CN101367976A - Preparation method for continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer - Google Patents
Preparation method for continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer Download PDFInfo
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- CN101367976A CN101367976A CNA2008100414849A CN200810041484A CN101367976A CN 101367976 A CN101367976 A CN 101367976A CN A2008100414849 A CNA2008100414849 A CN A2008100414849A CN 200810041484 A CN200810041484 A CN 200810041484A CN 101367976 A CN101367976 A CN 101367976A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
The invention relates to a method for preparing continuous glass fiber reinforced styrene-acrylonitrile copolymers. Styrene-acrylonitrile is taken as matrix component, and continuous glass fibers and polyester resin are taken as reinforcing components. The method includes the following steps: 1) the components besides glass fibers are weighed out according to the weight percents correspondingly; 2) the components are placed in a high-speed mixer, mixed evenly under room temperature and fed into a double screw extruder; 3) the continuous glass fibers are added into the fourth temperature area of the extruder; 4) the components are extruded out, cooled, dried and cut into granules to achieve the desired product. The invention has the advantages that continuous glass fibers are taken as reinforcing component, styrene-acrylonitrile copolymers are introduced into polyester component to enhance the strength and toughness of the copolymers, the blend prepared by the method has relatively high tensile strength, bending modulus and impact strength.
Description
Technical field
The present invention relates to a kind of preparation method of continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer, belong to polymer processing field.
Background technology
Styrene-acrylonitrile resin (being designated hereinafter simply as AS) is a kind of universal phenylethylene resin series, can become plastics by direct injection, also can be used as the starting material of Acrylonitrile-butadiene-styrene Copolymer (ABS).And glass enhancing AS has good using value because of it has good processing properties, dimensional stability and tensile strength in household appliance technical field, as the axial flow in the air-conditioning, through-flow fan blade.But general glass strengthens the AS product in tensile strength, flexural strength and modulus, and the notched Izod impact strength aspect can not satisfy the requirement of application.Therefore, need be by further modification to improve its over-all properties.
Klumperman etc. (WO91/15543) were raw material with styrene-maleic anhydride copolymer (SMA), ABS, AS and glass once, and blend makes the ABS mixture.Though this mixture has improved vicat softening temperature, modulus in flexure is too low, has only 5000MPa.And, manufacturing cost is risen owing to added a large amount of ABS and SMA.In addition, among Chinese patent CN1362443A and the CN1352212A, adopted Methacrylate-butadiene-styrene (MBS), AS, SMA, ABS and glass as raw material, blend makes the AS mixture.But it has increased glass and has soaked stagnant treatment step, and particularly back one piece of patent more relates to expensive silane coupling agent and glass and soaks stagnant treatment step, and process complexity and cost further improve.In addition, Chinese patent CN 1218995C adopts the method for introducing PC (polycarbonate) and PC and MBS or styrene-butadiene-styrene multipolymer (SBS) in SMA, AS and glass fibre, can effectively improve modulus in flexure, the tensile strength of matrix material, but it adopts the higher PC of price, bigger increase material cost.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer of higher draw tensile strength, modulus in flexure and shock strength.
In order to achieve the above object, the present invention adopts styrene-acrylonitrile as matrix component, and continuous glass fibre and vibrin are as enhancement component.The technical scheme of being taked comprises the following steps:
1. get the raw materials ready with the weight percent proportioning:
Styrene-acrylonitrile copolymer 30～70
Continuous glass fibre 10～40
Vibrin 5～20
Toughner 5～15
Coupling agent 0.2～0.5
Compatilizer 5～15
Oxidation inhibitor 0.3～0.5
Wherein, described styrene-acrylonitrile copolymer is the outsourcing product, and vinylbenzene and vinyl cyanide weight percentage are respectively 65%～80% and 35%～20%.
Described continuous glass fibre is a kind of outsourcing alkali free glass fibre, and diameter is 10～25 μ m.
Described vibrin be polyethylene terephthalate and or polybutylene terephthalate.
Described toughner, outsourcing is the maleic anhydride graft polyolefin elastomer, ethene-butyl acrylate-glycidyl methacrylate copolymer etc.
Described coupling agent is an outsourcing aminosilane class coupling agent.
Described compatilizer is the outsourcing atactic styrene-maleic anhydride copolymer.
Described oxidation inhibitor is outsourcing four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester.
2. set the forcing machine working conditions: 180～200 ℃ of district's temperature, 210～220 ℃ of two district's temperature, the temperature in He Si district, three districts is respectively 220～230 ℃, and the temperature in five districts～nine districts is respectively 230～240 ℃; 300～400 rev/mins of engine speeds.
With described vinylbenzene-acrylonitrile copolymer, vibrin, toughner, coupling agent, compatilizer and oxidation inhibitor in super mixer, enter twin screw extruder after mixing at ambient temperature.
4. add the described continuous glass fibre of step 1 in forcing machine the 4th humidity province;
5. extruding postcooling, drying, pelletizing gets product.
Advantage of the present invention is to adopt continuous glass fibre as enhancement component, by introduce intensity and the toughness that polyester becomes to assign to increase multipolymer in styrene-acrylonitrile copolymer, the blend of preparation has higher draw tensile strength, modulus in flexure and shock strength.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
Matrix resin is vinylbenzene-acrylonitrile copolymer, and the prosperous chemical company of Zhenjiang state produces, and the trade mark is D168, is called for short SAN vinylbenzene and vinyl cyanide weight percentage and is respectively 65%～80% and 35%～20%; Continuous glass fibre adopts the ER13-2000-988A of Zhejiang megalith group; Vibrin is a polybutylene terephthalate, and engineering plastics factory of Yizheng branch office of assets management Management Co., Ltd of SINOPEC produces, and the trade mark is L2100, is called for short PBT, or polyethylene terephthalate, is called for short PET; Toughner adopts the ethene-butyl acrylate-glycidyl methacrylate copolymer of du pont company, and trade mark PTW is called for short PTW, or the maleic anhydride graft polyolefin elastomer, and trade mark 493D is called for short MPOE; Coupling agent is selected silane coupling agent for use, γ-An Bingjisanyiyangjiguiwan, and Jiang-Han Area, Jing Zhou Fine Chemical Co., Ltd produces, and the trade mark is KH550, is called for short KH550; The atactic styrene-maleic anhydride copolymer that compatilizer selects for use Shanghai Petroleum Chemical Engineering Institute to produce, the trade mark is SMA218, is called for short SMA; It is four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester that oxidation inhibitor is selected chemical name for use, and Switzerland Ciba company produces, and trade(brand)name Irganox 1010, is called for short 1010.
72A (length-to-diameter ratio is 40) the twin screw extruder production of adopting Rhea company to produce, 180～200 ℃ of complete processing such as next district's temperature, 210～220 ℃ of two district's temperature, the temperature in He Si district, three districts is respectively 220～230 ℃, and the temperature in five districts～nine districts is respectively 230～240 ℃; 300～400 rev/mins of engine speeds.
Embodiment 1
In super mixer, in weight percent, add 65%SAN, 5%PBT, 5%PTW, 0.2%KH550,5%SMA, 0.3%1010, mix at ambient temperature, entering twin screw extruder production, is 19.5% glass fibre in twin screw extruder the 4th humidity province adding weight percentage.Processing conditions is: 190 ℃ of district's temperature, and 210 ℃ of two district's temperature, 225 ℃ of three district's temperature, four districts, five districts, six districts He Jiu district temperature are respectively 230 ℃, and seven districts He Ba district temperature is respectively 240 ℃; 350 rev/mins of engine speeds.
Embodiment 2
In embodiment 1, the weight percentage of SAN changes 60% into, and PBT changes 10% into, and all the other are pressed embodiment 1 identical batching and processing conditions and operate.
Embodiment 3
In super mixer, in weight percent, add 54%SAN, 10%PBT, 5.4%MPOE, 0.3%KH550,5%SMA, 0.3%1010, put into super mixer, mixing at ambient temperature, enter twin screw extruder production, is 25% glass fibre in twin screw extruder the 4th humidity province adding weight percentage.Processing conditions is: 190 ℃ of district's temperature, and 210 ℃ of two district's temperature, 225 ℃ of three district's temperature, four districts, five districts, six districts He Jiu district temperature are respectively 230 ℃, and seven districts He Ba district temperature is respectively 240 ℃; 350 rev/mins of engine speeds.
Embodiment 4
In super mixer, in weight percent, add 50%SAN, 15%PET, 5%PTW, 0.5%KH550,5%SMA, 0.5%1010, mix at ambient temperature, entering twin screw extruder production, is 24% glass fibre in twin screw extruder the 4th humidity province adding weight percentage.Processing conditions is: 180 ℃ of district's temperature, and 220 ℃ of two district's temperature, 225 ℃ of three district's temperature, four districts, five districts, six districts He Jiu district temperature are respectively 230 ℃, and seven districts He Ba district temperature is respectively 240 ℃; 350 rev/mins of engine speeds.
Embodiment 5
In super mixer, in weight percent, add 50%SAN, 10%PBT, 15%MOPE, 0.2%KH550,10%SMA, 0.3%1010, mix at ambient temperature, entering twin screw extruder production, is 14.5% glass fibre in twin screw extruder the 4th humidity province adding weight percentage.Processing conditions is: 190 ℃ of district's temperature, and 210 ℃ of two district's temperature, three districts, four districts, five districts, six districts He Jiu district temperature are respectively 230 ℃, and seven districts He Ba district temperature is respectively 240 ℃; 300 rev/mins of engine speeds.
Embodiment 6
In super mixer, in weight percent, add 45%SAN, 5%PET, 5%MPOE, 0.2%KH550,6.5%SMA, 0.3%1010, mix at ambient temperature, entering twin screw extruder production, is 38% glass fibre in twin screw extruder the 4th humidity province adding weight percentage.Processing conditions is: 190 ℃ of district's temperature, and 210 ℃ of two district's temperature, 225 ℃ of three district's temperature, four districts, five districts, six districts He Jiu district temperature are respectively 230 ℃, and seven districts He Ba district temperature is respectively 240 ℃; 350 rev/mins of engine speeds.
Embodiment 7
In super mixer, in weight percent, add 35%SAN, 5%PBT and 5%PET, 9.5%PTW, 0.2%KH550,15%SMA, 0.3%1010, mix at ambient temperature, entering twin screw extruder production, is 30% glass fibre in twin screw extruder the 4th humidity province adding weight percentage.Processing conditions is: 190 ℃ of district's temperature, and 210 ℃ of two district's temperature, 225 ℃ of three district's temperature, four districts, five districts, six districts He Jiu district temperature are respectively 230 ℃, and seven districts He Ba district temperature is respectively 240 ℃; 400 rev/mins of engine speeds.
Embodiment 8
In super mixer, in weight percent, add 50%SAN, 5%PBT and 5%PET, 9.5%PTW, 0.2%KH550,10%SMA, 0.3%1010, mix at ambient temperature, entering twin screw extruder production, is 20% glass fibre in twin screw extruder the 4th humidity province adding weight percentage.Processing conditions is: 190 ℃ of district's temperature, and 210 ℃ of two district's temperature, 225 ℃ of three district's temperature, four districts, five districts, six districts He Jiu district temperature are respectively 230 ℃, and seven districts He Ba district temperature is respectively 240 ℃; 400 rev/mins of engine speeds.
Embodiment 9
In super mixer, in weight percent, add 50%SAN, 20%PET, 5.5%PTW, 0.2%KH550,14%SMA, 0.3%1010, put into super mixer, mixing at ambient temperature, enter twin screw extruder production, is 10% glass fibre in twin screw extruder the 4th humidity province adding weight percentage.Processing conditions is: 190 ℃ of district's temperature, and 210 ℃ of two district's temperature, 225 ℃ of three district's temperature, four districts, five districts, six districts He Jiu district temperature are respectively 230 ℃, and seven districts He Ba district temperature is respectively 240 ℃; 400 rev/mins of engine speeds.
The comparative example 1
In super mixer,, add 80%SAN in weight percent, 0.2%KH550,0.3%1010, mix at ambient temperature, entering twin screw extruder production, is 19.5% glass fibre in twin screw extruder the 4th humidity province adding weight percentage.Processing conditions is: 190 ℃ of district's temperature, and 210 ℃ of two district's temperature, 225 ℃ of three district's temperature, four districts, five districts, six districts He Jiu district temperature are respectively 230 ℃, and seven districts He Ba district temperature is respectively 240 ℃; 350 rev/mins of engine speeds.
The comparative example 2
In super mixer,, add 70%SAN in weight percent, 0.2%KH550,0.3%1010, mix at ambient temperature, entering twin screw extruder production, is 29.5% glass fibre in twin screw extruder the 4th humidity province adding weight percentage.Processing conditions is: 190 ℃ of district's temperature, and 210 ℃ of two district's temperature, 225 ℃ of three district's temperature, four districts, five districts, six districts He Jiu district temperature are respectively 230 ℃, and seven districts He Ba district temperature is respectively 240 ℃; 350 rev/mins of engine speeds.
Performance test
Notched Izod impact strength is tested by ASTM D256 standard, and specimen size is 64mm * 12.7mm * 3.2mm, and notch depth is 2.2mm.Testing apparatus is the Tinius Olisen shock-testing machine of U.S. Willow Grove company.
Tensile property test is tested by ASTM D638 standard, and specimen size is 168mm * 13mm * 3.2mm, and test speed is 50mm/min, and testing apparatus is the electronics pulling experiment machine of German Zwick company.
The test of bending property is tested by ASTM D790 standard, and specimen size is 64mm * 12.7mm * 3.2mm, and span is 50mm, and test speed is 1.26mm/min, and testing apparatus is the electronics pulling experiment machine of German Zwick company.
Embodiment and comparative example's prescription and performance are relatively
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | ||
| The comparative example | - | - | - | - | - | - | - | - | - | 1 | 2 |
| SAN | 65 | 60 | 54 | 50 | 50 | 45 | 35 | 50 | 50 | 79.5 | 69.5 |
| Glass fibre | 19.5 | 19.5 | 25 | 24 | 14.5 | 38 | 30 | 20 | 10 | 20 | 30 |
| PBT | 5 | 10 | 10 | 10 | - | 5 | 5 | - | - | - | |
| PET | - | - | - | 15 | - | 5 | 5 | 5 | 20 | - | |
| PTW | 5 | 5 | - | 5 | - | - | 9.5 | 9.5 | - | - | |
| MPOE | - | - | 5.4 | - | 15 | 5 | - | - | 5.5 | - | - |
| KH550 | 0.2 | 0.2 | 0.3 | 0.5 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| SMA | 5 | 5 | 5 | 5 | 10 | 6.5 | 15 | 10 | 14 | - | - |
| 1010 | 0.3 | 0.3 | 0.3 | 0.5 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| IZOD notched Izod impact strength (J/m) | 5.82 | 5.55 | 5.97 | 5.65 | 5.98 | 6.08 | 5.89 | 5.68 | 5.36 | 5.21 | 5.16 |
| Tensile break strength (MPa) | 110.8 | 112.5 | 118.5 | 127.9 | 114.6 | 112.9 | 129.8 | 118.6 | 119.6 | 105.4 | 113.8 |
| Elongation at break (%) | 3.8 | 3.7 | 4 | 3.8 | 4.1 | 3.9 | 3.9 | 3.5 | 3.1 | 3.2 | 3.1 |
| Flexural strength (MPa) | 163.5 | 168.4 | 172.5 | 178.9 | 165.7 | 166.7 | 180.5 | 175.7 | 185.7 | 149.4 | 159.8 |
| Modulus in flexure (MPa) | 7267 | 7453 | 7645 | 7986 | 7648 | 7698 | 7993 | 8325 | 8876 | 6634 | 7259 |
As can be seen from the above table, through elastomer-modified PC/SAN alloy, its shock strength and elongation at break greatly improve than the PC/SAN alloy of non-modified.
As can be seen from the above table, the adding of polyester can improve the mechanical property of glass fiber reinforced styrene-acrylonitrile copolymer, particularly tensile break strength and flexural strength, but little for the notched Izod impact strength influence; The adding of toughner can improve the notched Izod impact strength of multipolymer.By the present invention, can prepare and have the more glass fiber reinforced styrene of high tensile, modulus in flexure and shock strength-vinyl cyanide blend.
Claims (7)
1. the preparation method of a continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer adopts styrene-acrylonitrile as matrix component, and continuous glass fibre and vibrin is characterized in that as enhancement component, comprise the following steps,
1) gets the raw materials ready with the weight percent proportioning
Styrene-acrylonitrile copolymer 30～70,
Continuous glass fibre 10～40,
Vibrin 5～20,
Toughner 5～15,
Coupling agent 0.2～0.5,
Compatilizer 5～15,
Oxidation inhibitor 0.3～0.5.
2) set the forcing machine working conditions: 180～200 ℃ of district's temperature, 210～220 ℃ of two district's temperature, the temperature in He Si district, three districts is respectively 220～230 ℃, and the temperature in five districts～nine districts is respectively 230～240 ℃, 300～400 rev/mins of engine speeds;
4) the described vinylbenzene-acrylonitrile copolymer of step 1), vibrin, toughner, coupling agent, compatilizer and oxidation inhibitor are inserted super mixer, enter twin screw extruder after mixing under the room temperature;
5) add the described continuous glass fibre of step 1) in forcing machine the 4th humidity province;
6) extruding postcooling, drying, pelletizing gets product.
2. according to the preparation method of the described a kind of continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer of claim 1, it is characterized in that the described continuous glass fibre of step 1) is an alkali free glass fibre, diameter is 10～25 μ m.
3. according to the preparation method of the described a kind of continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer of claim 1, it is characterized in that, the described vibrin of step 1) be polyethylene terephthalate and or polybutylene terephthalate.
5. according to the preparation method of the described a kind of continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer of claim 1, it is characterized in that the described toughner of step 1) is maleic anhydride graft polyolefin elastomer or ethene-butyl acrylate-glycidyl methacrylate copolymer.
6. according to the preparation method of the described a kind of continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer of claim 1, it is characterized in that the described coupling agent of step 1) is an aminosilane class coupling agent.
7. according to the preparation method of the described a kind of continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer of claim 1, it is characterized in that the described compatilizer of step 1) is an atactic styrene-maleic anhydride copolymer.
8. according to the preparation method of the described a kind of continuous glass fiber reinforced vinyl benzene-acrylonitrile copolymer of claim 1, it is characterized in that the described oxidation inhibitor of step 1) is four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102558699A (en) * | 2010-12-30 | 2012-07-11 | 上海金发科技发展有限公司 | Glass fiber reinforced flame-retardant styrene-acrylonitrile copolymer/ polybutylene terephthalate (AS/ PBT) material and preparation method thereof |
| CN102702639A (en) * | 2012-05-30 | 2012-10-03 | 宁波镇洋化工发展有限公司 | Glass fiber reinforced styrene-acrylonitrile-N-phenylmaleimide-cyclic olefin copolymer compound |
| CN102702638A (en) * | 2012-05-30 | 2012-10-03 | 宁波镇洋化工发展有限公司 | Glass fiber-reinforced styrene-acrylonitrile-cycloolefin (SAN) copolymer composition |
| CN102786779A (en) * | 2011-05-16 | 2012-11-21 | 山东道恩高分子材料股份有限公司 | High-impact glass fiber reinforced halogen-free flame retardation PBT material |
| CN102807716A (en) * | 2012-07-27 | 2012-12-05 | 苏州市兴吴工程塑胶有限公司 | Novel formula of acrylonitrile-styrene (AS) plastic |
| CN102838824A (en) * | 2012-09-27 | 2012-12-26 | 贵州省复合改性聚合物材料工程技术研究中心 | High-strength antibacterial long-glass-fiber-reinforced AS (Acrylonitrile-Styrene Copolymer) composite material and preparation method thereof |
| CN103450583A (en) * | 2012-05-29 | 2013-12-18 | 广州市番禺区好友实业有限公司 | Abrasion-scratch resistant AS modified plastic |
| CN104448597A (en) * | 2014-11-26 | 2015-03-25 | 珠海格力电器股份有限公司 | Preparation method of glass-fiber-reinforced AS resin |
| CN107474421A (en) * | 2017-08-20 | 2017-12-15 | 佛山市北朝源科技服务有限公司 | A kind of modified phenylethylene acrylonitrile copolymer plastics |
| CN112961444A (en) * | 2021-02-05 | 2021-06-15 | 浙江科普特新材料有限公司 | Primer-free reinforced SAN material for soft PVC wrapping edges and preparation method and application thereof |
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| CN102558699A (en) * | 2010-12-30 | 2012-07-11 | 上海金发科技发展有限公司 | Glass fiber reinforced flame-retardant styrene-acrylonitrile copolymer/ polybutylene terephthalate (AS/ PBT) material and preparation method thereof |
| CN102786779A (en) * | 2011-05-16 | 2012-11-21 | 山东道恩高分子材料股份有限公司 | High-impact glass fiber reinforced halogen-free flame retardation PBT material |
| CN103450583A (en) * | 2012-05-29 | 2013-12-18 | 广州市番禺区好友实业有限公司 | Abrasion-scratch resistant AS modified plastic |
| CN102702639A (en) * | 2012-05-30 | 2012-10-03 | 宁波镇洋化工发展有限公司 | Glass fiber reinforced styrene-acrylonitrile-N-phenylmaleimide-cyclic olefin copolymer compound |
| CN102702638A (en) * | 2012-05-30 | 2012-10-03 | 宁波镇洋化工发展有限公司 | Glass fiber-reinforced styrene-acrylonitrile-cycloolefin (SAN) copolymer composition |
| 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 |
| CN102807716A (en) * | 2012-07-27 | 2012-12-05 | 苏州市兴吴工程塑胶有限公司 | Novel formula of acrylonitrile-styrene (AS) plastic |
| CN102838824A (en) * | 2012-09-27 | 2012-12-26 | 贵州省复合改性聚合物材料工程技术研究中心 | High-strength antibacterial long-glass-fiber-reinforced AS (Acrylonitrile-Styrene Copolymer) composite material and preparation method thereof |
| CN102838824B (en) * | 2012-09-27 | 2014-12-24 | 贵州省复合改性聚合物材料工程技术研究中心 | High-strength antibacterial long-glass-fiber-reinforced AS (Acrylonitrile-Styrene Copolymer) composite material and preparation method thereof |
| CN104448597A (en) * | 2014-11-26 | 2015-03-25 | 珠海格力电器股份有限公司 | Preparation method of glass-fiber-reinforced AS resin |
| CN107474421A (en) * | 2017-08-20 | 2017-12-15 | 佛山市北朝源科技服务有限公司 | A kind of modified phenylethylene acrylonitrile copolymer plastics |
| CN112961444A (en) * | 2021-02-05 | 2021-06-15 | 浙江科普特新材料有限公司 | Primer-free reinforced SAN material for soft PVC wrapping edges and preparation method and application thereof |
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