WO2016033992A1 - 具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物 - Google Patents

具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物 Download PDF

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WO2016033992A1
WO2016033992A1 PCT/CN2015/078632 CN2015078632W WO2016033992A1 WO 2016033992 A1 WO2016033992 A1 WO 2016033992A1 CN 2015078632 W CN2015078632 W CN 2015078632W WO 2016033992 A1 WO2016033992 A1 WO 2016033992A1
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aromatic polycarbonate
flame
weight
good appearance
flame retardant
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PCT/CN2015/078632
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English (en)
French (fr)
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陈锐
岑茵
郑一泉
孙东海
叶南飚
蔡彤旻
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金发科技股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/521Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant

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  • the invention relates to the technical field of polymer material modification, in particular to a flame-retardant aromatic polycarbonate composition having low precipitates and good appearance.
  • Polycarbonate PC is a thermoplastic engineering plastic with excellent physical and mechanical properties, especially its high transparency and high gloss. It is suitable for making all kinds of beautiful appearances. However, due to the rigidity of polycarbonate molecular chain, the melt High viscosity, not resistant to hydrolysis, prone to stress cracking, poor solvent resistance, poor wear resistance, etc., affecting its range of use.
  • the toughness of the polycarbonate composition is typically improved by the addition of impact modifiers. Since the impact modifier contains a paraffin component (the main component is a short-chain polyolefin), we have found in practical applications that a flame retardant polycarbonate composition is prepared using a short-chain polyolefin higher impact modifier. Surface watering and membrane scale are generated during the injection molding process, which seriously affects the appearance of the product and limits its application.
  • the invention has unexpectedly discovered in the research that the content of the short-chain polyolefin in the impact modifier is controlled within a certain range, which can solve the problems of surface water splash and film scale in the injection molding process, and significantly improve the appearance of the product.
  • the injection process produces the opportunity for surface water and scale.
  • a flame-retardant aromatic polycarbonate composition having low precipitates and good appearance comprising a phosphorus-containing flame retardant, an aromatic polycarbonate, and an impact modifier, the content of short-chain polyolefin in the impact modifier Less than 0.1% by weight.
  • the aromatic polycarbonate according to the present invention can be produced by a known melt transesterification method, interfacial polycondensation phosgenation method or the like.
  • the impact modifier of the present invention is a graft copolymer having a core/shell structure, the core layer being mainly selected from a diene rubber polymer of a group consisting of conjugated dienes, containing a copolymer of at least 50% by weight of a conjugated diene, an olefin rubber, a silicone rubber, an alkyl acrylate having a C1-C8 carbon atom in the alkyl group, a copolymer of an alkyl acrylate and styrene or butadiene, and Their mixture; the shell layer is a copolymer of styrene and acrylonitrile.
  • the impact modifier of the present invention include, but are not limited to, acrylonitrile-butadiene-styrene graft copolymer ABS, acrylonitrile-styrene-acrylic terpolymer ASA or methyl methacrylate-butyl A diene-styrene graft copolymer MBS, preferably an acrylonitrile-butadiene-styrene graft copolymer ABS.
  • the preparation of the impact modifier of the present invention can be prepared by a known bulk or emulsion method.
  • the preparation process for the impact modifier in the present invention is not a key technology, and the key point of the present invention is the short-chain polyolefin in the impact modifier.
  • the content of the short-chain polyolefin must be less than 0.1% by weight, and the molecular formula of the short-chain polyolefin is C n H 2n+2 , wherein 10 ⁇ n ⁇ 100, preferably 15 ⁇ n ⁇ 70, more preferably 18 ⁇ n ⁇ 45.
  • the flame retardant aromatic polycarbonate composition having low precipitates and good appearance comprises 40-90% by weight of aromatic polycarbonate, 5-20% by weight of phosphorus-containing flame retardant and 5-40% by weight Impact improver.
  • the composition comprises 60-80% by weight of an aromatic polycarbonate, 9-15% by weight of a phosphorus-containing flame retardant, and 7-25% by weight of an impact modifier.
  • At least one other additive such as an antioxidant, a stabilizer, a lubricant, a filler, a glass fiber or the like may also be added to the composition of the present invention.
  • the phosphorus-containing flame retardant of the present invention is a mixture of one or more of bisphenol A bis(diphenyl phosphate), resorcinol (diphenyl phosphate) or triphenyl phosphate.
  • the flame-retardant aromatic polycarbonate composition having low precipitates and good appearance according to the present invention can be produced by mixing the respective components in a known manner and then melt-extruding in a screw extruder.
  • the flame-retardant aromatic polycarbonate composition having low precipitates and good appearance according to the present invention can be applied to the fields of automobiles, electronics, communications, and the like.
  • the invention has the following beneficial effects:
  • the invention can significantly reduce the chance of surface water splash and membrane scale in the injection molding process by controlling the short-chain polyolefin content in the impact modifier to a certain range, and the obtained composition has low precipitates and good appearance characteristics, and its mechanical properties and Flame retardant performance is better, and can be widely used in automotive, electronics, communications and other fields.
  • the components were placed in a high-speed mixer for 3 minutes according to the weight percentage shown in Table 1, and then placed in a twin-screw extruder.
  • the temperature is controlled at 200 ° C ⁇ 300 ° C, extrusion granulation is obtained, wherein the impact modifier is ABS resin with a short-chain polyolefin content of 0.015 wt%, and the performance test results are shown in Table 1.
  • Appearance evaluation method injection molding 40*60*2mm square plate, visually observing the surface of the square plate, and counting the number of water splashes.
  • Membrane scale evaluation method injection molding 40*60*2mm square plate, continuous injection of 100 film, the weight of the film scale scraped from the fixed exhaust port.
  • Cantilever notched impact Test standard ASTM D256, tested on Zwick electronic universal testing machine;

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

一种具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,其中包括含磷阻燃剂、芳族聚碳酸酯和冲击改善剂,所述冲击改善剂中短链聚烯烃的含量低于0.1wt%。通过将冲击改善剂中短链聚烯烃含量控制在一定范围内,可以显著降低注塑过程产生表面水花和膜垢的机会,所得组合物具有低析出物和良好外观特点,并且其力学性能和阻燃性能还更好,可广泛应用于汽车、电子、通讯等领域中。

Description

具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物 技术领域
本发明涉及高分子材料改性技术领域,具体涉及一种具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物。
背景技术
聚碳酸酯PC是一种具有优良物理机械性能的热塑性工程塑料,尤其是其高透明性和高光泽性,适于制作各种外观精美的制品;但是由于聚碳酸酯分子链刚性大,熔体粘度高,不耐水解,容易产生应力开裂,抗溶剂性差,耐磨性欠佳等缺点,影响其使用范围。通常通过添加冲击改善剂来改善聚碳酸酯组合物的韧性。由于冲击改善剂会含有一种石蜡成分(主要成分是短链聚烯烃),我们在实际应用中发现,使用短链聚烯烃含量较高的冲击改善剂,制成阻燃聚碳酸酯组合物后,在注塑过程中会产生表面水花和膜垢,严重影响产品的外观,从而限制其应用。
本发明在研究中意外的发现,将冲击改善剂中短链聚烯烃的含量控制在一定范围内,可以解决注塑过程产生表面水花和膜垢等问题,显著改善产品的外观。
发明内容
本发明的目的在于提供一种具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,该组合物通过将冲击改善剂中短链聚烯烃的含量控制在一定范围内,可显著降低注塑过程产生表面水花和膜垢的机会。
本发明是通过以下技术方案实现:
一种具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,其中包括含磷阻燃剂、芳族聚碳酸酯和冲击改善剂,所述冲击改善剂中短链聚烯烃的含量低于0.1wt%。
本发明所述的芳族聚碳酸酯可通过公知的熔融酯交换法、界面缩聚光气化法等方法制备得到。
本发明所述冲击改善剂是一种具有芯/壳结构的接枝共聚物,所述芯层主要选自由下述组成的一组中的一种二烯橡胶聚合物:共轭二烯、含有至少50wt%共轭二烯的共聚物、烯烃橡胶、硅氧烷橡胶、烷基中含有C1-C8碳原子的丙烯酸烷基酯、丙烯酸烷基酯与苯乙烯或丁二烯的共聚物,以及他们的混合物;所述壳层是苯乙烯和丙烯腈共聚物。
本发明所述冲击改善剂的具体例子包括但不限于:丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、丙烯腈-苯乙烯-丙烯酸三元共聚物ASA或甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物MBS,优选丙烯腈-丁二烯-苯乙烯接枝共聚物ABS。
本发明所述冲击改善剂的制备可通过公知的本体法或乳液法制备,在本发明中用于冲击改善剂的制备工艺并非关键技术,本发明的关键点在于冲击改善剂中短链聚烯烃的含量必须低于0.1wt%,所述短链聚烯烃的分子式为CnH2n+2,其中10<n<100,优选15<n<70,更优选18<n<45。
本发明所述的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,包含40-90wt%的芳族聚碳酸酯、5-20wt%的含磷阻燃剂和5-40wt%的冲击改善剂。优选的,该组合物包含60-80wt%的芳族聚碳酸酯、9-15wt%的含磷阻燃剂和7-25wt%的冲击改善剂。
本发明组合物中还可以添加至少一种其他添加剂,如抗氧剂、稳定剂、润滑剂、填料、玻璃纤维等。
本发明所述含磷阻燃剂为双酚A双(磷酸二苯酯)、间苯二酚(二苯基磷酸酯)或磷酸三苯酯中的一种或几种的混合物。
本发明所述的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物可通过将各个组分按公知方式混合,然后加入螺杆挤出机中熔融挤出制成。
本发明所述的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物可应用于汽车、电子、通讯等领域中。
本发明与现有技术相比,具有如下有益效果:
本发明通过将冲击改善剂中短链聚烯烃含量控制在一定范围内,可以显著降低注塑过程产生表面水花和膜垢的机会,所得组合物具有低析出物和良好外观特点,并且其力学性能和阻燃性能还更好,可广泛应用于汽车、电子、通讯等领域中。
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。
实施例1
将各组分按表1所示重量百分比先放入高速混合器中混合3分钟,然后再放入双螺杆挤 出机,温度控制在:200℃~300℃,挤出造粒即得,其中,冲击改善剂为短链聚烯烃含量为0.015wt%的ABS树脂,性能测试结果见表1。
实施例2
各组分按表1所示,其中,冲击改善剂为短链聚烯烃含量为0.030wt%的ABS树脂,其余同实施例1,性能测试结果见表1。
实施例3
各组分按表1所示,其中,冲击改善剂为短链聚烯烃含量为0.045wt%的ABS树脂,其余同实施例1,性能测试结果见表1。
实施例4
各组分按表1所示,其中,冲击改善剂为短链聚烯烃含量为0.068wt%的ABS树脂,其余同实施例1,性能测试结果见表1。
实施例5
各组分按表1所示,其中,冲击改善剂为短链聚烯烃含量为0.095wt%的ABS树脂,其余同实施例1,性能测试结果见表1。
对比例1
各组分按表1所示,其中,冲击改善剂为短链聚烯烃含量为0.25wt%的ABS树脂,其余同实施例1,性能测试结果见表1。
对比例2
各组分按表1所示,其中,冲击改善剂为短链聚烯烃含量为0.5wt%的ABS树脂,其余同实施例1,性能测试结果见表1。
对比例3
各组分按表1所示,其中,冲击改善剂为短链聚烯烃含量为0.15wt%的ABS树脂,其余同实施例1,性能测试结果见表1。
表1阻燃芳族聚碳酸酯组合物组分及性能测试结果(表中组份含量为重量百分比)
Figure PCTCN2015078632-appb-000001
从表1结果中可以看出,使用短链聚烯烃含量低于0.1wt%的ABS,可以显著降低外观产生水花的机会,并且膜垢也更少,同时力学性能和阻燃性能较对比例还更好。
性能测试方法:
外观评价方法:注塑40*60*2mm的方板,肉眼观察方板表面,统计水花的数目。
膜垢评价方法:注塑40*60*2mm的方板,连续注塑100膜,从固定排气口可刮下来的膜垢重量。
拉伸强度:测试标准ASTM D638,在Zwick电子万能试验机上测试;
弯曲强度:测试标准ASTM D790,在Zwick电子万能试验机上测试;
悬臂梁缺口冲击:测试标准ASTM D256,在Zwick电子万能试验机上测试;
阻燃等级:测试标准UL94。

Claims (9)

  1. 一种具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,其中包括含磷阻燃剂、芳族聚碳酸酯和冲击改善剂,其特征在于,所述冲击改善剂中短链聚烯烃的含量低于0.1wt%。
  2. 根据权利要求1所述的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,其特征在于:所述短链聚烯烃的分子式为CnH2n+2,其中10<n<100,优选15<n<70,更优选18<n<45。
  3. 根据权利要求1所述的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,其特征在于:所述冲击改善剂是一种具有芯/壳结构的接枝共聚物。
  4. 根据权利要求3所述的的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,其特征在于:所述芯层主要选自由下述组成的一组中的一种二烯橡胶聚合物:共轭二烯、含有至少50wt%共轭二烯的共聚物、烯烃橡胶、硅氧烷橡胶、烷基中含有C1-C8碳原子的丙烯酸烷基酯、丙烯酸烷基酯与苯乙烯或丁二烯的共聚物,以及他们的混合物;所述壳层是苯乙烯和丙烯腈共聚物。
  5. 根据权利要求4所述的的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,其特征在于:所述冲击改善剂为丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、丙烯腈-苯乙烯-丙烯酸三元共聚物ASA或甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物MBS中的一种或几种的混合,优选丙烯腈-丁二烯-苯乙烯接枝共聚物ABS。
  6. 根据权利要求1所述的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,其特征在于:该组合物包含40-90wt%的芳族聚碳酸酯、5-20wt%的含磷阻燃剂和5-40wt%的冲击改善剂。
  7. 根据权利要求6所述的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,其特征在于:该组合物包含60-80wt%的芳族聚碳酸酯、9-15wt%的含磷阻燃剂和7-25wt%的冲击改善剂。
  8. 根据权利要求1所述的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物,其特征在于:所述含磷阻燃剂为双酚A双(磷酸二苯酯)、间苯二酚(二苯基磷酸酯)或磷酸三苯酯中的一种或几种的混合物。
  9. 权利要求1-8任一项所述的具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物在汽车、电子、通讯领域中的应用。
PCT/CN2015/078632 2014-09-02 2015-05-10 具有低析出物和良好外观的阻燃芳族聚碳酸酯组合物 WO2016033992A1 (zh)

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