CN113354914B - 一种可低温爆破聚丙烯复合材料及其制备方法和应用 - Google Patents

一种可低温爆破聚丙烯复合材料及其制备方法和应用 Download PDF

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CN113354914B
CN113354914B CN202110542310.6A CN202110542310A CN113354914B CN 113354914 B CN113354914 B CN 113354914B CN 202110542310 A CN202110542310 A CN 202110542310A CN 113354914 B CN113354914 B CN 113354914B
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polypropylene
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composite material
parts
ethylene
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CN113354914A (zh
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钱志军
陈平绪
黄险波
俞飞
唐宇航
郭唐华
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Kingfa Science and Technology Co Ltd
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Abstract

本发明公开了一种可低温爆破聚丙烯复合材料及其制备方法和应用。该聚丙烯复合材料包括以下重量份数的组分：特殊聚丙烯A 35～75份，特殊聚丙烯B 3～10份，填料15～30份，特殊增韧剂2～10份，增韧剂15～25份，润滑剂0.1～0.3份，光稳剂0.1～0.3份，抗氧剂0.2～0.6份；其中，特殊增韧剂包括超高分子量聚乙烯和茂金属乙烯‑丙烯共聚物。通过使用特殊聚丙烯A、特殊聚丙烯B、特殊增韧剂结合普通填料和增韧剂制备出可低温爆破且具有良好刚性的聚丙烯复合材料，具有广泛的应用前景(如可低温爆破无包覆立柱等汽车内饰零部件中)。

Description

一种可低温爆破聚丙烯复合材料及其制备方法和应用
技术领域
本发明属于聚丙烯复合材料技术领域，具体涉及一种可低温爆破聚丙烯复合材料及其制备方法和应用。
背景技术
汽车立柱作为一种汽车内饰件，里面都会集成安全气囊，能够对车内乘客在受到意外冲击时进行防护。因此，立柱材料必须达到一定的耐低温冲击要求。传统的汽车立柱材料通常采用聚丙烯、滑石粉以及热塑性弹性体共混制备而成，耐低温性能差，韧性差，不能满足汽车内饰件的要求和标准。
目前改性聚丙烯行业，立柱材料的配方体系大部分是由滑石粉、普通乙烯-丙烯嵌段共聚聚丙烯(分散性指数PDI在2～5)、常规增韧剂POE(乙烯-辛烯无规共聚物)、抗氧剂、润滑剂、光稳剂组成。其中公开号为CN111763399A也有采用高密度聚乙烯和乙烯-辛烯无规共聚物共同使用来进行聚丙烯增韧改性，但在提高了材料韧性(如悬臂梁缺口冲击强度为49KJ/m2)的同时，刚性(如拉伸强度为16.7MPa、弯曲强度为22.3MPa、弯曲模量为1530MPa)没有明显提高。现有技术中公开的聚丙烯复合材料没有获得令人满意的低温冲击韧性和良好的刚性的综合性能。
因此，开发一种可低温爆破且刚性好的无包覆立柱材料具有重要的研究意义和经济价值。
发明内容
为克服现有技术中无法同时保证汽车立柱材料低温冲击韧性和良好的刚性的综合性能问题，本发明的目的在于提供一种聚丙烯复合材料。本发明通过以特定比例的超高分子量聚乙烯和茂金属乙烯-丙烯共聚物作为特殊增韧剂，配合特殊聚丙烯A和特殊聚丙烯B制备出了满足低温-35℃爆破要求且具有良好刚性的聚丙烯复合材料。
本发明的另一目的在于提供上述聚丙烯复合材料的制备方法。
本发明的另一目的在于提供上述聚丙烯复合材料在制备汽车无包覆立柱材料中的应用。
为实现上述发明目的，本发明采用如下技术方案：
一种聚丙烯复合材料，包括以下重量份数的组分：特殊聚丙烯A 35～75份、特殊聚丙烯B 3～10份、填料15～30份、特殊增韧剂2～10份、增韧剂15～25份、润滑0.1～0.3份、光稳剂0.1～0.3份、抗氧剂0.2～0.6份；
所述特殊聚丙烯A为乙烯、丙烯合成的二元嵌段共聚聚丙烯；
所述特殊聚丙烯B为由1-丁烯、乙烯、丙烯合成的三元无规共聚聚丙烯；
所述特殊增韧剂为超高分子量聚乙烯和茂金属乙烯-丙烯共聚物复配，质量比为(2～9):1；其中，超高分子量聚乙烯的分子量不低于100万。
专利CN111763399A采用聚丙烯A和聚丙烯B复配作为改性PP的基料，可同时满足良外观和低温爆破性能；同时采用高密度聚乙烯和常规增韧剂乙烯-辛烯无规共聚物共同使用来进行聚丙烯增韧改性，可提升材料的光泽度和低温韧性，对复合材料的外观和低温爆破有很大的益处。但从其性能测试结果可看出，在改善了材料外观并提高了材料韧性的同时，材料的刚性(例如拉伸强度、弯曲强度)没有明显提高。
超高分子量聚乙烯(UHMWPE)是指相对分子量在100万以上的聚乙烯，是一种在工程塑料中综合性能最佳的新型工程塑料。超高分子量聚乙烯分子结构排列与普通聚乙烯完全相同，但由于它非常高的相对分子量，具有了许多普通聚乙烯材料所不具备的优异性能：如耐磨损性能卓越、冲击强度极高、不易粘附异物，滑动时有优良的抗粘着性等。由于其优异的拉伸强度和断裂伸长率，冲击强度比聚碳酸酯还高1.5倍；与含有乙烯链节的共聚型聚丙烯相容性好，进行共混改性时效果显著。
茂金属乙烯-丙烯共聚物的主要成分为丙烯，乙烯含量较少。该聚合物的结晶度很低，具有很强的非晶态特征，并且表现出其它烯烃弹性体材料所无法获得的优良弹性。作为新型弹性体可很好地用于聚丙型改性，增强其弹性和韧性。
在本发明的技术方案中，以超高分子量聚乙烯和茂金属乙烯-丙烯共聚物特定比例复配作为特殊增韧剂对聚丙烯进行增韧改性。其中超高分子量聚乙烯的分子量大，在复合材料中起到交织网络的作用，从而可以提高复合材料的韧性；而茂金属乙烯-丙烯共聚物可起到聚丙烯和聚乙烯相容剂的作用，进一步增强复合材料的综合性能，特别是刚性。
本发明通过使用特殊聚丙烯A和特殊聚丙烯B作为改性PP的基料，并以超高分子量聚乙烯和茂金属乙烯-丙烯共聚物特定比例复配作为特殊增韧剂对聚丙烯进行增韧改性，使制备得到的聚丙烯复合材料同时具备良好的刚性(例如拉伸强度、弯曲强度)和低温爆破性能，可应用于汽车无包覆立柱材料。
优选地，所述聚丙烯复合材料，包括以下重量份数的组分：特殊聚丙烯A 40～45份、特殊聚丙烯B 5～6份、填料20～25份、特殊增韧剂3～5份、常规增韧剂15～20份、润滑0.1～0.2份、光稳剂0.1～0.2份、抗氧剂0.2～0.4份。
优选地，所述超高分子量聚乙烯的分子量为100～300万。
优选地，所述茂金属乙烯-丙烯共聚物中乙烯的含量为9～15％。
优选地，所述特殊聚丙烯A的分散性指数PDI为6～10。
优选地，所述特殊聚丙烯B的熔融温度(Tm)为130～135℃。
优选地，所述特殊增韧剂中超高分子量聚乙烯和茂金属乙烯-丙烯共聚物的质量比为8～9:1。
优选地，所述填料为滑石粉或碱式硫酸镁晶须中的一种或以上。
优选地，所述增韧剂为乙烯-辛烯无规共聚物或乙烯-辛烯嵌段共聚物中的一种或以上。
优选地，所述润滑剂为酰胺类、硬脂酸盐类中的一种或以上；所述抗氧剂为受阻酚类、亚磷酸酯类中的一种或以上；所述光稳剂为受阻胺类。
本发明还提供一种上述聚丙烯复合材料的制备方法，包括以下步骤：
称取特殊聚丙烯A、特殊聚丙烯B、特殊增韧剂、常规增韧剂、光稳剂、润滑剂、抗氧剂混合均匀；接着加入填料，待混合均匀后，将所得混合物进行熔融共混、挤出造粒。
上述聚丙烯复合材料在制备汽车无包覆立柱材料中的应用也在本发明的保护范围内。
与现有技术相比，本发明具有如下有益效果：
(1)本发明通过使用特殊聚丙烯A和特殊聚丙烯B复配作为改性聚丙烯的基料，可提升材料的低温爆破性能。
(2)本发明通过使用超高分子量聚乙烯和茂金属乙烯-丙烯共聚物复配使用作为特殊增韧剂改性聚丙烯，可同时提升材料的刚性和低温爆破性能。
(3)本发明通过同时使用特殊聚丙烯A、特殊聚丙烯B和复配的特殊增韧剂，使制备得到的聚丙烯复合材料同时具备良好的刚性和低温爆破性能，可应用于汽车无包覆立柱材料；且生产工艺简单、适合大批量生产。
具体实施方式
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
本发明各实施例及对比例选用的部分试剂说明如下：
特殊聚丙烯A：
型号：X1956A(PDI＝6)厂家：利安德巴塞尔；
型号：BI871(PDI＝7.5)厂家：韩华道达尔；
特殊聚丙烯B：
型号：C5608(Tm＝130℃)厂家：中石化；
型号：ADSYL 6089(Tm＝133℃)厂家：利安德巴塞尔；
普通共聚聚丙烯：
型号：EP648U(PDI＝3.8)厂家：中海壳牌；
特殊增韧剂：
UHMWPE型号：U010P(分子量100万)厂家：大韩油化；
UHMWPE型号：9300GK1(分子量300万)厂家：中石化；
茂金属乙烯-丙烯共聚物型号：Vistamaxx 6202，乙烯含量15％，供应商：埃克森美孚；
茂金属乙烯-丙烯共聚物型号：Vistamaxx 3980FL，乙烯含量9％，供应商：埃克森美孚；
增韧剂：乙烯-辛烯无规共聚物(POE)：
型号：Engage 8842厂家：陶氏化学；
滑石粉：
型号：HTPultra5L厂家：依米法比；
抗氧剂：受阻酚类
型号：1010厂家：山东三丰；
光稳剂：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。
本发明各实施例及对比例的聚丙烯复合材料通过如下过程制备得到：
按组分称取原料特殊聚丙烯A、特殊聚丙烯B、特殊增韧剂、增韧剂、光稳剂、润滑剂、抗氧剂、普通共聚聚丙烯(如有)，投入高速混合机中混合43～5min，其中高速混合机的转速为200～300250转/分钟；接着称取填料加入高速混合机中混合53～5分钟，其中高速混合机的转速为200～300转/分钟；待混合均匀后，将混合物加入双螺杆挤出机中，进行熔融共混、挤出造粒。双螺杆挤出机的温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃。挤出采用双真空工艺且真空度要求≤-0.08MPa。
本发明各实施例及对比例的聚丙烯复合材料的性能测试方法和标准如下：
(1)密度：采用ISO 1183-1-2012标准；
(2)拉伸强度：按照ISO 527-2-2016进行测试，拉伸速度为50mm/min；
(3)弯曲性能：将样品注塑成力学样条，按照ISO 178-2010进行测试，弯曲速度2mm/min。
(4)悬臂梁缺口冲击强度：按照ISO 180-2000进行测试；
(5)低温-35℃多轴冲击：参考ISO 6603-2-2000标准测试(2mm厚度方板评价、4.4m/s冲击速度，一般认为破坏形式为YD&YS可以满足爆破要求，YU&NY不满足爆破要求)。
实施例1～10
本实施例提供一系列的聚丙烯复合材料，其配方如表1。
表1实施例1～10的配方(份)
Figure BDA0003072046990000051
Figure BDA0003072046990000061
对比例1～5
本对比例提供一系列聚丙烯复合材料，其配方如表2。
表2对比例1～5的配方(份)
Figure BDA0003072046990000062
Figure BDA0003072046990000071
按照上述提及的方法对各实施例和对比例的聚丙烯复合材料的性能进行测定，结果如表3。
表3各实施例和对比例的性能测试结果
Figure BDA0003072046990000072
从表3可以看出，本发明实施例1～10所制备得到的聚丙烯复合材料均具有较好的力学性能和耐低温冲击性能。实施例6和实施例7中调节特殊增韧剂中超高分子量聚乙烯和茂金属乙烯-丙烯共聚物的质量比时，其低温多轴性能虽仍能满足要求，但会使所制备得到的聚丙烯复合材料刚性(拉伸强度、弯曲强度、弯曲模量)略变差。
而将实施例1与对比例1～5比较可知，配方中的主要成分任何一种被换掉之后综合性能都达不到汽车无包覆立柱材料的要求。
对比例1中用普通聚丙烯换掉特殊聚丙烯A后，其低温多轴性能虽能满足要求，但弯曲模量明显降低；对比例2中用普通聚丙烯换掉特殊聚丙烯B，其低温多轴性能不能满足要求，并且拉伸强度、弯曲强度、弯曲模量和悬臂梁缺口冲击强度均明显降低，刚性和低温韧性均变差。对比例3中不加特殊增韧剂，其拉伸强度、弯曲模量和悬臂梁缺口冲击强度均明显降低，刚性严重下降，低温多轴性能不满足要求。
对比例4中仅加入茂金属乙烯-丙烯共聚物作为特殊增韧剂，其低温多轴性不能满足要求，并且刚性(拉伸强度、弯曲强度、弯曲模量)与实施例相比明显降低。而对比例5中仅采用超高分子量聚乙烯作为特殊增韧剂，其低温多轴性能虽能满足要求，但刚性与实施例相比也明显降低。表明将超高分子量聚乙烯和茂金属乙烯-丙烯共聚物复配使用且采用特定比例能协同提升聚丙烯复合材料的综合性能，使其同时具备良好的刚性和低温爆破性能。
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 (9)

1.一种聚丙烯复合材料，其特征在于，包括以下重量份数的组分：特殊聚丙烯A 35~75份、特殊聚丙烯B 3~10份、填料15~30份、特殊增韧剂 2~10份、增韧剂15~25份、润滑剂0.1~0.3份、光稳剂0.1~0.3份、抗氧剂0.2~0.6份；
所述特殊聚丙烯A为由乙烯、丙烯合成的二元嵌段共聚聚丙烯；
所述特殊聚丙烯B为由1-丁烯、乙烯、丙烯合成的三元无规共聚聚丙烯；
所述特殊增韧剂包括超高分子量聚乙烯和茂金属乙烯-丙烯共聚物，两者质量比为(2~9):1；其中，超高分子量聚乙烯的分子量不低于100万；
所述特殊聚丙烯A的分散性指数PDI为6~10；
所述增韧剂为乙烯-辛烯无规共聚物或乙烯-辛烯嵌段共聚物中的至少一种。
2.根据权利要求1所述聚丙烯复合材料，其特征在于，所述超高分子量聚乙烯的分子量为100~300万。
3.根据权利要求1所述聚丙烯复合材料，其特征在于，所述茂金属乙烯-丙烯共聚物中的乙烯含量为9~15%。
4.根据权利要求1所述聚丙烯复合材料，其特征在于，所述特殊聚丙烯B的熔融温度为130~135℃。
5.根据权利要求1所述聚丙烯复合材料，其特征在于，所述超高分子量聚乙烯和茂金属乙烯-丙烯共聚物的质量比为8~9:1。
6.根据权利要求1所述聚丙烯复合材料，其特征在于，所述填料为碱式硫酸镁晶须或滑石粉中的至少一种。
7.根据权利要求1所述聚丙烯复合材料，其特征在于，所述润滑剂为酰胺类、硬脂酸盐类中的至少一种；所述抗氧剂为受阻酚类或亚磷酸酯类；所述光稳剂为受阻胺类。
8.权利要求1~7任一所述聚丙烯复合材料的制备方法，其特征在于，包括以下步骤：称取特殊聚丙烯A、特殊聚丙烯B、特殊增韧剂、增韧剂、光稳剂、润滑剂、抗氧剂混合均匀；接着加入填料，待混合均匀后，将混合物进行熔融共混、挤出造粒。
9.权利要求 1~7 任一所述聚丙烯复合材料在制备汽车无包覆立柱材料中的应用。
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