WO2018076967A1 - 一种增强芳族乙烯基共聚物组合物及其应用 - Google Patents

一种增强芳族乙烯基共聚物组合物及其应用 Download PDF

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WO2018076967A1
WO2018076967A1 PCT/CN2017/102494 CN2017102494W WO2018076967A1 WO 2018076967 A1 WO2018076967 A1 WO 2018076967A1 CN 2017102494 W CN2017102494 W CN 2017102494W WO 2018076967 A1 WO2018076967 A1 WO 2018076967A1
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aromatic vinyl
vinyl copolymer
parts
copolymer composition
reinforced aromatic
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English (en)
French (fr)
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魏金刚
陈平绪
官焕祥
李玉虎
何超雄
肖鹏
叶南飚
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金发科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Definitions

  • the invention relates to the field of polymer materials, in particular to a reinforced aromatic vinyl copolymer composition and application thereof.
  • Rubber-modified aromatic vinyl copolymer resins such as ABS (a copolymer of acrylonitrile, butadiene and styrene), MABS (a copolymer of acrylate, acrylonitrile, butadiene and styrene), ASA (acrylic rubber, acrylonitrile, styrene copolymer) AES (acrylonitrile, EPDM, styrene copolymer), etc. are easy to process, suitable for injection molding, extrusion molding, blow molding, etc. With good comprehensive mechanical properties, it is widely used in packaging, daily necessities, electronic appliances, toys, instrumentation, transportation and machine manufacturing.
  • the glass-reinforced rubber-modified aromatic vinyl copolymer can significantly improve the mechanical properties and improve the heat resistance, and at the same time, can improve the dimensional stability by lowering the linear thermal expansion coefficient and the molding shrinkage.
  • the components with high-gloss effect have visual aesthetics, which are more appealing to consumers.
  • glass fiber flow orientation problems in the injection molding process of glass fiber reinforced products, and obvious glass fiber flow patterns appear, resulting in the surface of the injection molded parts.
  • the appearance of the outer leakage of the floating fiber will affect the flatness of the surface of the injection molded part and greatly reduce the surface gloss.
  • the surface of the product is required to be smooth, smooth, and free of defects.
  • the existing glass fiber reinforced aromatic vinyl copolymers can not meet the appearance requirements of the parts, and the application thereof is limited.
  • CN 103483761 A discloses a fiber reinforced ABS material and a preparation method thereof, and the subsequent molding process is a high-speed high-temperature molding technology (RHCM), which obtains a high-gloss glass fiber reinforced ABS product, but the RHCM technology equipment has large investment, high energy consumption, and is not in conformity with low Environmental concept of carbon, energy saving and emission reduction;
  • patent CN101469107 B discloses a good surface, high flow glass fiber reinforced PBT/ABS composite material, which improves the surface effect by adding a large amount of lubricant in a single polyester system PBT and patent CN 101864117 B reported the addition of small molecule plasticizers such as bisphenol A bis(diphenyl phosphate) in the ABS system to increase the fluidity of the system and reduce the leakage of glass fibers to obtain a good surface.
  • patent CN 103275454 A pre-treats the glass beads with a coupling agent and adds SAN to the resin to improve the gloss and strength of the ABS plastic.
  • the activation process of the glass microbeads is complicated and time consuming, and the enhancement effect is far less than that of the glass fiber, the application is limited. Therefore, how to obtain a glass fiber reinforced rubber modified aromatic vinyl copolymer product with good mechanical properties, high dimensional stability and high gloss appearance while avoiding high energy consumption spraying or high speed high temperature forming technology is an industry. Technical problems that are faced and urgently solved.
  • a reinforced aromatic vinyl copolymer composition comprising, by weight, parts by weight:
  • the flow promoter is composed of 60-90 wt% of crystalline polyester and 10-40 wt% of amorphous polyester, preferably flow promoter from 70-85 wt% of crystalline polyester and 15-30 wt% Non-crystalline polyester composition.
  • the reinforced aromatic vinyl copolymer composition comprises, in parts by weight, the following components: an aromatic vinyl copolymer 30.0-80.0 parts
  • the flow promoter has an intrinsic viscosity of 0.6 to 1.5 dL/g, preferably 0.7 to 1.0 dL/g, and an intrinsic viscosity using phenol-carbon tetrachloride (3:2) as a solvent according to standard ISO 1638-5. Viscometer test results.
  • the crystalline polyester is selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate or polynaphthalene dicarboxylate.
  • One or more of the glycol esters; the non-crystalline polyester is selected from the group consisting of polycarbonate, poly(1,4-cyclohexanedimethylene terephthalate), and polyethylene terephthalate- Mixing one or more of 1,4-cyclohexanedimethanol ester.
  • the aromatic vinyl copolymer has a melt flow rate at 220 ° C under a load of 10 kg of 5 to 120 g/10 min, preferably 8 to 40 g/10 min.
  • the aromatic vinyl copolymer is selected from the group consisting of acrylonitrile-butadiene-styrene copolymer ABS, methyl methacrylate-acrylonitrile-butadiene-styrene copolymer MABS, acrylonitrile-styrene-acrylate One or more of copolymer ASA, acrylonitrile-ethylene propylene diene monomer-styrene copolymer AES, acrylonitrile-silicone rubber-styrene copolymer SAS, preferably acrylonitrile-butadiene-styrene Copolymer ABS or acrylonitrile-styrene-acrylate copolymer ASA.
  • the reinforcing agent is selected from the group consisting of glass fibers, carbon fibers, talc, wollastonite, whiskers, glass microbeads, or a mixture of several, preferably glass fibers or carbon fibers, more preferably 6 to 20 microns in diameter. glass fiber.
  • the reinforced aromatic vinyl copolymer composition of the present invention further includes a compatibilizing agent of 1-10 parts, a coupling agent of 0.1 - 5 parts, a lubricant of 0.1 - 5 parts, etc., according to actual performance requirements.
  • the compatibilizer is selected from the group consisting of ABS-g-MAH, ABS-g-GMA, AS-g-MAH, N-phenylmaleimide-styrene-maleic anhydride copolymer, styrene-maleic anhydride One or more of a copolymer, a styrene-acrylonitrile-glycidyl methacrylate copolymer;
  • the coupling agent is selected from one or a mixture of two or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent;
  • the lubricant is selected from the group consisting of a fatty acid salt, a fatty acid amide, pentaerythritol stearate, a solid paraffin, a liquid paraffin, a stearate, a silicone, an N, N'-ethylene bis stearic acid amide or Mix more than two.
  • the reinforced aromatic vinyl copolymer composition of the present invention can be obtained by a known method, and the specific steps are as follows:
  • the components are uniformly mixed in a high-speed stirring mixer, and then the uniformly mixed material is placed in a twin-screw extruder, wherein the reinforcing agent is added through the side feeding system, and is melted and squeezed by the twin-screw machine. Out, granulation is available.
  • the feeding speed of the twin-screw extruder is 200-350 rpm; the temperature of each screw of the twin-screw extruder is preferably 220-250 ° C from the feeding port to the head, respectively, and the second zone 220 ⁇ 270 ° C, three zones 210 ⁇ 260 ° C, four zones 210 ⁇ 260 ° C, five zones 210 ⁇ 260 ° C, die temperature 220 ⁇ 260 ° C, the host speed is 100 ⁇ 500r / min, the vacuum is less than 0.1MPa.
  • the invention also provides the use of the above-mentioned reinforced aromatic vinyl copolymer composition in the fields of home appliances, audio-visual equipment, office supplies and handicrafts.
  • the invention has the following beneficial effects:
  • the present invention is added to a reinforcing aromatic vinyl by using a crystalline polyester and a non-crystalline polyester compound as a flow promoter
  • the viscosity is low during the melting process, and the fluidity at the time of melting of the aromatic vinyl copolymer composition can be remarkably improved, so that the polyester resin forms a skin layer during the injection molding process, and the aromatic vinyl copolymer
  • the core material is formed with the glass fiber material, so that the typical core-core structure can effectively prevent the leakage of the glass fiber and make the surface of the injection molded part have a high gloss.
  • the present invention avoids the introduction of a large amount of plasticizer small molecules in the conventional method to achieve a surface highlight effect, and thus does not Surface deposition problems occur during long-term placement of the product;
  • the extruded particles obtained by the invention can be directly injection molded by using a conventional oil temperature mold, eliminating the use of high-speed high-temperature (RHCM) molding technology, which is more energy-saving and environmentally friendly, and reduces processing costs.
  • RHCM high-speed high-temperature
  • the raw materials used in the present invention are as follows:
  • ABS2 ABS2, ABS HI-121, LG, melt flow rate 15g/10min;
  • Polyethylene terephthalate PET1 intrinsic viscosity 0.8dL/g
  • Polyethylene terephthalate PET2 intrinsic viscosity 0.6dL/g
  • Polycarbonate PC intrinsic viscosity 1.2dL/g
  • the components are uniformly mixed in a high-speed stirring mixer according to the ratio of Table 1, and then the uniformly mixed materials are placed in a twin-screw extruder, wherein the reinforcing agent is added through the side feeding system, and the double is added.
  • the screw machine melts, extrudes, and granulates to obtain an aromatic vinyl copolymer composition containing polyester, and then is injection-molded by an injection molding machine at a mold temperature of not lower than 80 ° C to obtain a product, and the performance results are shown in Table 1. Show.
  • the feeding speed of the twin-screw extruder is 200-350 rpm; the temperature of each section of the twin-screw extruder from the feeding port to the head is preferably 220-250 ° C in one zone and 220-250 in the second zone. 270 ° C, three zones 210 ⁇ 260 ° C, four zones 210 ⁇ 260 ° C, five zones 210 ⁇ 260 ° C, die temperature 220 ⁇ 260 ° C, the host speed is 100 ⁇ 500r / min, the vacuum is less than 0.1MPa.
  • Gloss test standard ASTM D523, take 60 ° angle test value, the greater the gloss, the flatter the surface, the less floating fiber.
  • Floating fiber The surface floating fiber is evaluated by square plate, and the sample is observed under a two-dimensional optical microscope. The fiber grade is divided into three grades:
  • Grade 1 no floating fiber on the surface
  • grade 2 slight floating fiber on the surface
  • grade 3 obvious floating fiber on the surface
  • the present invention can effectively prevent the leakage of the glass fiber by adding the crystalline polyester and the non-crystalline polyester compound as a flow promoter to the reinforcing aromatic vinyl copolymer composition. And make the surface of the injection molded part show a high gloss.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

本发明公开了一种增强芳族乙烯基共聚物组合物及其应用，包括组分:芳族乙烯基共聚物 20.0～90.0份流动促进剂 2.0～60.0份增强剂 5.0～40.0份, 其中，流动促进剂由60-90％的结晶性聚酯和10-40％的非结晶透明聚酯组成。本发明通过将结晶性聚酯和非结晶性聚酯复配物作为流动促进剂添加到增强芳族乙烯基共聚物组合物中，其在熔融过程中粘度低，可以显著提高增强芳族乙烯基共聚物组合物熔融时的流动性，使聚酯树脂在注塑过程中形成皮层，芳族乙烯基共聚物和玻璃纤维材料形成芯材，这样典型的皮芯结构可以有效的防止玻纤外漏，并使得注塑制件表面呈现出较高光泽。

Description

一种增强芳族乙烯基共聚物组合物及其应用 技术领域
本发明涉及高分子材料领域，特别涉及一种增强芳族乙烯基共聚物组合物及其应用。
背景技术
橡胶改性的芳族乙烯基共聚物树脂如如ABS(丙烯腈、丁二烯和苯乙烯组成的共聚物)、MABS(丙烯酸酯、丙烯腈、丁二烯和苯乙烯组成的共聚物)、ASA(丙烯酸酯橡胶、丙烯腈、苯乙烯共聚物)AES(丙烯腈、三元乙丙橡胶、苯乙烯共聚物)等具有容易加工，适合注射、挤塑、吹塑等多种成型方法，而且具有较好的综合力学性能，因此被广泛应用于包装、日用品、电子电器、玩具、仪表、运输和机器制造等领域。然而对于一些高力学强度要求的结构制件，如冰箱门拉手、电视机边框和电视机支撑底座等，普通橡胶改性的芳族乙烯基共聚物基材或矿物填充橡胶改性的芳族乙烯基共聚物难以满足力学性能和尺寸稳定要求。通常采用玻纤增强橡胶改性的芳族乙烯基共聚物可显著提高机械性能，改善耐热性能，同时可以通过降低线性热膨胀系数和成型收缩率，进而提高其尺寸稳定性。
消费市场上具有高光效果外观部件具有视觉上的美感，更能引起消费者的青睐，然而玻纤增强产品注塑过程中存在玻纤流动取向问题，出现明显的玻璃纤维流纹，导致注塑件表面有浮纤出现外漏会影响注塑制件表面平整度，大大降低了表面光泽度。而对于外观制件来说，要求制品表面平整、光滑，不存在缺陷。然而、现有的玻纤增强芳族乙烯基共聚物多不能满足制件的外观要求，限制了其的应用。
在“浮纤”现象消除的研究中，喷涂是常见的对塑料制品进行表面装饰的处理工艺。然而喷涂存在如环境污染、总体成本高、生产流程长效率低、漆膜在运输和使用存在脱落概率；另外，现有研究者开发出从设备及材料配方上改善玻纤增强材料表面，如专利CN 103483761 A报道了一种纤维增强ABS材料及其制备方法，后续成型工艺为高速高温成型技术(RHCM),得到高光玻纤增强ABS制品，但是RHCM技术设备投入大、能耗高，不符合低碳、节能减排的环保理念；专利CN101469107 B公开了一种良好表面、高流动玻璃纤维增强PBT/ABS复合材料，在单一聚酯体系PBT中通过添加大量的润滑剂改善表面效果以及专利CN 101864117 B报道了在增强ABS体系中添加小分子增塑剂如双酚A双(磷酸二苯酯)，增加体系流动性减少玻纤外漏来获得良好表面，然而这些润滑剂或磷酸酯化合物等分子量低，容易随制品放置而表面析出，存在质量隐患，同时光泽度依然低于80°，改 善效果依然不理想；专利CN 103275454 A利用偶联剂预先处理玻璃微珠并在树脂中加入SAN，提高ABS塑料的光泽度和强度。但由于玻璃微珠前期活化处理复杂耗时，且增强效果远不如玻纤，应用受限。因此，如何在避免高能耗的喷涂或高速高温成型技术下，获得同时有良好机械性能、高尺寸稳定性及外观光泽度高的玻纤增强橡胶改性的芳族乙烯基共聚物制品，是行业共同面临并亟待解决的技术难题。
发明内容
为解决上述问题，本发明的目的在于提供一种增强芳族乙烯基共聚物组合物，该组合物具有明显改善的外观及较高的光泽度。
一种增强芳族乙烯基共聚物组合物，按重量份数计，包括如下组分：
芳族乙烯基共聚物     20.0～90.0份
流动促进剂        2.0～60.0份
增强剂         5.0～40.0份，
其中，所述流动促进剂由60-90wt％的结晶性聚酯和10-40wt％的非结晶性聚酯组成，优选流动促进剂由70-85wt％的结晶性聚酯和15-30wt％的非结晶性聚酯组成。
优选的，所述的一种增强芳族乙烯基共聚物组合物，按重量份数计，包括如下组分：芳族乙烯基共聚物     30.0～80.0份
流动促进剂        10～40.0份
增强剂         5.0～40.0份。
所述流动促进剂的特性粘度在0.6～1.5dL/g，优选为0.7～1.0dL/g，特性粘度根据标准ISO 1638-5以苯酚-四氯化碳(3：2)作为溶剂利用乌氏粘度计测试所得。
所述结晶性聚酯选自聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯或聚萘二甲酸丁二醇酯中的一种或几种；所述非结晶性聚酯选自聚碳酸酯、聚对苯二甲酸1,4-环己烷二甲酯、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯中的一种或几种的混合。
所述芳族乙烯基共聚物在220℃，10kg载荷条件下的熔体流动速率为5～120g/10min，优选8～40g/10min。
所述芳族乙烯基共聚物选自丙烯腈-丁二烯-苯乙烯共聚物ABS、甲基丙烯酸甲酯-丙烯腈-丁二烯-苯乙烯共聚物MABS、丙烯腈-苯乙烯-丙烯酸酯共聚物ASA、丙烯腈-三元乙丙橡胶-苯乙烯共聚物AES、丙烯腈-硅丙橡胶-苯乙烯共聚物SAS中的一种或几种，优选为丙烯腈-丁二烯-苯乙烯共聚物ABS或丙烯腈-苯乙烯-丙烯酸酯共聚物ASA。
所述增强剂选自玻璃纤维、碳纤维、滑石粉、硅灰石、晶须、玻璃微珠中的一种或几种的混合物，优选玻璃纤维或碳纤维，更优选为直径为6～20微米的玻璃纤维。
根据实际性能需要，本发明的增强芳族乙烯基共聚物组合物还包括相容剂1-10份，偶联剂0.1-5份，润滑剂0.1-5份等。
所述相容剂选自ABS-g-MAH、ABS-g-GMA、AS-g-MAH、N-苯基马来酰亚胺-苯乙烯-马来酸酐共聚物、苯乙烯-马来酸酐共聚物、苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物中的一种或两种以上混合；
所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、锆酸酯偶联剂中的一种或两种以上混合；
所述润滑剂选自脂肪酸盐、脂肪酸酰胺、季戊四醇硬脂酸酯、固体石蜡、液体石蜡、硬脂酸盐、硅酮、N,N'-乙撑双硬脂酸酰胺中的一种或两种以上混合。
本发明所述的增强芳族乙烯基共聚物组合物可通过已知方法制得，具体步骤如下：
除增强剂外，将各组分在高速搅拌混料机中混合均匀，然后将混合均匀的物料置于双螺杆挤出机中，其中增强剂通过侧喂系统加入，经双螺杆机熔融、挤出，造粒即得。
优选的，所述双螺杆挤出机的喂料转速为200～350rpm；双螺杆挤出机的各段螺杆温度从加料口到机头的温度分别优选为一区220～250℃，二区220～270℃，三区210～260℃，四区210～260℃，五区210～260℃，口模温度220～260℃，主机转速是100～500r/min，真空度低于0.1MPa。
本发明还提供了上述增强芳族乙烯基共聚物组合物在家电、视听设备、办公用品、工艺品领域中的应用。
本发明与现有技术相比，具有如下有益效果：
(1)本发明通过将结晶性聚酯和非结晶性聚酯复配物作为流动促进剂添加到增强芳族乙烯
基共聚物组合物中，其在熔融过程中粘度低，可以显著提高增强芳族乙烯基共聚物组合物熔融时的流动性，使聚酯树脂在注塑过程中形成皮层，芳族乙烯基共聚物和玻璃纤维材料形成芯材，这样典型的皮芯结构可以有效的防止玻纤外漏，并使得注塑制件表面呈现出较高光泽。
(2)相容剂和偶联剂的加入大大增加了增强橡胶增韧芳族乙烯基共聚物、流动促进剂和玻纤之间的结合力、相容性，尤其是增强苯乙烯基材对玻纤的包覆和裹挟能力，不但使制品具备较高的综合力学性能，也在一定程度上抑制了浮纤；
(3)本发明避免了传统方法中引入大量的增塑剂小分子来达到表面高光效果，进而不会出 现制品长时间放置过程中出现表面析出问题；
(4)本发明所得的挤出粒子可直接使用常规油温模具注塑，省去了使用高速高温(RHCM)成型技术，更节能环保，减少加工成本。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
本发明所使用的原料如下：
ASA，Luran S 777K，苯领公司，熔体流动速率15g/10min；
AES，AES HW500E，韩国锦湖，熔体流动速率12g/10min；
SAS，DIALAC E259B，日本UMG，熔体流动速率15g/10min；
ABS1，ABS AG10NP，台化，熔体流动速率6g/10min；
ABS2，ABS HI-121，LG，熔体流动速率15g/10min；
聚对苯二甲酸乙二醇酯PET1：特性粘度为0.8dL/g
聚对苯二甲酸乙二醇酯PET2：特性粘度为0.6dL/g，
聚碳酸酯PC：特性粘度为1.2dL/g，
增强剂，玻璃纤维，ECS13-4.5-534A，桐乡巨石，直径为13μm。
相容剂，马来酸酐-苯乙烯共聚物，SMA-700，上海华雯公司；
偶联剂，KH560，沸点化工；
润滑剂，N,N'-亚乙基双硬脂酰胺，上海宁成；
含有聚酯的增强芳族乙烯基共聚物组合物的制备：
除增强剂外，按表1配比将各组分在高速搅拌混料机中混合均匀，然后将混合均匀的物料置于双螺杆挤出机中，其中增强剂通过侧喂系统加入，经双螺杆机熔融、挤出，造粒即得含有聚酯的芳族乙烯基共聚物组合物，然后经注塑机在不低于80℃模具温度下注塑成型即可得到制品，性能结果见表1所示。
其中，所述双螺杆挤出机的喂料转速为200～350rpm；双螺杆挤出机的各段螺杆温度从加料口到机头的温度分别优选为一区220～250℃，二区220～270℃，三区210～260℃，四区210～260℃，五区210～260℃，口模温度220～260℃，主机转速是100～500r/min，真空度低于0.1MPa。
光泽度的测试标准：ASTM D523，取60°角测试值，光泽度越大，代表表面越平整，浮纤越少。
浮纤：表面浮纤使用方板评估，将样板在二次元光学显微镜下观察观察，将纤等级分为3个等级：
等级1：表面无浮纤；等级2：表面有轻微浮纤；等级3：表面有明显浮纤；
表1实施例1～14各组成的具体配比及其测试性能结果(重量份)
Figure PCTCN2017102494-appb-000001
续表1：
Figure PCTCN2017102494-appb-000002
由表1结果可以看出，本发明通过将结晶性聚酯和非结晶性聚酯复配物作为流动促进剂添加到增强芳族乙烯基共聚物组合物中，可以有效的防止玻纤外漏，并使得注塑制件表面呈现出较高光泽。

Claims (9)

  1. 一种增强芳族乙烯基共聚物组合物，其特征在于，按重量份数计，包括如下组分：
    芳族乙烯基共聚物    20.0～90.0份
    流动促进剂       2.0～60.0份
    增强剂         5.0～40.0份，
    其中，所述流动促进剂由60-90wt％的结晶性聚酯和10-40wt％的非结晶性聚酯组成，优选流动促进剂由70-85wt％的结晶性聚酯和15-30wt％的非结晶聚酯组成。
  2. 根据权利要求1所述的一种增强芳族乙烯基共聚物组合物，其特征在于，按重量份数计，包括如下组分：
    芳族乙烯基共聚物    30.0～80.0份
    流动促进剂        10～40.0份
    增强剂         5.0～40.0份。
  3. 根据权利要求1或2所述的一种增强芳族乙烯基共聚物组合物，其特征在于，所述流动促进剂的特性粘度在0.6～1.5dL/g，优选为0.7～1.0dL/g，特性粘度根据标准ISO 1638-5以苯酚-四氯化碳3：2作为溶剂利用乌氏粘度计测试所得。
  4. 根据权利要求3所述的一种增强芳族乙烯基共聚物组合物，其特征在于，所述结晶性聚酯选自聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯或聚萘二甲酸丁二醇酯中的一种或几种；所述非结晶性聚酯选自聚碳酸酯、聚对苯二甲酸1,4-环己烷二甲酯、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯中的一种或几种的混合。
  5. 根据权利要求1或2所述的一种增强芳族乙烯基共聚物组合物，其特征在于，所述芳族乙烯基共聚物在220℃，10kg载荷条件下的熔体流动速率为5～120g/10min，优选为8～40g/10min。
  6. 根据权利要求5所述的一种增强芳族乙烯基共聚物组合物，其特征在于，所述芳族乙烯基共聚物选自丙烯腈-丁二烯-苯乙烯共聚物ABS、甲基丙烯酸甲酯-丙烯腈-丁二烯-苯乙烯共聚物MABS、丙烯腈-苯乙烯-丙烯酸酯共聚物ASA、丙烯腈-三元乙丙橡胶-苯乙烯共聚物AES、丙烯腈-硅丙橡胶-苯乙烯共聚物SAS中的一种或几种，优选为丙烯腈-丁二烯-苯乙烯共聚物ABS或丙烯腈-苯乙烯-丙烯酸酯共聚物ASA。
  7. 根据权利要求1或2所述的一种增强芳族乙烯基共聚物组合物，其特征在于，所述增强剂选自玻璃纤维、碳纤维、滑石粉、硅灰石、晶须、玻璃微珠中的一种或几种的混合物，优选玻璃纤维或碳纤维，更优选为直径为6～20微米的玻璃纤维。
  8. 根据权利要求1或2所述的一种增强芳族乙烯基共聚物组合物，其特征在于，所述增强芳族乙烯基共聚物组合物还包括相容剂1-10份，偶联剂0.1-5份，润滑剂0.1-5份。
  9. 根据权利要求1-8任一项所述的一种增强芳族乙烯基共聚物组合物在家电、视听设备、办公用品、工艺品领域中的应用。
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