CN103865177A - 一种汽车保险杠专用聚丙烯复合材料及其制备方法 - Google Patents

一种汽车保险杠专用聚丙烯复合材料及其制备方法 Download PDF

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CN103865177A
CN103865177A CN201210541631.5A CN201210541631A CN103865177A CN 103865177 A CN103865177 A CN 103865177A CN 201210541631 A CN201210541631 A CN 201210541631A CN 103865177 A CN103865177 A CN 103865177A
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polypropylene
temperature
district
composite material
bumper
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孙刚
周英辉
李国明
程文超
李欣
李志平
陈延安
丁超
罗忠富
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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Shanghai Kingfa Science and Technology Co Ltd
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Abstract

一种汽车保险杠专用超高断裂延伸率聚丙烯复合材料，其特征在于，按重量百分数计，其组分包括：聚丙烯53～88%，热稳定剂0～1%，加工助剂0～1%，相容剂0～5%，茂金属弹性体7～20%，超细滑石粉5～20%。本发明的汽车保险杠专用超高断裂延伸率聚丙烯复合材料及其制备方法具有以茂金属弹性体替代传统的POE弹性体作为保险杠材料增韧剂，优异的韧性、高流动性，断裂延伸率超过400%和使制成的保险杠产品性价比合理的优点。

Description

一种汽车保险杠专用聚丙烯复合材料及其制备方法
技术领域
本发明涉及一种聚丙烯复合材料，具体地说，是一种汽车保险杠专用超高断裂延伸率聚丙烯复合材料及其制备方法。
背景技术
汽车保险杠是吸收缓和外界冲击力、防护车身前后部的安全装置。保险杠材料的断裂延伸率对汽车发生碰撞时吸收碰撞能量有着重要作用，材料的断裂延伸率越高，发生碰撞断裂时吸收的碰撞能量越高，因此各大汽车主机厂对保险杠材料的断裂延伸率要求越来越高。
目前汽车保险杠材料基体树脂主要采用聚丙烯，增强填料采用滑石粉，增韧橡胶采用乙烯辛烯共聚物（POE）热塑性弹性体，通过双螺杆挤出机共混制备，这种保险杠材料具有优异的韧性以及加工性能，但是断裂延伸率一般都低于200%，难以满足汽车主机厂对保险杠材料断裂延伸率日益提高的标准要求。
中国专利CN101759923A于2010年6月30日公开了一种用于汽车保险杠的聚丙烯组合物及其制备方法，其中该组合物按以下重量配比称量物料：聚丙烯树脂50～80％，无机填料10～25％，增韧剂9～25％，偶联剂0～0.5％，抗氧剂0.1～1％，润滑剂0.1～1％。但其缺口冲击强度KJ/m2平均值仅为32.84，断裂延伸率均值为350%，这些数据说明该聚丙烯组合物的流动性，抗冲击强度及其他力学性能差，结构强度弱。
因此已知的用于汽车保险杠的聚丙烯组合物存在着上述种种不便和问题。
发明内容
本发明的目的，在于提出一种断裂延伸率≥400%的汽车保险杠专用超高断裂延伸率聚丙烯复合材料。
本发明的另一目的，在于提出一种断裂伸长率≥400%的汽车保险杠专用超高断裂延伸率聚丙烯复合材料的制备方法。
为实现上述目的，本发明的技术解决方案是：
一种汽车保险杠专用超高断裂延伸率聚丙烯复合材料，其特征在于，按重量百分数计，其组分包括：
聚丙烯                53～88%，
热稳定剂              0～1%，
加工助剂              0～1%，
相容剂                0～5%，
茂金属弹性体          7～20%，
超细滑石粉            5～20%，
所述聚丙烯为熔体流动速率为0.01～100g/10min的共聚聚丙烯；
所述热稳定剂选自下组：酚类、胺类、亚磷酸酯类、半受阻酚类、丙烯酰基官能团与硫代酯的复合物类、杯芳烃、或其组合；
所述加工助剂选自下组：低分子酯类、金属皂类、硬脂酸复合酯类、酰胺类、或其组合；
所述相容剂为极性单体接枝聚合物，其中：所述聚合物基体选自下组：聚乙烯、聚丙烯、乙烯-α-乙烯-辛烯共聚物、苯乙烯与丁二烯的共聚物、聚乙烯-聚苯乙烯-聚丙烯三元共聚物、乙烯-丙烯-丁二烯三元共聚物、乙烯-丙烯酸酯共聚物、乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯共聚物、或其组合；所述极性单体选自下组：马来酸酐及其类似物，丙烯酸及其酯类衍生物、或其组合。
所述茂金属弹性体是丙烯含量在80～99%，熔体流动速率在0.5～100g/10min之间的茂金属弹性体；
所述超细滑石粉为目数在3000目以上的超细滑石粉。
本发明的汽车保险杠专用超高断裂延伸率聚丙烯复合材料还可以采用以下的技术措施来进一步实现。
前述的汽车保险杠专用超高断裂延伸率聚丙烯复合材料，其中所述马来酸酐及其类似物为富马酸、衣康酸、柠康酸、柠康酸酐或乙烯基丁二酸酐。
前述的汽车保险杠专用超高断裂延伸率聚丙烯复合材料，其中所述丙烯酸及其酯类衍生物为丙烯酸、甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯或甲基丙烯酸环氧丙酯
一种如权利要求1所述的汽车保险杠专用超高断裂延伸率聚丙烯复合材料制备方法，其特征在于包括以下步骤：
a、称取包括如下重量百分比的组合物各组分：
聚丙烯              53～88%，
热稳定剂            0～1%，
加工助剂            0～1%，
相容剂              0～5%，
茂金属弹性体        7～20%，
超细滑石粉          5～20%，
b、将聚丙烯和将增韧剂置于混合机中进行混合3～5分钟，混合机的转速为200～500r/min；
c、将无机填料、抗氧剂、加工助剂加入到混合机中混合3～5分钟，混合机的转速为450～500r/min；
d、将步骤b所得产物和步骤c所得产物一起加入到双螺杆挤出机中熔融挤出、剪切、造粒；设置各温区的温度为一区温度190℃、二区温度200℃、三区温度200℃、四区温度200℃、五区温度200℃、六区温度200℃、七区温度200℃、八区温度200℃、九区温度200℃，主机转速为280r/min；停留时间为1～2分钟，压力为12～18Mpa；然后冷却、切粒、烘干。
本发明的汽车保险杠专用超高断裂延伸率聚丙烯复合材料制备方法还可以采用以下的技术措施来进一步实现。
前述的方法，其中所述双螺杆挤出机的长径比为40：1。
采用上述技术方案后，本发明的汽车保险杠专用超高断裂延伸率聚丙烯复合材料及其制备方法具有以下优点：
1、以茂金属弹性体替代传统的POE弹性体作为保险杠材料增韧剂；
2、优异的韧性、高流动性，断裂延伸率超过400%；
3、使制成的保险杠产品性价比合理。
具体实施方式
以下通过具体实施例进一步说明本发明。
实施例1
按照组份比率，使用87.8公斤市售聚丙烯M2600R，0.1公斤CIBA公司生产的酚类热稳定剂Irganox 1010，0.1公斤加工助剂硬脂酸钙，7公斤埃克森美孚茂金属弹性体VM6202和5公斤3000目滑石粉。
本发明的的汽车保险杠专用超高断裂延伸率聚丙烯复合材料制备方法，其特征在于包括以下步骤：
a、称取包括如下重量百分比的组合物各组分：
聚丙烯M2600R                  87.8%，
热稳定剂Irganox 1010          0.1%，
加工助剂硬脂酸钙              0.1%，
相容剂                        0%，
茂金属弹性体VM6202            7%，
超细滑石粉                    5%，
b、将聚丙烯和将增韧剂置于混合机中进行混合3～5分钟，混合机的转速为200～500r/min；
c、将无机填料、抗氧剂、加工助剂加入到混合机中混合3～5分钟，混合机的转速为450～500r/min；
d、将步骤b所得产物和步骤c所得产物一起加入到长径比为40：1的双螺杆挤出机中熔融挤出、剪切、造粒；设置各温区的温度为一区温度190℃、二区温度200℃、三区温度200℃、四区温度200℃、五区温度200℃、六区温度200℃、七区温度200℃、八区温度200℃、九区温度200℃，主机转速为280r/min；停留时间为1～2分钟，压力为12～18Mpa；然后冷却、切粒、烘干。
本实施例制品具有优异的韧性、高流动性以及极高的断裂伸长率，其测试性能参见表1。
表1聚丙烯复合材料的测试性能
性能 单位 测试标准 测试结果
熔体流动速率 g/10min ISO1133 20
拉伸强度 MPa ISO527/2-93 21
断裂延伸率 % ISO527/2-93 420
弯曲模量 MPa ISO178-93 1300
常温（23℃）缺口冲击强度 KJ/m2 ISO180-93 42
常温（-30℃）缺口冲击强度 KJ/m2 ISO180-93 6.2
热变形温度 ℃ ISO75 105
实施例2
本实施例按照组份比率，使用75.5公斤聚丙烯AZ564，0.3公斤酚类热稳定剂Irganox1010（CIBA公司），0.2公斤加工助剂硬脂酸钙，12公斤埃克森美孚茂金属弹性体VM6102，2公斤埃克森美孚相容剂CA-100和10公斤3000目滑石粉。
本实施例的其余部分同实施例1，其测试性能参见表2。
表2聚丙烯复合材料的测试性能
Figure BDA00002581929300061
实施例3
本实施例按照组份比率：使用64公斤聚丙烯PP AZ564，0.5公斤酚类热稳定剂Irganox1010（CIBA公司），0.5公斤加工助剂硬脂酸钙，17公斤埃克森美孚茂金属弹性体VM3980，3公斤Bondyram公司相容剂Bondyram7003和15公斤5000目滑石粉。
本实施例的其余部分同实施例1，其测试性能参见表3。
表3聚丙烯复合材料的测试性能
实施例4
本实施例按照组份比率：使用53公斤聚丙烯PP M2600R，1公斤酚类热稳定剂Irganox1010（CIBA公司），1公斤加工助剂硬脂酸钙，20公斤埃克森美孚茂金属弹性体VM3020，5公斤Bondyram公司相容剂Bondyram1001和20公斤5000目滑石粉。
本实施例的其余部分同实施例1，其测试性能参见表4。
表4聚丙烯复合材料的测试性能
Figure BDA00002581929300071
本发明具有实质性特点和显著的技术进步，本发明的汽车保险杠专用超高断裂延伸率聚丙烯复合材料及其制备方法采用茂金属弹性体替代传统的POE弹性体作为保险杠材料增韧剂，外加适当的相容剂以及高目数滑石粉，成功制备了断裂延伸率定超过400%的保险杠专用料。
以上实施例仅供说明本发明之用，而非对本发明的限制，有关技术领域的技术人员，在不脱离本发明的精神和范围的情况下，还可以作出各种变换或变化。因此，所有等同的技术方案也应该属于本发明的范畴，应由各权利要求限定。

Claims (5)

1.一种汽车保险杠专用超高断裂延伸率聚丙烯复合材料，其特征在于，按重量百分数计，其组分包括： 
聚丙烯                  53～88%， 
热稳定剂                0～1%， 
加工助剂                0～1%， 
相容剂                  0～5%， 
茂金属弹性体            7～20%， 
超细滑石粉              5～20%， 
所述聚丙烯为熔体流动速率为0.01～100g/10min的共聚聚丙烯； 
所述热稳定剂选自下组：酚类、胺类、亚磷酸酯类、半受阻酚类、丙烯酰基官能团与硫代酯的复合物类、杯芳烃、或其组合； 
所述加工助剂选自下组：低分子酯类、金属皂类、硬脂酸复合酯类、酰胺类、或其组合； 
所述相容剂为极性单体接枝聚合物，其中：所述聚合物基体选自下组：聚乙烯、聚丙烯、乙烯-α-乙烯-辛烯共聚物、苯乙烯与丁二烯的共聚物、聚乙烯-聚苯乙烯-聚丙烯三元共聚物、乙烯-丙烯-丁二烯三元共聚物、乙烯-丙烯酸酯共聚物、乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯共聚物、或其组合；所述极性单体选自下组：马来酸酐及其类似物，丙烯酸及其酯类衍生物、或其组合。 
所述茂金属弹性体是丙烯含量在80～99%，熔体流动速率在0.5～100g/10min之间的茂金属弹性体； 
所述超细滑石粉为目数在3000目以上的超细滑石粉。 
2.如权利要求1所述的汽车保险杠专用超高断裂延伸率聚丙烯复合材料，其特征在于，所述马来酸酐及其类似物为富马酸、衣康酸、柠康酸、柠康酸酐或乙烯基丁二酸酐。 
3.如权利要求1所述的汽车保险杠专用超高断裂延伸率聚丙烯复合材料，其特征在于，所述丙烯酸及其酯类衍生物为丙烯酸、甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯或甲基丙烯酸环氧丙酯。
4.一种如权利要求1所述的汽车保险杠专用超高断裂延伸率聚丙烯复合材料制备方法，其特征在于包括以下步骤： 
a、称取包括如下重量百分比的组合物各组分： 
聚丙烯                53～88%， 
热稳定剂              0～1%， 
加工助剂              0～1%， 
相容剂                0～5%， 
茂金属弹性体          7～20%， 
超细滑石粉            5～20%， 
b、将聚丙烯和将增韧剂置于混合机中进行混合3～5分钟，混合机的转速为200～500r/min； 
c、将无机填料、抗氧剂、加工助剂加入到混合机中混合3～5分钟，混合机的转速为450～500r/min； 
d、将步骤b所得产物和步骤c所得产物一起加入到双螺杆挤出机中熔融挤出、剪切、造粒；设置各温区的温度为一区温度190℃、二区温度200℃、三区温度200℃、四区温度200℃、五区温度200℃、六区温度200℃、七区温度200℃、八区温度200℃、九区温度200℃，主机转速为280r/min；停留时间为1～2分钟，压力为12～18Mpa；然后冷却、切粒、烘干。 
5.如权利要求4所述的汽车保险杠专用超高断裂延伸率聚丙烯复合材料制备方法，其特征在于，所述双螺杆挤出机的长径比为40：1。 
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