WO2020186977A1 - 一种聚丙烯组合物及其制备方法 - Google Patents

一种聚丙烯组合物及其制备方法 Download PDF

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WO2020186977A1
WO2020186977A1 PCT/CN2020/076585 CN2020076585W WO2020186977A1 WO 2020186977 A1 WO2020186977 A1 WO 2020186977A1 CN 2020076585 W CN2020076585 W CN 2020076585W WO 2020186977 A1 WO2020186977 A1 WO 2020186977A1
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polypropylene
polypropylene composition
copolymerized
molecular weight
nucleating agent
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PCT/CN2020/076585
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English (en)
French (fr)
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陈嘉杰
黄险波
叶南飚
俞飞
吴国峰
丁正亚
罗忠富
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金发科技股份有限公司
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Priority to JP2021554373A priority Critical patent/JP2022524402A/ja
Publication of WO2020186977A1 publication Critical patent/WO2020186977A1/zh

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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • 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
    • C08L2205/24—Crystallisation aids

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a polypropylene composition and a preparation method thereof.
  • Polypropylene (PP for short) is a semi-crystalline thermoplastic polymerized by propylene.
  • polypropylene material has a large production and sales volume and a low price. It is used in various industries such as household appliances, packaging, and automobiles.
  • the wide application of polypropylene materials is attributed to its advantages, such as low density, low water absorption, good insulation, excellent physical properties, easy availability of raw materials, and low prices.
  • polypropylene materials also have some inevitable disadvantages: such as the presence of tertiary hydrocarbons in the polypropylene chain segment, its chemical environment is active, and it is prone to aging and yellowing under light, heat and other inducements; polypropylene has low solubility parameters and is easy to It is corroded by non-polar chemicals and appears into the phenomenon of chemical intolerance such as dissolution and cracking.
  • the above disadvantages are not conducive to the development of polypropylene materials in many fields. According to the "Energy-saving and New Energy Vehicle Industry Development Plan (2012-2020)" promulgated by my country, the development and application of lightweight automotive materials is imperative for both traditional fuel vehicles and new energy vehicles.
  • Automobile interior and exterior trim and functional parts are the main battlefields of automobile lightweight. Many interior and exterior trim and functional parts materials have been replaced and upgraded by "plastics instead of steel", and polypropylene material has played an indispensable role as the preferred material for automobile lightweight Missing role.
  • polypropylene materials around engines such as automobile auxiliary water tanks, low-temperature water chambers, etc.
  • the working environment temperature is relatively high, and there are many strong non-polar solvents such as organic oils and lubricants around the engine compartment. Challenges were raised.
  • a polypropylene material that can be used in automotive functional parts with chemical resistance and yellowing resistance has important development significance and broad application prospects.
  • Chinese patent CN109054184A uses modified polypropylene, blue acrylate resin powder and nano-silver modified polypropylene as raw materials. It is synthesized through hydrothermal reactors, ultrasonic reactors, spray dryers, ball mills, extruders and other equipment. The patented preparation method is complicated and involves a variety of production equipment and chemicals, which is not conducive to large-scale industrial production.
  • Chinese patent CN103044776A uses polypropylene resin, minerals, main antioxidants, deodorants, compatibilizers, processing aids and colorants as raw materials, the main antioxidant and auxiliary antioxidant
  • the agent constitutes a high-temperature-resistant antioxidant system, which can effectively prevent product aging and yellowing.
  • the polypropylene material prepared by this method has certain yellowing resistance and heat resistance, but is sensitive to the chemical environment around the engine compartment, and the application of polypropylene material near the engine compartment does not require odor.
  • the purpose of the present invention is to provide a polypropylene composition, which has the advantages of resistance to yellowing and chemicals.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polypropylene composition.
  • a polypropylene composition in parts by weight, comprising the following components:
  • the molecular weight of copolymerized polypropylene is 25000-30000
  • the molecular weight distribution (MWD) is in the range of 2.5-3.0
  • the isotacticity of copolymerized polypropylene is in the range of 90%-95%
  • aPP accounts for 0.5%-1.5% of the total weight of copolymerized polypropylene.
  • EP accounts for 0.5%-5.0% of the total weight of the copolymer polypropylene.
  • aPP refers to the random segment of polypropylene and a small amount of polyethylene in the copolymerized polypropylene
  • EP refers to the ethylene-propylene rubber segment in the copolymerized polypropylene.
  • the molecular weight of general copolymer polypropylene is 20000-200000, the molecular weight distribution range is 2-10, the isotacticity range is 85%-99%, aPP accounts for 0.5%-2.5% of the total weight of the copolymer polypropylene, and EP accounts for the total weight of the copolymer polypropylene. 0.5%-15% by weight.
  • the present invention investigates the microstructure of copolymerized polypropylene, and its characteristics include the following aspects: 1. Low molecular weight and low entanglement characteristics with high fluidity; 2. High isotacticity, low aPP content and low EP content to ensure copolymerization
  • the main chain segment of polypropylene has high flexibility and low defect points; 3. The length and structure of each main chain segment on the surface of the narrow molecular weight distribution are similar, which reduces the risk of multiple defects caused by excessive entanglement of short and ultra-long chain segments.
  • the molecular weight of the branched polyethylene is 250,000-350,000, the degree of branching ranges from 11.0-15.0, the content of methyl branches in the branches ranges from 51.0% to 60.0%, and the content of ethyl branches ranges from 25.0%. -30.0%, the content of propyl group and branches with more than 4 carbons ranges from 10.0% to 19.0%.
  • the content of each branch in the branched polyethylene is determined by a combination of 13 CNMR and two-dimensional DEPT maps.
  • the preferred branched polyethylene and the copolymerized polypropylene of the present invention are matched with each other to more effectively reduce the interfacial energy of the copolymerized polypropylene and the polyethylene, enhance the interfacial bonding force between the two resins, and reduce the chain segment and lattice defects.
  • the molecular weight of general branched polyethylene is 130,000-400000, the degree of branching ranges from 6.0 to 17.0, the content of methyl branches in the branches ranges from 25.0% to 75.0%, and the content of ethyl branches ranges from 20.0% to 50.0. %, the content of propyl group and branches with more than 4 carbons ranges from 5.0% to 30.0%.
  • the present invention investigates the microstructure of branched polyethylene, which is characterized by high degree of branching, a high proportion of methyl branches in branch chains, high chain segment flexibility and avoiding excessive entanglement caused by long branches. Knot.
  • polyethylene has a degree of branching, and the industry generally refers to polyethylene with a degree of branching lower than 3 as unbranched polyethylene.
  • a branched polyethylene of a specific structure is compounded by a copolymer polypropylene of a specific structure, the branched polyethylene is dispersed in the continuous phase of the copolymerized polypropylene to form an "sea-island" phase, and the branched polyethylene is dispersed as an "island" state
  • its specific branched segment structure can reduce the interfacial entanglement of copolymerized polypropylene and polyethylene, improve the compatibility of copolymerized polypropylene and polyethylene, and reduce the occurrence of interface defects.
  • the high crystallinity of polyethylene itself is combined with a copolymer polypropylene with a specific structure.
  • the high flexibility, high isotacticity and low defectivity of the two are important reasons for resistance to non-polar chemicals and yellowing resistance.
  • nucleating agents such as sodium benzoate, aluminum adipate, sodium cinnamate, rosin acid soap, etc. have good nucleation effects and can promote the interfacial bonding of copolymerized polypropylene and branched polyethylene.
  • the nucleating agent is at least one selected from the group consisting of organic phosphate nucleating agents and sorbitol derivative nucleating agents.
  • the preferred nucleating agent compared with ordinary polypropylene nucleating agent, has the advantages of high heat resistance stability, good processing performance, etc., especially it can induce copolymer polypropylene to form ⁇ crystal form with high isotacticity, high strength, and refined crystal nucleus. Improve crystallinity.
  • the organophosphate nucleating agent is selected from 2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphate sodium, 2,2'-methylene-bis(4, At least one of 6-di-tert-butyl phenyl phosphate) basic aluminum and 2,2'-methylene-bis(4,6-di-tert-butyl phenyl) sodium phosphate.
  • the sorbitol derivative nucleating agent is selected from 1,3:2,4-bis(3,4-dimethylbenzylidene)-D-sorbitol, (1,3:2,4)- At least one of dibenzylidene sorbitol and p-dimethyldibenzylidene sorbitol.
  • additives may be added, and 0.5-10 parts by weight of additives; the additives are selected from antioxidants, lubricants, colorants, and heat stabilizers. At least one of an anti-ultraviolet agent.
  • the lubricant is selected from at least one of stearate lubricants, fatty acid lubricants, and stearate lubricants; the stearate lubricant is selected from calcium stearate, At least one of 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 stearate lubricant is selected It 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.
  • Antioxidants include primary antioxidants or stabilizers (such as hindered phenols and/or secondary arylamines) and optional auxiliary 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
  • Suitable heat stabilizers include, for example, organic phosphites such as triphenyl phosphite, tris(2,6-dimethylphenyl) phosphite, tris(mixed mono- and dinonylphenyl) phosphite , 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) phosphite , Etc.
  • phosphonates such as dimethylphenylphosphonate, etc.
  • phosphates such as trimethyl phosphate, etc.
  • 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 include at least one combination of the foregoing light stability.
  • Suitable anti-ultraviolet agents 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-dipheny
  • the preparation method of the above-mentioned polypropylene composition includes the following steps: the copolymerized polypropylene, branched polyethylene, auxiliary agent, and nucleating agent are mixed uniformly and then added to the twin-screw extruder, melted and mixed, and the temperature of the melted and mixed The temperature is 190-210°C, the rotation speed of the screw is 450-550 rpm, and the polypropylene composition is obtained by extrusion granulation.
  • the invention effectively reduces the interfacial energy of copolymerized polypropylene and polyethylene by designing the microstructure of the copolymerized polypropylene chain segment and selecting the branched polyethylene with a specific segment structure, thereby improving the interfacial bonding force between the two resins and reducing the chain Segment and lattice defects, combined with high-efficiency nucleating agents, have the advantages of resistance to yellowing and chemicals.
  • the raw materials used in the examples and comparative examples are all commercially available.
  • Copolypropylene A The molecular weight is 29,000, the molecular weight distribution is 2.7, the isotacticity is 92%, aPP accounts for 1.3% of the total weight of the copolymerized polypropylene, and EP accounts for 4.5% of the total weight of the copolymerized polypropylene;
  • Copolypropylene B The molecular weight is 25400, the molecular weight distribution is 2.9, the isotacticity is 95%, aPP accounts for 0.7% of the total weight of the copolymer polypropylene, and EP accounts for 1.7% of the total weight of the copolymer polypropylene;
  • Copolypropylene C The molecular weight is 48,000, the molecular weight distribution is 4.8, the isotacticity is 91%, aPP accounts for 1.9% of the total weight of the copolymer polypropylene, and EP accounts for 8% of the total weight of the copolymer polypropylene;
  • Copolypropylene D The molecular weight is 27000, the molecular weight distribution is 2.3, the isotacticity is 86%, aPP accounts for 0.3% of the total weight of the copolymer polypropylene, and EP accounts for 2.1% of the total weight of the copolymer polypropylene;
  • Branched polyethylene A molecular weight 310,000, degree of branching is 13, methyl content is 54%, ethyl content is 27%, propyl group and branches with more than 4 carbon content are 19%;
  • Branched polyethylene B molecular weight 290,000, degree of branching is 11.5, methyl branch content is 56%, ethyl content is 26%, propyl group and branches containing more than 4 carbon content are 18%;
  • Branched polyethylene C molecular weight 270,000, degree of branching is 8.7, methyl branch content is 48%, ethyl content is 31%, propyl group and branches containing more than 4 carbon content are 21%;
  • Unbranched polyethylene 7049 molecular weight 190,000, degree of branching is 2.13, methyl branch content is 72%, ethyl content is 23%, propyl group and branches with more than 4 carbon content are 5%;
  • Nucleating agent A sodium 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate
  • Nucleating agent B p-dimethyldibenzylidene sorbitol
  • Nucleating agent C sodium benzoate
  • Antioxidant Antioxidant 1010/Antioxidant 168;
  • Lubricant zinc stearate.
  • Table 1 The distribution ratio (parts by weight) of each group of the embodiment and the comparative example and the performance test results
  • the present invention optimizes and screens the micro-segment structure of copolymerized polypropylene and branched polyethylene to reduce the entanglement between molecules and improve the interface bonding force between the two resins.
  • Example 2/3/7 it can be seen from Example 2/3/7 that the preferred branched polyethylene of the present invention more effectively reduces the interfacial energy of copolymerized polypropylene and polyethylene, improves the interfacial bonding force between the two resins, and reduces chain segments and crystal lattices. defect.
  • the preferred nucleating agent can induce the copolymer polypropylene matrix to form a high isotacticity, high strength, and crystallinity.
  • the alpha crystal form with refined core improves crystallinity.

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Abstract

本发明公开了一种聚丙烯组合物，按重量份计，包括以下组分：共聚聚丙烯90-100份；支化聚乙烯1-10份；成核剂0.1-0.5份；其中，共聚聚丙烯分子量为25000-30000，分子量分布(MWD)范围为2.5-3.0，聚丙烯等规度范围为90％-95％，aPP占共聚聚丙烯总重量的0.5％-1.5％，EP占共聚聚丙烯总重量的0.5％-5.0％。本发明的聚丙烯组合物，以聚丙烯为树脂基体的主体，通过对聚丙烯链段的微观结构进行设计以及选用特定链段结构的支化聚乙烯，有效降低聚丙烯和聚乙烯的界面能，提升了两种树脂间界面结合力，减少链段及晶格缺陷，配合高效成核剂，具有耐黄变、耐化学品的优点。

Description

一种聚丙烯组合物及其制备方法 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组合物及其制备方法。
背景技术
聚丙烯(Polypropylene，简称PP)是一种由丙烯聚合而成的半结晶型热塑性塑料。聚丙烯材料作为五种通用塑料之首，产销量大，价格便宜，应用于家电、包装、汽车等生活中的各行各业。聚丙烯材料的广泛应用归因于其优势，如密度低、吸水率低、绝缘性好、物理性能优异，原材料易得，价格便宜等。但聚丙烯材料也存在一些不可避免的劣势：如聚丙烯链段上存在叔碳氢，其化学环境活泼，在光、热等诱因下容易发生老化黄变；聚丙烯溶度参数较低，容易受到非极性化学品的侵蚀，出现溶解开裂等不耐化学品现象。以上劣势均不利于聚丙烯材料在众多领域的开拓发展。根据我国颁布的《节能与新能源汽车产业发展规划(2012-2020年)》，无论是传统燃油汽车还是新能源汽车，汽车材料轻量化的开发与应用势在必行。汽车内外饰及功能件作为汽车轻量化的主战场，众多的内外饰及功能件材料均已实现“以塑代钢”的替换升级，而聚丙烯材料作为汽车轻量化的首选材料起到了不可或缺的作用。针对目前聚丙烯材料在发动机周边的应用，如汽车副水箱、低温水室等，工作环境温度较高，且发动机舱周边多有机油、润滑油等强非极性溶剂，对聚丙烯发动机周边应用提出了挑战。基于目前汽车轻量化发展趋势及聚丙烯材料的汽车功能件应用，一款能够应用在汽车功能件的同时具有耐化学品和耐黄变的聚丙烯材料具有重要的开发意义和广阔的应用前景。
为提高聚丙烯的耐化学品性能，常添加特殊聚丙烯改性剂。中国专利CN109054184A采用改性聚丙烯、蓝光丙烯酸酯树脂粉和纳米银改性聚丙烯作为原材料，通过水热反应釜、超声反应器、喷雾干燥器、球磨机、挤出机等设备合成，反应及造粒，制得具有耐黄变性能的聚丙烯材料，该专利制备方法复杂，涉及多款生产设备及化学品，不利于大规模产业化生产。为了提高聚丙烯的耐黄变性能，中国专利CN103044776A采用聚丙烯树脂、矿物、主抗氧剂、除味剂、相容剂、加工助剂及着色剂作为原材料，主抗氧剂和辅助抗氧剂组成耐高温的抗氧体系，有效防止制品老化、黄变。该方法制备所得的聚丙烯材料具备一定的耐 黄变和耐热性能，但对发动机舱周边的化学品环境敏感，且发动机舱附近的聚丙烯材料应用并无气味要求。
发明内容
本发明的目的在于，提供一种聚丙烯组合物，其具有耐黄变和耐化学品的优点。
本发明的另一目的在于，提供上述聚丙烯组合物的制备方法。
本发明是通过以下技术方案实现的：
一种聚丙烯组合物，按重量份计，包括以下组分：
共聚聚丙烯            90-100份；
支化聚乙烯            1-10份；
成核剂                0.1-0.5份；
其中，共聚聚丙烯分子量为25000-30000，分子量分布(MWD)范围为2.5-3.0，共聚聚丙烯等规度范围为90％-95％，aPP占共聚聚丙烯总重量的0.5％-1.5％，EP占共聚聚丙烯总重量的0.5％-5.0％。
aPP是指共聚聚丙烯中聚丙烯和少量聚乙烯的无规链段，EP是指共聚聚丙烯中的乙丙橡胶链段。aPP和EP的测试方法均采用凝胶渗透色谱，描述含量均为质量含量百分数。
一般的共聚聚丙烯分子量为20000-200000，分子量分布范围为2-10，等规度范围为85％-99％，aPP占共聚聚丙烯总重量的0.5％-2.5％，EP占共聚聚丙烯总重量的0.5％-15％。本发明对共聚聚丙烯的微观结构进行考察，其特征有以下几个方面：一、具有较低分子量高流动性的低缠结特点；二、高等规度、低aPP含量和低EP含量确保共聚聚丙烯主链段的高柔顺性和低缺陷点；三、窄分子量分布表面各主链段长度及结构相近，减少因短链段和超长链段的过度缠结造成多缺陷的风险。
优选的，支化聚乙烯的分子量为250000-350000，支化度范围为11.0-15.0，支链中甲基支链的含量范围为51.0％-60.0％，乙基支链的含量范围为25.0％-30.0％，丙基及含4个碳以上的支链含量范围为10.0％-19.0％。支化聚乙烯中各支链的含量用核磁碳谱 13CNMR和二维DEPT图结合的方法确定。优选的支化聚乙烯与本发明共聚聚丙烯相互搭配，更有效降低共聚聚丙烯和聚乙烯的 界面能，提升了两种树脂间界面结合力，减少链段及晶格缺陷。
一般支化聚乙烯的分子量130000-400000，支化度范围为6.0-17.0，支链中中甲基支链的含量范围为25.0％-75.0％，乙基支链的含量范围为20.0％-50.0％，丙基及含4个碳以上的支链含量范围为5.0％-30.0％。本发明对支化聚乙烯的微观结构进行考察，其特征是支化度高，同时甲基支链在支链中占比高，链段柔顺度高同时避免了长支链导致的过多缠结。
一般聚乙烯都具有支化度，业内一般将支化度低于3的聚乙烯称为非支化聚乙烯。
本发明通过特定结构的共聚聚丙烯复配特定结构的支化聚乙烯，支化聚乙烯分散在共聚聚丙烯的连续相中形成“海岛”相态，支化聚乙烯作为“岛”态分散在共聚聚丙烯的“海”态中，其特定的支化链段结构能使共聚聚丙烯和聚乙烯界面缠结界面能降低，提高共聚聚丙烯和聚乙烯的相容性，降低界面缺陷产生。聚乙烯自身的高结晶特性配合优选特定结构的共聚聚丙烯结合，两者的高柔顺性、高等规度和低缺陷性是抵抗非极性化学品和耐黄变的重要原因。
其他的成核剂比如苯甲酸钠、己二酸铝、肉桂酸钠、松香酸皂等具有良好的成核作用，可以促进共聚聚丙烯和支化聚乙烯的界面结合。优选的，所述的成核剂选自有机磷酸盐类成核剂、山梨醇衍生物类成核剂中的至少一种。优选的成核剂，对比普通聚丙烯成核剂具有高耐热稳定性、加工性能好等优势，尤其能诱导共聚聚丙烯形成等规度高、强度高、晶核细化的α晶型，提高结晶度。
所述的有机磷酸盐类成核剂选自2,2'-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠、2,2'-亚甲基-双(4,6-二叔丁基苯基磷酸)碱式铝、2,2'-亚甲基-双(4,6-二叔丁基苯基)磷酸钠中的至少一种。
所述的山梨醇衍生物类成核剂选自1,3:2,4-二(3,4-二甲基亚苄基)-D-山梨醇、(1,3:2,4)-二亚苄基山梨醇、对二甲基二亚苄基山梨醇中的至少一种。
根据聚丙烯组合物的其他性能，还可以加入其他助剂，按重量份计，还包括0.5-10份的助剂；所述的助剂选自抗氧剂、润滑剂、着色剂、热稳定剂、抗紫外线剂中的至少一种。
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。
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/或抗紫外线剂。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。合适的抗紫外线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；或含至少一种前述抗紫外线剂的组合。
上述的聚丙烯组合物的制备方法，包括以下步骤：将共聚聚丙烯、支化聚乙烯、助剂、成核剂混合均匀后加入双螺杆挤出机中，进行熔融混炼，熔融混炼温度为190～210℃，螺杆转速为450～550转/分，挤出造粒，得到聚丙烯组合物。
本发明具有如下有益效果
本发明通过对共聚聚丙烯链段的微观结构进行设计以及选用特定链段结构的支化聚乙烯，有效降低共聚聚丙烯和聚乙烯的界面能，提升了两种树脂间界面结合力，减少链段及晶格缺陷，配合高效成核剂，具有耐黄变、耐化学品的优点。
具体实施方式
本发明通过以下实施例来进一步说明本发明，但是本发明的保护范围不受以下实施例所限制。
实施例和对比例所用的原料均来源于市售。
共聚聚丙烯A：分子量为29000，分子量分布为2.7，等规度为92％，aPP占共聚聚丙烯总重量的1.3％，EP占共聚聚丙烯总重量的4.5％；
共聚聚丙烯B：分子量为25400，分子量分布为2.9，等规度为95％，aPP占共聚聚丙烯总重量的0.7％，EP占共聚聚丙烯总重量的1.7％；
共聚聚丙烯C：分子量为48000，分子量分布为4.8，等规度为91％，aPP占共聚聚丙烯总重量的1.9％，EP占共聚聚丙烯总重量的8％；
共聚聚丙烯D：分子量为27000，分子量分布为2.3，等规度为86％，aPP占共聚聚丙烯总重量的0.3％，EP占共聚聚丙烯总重量的2.1％；
支化聚乙烯A：分子量310000，支化度为13，甲基含量为54％，乙基含量为27％，丙基及含4个碳以上支链含量为19％；
支化聚乙烯B：分子量290000，支化度为11.5，甲基支链含量为56％，乙基含量为26％，丙基及含4个碳以上支链含量为18％；
支化聚乙烯C：分子量270000，支化度为8.7，甲基支链含量为48％，乙基含量为31％，丙基及含4个碳以上支链含量为21％；
非支化聚乙烯7049：分子量190000，支化度为2.13，甲基支链含量为72％，乙基含量为23％，丙基及含4个碳以上支链含量为5％；
成核剂A：2,2'-亚甲基-双(4,6-二叔丁基苯基)磷酸钠；
成核剂B：对二甲基二亚苄基山梨醇；
成核剂C：苯甲酸钠；
抗氧剂：抗氧剂1010/抗氧剂168；
润滑剂：硬脂酸锌。
各项性能测试方法：
(1)耐化学品外观测试：样品在标准环境调节24h后，在其表面滴0.1mL化学品，在室温条件下静置24h，除去化学品并观察色板表面外观变化。
(2)吸油率测试：待力学样条在标准环境调节24h后，称量样品质量M0，浸泡于适量的汽油中，在室温和高温条件下静置24h，取出力学样条后在标准状态下调节30min，除去汽油并称量样品质量Mi；吸油率＝(Mi-M0)÷M0×100％。
(3)性能衰减率测试：参考EN50342-5标准执行，力学样条在标准环境调节24h后，分两组测试。第一组测试吸油前样品拉伸强度K0；第二组标准环境调节后浸泡于适量的化学品中，在室温和高温条件下静置24h，取出力学样条后在标准状态下调节30min，除去表面明显的汽油并测试样品吸油后的拉伸强度Ki；性能衰减率＝(K0-Ki)÷K0×100％；拉伸强度按ISO 527标准执行。
(4)耐黄变评价方法：注塑后的100×100×2mm方板样片置于标准环境调节24h后，采用Color Eye 7000A分光光度计测试方板样片的LAB值，测试完毕后放置入精密恒温老化箱中，设定精密恒温老化箱内温度150℃，换气速率5-10次/hrs，老化时间为72hrs。待老化时间结束，取方板样片至标准环境调节24h后，采用Color Eye 7000A分光光度计测试方板样片的LAB值，得出老化实验前后的b值差异△b，由此评估样品的耐黄变性能。
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
Figure PCTCN2020076585-appb-000001
Figure PCTCN2020076585-appb-000002
续表1
Figure PCTCN2020076585-appb-000003
Figure PCTCN2020076585-appb-000004
从上表的实施例和对比例可以看出，本发明通过对共聚聚丙烯和支化聚乙烯的微观链段结构进行优化筛选，减少分子之间的缠结，提高两种树脂间界面结合力，减少链段及晶格缺陷，配合高效成核剂，使产品具有优良的耐黄变、耐化学品的性能。
从实施例2/3/7可以看出，本发明优选的支化聚乙烯，更有效降低共聚聚丙烯和聚乙烯的界面能，提升了两种树脂间界面结合力，减少链段及晶格缺陷。
从实施例1/4/6可以看出，在本发明的配方中，相比于一般的成核剂，优选的成核剂更能够诱导共聚聚丙烯基体形成等规度高、强度高、晶核细化的α晶型，提高结晶度。

Claims (7)

  1. 一种聚丙烯组合物，其特征在于，按重量份计，包括以下组分：
    共聚聚丙烯             90-100份；
    支化聚乙烯             1-10份；
    成核剂                 0.1-0.5份；
    其中，共聚聚丙烯分子量为25000-30000，分子量分布(MWD)范围为2.5-3.0，共聚聚丙烯等规度范围为90％-95％，aPP占共聚聚丙烯总重量的为0.5％-1.5％，EP占共聚聚丙烯总重量的0.5％-5.0％。
  2. 根据权利要求1所述的聚丙烯组合物，其特征在于，所述的支化聚乙烯的分子量为250000-350000，支化度范围为11.0-15.0，各支链的含量为：甲基支链含量范围为51.0％-60.0％，乙基支链含量范围为25.0％-30.0％，丙基及含4个碳以上的支链含量范围为10.0％-19.0％。
  3. 根据权利要求1所述的聚丙烯组合物，其特征在于，所述的成核剂选自有机磷酸盐类成核剂、山梨醇衍生物类成核剂中的至少一种。
  4. 根据权利要求3所述的聚丙烯组合物，其特征在于，所述的有机磷酸盐类成核剂选自2,2'-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠、2,2'-亚甲基-双(4,6-二叔丁基苯基磷酸)碱式铝、2,2'-亚甲基-双(4,6-二叔丁基苯基)磷酸钠中的至少一种。
  5. 根据权利要求3所述的聚丙烯组合物，其特征在于，所述的山梨醇衍生物类成核剂选自1,3:2,4-二(3,4-二甲基亚苄基)-D-山梨醇、(1,3:2,4)-二亚苄基山梨醇、对二甲基二亚苄基山梨醇中的至少一种。
  6. 根据权利要求1所述的聚丙烯组合物，其特征在于，按重量份计，还包括0.5-10份的助剂；所述的助剂选自抗氧剂、润滑剂、着色剂、热稳定剂、抗紫外线剂中的至少一种。
  7. 权利要求6所述的聚丙烯组合物的制备方法，其特征在于，包括以下步骤：将共聚聚丙烯、支化聚乙烯、助剂、成核剂混合均匀后加入双螺杆挤出机中，进行熔融混炼，熔融混炼温度为190～210℃，螺杆转速为450～550转/分，挤出造粒，得到聚丙烯组合物。
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CN115368675B (zh) * 2022-09-19 2024-03-29 会通新材料股份有限公司 一种易于等离子处理的聚丙烯组合物及其制备方法和应用
CN115386170A (zh) * 2022-09-30 2022-11-25 天津金发新材料有限公司 一种良好油漆附着力聚丙烯复合材料及其制备和应用
CN115386170B (zh) * 2022-09-30 2023-08-08 天津金发新材料有限公司 一种良好油漆附着力聚丙烯复合材料及其制备和应用

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