CN103788634B - 低收缩率玻纤增强pp/pa复合材料组合物及其制备方法 - Google Patents

低收缩率玻纤增强pp/pa复合材料组合物及其制备方法 Download PDF

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CN103788634B
CN103788634B CN201410040686.7A CN201410040686A CN103788634B CN 103788634 B CN103788634 B CN 103788634B CN 201410040686 A CN201410040686 A CN 201410040686A CN 103788634 B CN103788634 B CN 103788634B
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金幸�
杨涛
孟成铭
郭建鹏
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Shanghai Rizhisheng New Technology Development Co Ltd
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Abstract

本发明公开了一种低收缩率玻纤增强PP/PA复合材料组合物及其制备方法；所述组合物包括：聚丙烯10～80份，聚酰胺10～80份，相容剂5～25份，玻璃纤维10～80份，抗氧剂0.1～5份，润滑分散剂0.1～5份。制备时，所述聚酰胺与相容剂a(乙烯-辛烯共聚热塑性弹性体接枝马来酸酐)共混，出料，挤出造粒得到聚酰胺母粒A；聚酰胺母粒A再与聚丙烯，抗氧剂，润滑分散剂，相容剂b(均聚聚丙烯接枝马来酸酐)共混，出料，双螺杆挤出机挤出造粒，即可。本发明玻纤增强PP/PA复合材料具有高强度、高韧性、收缩率低、质量稳定、综合力学性能优良的优点，可以广泛应用于汽车内外部件、电子电器等领域的产品。

Description

低收缩率玻纤增强PP/PA复合材料组合物及其制备方法
技术领域
本发明涉及PP/PA复合材料，尤其是涉及一种低收缩率玻纤增强PP/PA复合材料组合物及其制备方法。
背景技术
聚酰胺(简称PA)，俗称尼龙，因其具有很好的强度、耐磨性、耐油性和较大的温度使用范围，从而在汽车、电子、机械等领域得到了广泛应用。但是，随着近年来电子电气以及汽车工业迅速发展，对高强度、高韧性的工程塑料的需求日益增长，常用的聚酰胺工程塑料因其吸水率大、低温和干态冲击强度低的缺点逐渐无法满足许多汽车及电器部位制件的性能要求。聚丙烯(简称PP)，具有较好的韧性、低密度的特点，但其耐热性较差。用PP与PA制备合金能够有效地将两者的优势互补，改善PA的缺点，扩大PA的应用领域。然而纯PP与PA并不能良好地相容，直接共混挤出得到的合金的性能很一般，PP的加入对PA材料的强度有减弱作用。另外，PP、PA都存在收缩率较大的缺陷。
发明内容
本发明的目的在于针对上述现有技术中的不足，提供一种高强度、高韧性的低收缩率玻纤增强PP/PA复合材料组合物及其制备方法。
本发明的目的是通过以下技术方案来实现的：
本发明涉及一种低收缩率玻纤增强PP/PA复合材料组合物，所述组合物包括以下组分和重量份数：聚丙烯10～80份，聚酰胺10～80份，相容剂5～25份，玻璃纤维10～80份，抗氧剂0.1～5份，润滑分散剂0.1～5份。
优选的，所述聚酰胺为聚己内酰胺，其特性粘度为2.4dl/g。
优选的，所述聚丙烯包括通用级均聚或共聚聚丙烯。
优选的，所述玻璃纤维为无碱玻璃纤维，其表面经硅烷偶联剂处理。
优选的，所述相容剂包括乙烯-辛烯共聚热塑性弹性体接枝马来酸酐、均聚聚丙烯接枝马来酸酐。
更优选的，所述乙烯-辛烯共聚热塑性弹性体接枝马来酸酐与均聚聚丙烯接枝马来酸酐的用量比为2∶3～6∶5。最优选为2∶3。
优选的，所述抗氧剂为分子量受阻酚类抗氧剂。
优选的，所述分散剂为硅酮。
本发明还涉及一种上述的低收缩率玻纤增强PP/PA复合材料组合物的制备方法，所述方法包括如下步骤：
A、所述聚酰胺与相容剂a放入高混机中混合2～5分钟，出料，双螺杆挤出机挤出造粒，加工温度为220～255℃，得到聚酰胺母粒A；所述相容剂a为乙烯-辛烯共聚热塑性弹性体接枝马来酸酐；
B、所述聚酰胺母粒A与聚丙烯、抗氧剂、润滑分散剂、相容剂b放入高混机中混合2～5分钟，出料，采用双螺杆挤出机挤出造粒，挤出过程中由侧向喂料口加入所述玻璃纤维，加工温度为210～245℃；所述相容剂b为均聚聚丙烯接枝马来酸酐。
优选的，所述步骤A、B中双螺杆挤出机的螺杆转数为30～40Hz。更优选为40Hz。
优选的，步骤A中，双螺杆挤出机加工温度：一段为220℃，二段为225℃，三段为230℃，四段为235℃，五段为235℃，六段为235℃，七段为230℃，八段为225℃，九段为220℃。
优选的，步骤B中，双螺杆挤出机加工温度：一段为210℃，二段为215℃，三段为220℃，四段为225℃，五段为235℃，六段为225℃，七段为220℃，八段为215℃，九段为210℃。
与现有技术相比，本发明具有如下有益效果：
1、采用分次挤出造粒的方式，先将聚酰胺与相容剂a(乙烯-辛烯共聚热塑性弹性体接枝马来酸酐)结合，再与聚丙烯、相容剂b(均聚聚丙烯接枝马来酸酐)以及玻纤共挤出造粒。与使用单一相容剂与PP、PA共混挤出造粒的工艺相比，能够使PA、PP分子基团之间结合更加紧密，增加PP、PA的相容性，从而更好地结合PP与PA的优点，提高合金的韧性和强度；
2、受阻酚类抗氧剂可提高组合物在加工过程的抗氧化性能和使用过程中的抗老化性能；
3、润滑分散剂硅酮能提高材料加工流动性，降低摩擦系数，提高滑爽性，在特定的加工条件下采用分散性较好、停留时间短、剪切稍弱的组合，能保证复合材料的质量稳定；
4、由于玻璃纤维的加入，很大程度上提高了复合材料的刚性和强度，并有效降低了复合材料的收缩率；
5、本发明产品高强度、高韧性、低收缩玻纤增强PP/PA复合材料可以广泛应用于汽车内外部件、电子电器等领域的产品中。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明的实施例与对比例中，所述的聚酰胺优选为市售聚酰胺6，即PA6，其特性粘度为2.4dL/g。所述聚丙烯包括市售通用级均聚或共聚聚丙烯，优选为均聚聚丙烯。所述玻璃纤维优选为表面经硅烷偶联剂处理过的无碱玻璃纤维。抗氧剂优选为受阻酚类抗氧剂，具体选用168和1010，润滑分散剂优选为硅酮。相容剂包括乙烯-辛烯共聚热塑性弹性体接枝马来酸酐和均聚聚丙烯接枝马来酸酐。
实施例1～3
本实施例1～3涉及一种高强度、高韧性的低收缩率玻纤增强PP/PA复合材料组合物；其制备方法包括如下步骤：
1.1聚酰胺母粒A的制备
按照表1重量份数称取各原料，其中相容剂a为乙烯-辛烯共聚热塑性弹性体接枝马来酸酐。
表1
原料名称
聚酰胺 80 80
相容剂a 10 0
挤出造粒产物 A1 A2
将称取好的原料放入高混机中混合2～5分钟，出料，然后用双螺杆挤出机挤出造粒，加工温度为220～255℃，具体为：一段为220℃，二段为225℃，三段为230℃，四段为235℃，五段为235℃，六段为235℃，七段为230℃，八段为225℃，九段为220℃，螺杆转数可为30～40Hz，本实施例1～3中均优选为40Hz，分别得到聚酰胺母粒A1和A2。
1.2高强度、高韧性、低收缩率玻纤增强PP/PA复合材料组合物的制备
按照表2重量份数称取各原料，其中相容剂b为均聚聚丙烯接枝马来酸酐。
表2
将称取好的原料放入高混机中混合2～5分钟，出料，然后用双螺杆挤出机挤出造粒，挤出过程中将玻璃纤维在侧向喂料口加入，加工温度为210～245℃，具体为：一段为210℃，二段为215℃，三段为220℃，四段为225℃，五段为235℃，六段为225℃，七段为220℃，八段为215℃，九段为210℃，螺杆转数可为30～40Hz，本实施例1～3中均优选为40Hz。
对比例1～5
对比例1～5涉及玻纤增强PP/PA复合材料，其制备工艺同实施例1；所不同之处在于组分与用量，具体见表2。
将实施例1～3和对比例1～5制备得到的复合材料进行性能测试，采用ASTM标准，性能测试结果见表3。
表3
从表3可看出，实施例1和对比例1、2相比，只添加一种相容剂的对比例1、2制得的复合材料的拉伸强度、弯曲强度和抗冲击强度均要差一些；与对比例3相比发现，不添加相容剂制得的复合材料无论拉伸强度、弯曲强度或抗冲击强度均要差许多。添加玻璃纤维重量份数少的实施例2、3与份数多的实施例1对比，制得的复合材料的强度比实施例1低许多，说明由于玻璃纤维的加入，很大程度上提高了复合材料的刚性和强度；而且添加玻璃纤维重量份数少的实施例2、3与份数多的实施例1对比，制得的复合材料的收缩率要大，说明玻璃纤维的加入很好地降低了PP/PA合金的收缩率。添加润滑分散剂和抗氧剂少的对比例4与添加多的实施例2相比，添加润滑分散剂和抗氧剂少的对比例5与添加多的实施例3相比，强度数据略有下降，说明润滑分散剂对复合材料的各项性能有促进作用。
实施例4～6
本实施例4～6涉及一种高强度、高韧性的低收缩率玻纤增强PP/PA复合材料组合物；其制备方法同实施例1，所不同之处在于：
1、按照表4所示的重量份数称取各原料，制备聚酰胺母粒A3、A4、A5。
表4
原料名称
聚酰胺 10 30 60
相容剂a 2 8 12
挤出造粒产物 A3 A4 A5
2、按照表5重量份数称取各原料，制备高强度、高韧性、低收缩率玻纤增强PP/PA复合材料组合物。
表5
原料名称 实施例4 实施例5 实施例6
A3 12
A4 38
A5 72
聚丙烯 10 40 80
相容剂b 3 7 10
玻璃纤维 10 30 80
抗氧剂 0.1 2 5
润滑分散剂 0.1 5 2
将实施例4～6制备得到的复合材料进行性能测试，采用ASTM标准，性能测试结果见表6。
表6
测试参数 实施例4 实施例5 实施例6
拉伸强度(MPa) 129 116 113
弯曲强度(MPa) 150 135 132
弯曲模量(MPa) 6700 6300 6200
缺口冲击强度(J/m) 201 179 175
收缩率(％) 1.2 1.4 1.2
由上表3、6可以看出本发明样品本发明玻纤增强PP/PA复合材料具有高强度、高韧性、收缩率低、质量稳定、综合力学性能优良的优点，可以广泛应用于汽车内外部件、电子电器等领域的产品中。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (7)

1.一种低收缩率玻纤增强PP/PA复合材料组合物，其特征在于，所述组合物包括以下组分和重量份数：聚丙烯10～80份，聚酰胺10～80份，相容剂5～25份，玻璃纤维10～80份，抗氧剂0.1～5份，润滑分散剂0.1～5份；
所述相容剂由乙烯-辛烯共聚热塑性弹性体接枝马来酸酐、均聚聚丙烯接枝马来酸酐组成；
所述乙烯-辛烯共聚热塑性弹性体接枝马来酸酐与均聚聚丙烯接枝马来酸酐的用量比为2:3～6:5；
所述的低收缩率玻纤增强PP/PA复合材料组合物的制备方法，包括如下步骤：
A、所述聚酰胺与相容剂a放入高混机中混合2～5分钟，出料，双螺杆挤出机挤出造粒，加工温度为220～255℃，得到聚酰胺母粒A；所述相容剂a为乙烯-辛烯共聚热塑性弹性体接枝马来酸酐；
B、所述聚酰胺母粒A与聚丙烯、抗氧剂、润滑分散剂、相容剂b放入高混机中混合2～5分钟，出料，采用双螺杆挤出机挤出造粒，挤出过程中由侧向喂料口加入所述玻璃纤维，加工温度为210～245℃；所述相容剂b为均聚聚丙烯接枝马来酸酐。
2.根据权利要求1所述的低收缩率玻纤增强PP/PA复合材料组合物，其特征在于，所述聚酰胺为聚己内酰胺，其特性粘度为2.4dl/g。
3.根据权利要求1所述的低收缩率玻纤增强PP/PA复合材料组合物，其特征在于，所述聚丙烯包括通用级均聚或共聚聚丙烯。
4.根据权利要求1所述的低收缩率玻纤增强PP/PA复合材料组合物，其特征在于，所述玻璃纤维为无碱玻璃纤维，其表面经硅烷偶联剂处理。
5.根据权利要求1所述的低收缩率玻纤增强PP/PA复合材料组合物，其特征在于，所述抗氧剂为受阻酚类抗氧剂。
6.根据权利要求1所述的低收缩率玻纤增强PP/PA复合材料组合物，其特征在于，所述分散剂为硅酮。
7.如权利要求1所述的低收缩率玻纤增强PP/PA复合材料组合物的制备方法，其特征在于，所述步骤A、B中双螺杆挤出机的螺杆转数为30～40Hz。
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