kilograms test condition, and melting index is greater than 10g/10min, and transparence is between 80～90%.
3. transparent K glue according to claim 1/GPPS alloy material is characterized in that, described GPPS is under 200 degree, 5 kilograms test condition, and melting index is greater than 10g/10min, and transparence is between 88～92%.
4. transparent K glue according to claim 1/GPPS alloy material is characterized in that, said lubricant is interior lubricated and outer lubricated compound system, and internal lubricant is a calcium stearate, and external lubricant is PE wax or OP wax.
5. transparent K glue according to claim 1/GPPS alloy material is characterized in that said oxidation inhibitor is composite antioxidant; Primary antioxidant is that four [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester).
6. transparent K glue according to claim 1/GPPS alloy material is characterized in that, and is composed of the following components by weight percentage:
K glue 76-78%;
GPPS 21-23％；
Lubricant 0.5-0.7%;
Oxidation inhibitor 0.3-0.5%.
7. the said transparent K glue of claim 1/GPPS preparation methods may further comprise the steps:
A: take by weighing raw material and mix by the described weight percent of claim 1;
B: mixed raw materials among the step a is put into the loading hopper of twin screw extruder, through melt extruding granulation; Complete processing is following: twin screw extruder one district temperature 190-200 ℃, two district temperature 210-220 ℃, three district temperature 220-225 ℃, four district temperature 210-220 ℃, head 200-205 ℃, the residence time 1～2min, pressure are 10-20MPa.
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| CN2010105985552A CN102311589B (en) | 2010-12-21 | 2010-12-21 | Transparent K-resin/GPPS (general purpose polystyrene) alloy material and preparation method thereof |
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| CN2010105985552A CN102311589B (en) | 2010-12-21 | 2010-12-21 | Transparent K-resin/GPPS (general purpose polystyrene) alloy material and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044797A (en) * | 2013-01-22 | 2013-04-17 | 贵州省复合改性聚合物材料工程技术研究中心 | Transparent K glue composite AS (Acrylonitrile-Styrene Copolymers) alloy material and preparation method thereof |
| CN103073805A (en) * | 2013-01-21 | 2013-05-01 | 东莞市欣隆光电材料有限公司 | High impact strength photodiffusion polystyrene material and preparation method thereof |
| CN103756173A (en) * | 2014-01-20 | 2014-04-30 | 苏州新区特氟龙塑料制品厂 | Improved GPPS (General Purpose Polystyrene) formula |
| CN104004283A (en) * | 2014-06-10 | 2014-08-27 | 深圳永合高分子材料有限公司 | Environment-friendly two-way stretching polystyrene sheet material for printing and manufacture method thereof |
| CN104004286A (en) * | 2014-06-10 | 2014-08-27 | 深圳永合高分子材料有限公司 | High-light-transmittance and high-impact-resistant polystyrene sheet and manufacturing method thereof |
| CN104004285A (en) * | 2014-06-10 | 2014-08-27 | 深圳永合高分子材料有限公司 | High-antifogging polystyrene sheet suitable for special food packaging and manufacturing method thereof |
| CN104004284A (en) * | 2014-06-10 | 2014-08-27 | 深圳永合高分子材料有限公司 | High-toughness polystyrene sheet and manufacturing method thereof |
| CN104031324A (en) * | 2014-06-10 | 2014-09-10 | 深圳永合高分子材料有限公司 | Antistatic biaxial oriented polystyrene sheet and manufacturing method thereof |
| CN104086911A (en) * | 2014-07-14 | 2014-10-08 | 东莞市德诚塑化科技有限公司 | Transparent impact-resistance polystyrene and preparation method thereof |
| CN104448595A (en) * | 2014-12-19 | 2015-03-25 | 深圳市鑫恒力科技有限公司 | Gpps transparent liquid toughening agent |
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| CN109666240A (en) * | 2018-12-26 | 2019-04-23 | 金旸（厦门）新材料科技有限公司 | A kind of high rigidity light diffusion K resin material and preparation method thereof |
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Cited By (15)
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| CN103073805A (en) * | 2013-01-21 | 2013-05-01 | 东莞市欣隆光电材料有限公司 | High impact strength photodiffusion polystyrene material and preparation method thereof |
| CN103044797A (en) * | 2013-01-22 | 2013-04-17 | 贵州省复合改性聚合物材料工程技术研究中心 | Transparent K glue composite AS (Acrylonitrile-Styrene Copolymers) alloy material and preparation method thereof |
| CN103756173A (en) * | 2014-01-20 | 2014-04-30 | 苏州新区特氟龙塑料制品厂 | Improved GPPS (General Purpose Polystyrene) formula |
| CN104004284A (en) * | 2014-06-10 | 2014-08-27 | 深圳永合高分子材料有限公司 | High-toughness polystyrene sheet and manufacturing method thereof |
| CN104004286A (en) * | 2014-06-10 | 2014-08-27 | 深圳永合高分子材料有限公司 | High-light-transmittance and high-impact-resistant polystyrene sheet and manufacturing method thereof |
| CN104004285A (en) * | 2014-06-10 | 2014-08-27 | 深圳永合高分子材料有限公司 | High-antifogging polystyrene sheet suitable for special food packaging and manufacturing method thereof |
| CN104004283A (en) * | 2014-06-10 | 2014-08-27 | 深圳永合高分子材料有限公司 | Environment-friendly two-way stretching polystyrene sheet material for printing and manufacture method thereof |
| CN104031324A (en) * | 2014-06-10 | 2014-09-10 | 深圳永合高分子材料有限公司 | Antistatic biaxial oriented polystyrene sheet and manufacturing method thereof |
| CN104086911A (en) * | 2014-07-14 | 2014-10-08 | 东莞市德诚塑化科技有限公司 | Transparent impact-resistance polystyrene and preparation method thereof |
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