WO2021057357A1 - 聚丙烯用超低线性膨胀系数母粒及其应用 - Google Patents

聚丙烯用超低线性膨胀系数母粒及其应用 Download PDF

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WO2021057357A1
WO2021057357A1 PCT/CN2020/110659 CN2020110659W WO2021057357A1 WO 2021057357 A1 WO2021057357 A1 WO 2021057357A1 CN 2020110659 W CN2020110659 W CN 2020110659W WO 2021057357 A1 WO2021057357 A1 WO 2021057357A1
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parts
expansion coefficient
linear expansion
ultra
polypropylene
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PCT/CN2020/110659
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English (en)
French (fr)
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钱志军
俞飞
黄险波
叶南飚
罗忠富
陈嘉杰
李志鹏
李振华
吴国峰
杨波
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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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C08K13/02—Organic and 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds

Definitions

  • the invention relates to a masterbatch for polypropylene, in particular to an ultra-low linear expansion coefficient masterbatch for polypropylene and its application.
  • Polypropylene materials are widely used in automobiles, home appliances, packaging, electronic appliances and other fields due to their low price and light weight.
  • polypropylene is a semi-crystalline polymer, which has disadvantages such as large shrinkage rate, poor dimensional stability, and large linear expansion coefficient (abbreviation: CLTE). It is difficult to meet the dimensional requirements of precision parts and the dimensional instability caused by temperature changes.
  • the mainstream of the modified polypropylene industry is to fill modified polypropylene with fillers such as ordinary talc or calcium carbonate.
  • This type of filled modified polypropylene composite can be widely used in automotive interior and exterior trim parts, but for parts with special requirements, such as plastics Fenders, plastic tailgates, etc. have very high requirements for shrinkage and fenders. At this time, ordinary modification cannot meet the existing requirements.
  • Sc 2 W 3 O 12 is a typical negative thermal expansion (NTE) compound.
  • NTE negative thermal expansion
  • the NTE effect exists in a wide temperature range (at least -260 ⁇ 920°C), and it may continue to its melting point ( ⁇ 1652). °C), this unique performance can be used to prepare materials with high precision control, low linear expansion coefficient or zero linear expansion coefficient.
  • Polyborosiloxane is a new type of organic polymer material. It is a polymer obtained by introducing boron element into the silicon oxygen skeleton of polysiloxane. Compared with ordinary organosiloxane, it has more excellent high temperature resistance. And the bonding performance, adding it to the polypropylene material can significantly increase the surface tension of the material, which is conducive to the bonding and spraying of the material surface.
  • Chinese patent CN 106317607 A uses Sc 2 W 3 O 12 as a modifier to reduce CLTE, but dispersibility in polypropylene is a problem;
  • Chinese patent CN 106147034 A uses phlogopite as a modifier, its appearance effect is not good, and The shrinkage rate is only 6 ⁇ 8 ⁇ , and CLTE is 5 ⁇ 7*10 -5 1/K.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide an ultra-low linear expansion coefficient master batch for polypropylene.
  • an ultra-low linear expansion coefficient masterbatch for polypropylene including the following components by weight: Sc 2 W 3 O 12 30-69 parts, polyborosilicate 10-20 parts of alkane, 20-45 parts of base resin and 1-5 parts of surface treatment agent.
  • the present invention uses Sc 2 W 3 O 12 and polyborosiloxane as the main part of the masterbatch, and then cooperates with a surface treatment agent to enhance its dispersion effect in polypropylene, and finally a composite with low linear expansion coefficient and high surface tension can be prepared.
  • the material has made a strong technical reserve for the lightweight of the car.
  • the Sc 2 W 3 O 12 is Sc 2 W 3 O 12 powder, and the particle size D50 of the Sc 2 W 3 O 12 powder is 100-300 nanometers.
  • the matrix resin is at least one of ethylene-butene copolymer, ethylene-octene copolymer, and ethylene-propylene copolymer.
  • the surface treatment agent is at least one of polypropylene grafted maleic anhydride and silane coupling agent.
  • the ultra-low linear expansion coefficient masterbatch for polypropylene further contains the following components by weight: 0.05-0.3 parts of lubricant, 0.05-0.3 parts of light stabilizer, and 0.1-0.6 parts of antioxidant;
  • the lubricant is a stearate lubricant
  • the antioxidant is at least one of a hindered phenolic antioxidant and a phosphite antioxidant
  • the light stabilizer is a hindered amine light stabilizer.
  • the polyborosiloxane is prepared by the following method:
  • step (1) Add 75 to 125 parts by weight of silicon tetrachloride and distilled water to the three-necked flask of step (1), and react for 6 to 8 hours to obtain a hydrolysate.
  • the hydrolysate is washed with deionized water at a temperature of 125 to 135°C. Under reduced pressure distillation to remove small molecules to obtain polyborosiloxane.
  • the metallocene catalyst and the co-catalyst are added for 50-60 minutes, and nitrogen protection is introduced during the whole process; in the step (2), the silicon tetrachloride , The time for adding distilled water is 25-40 minutes, and nitrogen protection is introduced during the whole process.
  • the metallocene catalyst is titanocene dichloride or zirconocene dichloride, and the co-catalyst is trimethylaluminum or triethylaluminum.
  • the present invention also discloses a modified polypropylene material, comprising the above-mentioned ultra-low linear expansion coefficient masterbatch for polypropylene, and the mass percentage of the masterbatch in the modified polypropylene material is 3-15%.
  • the content of the masterbatch is less than 3%, the effect on the linear expansion coefficient is small; when the content of the masterbatch is higher than 15%, the cost of the composite material is higher. Therefore, comprehensive consideration should be given to choosing 3-15 %.
  • the present invention also discloses a preparation method of the said ultra-low linear expansion coefficient masterbatch for polypropylene.
  • the method is: mixing the components uniformly and adding them to a single screw extruder for granulation to obtain The ultra-low linear expansion coefficient masterbatch for polypropylene, wherein the temperature of the single-screw extruder from the feeding section to the die is 170°C, 200°C, 200°C, 210°C, 210°C, 205 °C, 205°C, 205°C, 200°C, 200°C.
  • the present invention uses a special surface treatment agent and a special matrix resin to increase its dispersion effect in polypropylene;
  • the production process of the invention is simple and suitable for mass production.
  • the temperature range is 23°C ⁇ 85°C, the middle position of 150*150*3mm square plate
  • MD means CLTE in the flow direction
  • TD means vertical
  • AVG refers to the average value of MD and TD.
  • the specific surface tension solution preparation comparison table is shown in Table 1. :
  • Matrix resin A ethylene-butene copolymer (POE 7447) supplier: Dow, USA;
  • Matrix resin B ethylene-octene copolymer (POE 8137) supplier: Dow, USA;
  • Matrix resin C ethylene-propylene copolymer (VM6202) supplier: ExxonMobil;
  • Base resin D Polypropylene (EP548R) Supplier: CNOOC and Shell;
  • Surface treatment agent B silane coupling agent (KH550) supplier: Nanjing Xiangqian Chemical Co., Ltd.;
  • Hindered phenol type number SONOX 1010 Manufacturer: Shandong Sanfeng;
  • Phosphite type number SONOX 168 Manufacturer: Shandong Sanfeng;
  • Zinc Stearate Model BS-2818 Manufacturer: Huamingtai Chemical.
  • the ultra-low linear expansion coefficient masterbatch for polypropylene of the present invention, and the ultra-low linear expansion coefficient masterbatch for polypropylene described in this embodiment, contain the following components by weight:
  • polyborosiloxane is prepared by the following method:
  • the components are mixed uniformly and added to a single-screw extruder for granulation to obtain the ultra-low linear expansion coefficient masterbatch for polypropylene.
  • the single-screw extruder is from the feeding section to the die
  • the temperature is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 205°C, 200°C, 200°C.
  • the components are mixed uniformly and added to a single-screw extruder for granulation to obtain the ultra-low linear expansion coefficient masterbatch for polypropylene.
  • the single-screw extruder is from the feeding section to the die
  • the temperature is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 205°C, 200°C, 200°C.
  • the ultra-low linear expansion coefficient masterbatch for polypropylene of the present invention, and the ultra-low linear expansion coefficient masterbatch for polypropylene described in this embodiment, contain the following components by weight:
  • polyborosiloxane is prepared by the following method:
  • the components are mixed uniformly and added to a single-screw extruder for granulation to obtain the ultra-low linear expansion coefficient masterbatch for polypropylene.
  • the single-screw extruder is from the feeding section to the die
  • the temperature is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 205°C, 200°C, 200°C.
  • Comparative example 1 Except that it does not contain Sc 2 W 3 O 12 , the others are the same as in Example 1;
  • Comparative Example 2 Except that it does not contain polyborosiloxane, the others are the same as in Example 1;
  • Example 4 Except that the choice of matrix resin is different from that of Example 1, everything else is the same as that of Example 1.
  • the matrix resin is EP548R;
  • Example 5 Except that the choice of surface treatment agent is different from that of Example 1, everything else is the same as that of Example 1, and the surface treatment agent is CS-101;
  • Comparative Example 1 does not contain Sc 2 W 3 O 12 and has a relatively high linear expansion coefficient
  • Comparative Example 2 does not contain polyborosiloxane and has low interfacial tension, while in Examples 1 to 3 at the same time Containing Sc 2 W 3 O 12 and polyborosiloxane, it also has the characteristics of low linear expansion coefficient and high surface tension; it can be seen that Sc 2 W 3 O 12 and polyborosiloxane lack one of them Both reach not low linear expansion coefficient (CLTE ⁇ 3*10 -5 1/K) and high surface tension (>34.7mN/m).
  • the modified polypropylene material added to the masterbatch of the present invention can effectively reduce CLTE and improve Surface tension provides a strong technical reserve for the development of lightweight automobiles.
  • Example 4 comparing Example 4 with Examples 1 to 3, the matrix resin in Examples 1 to 3 is one of ethylene-butene copolymer, ethylene-octene copolymer, and ethylene-propylene copolymer.
  • the matrix resin in Example 4 is polypropylene EP548R; by comparison, it is found that the CLTE and surface tension of Example 4 are lower than those of Examples 1 to 3;
  • Example 5 Comparing Example 5 with Examples 1 to 3, the surface treatment agent in Examples 1 to 3 is one of polypropylene grafted maleic anhydride and silane coupling agent, while the surface treatment agent in Example 4 It is a titanate coupling agent CS-101; by comparison, it is found that the CLTE and surface tension of Example 5 are lower than those of Examples 1 to 3.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种聚丙烯用超低线性膨胀系数母粒，包括以下重量份的组分：Sc 2W 3O 1230～69份、聚硼硅氧烷10～20份、基体树脂20～45份和表面处理剂1～5份。采用Sc 2W 3O 12和聚硼硅氧烷作为母粒的主体部分，再配合表面处理剂加强其在聚丙烯中分散效果，最终制备出低线性膨胀系数和高表面张力的复合材料。同时，还公开一种所述聚丙烯用超低线性膨胀系数母粒的制备方法及应用。

Description

[根据细则37.2由ISA制定的发明名称]　聚丙烯用超低线性膨胀系数母粒及其应用 技术领域
本发明涉及一种聚丙烯用母粒，尤其是一种聚丙烯用超低线性膨胀系数母粒及其应用。
背景技术
聚丙烯材料由于其价格低廉质轻等优点，广泛应用于汽车、家电、包装、电子电器等领域。但是聚丙烯是半结晶聚合物，本身存在收缩率大、尺寸稳定性差、线性膨胀系数(简称：CLTE)大等缺点，较难满足精密零部件的尺寸要求和温差变化带来的尺寸不稳定。目前改性聚丙烯行业主流是利用普通滑石粉或碳酸钙等填料填充改性聚丙烯，此类填充改性聚丙烯复合可广泛应用于汽车内外饰件，但是对于特殊要求的零部件，如塑料翼子板、塑料尾门等对收缩率和翼子板都提出了很高的要求，这时普通改性是满足不了现有要求的。
Sc 2W 3O 12是一种典型的负热膨胀化合物(negative thermal expansion，简称NTE)，在很宽的温度范围(至少-260～920℃)存在NTE效应，并可能持续到其熔点(～1652℃)，这种独特的性能可以用于制备高精控、低线性膨胀系数或零线性膨胀系数的材料。
聚硼硅氧烷是一种新型的有机高分子材料，它是将硼元素引入聚硅氧烷的硅氧骨架中而得到的聚合物，较普通的有机硅氧烷有更加优异的耐高温性能和粘接性能，将其加入到聚丙烯材料中可显著提高材料的表面张力，有利于材料表面的粘接和喷涂。
中国专利CN 106317607 A采用Sc 2W 3O 12作为降低CLTE的改性剂，但是在聚丙烯中分散性是个难题；中国专利CN 106147034 A采用金云母作为改性剂，其外观效果不好，另外收缩率也只是6～8‰，CLTE为5～7*10 -51/K。
发明内容
基于此，本发明的目的在于克服上述现有技术的不足之处而提供一种聚丙 烯用超低线性膨胀系数母粒。
为实现上述目的，本发明所采取的技术方案为：一种聚丙烯用超低线性膨胀系数母粒，包括以下重量份的组分：Sc 2W 3O 1230～69份、聚硼硅氧烷10～20份、基体树脂20～45份和表面处理剂1～5份。
本发明采用Sc 2W 3O 12和聚硼硅氧烷作为母粒的主体部分，再配合表面处理剂加强其在聚丙烯中分散效果，最终可以制备出低线性膨胀系数和高表面张力的复合材料，为汽车的轻量化做了强大的技术储备。
优选地，所述Sc 2W 3O 12为Sc 2W 3O 12粉末，所述Sc 2W 3O 12粉末的粒径D50为100～300纳米。
优选地，所述基体树脂为乙烯-丁烯共聚物、乙烯-辛烯共聚物、乙烯-丙烯共聚物中的至少一种。
优选地，所述表面处理剂为聚丙烯接枝马来酸酐、硅烷偶联剂中的至少一种。
优选地，所述的聚丙烯用超低线性膨胀系数母粒，还包含以下重量份的成分：润滑剂0.05～0.3份、光稳剂0.05～0.3份和抗氧剂0.1～0.6份；所述润滑剂为硬脂酸盐类润滑剂，所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂中的至少一种，所述光稳剂为受阻胺类光稳剂。
优选地，所述聚硼硅氧烷通过以下方法制备所得：
(1)制备聚硼硅氧烷中间体
将100重量份的三乙氧基硼烷和0.8～8重量份的四氯化硅置于三口烧瓶中，在85～95℃下加热、搅拌，然后缓慢加入0.006～0.025重量份的茂金属催化剂和0.02～0.04重量份的助催化剂，反应6～8小时，得到聚硼硅氧烷中间体；
(2)制备聚硼硅氧烷
在步骤(1)的三口烧瓶中加入75～125重量份的四氯化硅、蒸馏水，反应6～8小时，得到水解产物，将所得水解产物进行去离子水洗涤，在125～135℃的温度下进行减压蒸馏去除小分子，得到聚硼硅氧烷。
优选地，所述步骤(1)中，所述茂金属催化剂和助催化剂加入的时间为50～60分钟，整个过程中通入氮气保护；所述步骤(2)中，所述四氯化硅、蒸馏水加入的时间为25～40分钟，整个过程中通入氮气保护。
优选地，所述步骤(1)中，所述茂金属催化剂为二氯二茂钛或二氯二茂锆，所述助催化剂为三甲基铝或三乙基铝。
同时，本发明还公开一种改性聚丙烯材料，包含上述聚丙烯用超低线性膨胀系数母粒，所述母粒在改性聚丙烯材料中的质量百分含量为3-15％。当所述母粒的含量低于3％时，对线性膨胀系数影响效果较小；当所述母粒的含量高于15％时，复合材料的成本较高，因此，综合考虑选择3-15％。
此外，本发明还公开一种所述的聚丙烯用超低线性膨胀系数母粒的制备方法，所述方法为：将各组分混合均匀，加入到单螺杆挤出机中进行造粒，得到所述聚丙烯用超低线性膨胀系数母粒，其中，所述单螺杆挤出机，从喂料段到机头的温度依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃。
相对于现有技术，本发明的有益效果为：
1、本发明通过Sc 2W 3O 12和聚硼硅氧烷复配，可以同时兼顾线性膨胀系数和表面张力；
2、本发明使用特殊的表面处理剂和特殊的基体树脂，增加了其在聚丙烯中分散效果；
3、本发明生产工艺简单、适合大批量生产。
具体实施方式
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明；以下实施例只是本发明的典型例，本发明的保护范围并不局限于此。
本发明实施例及对比例中具体性能的测试方法如下：
(1)线性膨胀系数(简称：CLTE)
按ISO 11359测试，温度范围23℃～85℃，150*150*3mm方板中间位置截
取10*10*3mm尺寸样片进行测试，MD是指流动方向的CLTE，TD是指垂
直流动方向的CLTE，AVG是指MD与TD的平均值。
(2)表面张力
表面张力按照Ford BO 116-03标准进行测试分析，按照福特主机厂的标准，水+乙醇＝50ml，通过不同比例配制得到不同的表面张力测试溶液，具体表面张力溶液配制对比表如表1所示：
表1 表面张力溶液配制对比表
序号 水/ml 乙醇/ml 表面张力/(mN/m)
1 0 50 22.3
2 1.25 48.75 22.8
3 5.25 44.75 24.2
4 9.5 40.5 26.1
5 13.25 36.75 27.5
6 17.5 32.5 29.5
7 21.25 28.75 31.5
8 24.25 25.75 33
9 27 23 34.7
10 29.5 20.5 36.9
11 31.75 18.25 39.3
12 33.75 16.25 42.5
13 35.75 14.25 48
14 37.35 12.65 48.8
15 39 11 51.7
16 40.15 9.85 53.7
17 41.5 8.5 56
18 43.5 6.5 59.5
19 45.35 4.65 62.7
20 46.85 3.15 65.7
21 48.25 1.75 68.7
22 49.5 0.5 71
23 50 0 72
本发明实施例和对比例中用到的主要代表材料如下，其他未做说明的原料，均为本领域所公知的可市购产品：
基体树脂：
基体树脂A：乙烯-丁烯共聚物(POE 7447)供应商：美国陶氏；
基体树脂B：乙烯-辛烯共聚物(POE 8137)供应商：美国陶氏；
基体树脂C：乙烯-丙烯共聚物(VM6202)供应商：美国埃克森美孚；
基础树脂D：聚丙烯(EP548R)供应商：中海壳牌；
表面处理剂：
表面处理剂A：聚丙烯接枝马来酸酐(CA100)供应商：法国阿克玛；
表面处理剂B：硅烷偶联剂(KH550)供应商：南京向前化工有限公司；
表面处理剂C：钛酸酯偶联剂(CS-101)供应商：南京创世化工助剂有限公司；
聚丙烯PP：
PP：H9018(均聚，MFR＝50-60g/10min)供应商：兰州石化；
填料：
特殊填料：HAR T84(1250目滑石粉，径厚比30)供应商：法国Imerys；
抗氧剂：
受阻酚类型号：SONOX 1010       厂家：山东三丰；
亚磷酸酯类型号：SONOX 168      厂家：山东三丰；
光稳定剂：
受阻胺类 型号：UV-3808PP5    厂家：比利时索尔维；
润滑剂：
硬脂酸锌 型号：BS-2818    厂家：华明泰化工。
Sc 2W 3O 12
Sc 2W 3O 12粉末，粒径D50为100～300纳米，厂家：金发科技股份有限公司。
实施例1
本发明所述聚丙烯用超低线性膨胀系数母粒，本实施例所述聚丙烯用超低线性膨胀系数母粒，包含以下重量份的成分：
Sc 2W 3O 1230份、聚硼硅氧烷10份、基体树脂POE 7447 20份、表面处理剂CA100 5份、润滑剂(硬脂酸锌BS-2818)0.05份、光稳剂(受阻胺类UV-3808PP5)0.05份、抗氧剂0.1份(SONOX 1010:SONOX 168＝1:1)；
其中，聚硼硅氧烷由如下方法制得：
第一步：制备聚硼硅氧烷中间体
首先称取100份的三乙氧基硼烷和0.8份的四氯化硅于5000ml的三口烧瓶中，置于加热套中加热、搅拌(温度保持85℃、搅拌速度保持220转/分钟)，接着同时且缓慢加入0.006份茂金属催化剂(茂金属催化剂为二氯二茂钛)和0.02份助催化剂(助催化剂为三甲基铝)，加完催化剂后反应6小时(反应过程中一直处于加热和搅拌状态)，得聚硼硅氧烷中间体；茂金属催化剂和助催化剂缓慢加入的时间为50分钟。整个过程中需要通入氮气保护。
第二步：制备聚硼硅氧烷
接着同时称取75份的四氯化硅和过量的蒸馏水(如：1000份)缓慢加入三口烧瓶中，加完后进行反应6小时，最后得水解产物。所得水解产物进行去离子水洗涤，最后在125℃的温度下进行减压蒸馏去除小分子，最后得聚硼硅氧烷；第二步中的四氯化硅和过量的蒸馏水缓慢加入的时间为25分钟。整个过程中需要通入氮气保护。
将各组分混合均匀，加入到单螺杆挤出机中进行造粒，得到所述聚丙烯用超低线性膨胀系数母粒，其中，所述单螺杆挤出机，从喂料段到机头的温度依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃。
将3重量份上述聚丙烯用超低线性膨胀系数母粒加入到改性聚丙烯材料(77重量份PPH9018、20重量份滑石粉HAR T84)中，测得性能见表2。
实施例2
本发明所述聚丙烯用超低线性膨胀系数母粒，本实施例所述聚丙烯用超低线性膨胀系数母粒，包含以下重量份的成分：
Sc 2W 3O 1269份、聚硼硅氧烷20份、基体树脂POE 8137为20份、基体树脂VM6202为25份、表面处理剂KH550为1份、润滑剂(硬脂酸锌BS-2818)0.3份、光稳剂(受阻胺类UV-3808PP5)0.3份、抗氧剂0.6份(SONOX 1010:SONOX 168＝1:2)；
其中，聚硼硅氧烷由如下方法制得：
第一步：制备聚硼硅氧烷中间体
首先称取100份的三乙氧基硼烷和8份的四氯化硅于5000ml的三口烧瓶中，置于加热套中加热、搅拌(温度保持95℃、搅拌速度保持220转/分钟)，接着同时且缓慢加入0.025份茂金属催化剂(茂金属催化剂为二氯二茂锆)和0.04份助催化剂(助催化剂为三乙基铝)，加完催化剂后反应8小时(反应过程中一直处于加热和搅拌状态)，得聚硼硅氧烷中间体；茂金属催化剂和助催化剂缓慢加入的时间为60分钟，整个过程中需要通入氮气保护。
第二步：制备聚硼硅氧烷
接着同时称取125份的四氯化硅和过量的蒸馏水(如：1000份)缓慢加入三口烧瓶中，加完后进行反应8小时，最后得水解产物。所得水解产物进行去离子水洗涤，最后在135℃的温度下进行减压蒸馏去除小分子，最后得聚硼硅氧烷；第二步中的四氯化硅和过量的蒸馏水缓慢加入的时间为40分钟，整个过程中需要通入氮气保护。
将各组分混合均匀，加入到单螺杆挤出机中进行造粒，得到所述聚丙烯用超低线性膨胀系数母粒，其中，所述单螺杆挤出机，从喂料段到机头的温度依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃。
将15重量份上述聚丙烯用超低线性膨胀系数母粒加入到改性聚丙烯材料(70重量份PP H9018、15重量份滑石粉HAR T84)中，测得性能见表2。
实施例3
本发明所述聚丙烯用超低线性膨胀系数母粒，本实施例所述聚丙烯用超低线性膨胀系数母粒，包含以下重量份的成分：
Sc 2W 3O 1244份、聚硼硅氧烷17份、基体树脂POE 7447 13份、基体树脂VM6202为21份、表面处理剂KH550为1份、表面处理剂CA100为1.3份、润滑剂(硬脂酸锌BS-2818)0.16份、光稳剂(受阻胺类UV-3808PP5)0.21份、抗氧剂0.45份(SONOX 1010:SONOX 168＝1:2)；
其中，聚硼硅氧烷由如下方法制得：
第一步：制备聚硼硅氧烷中间体
首先称取100份的三乙氧基硼烷和4.3份的四氯化硅于5000ml的三口烧瓶中，置于加热套中加热、搅拌(温度保持85℃、搅拌速度保持220转/分钟)，接着同时且缓慢加入0.011份茂金属催化剂(茂金属催化剂为二氯二茂钛)和0.02份助催化剂(助催化剂为三乙基铝)，加完催化剂后反应6.7小时(反应过程中一直处于加热和搅拌状态)，得聚硼硅氧烷中间体；茂金属催化剂和助催化剂缓慢加入的时间为54分钟，整个过程中需要通入氮气保护。
第二步：制备聚硼硅氧烷
接着同时称取82份的四氯化硅和过量的蒸馏水(如：1000份)缓慢加入三口烧瓶中，加完后进行反应6.8小时，最后得水解产物。所得水解产物进行去离子水洗涤，最后在125℃的温度下进行减压蒸馏去除小分子，最后得聚硼硅氧烷；第二步中的四氯化硅和过量的蒸馏水缓慢加入的时间为29分钟。整个过程中需要通入氮气保护。
将各组分混合均匀，加入到单螺杆挤出机中进行造粒，得到所述聚丙烯用超低线性膨胀系数母粒，其中，所述单螺杆挤出机，从喂料段到机头的温度依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃。
将12重量份上述聚丙烯用超低线性膨胀系数母粒加入到改性聚丙烯材料(70重量份PP H9018、18重量份滑石粉HAR T84)中，测得性能见表2。
对比例1：除不含有Sc 2W 3O 12外，其他均与实施例1相同；
对比例2：除不含有聚硼硅氧烷外，其他均与实施例1相同；
实施例4：除基体树脂的选择与实施例1不同外，其他均与实施例1相同，其基体树脂为EP548R；
实施例5：除表面处理剂的选择与实施例1不同外，其他均与实施例1相同，其表面处理剂为CS-101；
表2 实施例1-5与对比例1-2聚丙烯复合材料的CLTE和表面张力
Figure PCTCN2020110659-appb-000001
从表2可以看出，对比例1不含有Sc 2W 3O 12，线性膨胀系数较高；对比例2中不含有聚硼硅氧烷，界面张力较低，而实施例1～3中同时含有Sc 2W 3O 12和聚硼硅氧烷，同时具有低线性膨胀系数和高表面张力的特点；由此可知，Sc 2W 3O 12和聚硼硅氧烷，两者缺少其中之一都达到不低线性膨胀系数(CLTE＜3*10 -51/K)和高表面张力(＞34.7mN/m)，本发明的母粒加入的改性聚丙烯材料中可有效降低CLTE和提高表面张力，对汽车轻量化的发展提供的强有力的技术储备。
此外，将实施例4与实施例1～3进行对比，实施例1～3中的基体树脂为乙烯-丁烯共聚物、乙烯-辛烯共聚物、乙烯-丙烯共聚物中的一种，而实施例4中的基体树脂为聚丙烯EP548R；通过对比发现，实施例4的CLTE与表面张力都不及实施例1～3；
将实施例5与实施例1～3进行对比，实施例1～3中的表面处理剂为聚丙烯接枝马来酸酐、硅烷偶联剂中的一种，而实施例4中的表面处理剂为钛酸酯偶联剂CS-101；通过对比发现，实施例5的CLTE与表面张力都不及实施例1～3。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种聚丙烯用超低线性膨胀系数母粒，其特征在于，包括以下重量份的组分：Sc 2W 3O 1230～69份、聚硼硅氧烷10～20份、基体树脂20～45份和表面处理剂1～5份。
  2. 如权利要求1所述的聚丙烯用超低线性膨胀系数母粒，其特征在于，所述Sc 2W 3O 12为Sc 2W 3O 12粉末，所述Sc 2W 3O 12粉末的粒径D50为100～300纳米。
  3. 如权利要求1所述的聚丙烯用超低线性膨胀系数母粒，其特征在于，所述基体树脂为乙烯-丁烯共聚物、乙烯-辛烯共聚物、乙烯-丙烯共聚物中的至少一种。
  4. 如权利要求1所述的聚丙烯用超低线性膨胀系数母粒，其特征在于，所述表面处理剂为聚丙烯接枝马来酸酐、硅烷偶联剂中的至少一种。
  5. 如权利要求1所述的聚丙烯用超低线性膨胀系数母粒，其特征在于，还包含以下重量份的成分：润滑剂0.05～0.3份、光稳剂0.05～0.3份和抗氧剂0.1～0.6份；所述润滑剂为硬脂酸盐类润滑剂，所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂中的至少一种，所述光稳剂为受阻胺类光稳剂。
  6. 如权利要求1～5任一项所述的聚丙烯用超低线性膨胀系数母粒，其特征在于，所述聚硼硅氧烷通过以下方法制备所得：
    (1)制备聚硼硅氧烷中间体
    将100重量份的三乙氧基硼烷和0.8～8重量份的四氯化硅置于三口烧瓶中，在85～95℃下加热、搅拌，然后缓慢加入0.006～0.025重量份的茂金属催化剂和0.02～0.04重量份的助催化剂，反应6～8小时，得到聚硼硅氧烷中间体；
    (2)制备聚硼硅氧烷
    在步骤(1)的三口烧瓶中加入75～125重量份的四氯化硅、蒸馏水，反应6～8小时，得到水解产物，将所得水解产物进行去离子水洗涤，在125～135℃的温度下进行减压蒸馏去除小分子，得到聚硼硅氧烷。
  7. 如权利要求6所述的聚丙烯用超低线性膨胀系数母粒，其特征在于，所 述步骤(1)中，所述茂金属催化剂和助催化剂加入的时间为50～60分钟，整个过程中通入氮气保护；所述步骤(2)中，所述四氯化硅、蒸馏水加入的时间为25～40分钟，整个过程中通入氮气保护。
  8. 如权利要求6所述的聚丙烯用超低线性膨胀系数母粒，其特征在于，所述步骤(1)中，所述茂金属催化剂为二氯二茂钛或二氯二茂锆，所述助催化剂为三甲基铝或三乙基铝。
  9. 一种改性聚丙烯材料，其特征在于，包含如权利要求1～8任一项所述的聚丙烯用超低线性膨胀系数母粒，所述母粒在改性聚丙烯材料中的质量百分含量为3-15％。
  10. 一种如权利要求1～9任一项所述的聚丙烯用超低线性膨胀系数母粒的制备方法，其特征在于，所述方法为：将各组分混合均匀，加入到单螺杆挤出机中进行造粒，得到所述聚丙烯用超低线性膨胀系数母粒，其中，所述单螺杆挤出机，从喂料段到机头的温度依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃。
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CN110511477A (zh) * 2019-09-26 2019-11-29 金发科技股份有限公司 一种聚丙烯用超低线性膨胀系数母粒及其应用

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