CN1200037C - Composition of fiber reinforced polymer - Google Patents
Composition of fiber reinforced polymer Download PDFInfo
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- CN1200037C CN1200037C CN 02111300 CN02111300A CN1200037C CN 1200037 C CN1200037 C CN 1200037C CN 02111300 CN02111300 CN 02111300 CN 02111300 A CN02111300 A CN 02111300A CN 1200037 C CN1200037 C CN 1200037C
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Abstract
The present invention relates to a composition of a fiber reinforced polymer, which mainly solves the problem of low impact strength existing in the performance of a fiber reinforced SMA compound in the previous art. The present invention nicely solves the problem by adopting the technical scheme that MBS, SAN and glass fibers are led into SMA, and simultaneously, the composition is enabled to have the advantages of good mechanical performance, favorable processing fluidity and good combination performance. The present invention can be used in the industrial production of plastic processing.
Description
Technical field
The present invention relates to the composition of fiber-reinforced polymer, particularly about the composition of the random copolymers of glass fibre reinforced styrene-maleic anhydride.
Background technology
Single macromolecular material often is difficult to satisfy the application requiring of various complexity, therefore the blend of multiple macromolecular material and with the compound of some filamentary material be the important means of improving single macromolecular material performance, wherein glass fibre is exactly a kind of widely used reinforcing fiber materials.Glass fibre can increase substantially some performance such as physical strength, rigidity, thermotolerance and the dimensional stability etc. of plastics as strongthener, and low price also is its a big advantage simultaneously.Glass filament reinforced plastics extensively is used in aspects such as household electrical appliance, office equipment, mechanical component or auto parts machinery, and some glass filament reinforced plastics such as glass fiber enhanced nylon, glass REINFORCED PET or glass strengthen polyoxymethylene etc. even can alternative metals use as structured material.
Glass fibre reinforced styrene-copolymer-maleic anhydride (SMA resin) becomes the strong rival of polycarbonate (PC) or polyphenylene oxide engineering plastics such as (PPO) owing to having good thermotolerance, dimensional stability, processing fluidity and lower cost, is mainly used in the injection molding of baroque large-scale thin wall parts such as fascia etc.Because the rigidity of vinylbenzene-copolymer-maleic anhydride molecular structure is very big, so there is the low shortcoming of resistance to impact shock in glass fibre reinforced styrene-copolymer-maleic anhydride.
The method that improves glass fibre reinforced styrene-copolymer-maleic anhydride shock strength generally reaches by vinylbenzene-copolymer-maleic anhydride is carried out toughening modifying.This generally has two kinds of methods: a kind of method is to introduce part rubber such as divinyl rubber, styrene-butadiene rubber(SBR) or chloroprene rubber etc. significantly improve the shock strength of SMA resin in making the SMA resin process, but this method exists complex process and the big shortcoming of investment; Another kind method be by melt blending make SMA resin and some thermoplastic elastomer such as styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene graft copolymer (MBS) or acrylate nucleocapsid multipolymer (ACR) thus etc. impact modifying agent mix the shock strength that makes the SMA resin and improve.Though this method is fairly simple, invest also less, but shock strength is greatly improved in general will uses more impact modifying agent, this can influence processing fluidity and rigidity that glass fibre strengthens the SMA resin, makes the SMA resin lose the inherent advantage.
Composition and manufacture method thereof that a kind of glass fibre strengthens the SMA resin complexes have been described among the document world patent WO 9115543.This method has adopted the grafted ABS resin as the properties-correcting agent that improves SMA resin shock strength (the SAN resin can be selected to add), and therefore the ratio of maleic anhydride weight content that requires the glass fibre weight content of whole mixture and SMA resin only is suitable for the SMA resin of maleic anhydride weight content higher (22～40%) between 0.62～1.40.The glass fibre of present method preparation strengthens the SMA resin complexes and has the low shortcoming of shock strength, and for example 20% glass fibre of their preparation enhancing (SMA40 weight part+ABS50 weight part+SAN10 weight part) composite I zod parallel direction shock strength is 9.8 joules per meter
2And the vertical direction shock strength only is 8.8 joules per meter
2, the non-notched Izod impact strength of Charpy only is 18.6 joules per meter
2The clear 62-48755 of Japanese Patent JP has reported that also a kind of glass fibre strengthens the manufacture method of SMA resin complexes, this method is to adopt the impact modifying agent of thermoplastic elastomers such as SBS or MBS as the SMA resin, but, strengthen (SMA85 weight part+MBS15 weight part) composite I zod shock strength as 20% glass fibre and have only 8.4 kilograms of cm/(82 joules per meter) owing to use SBS or MBS also to have the low shortcoming of shock strength separately as the glass fibre enhancing SMA resin complexes of the impact modifying agent preparation of SMA resin.This method generally is only applicable to the lower SMA resin of maleic anhydride content.
Summary of the invention
Technical problem to be solved by this invention is to overcome to have the low problem of shock strength in the performance that has fiber reinforcement SMA mixture in the above-mentioned document, and a kind of composition of new fiber-reinforced polymer is provided.Said composition not only has high shock strength, preferably mechanical property and have well processed flowability and better comprehensive performance.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of composition of fiber-reinforced polymer comprises following component in parts by weight:
A) molecular weight is 40～84 parts of the random copolymerss of 10～300,000 vinylbenzene and maleic anhydride, and wherein maleic anhydride content is 5～35% by weight percentage;
B) random copolymers of vinylbenzene and vinyl cyanide is 1～34 part, and wherein styrene content is 70～80% by weight percentage;
C) methyl methacrylate, divinyl and cinnamic graft copolymer are 15～25 parts, and wherein butadiene content is 50～90% by weight percentage;
D) glass fibre is 10～30 parts;
E) oxidation inhibitor four [β-(3,5-di-tert-butyl-hydroxy phenyl propionic acid)] tetramethylolmethane is 0.1～2 part.
In the technique scheme in parts by weight, the random copolymers consumption preferable range of vinylbenzene-maleic anhydride is 55～75 parts, the molecular weight preferable range of the random copolymers of vinylbenzene-maleic anhydride is 15～250,000, in the random copolymers of vinylbenzene-maleic anhydride maleic anhydride content by weight percentage preferable range be 15～25%.In methyl methacrylate, divinyl and the cinnamic graft copolymer butadiene content by weight percentage preferable range be 70～90%.In parts by weight glass fibre consumption preferable range is 15～20 parts; the glass fibre preferred version is an alkali free glass fibre; fiberglass surfacing is with being selected from triethoxyl silane, γ-methacryloyl propyl trimethoxy silicane, vinyl tris silane, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, N-aminopropyl triethoxysilane or γ-Racemic glycidol propyl ether Trimethoxy silane coupling agent treatment mistake, and the preferred version of coupling agent is for selecting γ-Racemic glycidol propyl ether Trimethoxy silane for use.Oxidation inhibitor four [β-(3,5-di-tert-butyl-hydroxy phenyl propionic acid)] tetramethylolmethane (abbreviation antioxidant 1010) consumption preferable range is 0.1～1 part.
Each component is character, preparation method and composed as follows described more specifically.
Component is the random copolymers (SMA resin) of vinylbenzene and maleic anhydride a), and vinylbenzene and maleic anhydride mixture that methods such as available ontologies polymerization, solution polymerization process or suspension polymerization are formed by a certain percentage by heating or free radical polymerization make.The quality percentage composition of the maleic anhydride of the SMA resin of using as engineering plastics generally between 5～35%, the maleic anhydride quality percentage composition of the SMA resin that the present invention uses with 15～25% for well.The maleic anhydride quality percentage composition of SMA resin is lower than 15%, and it is lower that resulting glass fibre strengthens SMA resin complexes thermotolerance; The maleic anhydride quality percentage composition of SMA resin is higher than 25%, and it is lower that resulting glass fibre strengthens SMA resin complexes shock strength.The SMA resin of using as engineering plastics also should have higher molecular weight, generally with 10～300,000 for well, is preferably between 15～250,000.
Components b) is meant organic polymer that those have high strength and modulus such as polystyrene (PS), polymethylmethacrylate (PMMA), styrene-acrylonitrile random copolymers (SAN resin) etc. for rigid organic polymer.Theory (Fracture Behaviour of Polymers.Applied Science Publishers Ltd. according to people such as A.J.Kinloch, lst Ed., 1983), the rigid organic polymer of this energy toughened matrix resin also should meet the following conditions: 1) the modulus E of matrix resin
1The modulus E of＜rigid organic polymer
2, the Poisson's ratio v of matrix resin
1The Poisson's ratio v of rigid organic polymer
22) matrix resin and rigid organic polymer should have certain tough crisp matching, and bonding interface is good.3) matrix resin itself will have certain tough ratio.4) content of rigid organic polymer should be suitable, too high or too lowly all can influence toughening effect.For matrix resin SMA rigid organic polymer with styrene-acrylonitrile random copolymers (SAN resin) for well, vinylbenzene in the SAN resin: the mass ratio of vinyl cyanide with between 80: 20 to 70: 30 for well.
Amount of component b), there is this compounds of better shock strength improvement effect that acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene graft copolymer (MBS resin) and acrylate nucleocapsid multipolymer (ACR) etc. are arranged to the SMA resin for the thermoplastic elastomer impact modifying agent is meant a class rubber compound that can improve plastic impact intensity and excellent processing fluidity.In these polymkeric substance the quality percentage composition of rubber with between 50%～90% for well, be preferably between 70%～90%.The preparation method obtains with letex polymerization monomers such as graft polymerization vinyl cyanide, methyl methacrylate or vinylbenzene on divinyl (or butylbenzene or acrylate) rubber, and concrete grammar can be with reference to U.S. Pat P4, and 443,585.Not only the shock strength improvement effect is different for the impact modifying agent of different varieties, and the glass fibre of preparation enhancing SMA mixture processing fluidity also has than big difference.It is considered herein that MBS resin modified effect is best and glass fibre enhancing SMA mixture processing fluidity preparation is also high.
Component d) be glass fibre with alkali free glass fibre (E type glass) for well, form can be a continuous fiber, also chopped strand.The most handy silane coupling agent of fiberglass surfacing is handled; the available silane coupling agent has triethoxyl silane, vinyl tris silane, γ-methacryloyl propyl trimethoxy silicane, N-β-(aminoethyl) γ-An Bingjisanjiayangjiguiwan, N-aminopropyl triethoxysilane or γ-Racemic glycidol propyl ether Trimethoxy silane among the present invention, and the preferred version of coupling agent is for selecting γ-Racemic glycidol propyl ether Trimethoxy silane for use.
Component e) important stablizer in the oxidation inhibitor polymer complex course of processing, oxidation inhibitor commonly used has hindered phenolic compound and organophosphorus ester compound.Hindered phenolic oxidation inhibitor has 2,6-di-tert-butyl-4-methy phenol (antioxidant 264), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 2, two (the 4-methyl-6-tert butyl) phenol (antioxidant 2246) of 2 '-methyne, β-(3, the 5-di-tert-butyl-hydroxy phenyl)-propionic acid ten caprylates (antioxidant 1076) or four [β-(3,5-di-tert-butyl-hydroxy phenyl propionic acid)] tetramethylolmethane (antioxidant 1010) etc., it is considered herein that four [β-(3,5-di-tert-butyl-hydroxy phenyl propionic acid)] tetramethylolmethane (antioxidant 1010) is better.
Glass of the present invention strengthens the SMA resin complexes except above-mentioned main component, also can add additives such as filler, pigment or ultra-violet stabilizer, does not describe in detail one by one at this.
The preparation method of glass-fibre reinforced resin mixture of the present invention can use Banbury (Banbury) Banbury mixer, single screw rod or twin screw extruder, and is wherein the most frequently used with twin screw extruder.Resin alloy and glass fibre strengthen and can divide secondary to finish also can once to finish, and secondary processes strengthens aforementioned blend with glass fibre more for the second time and obtains promptly earlier all resins and additive melt blending granulation in proportion under molten state.One-time process is that resin and additive and glass fibre obtain through a melt blending granulation.Take one-time process and secondary processes to depend primarily on processing units, more more economical from the energy consumption one-time process than secondary processes.Processing temperature generally can change between 200～300 ℃, but with best between 220～260 ℃.
Raw material of the present invention and testing method are as follows:
The SMA resin: Shanghai Petroleum Chemical Engineering Institute produces, maleic anhydride quality percentage composition 18%, T
g=136 ℃ (DSC method).
The SAN1 resin: produce in Shanghai Gaoqiao petrochemical complex company limited chemical plant, the HF type, and vinyl cyanide quality percentage composition is 23%
The SAN2 resin: produce in Shanghai Gaoqiao petrochemical complex company limited chemical plant, the HC type, and vinyl cyanide quality percentage composition is 30%
The MBS resin: Wu Yu chemistry (Singapore) company limited produces, trade mark BTA 751
Antioxidant 1010: Shanghai Gaoqiao-vapour clings to chemical company limited and produces
Alkali free glass fibre: huge strong glass fibre company limited of Tongxiang, Zhejiang megalith group, RP986,13 microns of diameters
Testing method
Glass fiber content is pressed ASTM D2584.
Melt flow rate (MFR) is pressed ASTM D1238, and 260 ℃ of test temperatures are loaded 5 kilograms
Tensile strength is pressed ASTM D638, I class sample, 5.1 millimeters/minute of draw speeds
Bending property is pressed ASTM D790, specimen size 130 (millimeter) * 13 (millimeter) * 6.4 (millimeter)
The Izod shock strength is pressed ASTM D256A, 3.2 mm thick samples
Heat-drawn wire (HDT) is pressed ASTM D648,1.82MPa load, the same bend specimen of specimen size.
Owing to adopt glass fibre to strengthen SMA the shock strength of composition is significantly improved among the present invention, add the further raising that SAN more helps shock strength in the composition, pass through to add MBS, SAN and glass fibre among the SMA, make composition not only have the shock strength height, and whole mechanical property is good, processing fluidity and over-all properties have all kept level preferably, have obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1 and comparative example 1～2]
Mixing in a container in back adding twin screw extruder first feeder (being fit to the pellet feeding) by proportion of composing in the table one through exsiccant SMA resin and SAN2 resin (Comparative Examples 1 and 2 does not add the SAN2 resin), MBS resin and 1010 oxidation inhibitor mix the back and add in twin screw extruder second feeder (being fit to powder feeding).Twin screw extruder (German Leistritz company, screw diameter Φ=27 millimeter, length-to-diameter ratio L/D=36) each section temperature (from charging opening to head) is set at 200 ℃ respectively, and 220 ℃, 230 ℃, 235 ℃, 240 ℃.SMA/SAN resin and MBS resin add the twin screw extruder simultaneously from first feeder and second feeder, and the screw speed of twin screw extruder main frame and an second feeder is respectively 115 rev/mins, and 50 rev/mins, 40 rev/mins.Alkali free glass fibre is introduced (Comparative Examples 1 does not add glass fibre) from forcing machine middle part charging opening continuously.Extrude bar-shaped sample and promptly obtain glass fibre enhancing SMA resin complexes through the water-cooled pelletizing.
Above-mentioned resin complexes is used plastic-injection moulding machine (model SZ-68/400 85 ℃ of dryings after 2 hours, China Liuzhou plastics machinery head factory Shanghai subsidiary factory) is injection molded into ASTM standard batten, injecting condition is 240 ℃ of injection temperatures, injection pressure 9MPa (gauge pressure), injection cycle 60 seconds.Batten carries out performance measurement after room temperature is placed at least 24 hours.The content of glass fiber of glass fibre enhancing SMA resin complexes can directly get granulated samples or the injection moulding batten is measured by ignition test.
Table one glass fibre strengthens the composition and the performance thereof of SMA resin complexes
| Numbering | Comparative example 1 | Comparative example 2 | Embodiment 1 |
| Form (phr) Annotate 1SMA SAN2 MBS antioxidant 1010 | 80 20 0.5 | 80 20 0.5 | 64 16 20 0.5 |
| The performance glass fiber content, % MFR Annotate 2260 ℃, 5 kilograms of tensile strengths, the MPa flexural strength, the MPa bending elastic modulus, MPa HDT (1.82MPa), ℃ Izod shock strength, joules per meter | 0 12 48 66 2260 107 40 | 17.9 6.8 83.5 91 3984 124 88 | 19.5 6.4 88.9 105 4547 118 101 |
Annotate the umber of certain component in per hundred parts of resins of 1:phr-part per hundred resen.
Annotate 2:MFR-Melt-Mass Flow Rate fusion mass flow rate.
From Comparative Examples 1 and 2 and the test result of embodiment 1 can find out, the Izod shock strength that glass fibre strengthens SMA resin complexes (Comparative Examples 2) is significantly improved than non-glass fiber enhancing SMA resin complexes (Comparative Examples 1), and this is because SMA resin and glass fibre have good bonding force to make the tensile strength of mixture and the result that flexural strength all significantly improves.And after the present invention adds a certain amount of rigid organic polymer SAN2 resin, the Izod shock strength that the glass fibre that obtains strengthens SMA resin complexes (embodiment 1) has further raising, and this explanation rigid organic polymer SAN2 resin has played the effect of toughness reinforcing enhancing SMA resin really.This can satisfy the condition of the toughness reinforcing SMA resin of rigid organic polymer from the SAN2 resin: the modulus E of SAN resin
2The modulus E of＞SMA resin
1, and in the SAN resin in vinyl cyanide group and the SMA resin special role of maleic anhydride group make SAN resin and SMA resin have good consistency to obtain explaining.Can find out also that from test result the glass fibre of the present invention's preparation strengthens the SMA resin complexes also higher draw tensile strength.Flexural strength and bending elastic modulus.
[embodiment 2～5 and comparative example 3]
The operational path identical with embodiment 1, just rigid organic polymer SAN2 resin changes SAN1 resin (acrylonitrile content is lower than SAN2 resin) into, SMA resin and SAN1 resin quality such as table 2, Comparative Examples 3 does not contain antioxidant 1010, and the gained glass fibre strengthens SMA resin complexes performance such as table 2.
Table two glass fibre strengthens the composition and the performance thereof of SMA resin complexes
| Numbering | Comparative example 3 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Form (phr) Annotate 1SMA SAN1 MBS antioxidant 1010 | 64 16 20 0 | 72 8 20 0.5 | 64 16 20 0.5 | 56 24 20 0.5 | 48 32 20 0.5 |
| The performance glass fiber content, % MFR Annotate 2260 ℃, 5 kilograms of tensile strengths, the MPa flexural strength, the MPa bending elastic modulus, MPa HDT (1.82MPa), ℃ Izod shock strength, joules per meter | 17.0 7.0 81.5 110 4467 120 91 | 17.6 6.6 84.0 103 4464 120 95 | 17.3 6.4 84.6 107 4461 119 98 | 17.3 6.0 85.5 109 4505 115 101 | 19.8 5.0 87.6 108 4396 113 89 |
Annotate the umber of certain component in per hundred parts of resins of 1:phr-part per hundred resen.
Annotate 2:MFR-Melt-Mass Flow Rate fusion mass flow rate.
Can find out from the test result of embodiment 2～5, the present invention adopts the glass fibre of rigid organic polymer SAN1 resin modified SMA resins to strengthen the SMA resin complexes and still has better comprehensive performance and high shock strength, still can toughness reinforcing enhancing SMA resin after the vinyl cyanide mass content that the SAN resin is described changes to 23% from 30%, this is because the vinyl cyanide mass content of SAN resin still has good consistency with the SMA resin in this scope, we think the vinyl cyanide mass content of SAN resin with 20～30% for well.Can find out from the test result of embodiment 5, the quality percentage composition of SAN resin in resin is formed reaches after 32%, the shock strength that glass fibre strengthens the SMA resin complexes has a declining tendency, and we think that the quality percentage composition of SAN resin is more suitable with 5～30%.Can find out from Comparative Examples 3, the glass fibre that does not add antioxidant 1010 strengthen SMA resin complexes tensile strength and shock strength all lower, so the present invention is to adopt the method for adding antioxidant 1010 for well.
Claims (9)
1, a kind of composition of fiber-reinforced polymer comprises following component in parts by weight:
A) molecular weight is 40～84 parts of the random copolymerss of 10～300,000 vinylbenzene and maleic anhydride, and wherein maleic anhydride content is 5～35% by weight percentage;
B) random copolymers of vinylbenzene and vinyl cyanide is 1～34 part, and wherein styrene content is 70～80% by weight percentage;
C) methyl methacrylate, divinyl and cinnamic graft copolymer are 15～25 parts, and wherein butadiene content is 50～90% by weight percentage;
D) glass fibre is 10～30 parts;
E) oxidation inhibitor four [β-(3,5-di-tert-butyl-hydroxy phenyl propionic acid)] tetramethylolmethane is 0.1～2 part.
2,, it is characterized in that in parts by weight the random copolymers consumption of vinylbenzene-maleic anhydride is 55～75 parts according to the composition of the described fiber-reinforced polymer of claim 1.
3, according to the composition of the described fiber-reinforced polymer of claim 1, the molecular weight that it is characterized in that the random copolymers of vinylbenzene-maleic anhydride is 15～250,000.
4,, it is characterized in that maleic anhydride content is 15～25% by weight percentage in the random copolymers of vinylbenzene-maleic anhydride according to the composition of the described fiber-reinforced polymer of claim 1.
5,, it is characterized in that butadiene content is 70～90% by weight percentage in methyl methacrylate, divinyl and the cinnamic graft copolymer according to the composition of the described fiber-reinforced polymer of claim 1.
6,, it is characterized in that in parts by weight glass fibre consumption be 15～20 parts according to the composition of the described fiber-reinforced polymer of claim 1.
7, according to the composition of the described fiber-reinforced polymer of claim 1; it is characterized in that fiberglass surfacing with being selected from triethoxyl silane, γ-methacryloyl propyl trimethoxy silicane, vinyl tris silane, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, N-aminopropyl triethoxysilane or γ-Racemic glycidol propyl ether Trimethoxy silane coupling agent treatment mistake, glass fibre is no alkaline glass fibre.
8,, it is characterized in that fiberglass surfacing γ-Racemic glycidol propyl ether Trimethoxy silane coupling agent treatment mistake according to the composition of the described fiber-reinforced polymer of claim 7.
9,, it is characterized in that in parts by weight oxidation inhibitor four [β-(3,5-di-tert-butyl-hydroxy phenyl propionic acid)] tetramethylolmethane consumption be 0.1～1 part according to the composition of the described fiber-reinforced polymer of claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766306A (en) * | 2012-08-14 | 2012-11-07 | 龙甲（上海）实业有限公司 | Spraying-free high-transparent high-glossy acrylonitrile butadiene styrene (ABS) material and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101888905B (en) * | 2007-11-06 | 2013-07-10 | 罗迪亚公司 | Articles having an interface between a polymer surface and a modified glass surface |
| CN102121563A (en) * | 2011-01-05 | 2011-07-13 | 湖南中财化学建材有限公司 | Plastic section and special production equipment and production method thereof |
| CN102329517A (en) * | 2011-07-26 | 2012-01-25 | 句容市百事特复合材料有限公司 | Long and short fiber hybrid reinforced plastic granule and production method thereof |
| CN102702638B (en) * | 2012-05-30 | 2014-04-16 | 宁波镇洋化工发展有限公司 | Glass fiber-reinforced styrene-acrylonitrile-cycloolefin (SAN) copolymer composition |
| CN105778377A (en) * | 2016-05-11 | 2016-07-20 | 南京京锦元科技实业有限公司 | Glass fiber reinforced polyacrylic resin composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102766306A (en) * | 2012-08-14 | 2012-11-07 | 龙甲（上海）实业有限公司 | Spraying-free high-transparent high-glossy acrylonitrile butadiene styrene (ABS) material and preparation method thereof |
| CN102766306B (en) * | 2012-08-14 | 2014-09-03 | 龙甲（上海）实业有限公司 | Spraying-free high-transparent high-glossy acrylonitrile butadiene styrene (ABS) material and preparation method thereof |
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