WO2021036615A1 - 一种聚丙烯聚苯醚聚苯乙烯三元合金及其制备方法 - Google Patents

一种聚丙烯聚苯醚聚苯乙烯三元合金及其制备方法 Download PDF

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WO2021036615A1
WO2021036615A1 PCT/CN2020/103917 CN2020103917W WO2021036615A1 WO 2021036615 A1 WO2021036615 A1 WO 2021036615A1 CN 2020103917 W CN2020103917 W CN 2020103917W WO 2021036615 A1 WO2021036615 A1 WO 2021036615A1
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polypropylene
polyphenylene ether
polystyrene
ternary alloy
block copolymer
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French (fr)
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王文超
黄险波
叶南飚
禹权
丁超
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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 technical field of polymer materials, in particular to a polypropylene polyphenylene ether polystyrene ternary alloy and a preparation method thereof.
  • Polyphenylene ether itself has higher heat resistance, better mechanical and electrical properties, but its price is more expensive, and its solvent resistance is poor; polypropylene (PP) is cheap, has excellent solvent resistance, but has better heat resistance low.
  • the usual polystyrene (PS) is an amorphous random polymer with excellent thermal insulation, insulation and transparency. The long-term use temperature is 0-70°C, but it is brittle and easy to crack at low temperature. The combination of the three can produce alloy materials with moderate price, balanced heat resistance and solvent resistance.
  • Citride CN102719014A discloses a polypropylene polyphenylene ether polystyrene ternary alloy, which has an excellent balance between rigidity, toughness, and processability, and can be used in various fields.
  • its compatibilizer is a selectively hydrogenated ABA triblock copolymer of alkenyl aromatic compound and conjugated diene, block B is a conjugated diene compound, and block A is a vinyl aromatic compound;
  • the vinyl aromatic compound is styrene, alkyl styrene, ethyl vinyl benzene or divinyl benzene, and the conjugated diene compound is butadiene or isoprene.
  • the toughening effect of the compatibilizer is very limited. In most applications, additional toughening agents are needed to improve toughness.
  • the purpose of the present invention is to provide a polypropylene polyphenylene ether polystyrene ternary alloy, which has the advantages of good compatibility and high toughness.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polypropylene polyphenylene ether polystyrene ternary alloy.
  • a polypropylene polyphenylene ether polystyrene ternary alloy in parts by weight, comprising the following components:
  • the A block is a copolymer of styrene and vinyl C4-C12 alkyl aromatic compounds
  • the B block is a selectively hydrogenated polymer of conjugated diene compounds with a molecular weight of 5 -300000.
  • the A block is a copolymer of styrene and vinyl C4-C12 alkyl aromatic compounds
  • the B block is a selectively hydrogenated polymer of conjugated diene compounds with a molecular weight of 5 -300000.
  • the polystyrene segment has good compatibility with polyphenylene ether, but it does not provide toughness addition;
  • B-block The segmented polyconjugated diene compound provides the required toughness.
  • the A block contains a long-chain alkyl group of a vinyl C4-C12 alkyl aromatic compound, and the long-chain alkyl group can provide a certain toughness addition. Therefore, the addition of the A-B-A type block copolymer of the present invention can more improve the toughness of the alloy and at the same time have good compatibility.
  • the polystyrene in the A-B-A type block copolymer accounts for 60%-99% of the molecular weight of the A block.
  • the content of vinyl C4-C12 alkyl aromatic compounds is less, because the steric hindrance effect of its long-chain alkyl will hinder the progress of polymerization, and the long-chain alkyl segment will hinder the progress of polymerization.
  • the compatibility of polystyrene segment with polyphenylene ether reduces processing performance.
  • the presence of propylene long-chain alkyl groups will hinder the contact of aryl groups with styrene and reduce compatibility. Therefore, keeping most of the styrene content can effectively ensure compatibility.
  • the conjugated diene compound in the ABA-type block copolymer of the present invention may be a conjugated diene compound commonly used in polymer synthesis. Based on cost considerations, the conjugated diene compound is selected from commonly used butane compounds on the market. At least one of diene and isoprene, the B block accounts for 45-80% of the molecular weight of the ABA block copolymer.
  • the C4-C12 alkyl group is located at the para position of the aromatic ring.
  • the C4-C12 alkyl group is linear.
  • the function of the straight chain alkyl group is to extend the long alkyl chain segment, which can improve the toughness. If C6 is hexyl, the addition to toughness is better than cyclohexane.
  • C4-C12 alkyl groups will undergo isomerization reactions to generate other non-linear C4-C12 alkyl groups. Generally, such reactions will not exceed 1% of the total C4-C12 alkyl groups.
  • the aromatic compound is selected from at least one of phenyl, naphthyl, and phenanthryl.
  • Aromatic compounds can also contain halogens and C3 or less alkyl groups, which will not have a greater impact on vinyl C4-C12 alkyl groups.
  • polypropylene accounts for 10-60%, polyphenylene ether for 10-60%, and polystyrene for 5-30%;
  • the polyphenylene ether used in the present invention can be poly2,6-dimethylphenol, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl) -1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) Base) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly( 2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene) ether, poly(2-methyl -At least one of 6-hydroxyethyl-1,4-phenylene) ether and poly(2-methyl-6-chloroethyl-1,4-pheny
  • the polypropylene used in the present invention can be a homopolypropylene or a copolymer polypropylene, and the copolymer polypropylene can be an ethylene/propylene copolymer. There is no special requirement for the melt index of polypropylene.
  • reinforcing fibers In parts by weight, it also includes 0-100 parts of reinforcing fibers; the reinforcing fibers are selected from at least one of glass fibers, carbon fibers, metal fibers, and whiskers.
  • auxiliary agent is selected from at least one of antioxidants, lubricants, flame retardants, heat stabilizers, light stabilizers, and ultraviolet light absorption additives.
  • Antioxidants include primary antioxidants or stabilizers (such as hindered phenols and/or secondary arylamines) and optional secondary antioxidants (such as phosphate esters and/or thioesters).
  • Suitable antioxidants include, for example, organic phosphates, such as tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylbenzene) Base) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, etc., alkylated monohydric phenols or polyhydric phenols; polyhydric phenols and diene alkylation reaction products, such as tetra[methylene (3 ,5-Di-tert-butyl-4-hydroxyhydrocinnamate)] methane, etc.; butylated reaction product of
  • Suitable heat stabilizers include, for example, organic phosphites such as triphenyl phosphite, tris(2,6-dimethylphenyl) phosphite, tris(mixed mono- and dinonylphenyl) phosphites , Etc.; phosphonates, such as dimethylphenylphosphonate, etc.; phosphates, such as trimethyl phosphate, etc.; or a combination containing at least one of the foregoing heat stabilizers.
  • organic phosphites such as triphenyl phosphite, tris(2,6-dimethylphenyl) phosphite, tris(mixed mono- and dinonylphenyl) phosphites , Etc.
  • phosphonates such as dimethylphenylphosphonate, etc.
  • phosphates such as trimethyl phosphate, etc.
  • Light stabilizers and/or ultraviolet light (UV) absorbing additives may be added.
  • Suitable light stabilizers include, for example, benzotriazoles, such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzene Triazole and 2-hydroxy-4-n-octyloxybenzophenone, etc., also include triazine-based ultraviolet light absorbers or a combination containing at least one of the foregoing light stability.
  • Suitable UV absorbing additives include, for example, hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates; oxalyl dianilides; benzoxazinones; 2-( 2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (CYASORM 5411); 2-hydroxy-4-n-octyloxybenzophenone ( CYASORM 531); 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol (1164); 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one)(CYASORM UV-3638); 1,3-bis[(2-cyano- 3,3-Diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacrylo
  • the lubricant is selected from at least one of stearate lubricants, fatty acid lubricants, stearate lubricants, and silicone lubricants; the stearate lubricants are selected At least one of calcium stearate, magnesium stearate, and zinc stearate; the fatty acid lubricant is selected from at least one of fatty acids, fatty acid derivatives, and fatty acid esters; the stearin
  • the ester lubricant is selected from at least one of pentaerythritol stearate; preferably, the lubricant is selected from at least one of fatty acid lubricants and stearate lubricants.
  • the flame retardant can be a polyphosphate compound (ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, etc.), or a bromine-antimony flame retardant system (octabromoether, decabromodiphenyl ethyl) Alkanes, brominated epoxy, brominated polystyrene, antimony-containing compounds, etc.).
  • a polyphosphate compound ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, etc.
  • bromine-antimony flame retardant system octabromoether, decabromodiphenyl ethyl Alkanes, brominated epoxy, brominated polystyrene, antimony-containing compounds, etc.
  • the preparation method of the above-mentioned polypropylene polyphenylene ether polystyrene ternary alloy includes the following steps: adding polypropylene, polyphenylene ether, polystyrene, ABA type block copolymers, and additives into a high-speed mixer according to the ratio. Mix it evenly, then put it into the twin-screw extruder, feed the reinforcing fiber on the side, extrude and granulate to obtain the polypropylene polyphenylene ether polystyrene ternary alloy, the temperature of each section of the screw is 180-195°C in the first zone, and the second to nine Zone 200-240°C.
  • the present invention has the following beneficial effects
  • the selective hydrogenation of the polypropylene polyphenylene ether polystyrene ternary alloy by adding a copolymer of styrene, vinyl C4-C12 alkyl aromatic compound, and B block of conjugated diene compound to the ternary alloy of polypropylene, polyphenylene ether and polystyrene
  • the polymer ABA type block copolymer is used as a compatible toughening agent. Compared with the existing ABA type toughening agent, it can ensure good compatibility while further improving the toughness of the alloy.
  • the application range of polypropylene polyphenylene ether polystyrene ternary alloy is expanded, and the addition of other toughening agents can also be reduced.
  • the preparation method of the polypropylene polyphenylene ether polystyrene ternary alloy of the embodiment and the comparative example add polypropylene, polyphenylene ether, polystyrene, ABA type block copolymer, and additives to the high-speed mixer according to the proportioning Mix it evenly, then put it into a twin-screw extruder, extrude and granulate to obtain a flame-retardant polypropylene polyphenylene ether polystyrene ternary alloy.
  • the temperature of each section of the screw is 180-195°C in the first zone and 200- in the second to the ninth zone. 240°C.
  • Polypropylene PP HP550J;
  • Polystyrene PS 350K;
  • a block is a copolymer of styrene and vinyl C7 linear alkyl phenyl, in which the content of styrene accounts for about 76% of the molecular weight of the A block, and the B block is selectively hydrogenated (Fully hydrogenated) polyisoprene, the B block accounts for 65% of the total molecular weight of the ABA block copolymer, and the total molecular weight is about 200,000;
  • a block is a copolymer of styrene and vinyl C4 linear alkyl naphthyl, in which the content of styrene accounts for about 76% of the molecular weight of the A block, and the B block is selectively hydrogenated (Fully hydrogenated) polyisoprene, the B block accounts for 65% of the total molecular weight of the ABA block copolymer, and the total molecular weight is about 200,000;
  • a block is a copolymer of styrene and vinyl C4 linear alkyl phenyl, in which the content of styrene accounts for about 76% of the molecular weight of the A block, and the B block is selectively hydrogenated (Fully hydrogenated) polyisoprene, the B block accounts for 40% of the total molecular weight of the ABA block copolymer, and the total molecular weight is about 200,000;
  • A-B-A type block copolymer D The A block is styrene, and the B block is hydrogenated polyisoprene.
  • the total molecular weight is about 200,000.
  • Toughening agent SEBS 6151;
  • Lubricant Silicone lubricant, MB50-002;
  • Antioxidant Antioxidant 168/1010;
  • Table 1 The distribution ratio (parts by weight) of each group of the embodiment and the comparative example and the results of each performance test
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Comparative example 1 Comparative example 2
  • Polyphenylene ether 60 60 60 60 60
  • Polystyrene 10 10 10 10 10 10 10 10 A-B-A type block copolymer A 5 10 18 25 - - - - - - A-B-A type block copolymer B - - - - 10 - - - A-B-A type block copolymer C - - - - - 10 - - A-B-A type block copolymer D - - - - - - 10 - Toughener - - - - - - - 10 Lubricant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
  • Example 2/5 and Comparative Example 1 and Comparative Example 2 it can be seen that the commonly used SEBS, polystyrene-hydrogenated polyisoprene-polystyrene three-component polypropylene polyphenylene ether polystyrene ternary alloy As a toughening agent, the metablock copolymer has a toughening effect that is worse than that of the ABA block copolymer used in the present invention.

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Abstract

本发明提供了一种聚丙烯聚苯醚聚苯乙烯三元合金，其特征在于，按重量份计，包括以下组分：聚丙烯和聚苯醚和聚苯乙烯100份，A-B-A型嵌段共聚物5-25份；其中，A-B-A型嵌段共聚物中，A嵌段为苯乙烯、乙烯基C4-C12烷基芳香族化合物的共聚物，B嵌段为共轭二烯化合物的选择性氢化聚合物，分子量为5-30万。本发明的聚丙烯聚苯醚聚苯乙烯三元合金具有相容性好、韧性高的优点。

Description

一种聚丙烯聚苯醚聚苯乙烯三元合金及其制备方法 技术领域
本发明涉及高分子材料技术领域，特别是涉及一种聚丙烯聚苯醚聚苯乙烯三元合金及其制备方法。
背景技术
聚苯醚(PPE)本身耐热性较高，力学性能和电性能较好，但是其价格较贵，耐溶剂性能差；聚丙烯(PP)价格便宜，耐溶剂性能优良，但是耐热性较低。通常的聚苯乙烯(PS)为非晶态无规聚合物，具有优良的绝热、绝缘和透明性，长期使用温度0～70℃，但脆，低温易开裂。三者结合，可以制备出价格适中、耐热性和耐溶剂性能均衡的合金材料。
但是，三元合金彼此之间的相容性不好，因此往往需要加入相容剂提高彼此之间的相容性。中国专利CN102719014A公开了一种聚丙烯聚苯醚聚苯乙烯三元合金，具有刚性、韧性、加工性能之间优良的平衡，可以应用于各个领域。主要的，其相容剂为链烯基芳香族化合物与共轭二烯烃的选择性氢化A-B-A型三嵌段共聚物，嵌段B为共轭二烯化合物，嵌段A为乙烯基芳香族化合物；乙烯基芳香族化合物为苯乙烯、烷基苯乙烯、乙基乙烯基苯或二乙烯基苯，所述共轭二烯化合物为丁二烯或异戊二烯。但是，在该配方中，相容剂的增韧效果很有限，在多数应用中需要额外加入增韧剂来提高韧性。
发明内容
本发明的目的在于，提供一种聚丙烯聚苯醚聚苯乙烯三元合金，具有相容性好、韧性高的优点。
本发明的另一目的在于，提供上述聚丙烯聚苯醚聚苯乙烯三元合金的制备方法。[0006]本发明是通过以下技术方案实现的：
一种聚丙烯聚苯醚聚苯乙烯三元合金，按重量份计，包括以下组分：
聚丙烯和聚苯醚和聚苯乙烯  100份，
A-B-A型嵌段共聚物         5-25份；
其中，A-B-A型嵌段共聚物中，A嵌段为苯乙烯、乙烯基C4-C12烷基芳香族化合物的共聚物，B嵌段为共轭二烯化合物的选择性氢化聚合物，分子量为5-30万。
优选的，按重量份计，包括以下组分：
聚丙烯和聚苯醚和聚苯乙烯  100份，
A-B-A型嵌段共聚物         10-18份；
其中，A-B-A型嵌段共聚物中，A嵌段为苯乙烯、乙烯基C4-C12烷基芳香族化合物的共聚物，B嵌段为共轭二烯化合物的选择性氢化聚合物，分子量为5-30万。
现有的聚苯乙烯-聚共轭二烯化合物-聚苯乙烯嵌段共聚物中，聚苯乙烯链段与聚苯醚的相容性较好，但是其不提供韧性的加成；B嵌段的聚共轭二烯化合物提供所需的韧性。
本发明使用的A-B-A型嵌段共聚物中A嵌段含有乙烯基C4-C12烷基芳香族化合物 的长链烷基，长链烷基能够提供一定的韧性加成。因此本发明的A-B-A型嵌段共聚物的加入能够更多的提升合金的韧性，同时能够具有良好的相容性。
所述的A-B-A型嵌段共聚物中聚苯乙烯占A嵌段分子量的60％-99％。
在A嵌段中，乙烯基C4-C12烷基芳香族化合物的含量较少，是因为其长链烷基的位阻效应会阻碍聚合的进行，并且过长的长链烷基链段会阻碍聚苯乙烯链段与聚苯醚的相容性，降低加工性能。而且，丙烯长链烷基的存在会阻碍芳基与苯乙烯的接触而降低相容性，因此保留多数的苯乙烯含量能够有效保障相容性。
本发明的A-B-A型嵌段共聚物中的共轭二烯化合物可以是高分子合成中常用的共轭二烯化合物，基于成本的考虑，所述的共轭二烯化合物选自市面上常用的丁二烯、异戊二烯中的至少一种，B嵌段占A-B-A型嵌段共聚物分子量的45-80％。
优选的，所述的乙烯基C4-C12烷基芳香族化合物中，C4-C12烷基位于芳环的对位。
优选的，所述的乙烯基C4-C12烷基芳香族化合物中，C4-C12烷基是直链的。直链烷基的作用是长长的烷基链段伸出，能够提高韧性。如C6是己基的话对韧性的加成比环己烷基好。但是，在合成过程中，有可能一些C4-C12烷基会发生异构化反应，生成其他非直链C4-C12烷基，一般此类反应不会超过总C4-C12烷基的1％。
所述的乙烯基C4-C12烷基芳香族化合物中，芳香族化合物选自苯基、萘基、菲基中的至少一种。芳香族化合物上也可以含有如卤素、C3以下的烷基，不会对乙烯基C4-C12烷基造成较大的影响。
三元合金中，聚丙烯占10-60％、聚苯醚占10-60％、聚苯乙烯占5-30％；
本发明使用的聚苯醚可以是聚2,6-二甲基苯酚、聚(2,6-二甲基-1,4-亚苯基)醚、聚(2-甲基-6-乙基-1,4-亚苯基)醚、聚(2,6-二乙基-1,4-亚苯基)醚、聚(2-乙基-6-正丙基-1,4-亚苯基)醚、聚(2,6-二正丙基-1,4-亚苯基)醚、聚(2-甲基-6-正丁基-1,4-亚苯基)醚、聚(2-乙基-6-异丙基-1,4-亚苯基)醚、聚(2-甲基-6-氯乙基-1,4-亚苯基)醚、聚(2-甲基-6-羟乙基-1,4-亚苯基)醚、聚(2-甲基-6-氯乙基-1,4-亚苯基)醚中的至少一种；优选为聚(2,6-二甲基-1,4-亚苯基)醚、聚(2-甲基-6-乙基-1,4-亚苯基)醚、聚(2,6-二乙基-1,4-亚苯基)醚、聚2,6-二甲基苯酚中的至少一种。
本发明使用的聚丙烯可以是均聚聚丙烯、共聚聚丙烯，共聚聚丙烯可以是乙烯/丙烯共聚物。对于聚丙烯的熔融指数没有特别的要求。
按重量份计，还包括0-100份的增强纤维；所述的增强纤维选自玻璃纤维、碳纤维、金属纤维、晶须中的至少一种。
按重量份计，还包括0-10份的助剂；所述的助剂选自抗氧剂、润滑剂、阻燃剂、热稳定剂、光稳定剂、紫外光吸收添加剂的至少一种。
抗氧剂包括主抗氧剂或稳定剂(如受阻酚和/或仲芳基胺)和任选的辅助抗氧化剂(例如磷酸酯和/或硫酯)。合适的抗氧化剂包括例如有机磷酸酯，例如亚磷酸三(壬基苯基)酯、亚磷酸三(2,4-二叔丁基苯基)酯、二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯等等，烷基化的一元酚或多元酚；多元酚与二烯的烷基化反应产物，例如四[亚甲基(3,5-二叔丁基-4-羟基氢化肉桂酸酯)]甲烷等等；对甲酚或二环戊二烯的丁基化反应产物；烷基化氢醌；羟基化硫代二苯醚；烷叉双酚；苄基化合物；β-(3,5-二叔丁基-4-羟基苯基)-丙酸与一元醇或多元醇的酯；β-(5-叔丁基-4-羟基-3-甲基苯基)-丙酸与 一元醇或多元醇的酯；硫烷基或硫芳基化合物的酯，例如二硬脂基硫代丙酸酯、二月桂基硫代丙酸酯、二(十三烷基)硫代丙酸酯、十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、季戊四醇-四[3-(3,5-二叔丁基-4-羟基苯基)]丙酸酯等等；β-(3,5-二叔丁基-4-羟基苯基)-丙酸的酰胺等等；或者包含至少一种前述抗氧化剂的组合。
合适的热稳定剂包括例如有机亚磷酸酯，例如亚磷酸三苯酯、亚磷酸三(2,6-二甲基苯基)酯、亚磷酸三(混合的单和二壬基苯基)酯，等等；膦酸酯，例如二甲基苯膦酸酯等等；磷酸酯，例如磷酸三甲基酯等等；或者包含至少一种前述热稳定剂的组合。
可以添加光稳定剂和/或紫外光(UV)吸收添加剂。合适的光稳定剂包括例如苯并三唑类，例如2-(2-羟基-5-甲基苯基)苯并三唑、2-(2-羟基-5-叔辛基苯基)-苯并三唑和2-羟基-4-正辛氧基二苯甲酮等等，也包括三嗪类的紫外光吸收剂或者包含至少一种前述光稳定的组合。
合适的UV吸收添加剂包括例如羟基二苯甲酮类；羟基苯并三唑类；羟基苯并三嗪类；氰基丙烯酸酯类；草酰二苯胺类；苯并噁嗪酮类；2-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚(CYASORM 5411)；2-羟基-4-正辛氧基二苯甲酮(CYASORM 531)；2-[4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-(辛氧基)苯酚(1164)；2,2’-(1,4-亚苯基)双(4H-3,1-苯并噁嗪-4-酮)(CYASORM UV-3638)；1,3-双[(2-氰基-3,3-二苯基丙烯酰基)氧基]-2，2-双[[(2-氰基-3,3-二苯基丙烯酰基)氧基]甲基]丙烷(UVINUL 3030)；纳米尺寸的无机材料，例如氧化钛、氧化铈和氧化锌，所有这些的粒度小于100nm，或类似物；或含至少一种前述UV吸收剂的组合。
所述的润滑剂选自硬脂酸盐类润滑剂、脂肪酸类润滑剂、硬脂酸酯类润滑剂、有机硅类润滑剂中的至少一种；所述的硬脂酸盐类润滑剂选自硬脂酸钙、硬脂酸镁、硬脂酸锌中的至少一种；所述的脂肪酸类润滑剂选自脂肪酸、脂肪酸衍生物、脂肪酸酯中的至少一种；所述的硬脂酸酯类润滑剂选自季戊四醇硬脂酸酯中的至少一种；优选的，所述的润滑剂选自脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种。
阻燃剂可以是聚磷酸盐类化合物(聚磷酸铵、三聚氰胺磷酸盐、三聚氰胺焦磷酸盐、三聚氰胺聚磷酸盐等)，也可以是溴-锑阻燃体系(八溴醚、十溴二苯乙烷、溴化环氧、溴化聚苯乙烯、含锑化合物等)等。
上述的聚丙烯聚苯醚聚苯乙烯三元合金的制备方法，包括以下步骤：按照配比将聚丙烯、聚苯醚、聚苯乙烯、A-B-A型嵌段共聚物、助剂加入高速混料机中混合均匀，再投入双螺杆挤出机中，侧喂增强纤维，挤出造粒得到聚丙烯聚苯醚聚苯乙烯三元合金，螺杆各区间温度为一区180-195℃，二至九区200-240℃。
本发明相对于现有技术，具有如下有益效果
本发明通过在聚丙烯聚苯醚聚苯乙烯三元合金加入A嵌段为苯乙烯、乙烯基C4-C12烷基芳香族化合物的共聚物、B嵌段为共轭二烯化合物的选择性氢化聚合物的A-B-A型嵌段共聚物作为相容增韧剂，相比于现有的A-B-A型增韧剂其保证良好的相容性的同时还能够进一步提升合金的韧性。扩大了聚丙烯聚苯醚聚苯乙烯三元合金的应用范围，也可以减少其他增韧剂的加入。
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。
实施例和对比例的聚丙烯聚苯醚聚苯乙烯三元合金的制备方法：按照配比将聚丙烯、聚苯醚、聚苯乙烯、A-B-A型嵌段共聚物、助剂加入高速混料机中混合均匀，再投入双螺杆挤出机中，挤出造粒得到阻燃聚丙烯聚苯醚聚苯乙烯三元合金，螺杆各区间温度为一区180-195℃，二至九区200-240℃。
实施例及对比例使用以下原料，但不限制本发明：
聚苯醚：PPE LXR040；
聚丙烯：PP HP550J；
聚苯乙烯：PS 350K；
A-B-A型嵌段共聚物A：A嵌段为苯乙烯、乙烯基C7直链烷基苯基的共聚物，其中苯乙烯的含量约占A嵌段的分子量76％，B嵌段为选择性氢化(完全氢化)的聚异戊二烯，B嵌段占A-B-A型嵌段共聚物总分子量的65％，总分子量约为20万；
A-B-A型嵌段共聚物B：A嵌段为苯乙烯、乙烯基C4直链烷基萘基的共聚物，其中苯乙烯的含量约占A嵌段分子量的76％，B嵌段为选择性氢化(完全氢化)的聚异戊二烯，B嵌段占A-B-A型嵌段共聚物总分子量的65％，总分子量约为20万；
A-B-A型嵌段共聚物C：A嵌段为苯乙烯、乙烯基C4直链烷基苯基的共聚物，其中苯乙烯的含量约占A嵌段分子量的76％，B嵌段为选择性氢化(完全氢化)的聚异戊二烯，B嵌段占A-B-A型嵌段共聚物总分子量的40％，总分子量约为20万；
A-B-A型嵌段共聚物D：A嵌段为苯乙烯，B嵌段为氢化的聚异戊二烯，总分子量约为20万。
增韧剂：SEBS 6151；
润滑剂：有机硅类润滑剂，MB50-002；
抗氧剂：抗氧剂168/1010；
各性能测试方法：
(1)拉伸强度：按照ISO 527标准；
(2)缺口冲击强度：按照ISO 180标准。
表1：实施例和对比例各组分配比(重量份)及各项性能测试结果
  实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 对比例1 对比例2
聚丙烯 30 30 30 30 30 30 30 30
聚苯醚 60 60 60 60 60 60 60 60
聚苯乙烯 10 10 10 10 10 10 10 10
A-B-A型嵌段共聚物A 5 10 18 25 - - - -
A-B-A型嵌段共聚物B - - - - 10 - - -
A-B-A型嵌段共聚物C - - - - - 10 - -
A-B-A型嵌段共聚物D - - - - - - 10 -
增韧剂 - - - - - - - 10
润滑剂 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
抗氧剂 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
拉伸强度，MPa 32 30 27 25 31 31 30 32
缺口冲击强度，kJ/m 2 8 16 25 29 15 12 9 7
从实施例1-4可以看出，随着A-B-A型嵌段共聚物用量的上升，产品的韧性上升。
从实施例2/5和对比例1和对比例2可以看出，聚丙烯聚苯醚聚苯乙烯三元合金中常用的SEBS、聚苯乙烯-氢化的聚异戊二烯-聚苯乙烯三元嵌段共聚物作为增韧剂其增韧效果要差于本发明所用的A-B-A型嵌段共聚物。

Claims (10)

  1. 一种聚丙烯聚苯醚聚苯乙烯三元合金，其特征在于，按重量份计，包括以下组分：
    聚丙烯和聚苯醚和聚苯乙烯            100份，
    A-B-A型嵌段共聚物                   5-25份；
    其中，A-B-A型嵌段共聚物中，A嵌段为苯乙烯、乙烯基C4-C12烷基芳香族化合物的共聚物，B嵌段为共轭二烯化合物的选择性氢化聚合物，分子量为5-30万。
  2. 根据权利要求1所述的聚丙烯聚苯醚聚苯乙烯三元合金，其特征在于，按重量份计，包括以下组分：
    聚丙烯和聚苯醚和聚苯乙烯            100份，
    A-B-A型嵌段共聚物                   10-18份；
    其中，A-B-A型嵌段共聚物中，A嵌段为苯乙烯、乙烯基C4-C12烷基芳香族化合物的共聚物，B嵌段为共轭二烯化合物的选择性氢化聚合物，分子量为5-30万。
  3. 根据权利要求1或2所述的聚丙烯聚苯醚聚苯乙烯三元合金，其特征在于，所述的A-B-A型嵌段共聚物中聚苯乙烯占A嵌段分子量的60％-99％。
  4. 根据权利要求3所述的聚丙烯聚苯醚聚苯乙烯三元合金，其特征在于，所述的共轭二烯化合物选自丁二烯、异戊二烯中的至少一种，B嵌段占A-B-A型嵌段共聚物总分子量的45-80％。
  5. 根据权利要求1或2所述的聚丙烯聚苯醚聚苯乙烯三元合金，其特征在于，所述的乙烯基C4-C12烷基芳香族化合物中，C4-C12烷基位于芳环的对位；优选的，所述的乙烯基C4-C12烷基芳香族化合物中，C4-C12烷基是直链的。
  6. 根据权利要求1或2所述的聚丙烯聚苯醚聚苯乙烯三元合金，其特征在于，所述的乙烯基C4-C12烷基芳香族化合物中，芳香族化合物选自苯基、萘基、菲基中的至少一种。
  7. 根据权利要求1或2所述的聚丙烯聚苯醚聚苯乙烯三元合金，其特征在于，聚丙烯占10-60％、聚苯醚占10-60％、聚苯乙烯占5-30％。
  8. 根据权利要求1或2所述的聚丙烯聚苯醚聚苯乙烯三元合金，其特征在于，按重量份计，还包括0-100份的增强纤维；所述的增强纤维选自玻璃纤维、碳纤维、金属纤维、晶须中的至少一种。
  9. 根据权利要求1或2所述的聚丙烯聚苯醚聚苯乙烯三元合金，其特征在于，按重量份计，还包括0-10份的助剂；所述的助剂选自抗氧剂、润滑剂、阻燃剂、热稳定剂、光稳定剂、紫外光吸收添加剂中的至少一种。
  10. 权利要求9所述的聚丙烯聚苯醚聚苯乙烯三元合金的制备方法，其特征在于，包括以下步骤：按照配比将聚丙烯、聚苯醚、聚苯乙烯、A-B-A型嵌段共聚物、助剂加入高速混料机中混合均匀，再投入双螺杆挤出机中，挤出造粒得到聚丙烯聚苯醚聚苯乙烯三元合金，螺杆各区间温度为一区180-195℃，二至九区200-240℃。
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