CN1479766A - 聚烯烃树脂组合物 - Google Patents

聚烯烃树脂组合物 Download PDF

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CN1479766A
CN1479766A CNA008200904A CN00820090A CN1479766A CN 1479766 A CN1479766 A CN 1479766A CN A008200904 A CNA008200904 A CN A008200904A CN 00820090 A CN00820090 A CN 00820090A CN 1479766 A CN1479766 A CN 1479766A
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resin composition
silicon
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polyethylene
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CN1247686C (zh
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金锡湲
金荣元
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Hanwha TotalEnergies Petrochemical Co Ltd
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Samsung General Chemicals 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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions 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
    • C08L51/06—Compositions 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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

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  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

本发明涉及聚烯烃树脂组合物，其包含(100)重量份的聚丙烯树脂，5－45重量份的无机填料和2－20重量份的硅接枝改性的聚乙烯。本发明的聚烯烃树脂组合物用于电子用具的各种外壳和机动车的零件，因为它具有几乎不退化的机械性能，以及具有杰出的耐划伤性，树脂流动性和脱模性。

Description

聚烯烃树脂组合物
技术领域
本发明涉及聚烯烃树脂组合物。更具体地，本发明涉及聚烯烃树脂组合物，其为具有极好耐划伤性和模压性能的复合树脂组合物，用于电子用具外壳和车用零件的材料。
背景技术
通常聚丙烯树脂具有低比重和良好的模压性能，并且可容易地再循环。聚丙烯树脂也显示优异的耐热、溶剂和化学品性。然而，聚丙烯树脂在耐划伤性和表面硬度方面是有缺陷的。尤其是，为了提高抗弯刚度和耐热性而添加了无机填料的聚丙烯树脂广泛用于家用电器产品的外壳和机动车的内部零件。但是，由于树脂中滑石的含量增加，抗弯刚度和耐热性提高，而耐划伤性降低，并且如果是复杂制品，在注射成型过程中不能适当形成模塑制品。迄今为止，进行了大量研究以解决这些问题。
作为一个代表性实例，韩国专利号117,571公开了通过使用无机填料使得在聚丙烯基体、橡胶组分和无机填料之间具有提高的结合力的聚丙烯树脂，所述无机填料用氨基硅烷偶联剂和用具有环氧化物官能团的α，β-不饱和酸的酯改性的乙烯-α-烯烃共聚的橡胶处理过，和韩国专利号52,816公开了通过使用用具有环氧化物官能团的α，β-不饱和酸的酯改性的乙烯-α-烯烃共聚的橡胶和用不饱和碳氢酸或它的衍生物改性的聚烯烃，使得在聚丙烯基体和橡胶组分之间具有提高的结合力，因而提高了耐划伤性和冲击强度的聚丙烯树脂。同样，日本公开的出版物Sho-53-118,055公开了通过使用玻璃纤维或薄片型云母而具有提高的耐划伤性的聚丙烯树脂，日本公开的出版物Sho-56-88,447公开了通过将用作基体的聚丙烯树脂的乙烯含量限制在某一范围，而具有提高的耐划伤性的聚丙烯树脂。
但即使用上述提及的方法，耐划伤性的改善是不够的。而且，在韩国专利号117,571和52,816中，其使用了用具有环氧化物官能团的α，β-不饱和酸的酯改性的乙烯-α-烯烃共聚的橡胶，由于加入了橡胶组分，树脂的抗弯刚性和流动性降低。同样，在日本公开的出版物Sho-53-118,055中，其使用了玻璃纤维或薄片型云母，树脂的流动性降低，并且外观变差，在Sho-56-88,447中，其限制了聚丙烯树脂的乙烯含量，由于吸收冲击的乙烯含量降低，模压性能也降低。
发明内容
本发明的目的是克服现有技术的缺陷，并提供具有改善的冲击强度，模压性能，流动性，外观和耐划伤性的聚烯烃树脂组合物。
本发明的聚烯烃树脂组合物包含100重量份的聚丙烯，5-45重量份的无机填料，和2-20重量份硅接枝的变形(metamotphic)聚乙烯。本发明的聚烯烃树脂组合物是新的树脂组合物，其比现有技术的聚烯烃树脂组合物显示更好的耐划伤性，树脂流动性和模压性能，而不损坏机械特征。
现在将详细描述本发明。
可在本发明的树脂组合物中使用的聚丙烯的实例是均聚物，嵌段共聚物，无规共聚物或三元共聚物，或它们的混合物。依照产品需要的特征可改变聚丙烯的类型。在需要耐冲击性的产品中，例如，使用嵌段共聚物，并且当弯曲模量比耐冲击性更重要时，使用均聚物。
为了加强聚丙烯树脂的物理性能，在本发明的树脂组合物中使用的无机填料的实例是一种或多种选自滑石，碳酸钙，玻璃纤维，云母和二氧化硅的物质。特别地，优选滑石和碳酸钙，因为它们在提高耐热性，弹性弯曲模量和比例稳定性以及考虑功效的成本效率方面是有效的。在本发明中，滑石的平均粒度为5-10微米，优选含量为5-45重量份。当滑石含量低于5重量份时，不能充分提高耐划伤性，当滑石含量高于45重量份时，会出现外观差的问题。
通过混合聚乙烯树脂、硅油、交联剂和交联活性助剂，并且通过利用反应挤出方法交联聚乙烯和硅来制备硅接枝的变形聚乙烯。除了硅油以外，硅接枝的聚乙烯不引起白化现象，不胶粘，并具有减少表面摩擦系数的优点。硅接枝的聚乙烯的优选含量是2-20重量份，或更优选5-10重量份。当含量低于20重量份时，难以提高耐划伤性，当含量高于20重量份时，弹性弯曲模量降低以及生产成本增加。
下面，参考实施例将更详细的描述本发明。
实施本发明的最佳方式
聚烯烃树脂的制备
通过干混合100重量份的聚丙烯树脂，20重量份用作无机填料的滑石和5重量份的硅接枝的聚乙烯(Luboten；OPTATECH Co.，)，然后通过引入到双螺杆挤出装置，以板状形式来制备聚烯烃树脂。
实施例和比较例
通过干混合表1和2中的每种物质，然后通过在双螺杆挤出装置中以熔融状态混合它们，以板状形式来制备树脂组合物，通过使用注塑机来生产样品，并用下述方法进行评估。
测试物理性能的方法
1.悬臂梁式冲击试验(切口部分)：ASTM D 256
2.弹性弯曲模量：ASTM D 789评估结果的表示：◎：杰出，△：良好，×：差
3.流动性：通过使用注塑机测量旋流值来比较流动性。(测试条件：压力40巴，注射时间25秒，冷却时间40秒，模具温度50℃)
4.模压性能：通过使用注塑机，在生产产品过程中，当样品从模具中渗出时，进行模压性能的感观评估。评估结果的表示：◎：杰出，△：良好，×：差
5.耐划伤性的评估：用平板型耐磨耗试验机测试每种组成的样品，并肉眼检查划伤程度。
评估结果的表示：◎：由于完全划伤没有变白，
○：由于划伤有非常少的变白
△：由于划伤但不严重，有一些变白
×：由于划伤严重变白表1
项目                          实施例
    1     2     3     4     5
聚丙烯树脂滑石硅接枝的PE     100202     100205     1002010     1002015     1002020
悬臂梁式冲击强度(kg.cm/cm)     6     7     8     8     9
弹性弯曲模量(Mpa)     ◎     ◎     ◎     ◎     △
流动性(mm)     132     134     135     138     142
模压性能     △     ◎     ◎     ◎     ◎
耐划伤性     ◎     ◎     ◎     ◎     ◎
表2
项目                     比较例
  1   2   3   4   5   6   7
聚丙烯树脂滑石硅接枝的PE乙烯-α-烯烃共聚物橡胶云母   100205   1002010   100203   100205   1002010   1002010   1002020
悬臂梁式冲击强度(kg.cm/cm)   7   8   8   9   12   7   5
弹性弯曲模量(Mpa)   ◎   ◎   ◎   △   ×   ◎   ◎
流动性(mm)   134   135   120   115   110   133   125
模压性能   ◎   ◎   △   ◎   ◎   ×   ×
耐划伤性   ◎   ◎   ×   ×   △   ×   ×
通过使用硅接枝的聚乙烯和通过加入适量的无机填料提高了聚乙烯基体树脂和无机填料的粘合性，提高了流动性，模压性能，耐划伤性和弹性弯曲模量，同时保持了耐冲击性。

Claims (3)

1.一种聚烯烃树脂组合物，其包含100重量份的聚丙烯，5-45重量份的无机填料，和2-20重量份的硅接枝的聚乙烯。
2.权利要求1的聚烯烃树脂组合物，其中所述无机填料是一种或多种选自滑石，碳酸钙，玻璃纤维，云母和二氧化硅的材料。
3.权利要求1的聚烯烃树脂组合物，其中通过混合聚乙烯树脂、硅油、交联剂和交联活性助剂，和通过利用反应挤出方法交联聚乙烯和硅来制备所述硅接枝的聚乙烯。
CNB008200904A 2000-12-22 2000-12-22 聚烯烃树脂组合物 Expired - Fee Related CN1247686C (zh)

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AT (1) ATE305490T1 (zh)
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CN111925598A (zh) * 2020-09-27 2020-11-13 江苏金发科技新材料有限公司 一种耐划伤聚丙烯复合材料及其制备方法

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EP1362080B1 (en) 2005-09-28
EP1362080A1 (en) 2003-11-19
CN1247686C (zh) 2006-03-29
DE60022915T2 (de) 2006-06-29
WO2002051934A1 (en) 2002-07-04
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