CN103992637A - 一种增韧增强尼龙6三元复合材料及其制备方法 - Google Patents

一种增韧增强尼龙6三元复合材料及其制备方法 Download PDF

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CN103992637A
CN103992637A CN201410222419.1A CN201410222419A CN103992637A CN 103992637 A CN103992637 A CN 103992637A CN 201410222419 A CN201410222419 A CN 201410222419A CN 103992637 A CN103992637 A CN 103992637A
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吴唯
蔺兴清
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East China University of Science and Technology
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Abstract

本发明公开了一种增韧增强尼龙6三元复合材料及其制备方法，属于高分子复合材料领域，涉及一种汽车内饰以及部分零件应用的尼龙6三元复合材料。包括：尼龙6、热塑性弹性体、碳纳米管，其重量份为：尼龙6 70～80份，热塑性弹性体20～30份，碳纳米管0.5～1.5份。本发明制得的尼龙6三元复合材料具有优良的缺口冲击性能和热性能，极大地改变了尼龙6缺口冲击强度低的致命缺点；同时不会牺牲尼龙6的弯曲性能和拉伸性能。进一步提高了尼龙6的应用领域，同时实验原料简单易得，方法可行性好。

Description

一种增韧增强尼龙6三元复合材料及其制备方法
技术领域
本发明属于高分子复合材料领域，具体涉及用于汽车内饰以及部分汽车零件且性能良好的热塑性弹性体、碳纳米管和尼龙6的三元复合材料及其制备技术。 
背景技术
尼龙6(PA6)是工程塑料中开发最早的品种，是目前聚酰胺塑料中产量最大的品种之一。与其他树脂材料相比，PA6具有力学强度高、电气性能良好、耐磨、抗震吸音、耐油、耐弱酸、弱碱、弱极性有机溶剂，加工流动性好等优点，广泛应用于汽车工业、电子、机械等领域。但是尼龙6缺口敏感材料，材料一旦出现细小缺口缝隙就会发生破损，影响产品继续应用。因此提高尼龙6的缺口冲击性能，对于尼龙6的进一步开发应用有很大价值。 
在现有技术中，为改善尼龙6的缺口冲击性能，往往利用一些无机添加物纤维等进行改性，由于无机颗粒或者纤维在尼龙6基体中易于团聚，分散性不好，虽然对缺口冲击性能有一定提高，提高有限，同时牺牲了尼龙本身优良的弯曲和拉伸性能。对于显著提高尼龙6冲击强度，同时又不牺牲尼龙6弯曲和拉伸性能的专利还没有提出。 
发明内容
鉴于以上问题，本发明的目的是提供一种各项力学性能优异，表现良好的尼龙6三元复合材料及其制备方法，具体技术方案如下： 
一种增韧增强尼龙6三元复合材料，所述复合材料包括如下重量分数的组分： 
其中，尼龙6和热塑性弹性体的重量份数之和为100。 
所述尼龙6的密度为1.1～1.17g/cm3，相对粘度为2.7～3，熔点为215～220℃。 
所述热塑性弹性体为马来酸酐接枝聚乙烯-辛烯嵌段共聚物，其中马来酸酐的接枝率为0.8～1.2；所述热塑性弹性体的熔融指数为3～7g/min，热塑性弹性体作为尼龙6增韧剂的同时还作为其增溶剂。 
所述热塑性弹性体为马来酸酐接枝的三元乙丙橡胶，其中马来酸酐的接枝率为0.5～1，三元乙丙橡胶中乙烯链段的重量百分含量为45～60％，三元乙丙橡胶既作增韧剂又作增溶剂。 
所述碳纳米管为多壁碳纳米管，直径为10～40nm，长度5～50μm，比表面积为50～160m2/g。 
所述碳纳米管是接枝羧基或羟基极性基团的改性碳纳米管。 
所述碳纳米管按如下方法加入：利用溶液法制备尼龙6和改性碳纳米管母料，通过母料将改性碳纳米管和尼龙6进行共混，有助于提高改性碳纳米管的利用率和分散性。 
所述抗氧剂选自抗氧剂2246、抗氧剂1010、抗氧剂4426、抗氧剂1076、抗氧剂300； 
抗氧剂2246的CAS号：119-47-1，分子式：C23H32O2，化学名：2,2'-亚甲基双(4-甲基-6-叔丁基苯酚)； 
抗氧剂1010的CAS号：6683-19-8，分子式：C73H108O12，化学名称：四(β-(3,5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯； 
抗氧剂4426的CAS号：118-82-1，分子式：C13H802，化学名称：4,4'-亚甲基双(2,6-二叔丁基苯酚)； 
抗氧剂1076的CAS号：2082-79-3，分子式：C35H62O3，化学名称：β-(4-羟基苯基-3,5-二叔丁基)丙酸正十八碳醇酯； 
抗氧剂300的CAS号：96-69-5，分子式：C22H30O2S,化学名称：4,4'-硫代双(6-叔丁基-3-甲基苯酚)或4,4'-硫代双(6-叔丁基间甲酚)。 
上述任一所述的增韧增强尼龙6三元复合材料的制备方法，包含如下步骤： 
(1)用浓硫酸和浓硝酸的重量比为3：1的混合液对0.5～1.5重量份碳纳米管进行回流处理，在所述碳纳米管上接枝羧基和羟基极性基团得到改性碳纳米管； 
(2)用100ml甲酸作溶剂，加入5重量份的尼龙6在80℃下油浴搅拌溶解； 
(3)用50ml甲酸做溶剂加入步骤(1)得到的改性碳纳米管，在80℃下油浴搅拌溶解； 
(4)将步骤(2)和步骤(3)得到的溶液混合均匀，用蒸馏水冲洗，多次洗涤，最后鼓风烘干直至甲酸全部挥发，得到尼龙6和改性碳纳米管母料； 
(5)将65～75重量份尼龙6、20～30重量份热塑性弹性体、0.1～0.5重量份抗氧剂以及步骤(4)得到的尼龙6与改性碳纳米管母料混合进行双螺杆挤出，各段温度为245～255℃，螺杆转速为60转/分钟，挤出切粒，得到所述复合材料； 
其中，尼龙6的总量和热塑性弹性体的重量份数之和为100。 
本发明具有优良的力学性能，且保证材料组分分布均匀，尤其是改性碳纳米管在尼龙6基体中分布均匀，确保复合材料的性能。由于聚乙烯辛烯嵌段共聚物的引入，复合材料的冲击性能较尼龙6纯样成倍数提高。碳纳米管的引入，确保复合材料的其他力学性能不会损失。 
具体实施方式
下面结合实施例对本发明的技术方案作进一步说明。 
实施例1 
(1)用浓硫酸和浓硝酸(重量比为3：1)对1.5重量份碳纳米管进行处理，先在50℃、60HZ下超声2小时，接着在100℃条件下回流2小时；酸化后用10倍蒸馏水洗涤，利用微孔滤膜减压抽滤，直至滤液pH值达到7。 
(2)将5重量份尼龙6加入100ml甲酸中，80℃油浴机械搅拌溶解，同时将步骤(1)中改性碳纳米管加入到甲酸溶液中超声，待尼龙6完全溶解后将改性碳纳米管甲酸混合液倒入溶有尼龙6的甲酸溶液中，机械搅拌100分钟，用蒸馏水冲洗，多次洗涤，最后鼓风烘干24小时，直至甲酸全部挥发，得到尼龙6与改性碳纳米管母料。 
(3)将剩余份数尼龙6(即，65重量份)在100℃条件下烘10小时，30重量份热塑性弹性体在60℃条件下烘6小时。 
(4)将步骤(3)中烘干的65重量份尼龙6、30重量份热塑性弹性体、0.5份抗氧剂以及步骤(2)得到的尼龙6与改性碳纳米管母料混合进行双螺杆挤出，各段温度为245～255℃，螺杆转速为60转/分钟，挤出切粒，得到性能优良的复合材料。 
(5)利用注塑机注塑用于力学测试的样条，注塑机各段温度为235～245℃。 
对于得到的注塑样条根据国标要求进行力学测试。 
按照GB/T1040-92进行样条拉伸试验。试验样品为哑铃型样品，样品总长150mm，夹距间距离115mm，标距50mm，拉伸速度50mm/min。 
按照GB/T9341-2000进行弯曲性嫩测试。样品长80mm，宽10mm，厚度4mm。 
按照GB/T1043-93进行冲击强度测试。样品长度80mm，宽度10mm，缺口为I性缺口0.25mm。 
所有样品在测试前，在25℃恒温条件下恒温24小时。测试温度为25℃。 
对于上述样品配比条件下，得到复合材料的冲击强度为62.32KJ/m2，相对于尼龙6原样，性能有将近6倍的显著提高。这样的结果远远高于一般无极填充颗粒和纤维的作用结果，不但改善了尼龙6的缺点，而且改善明显，使尼龙6的应用范围进一步扩大。 
材料的弯曲强度为108.66MPa，对于尼龙纯样与近17％的提高，拉伸强度为71.07MPa，较尼龙6纯样有18％的提高。 
发明所得尼龙6三元复合材料不仅明显改善了尼龙6冲击强度低的缺点，而且有效提高了其拉伸强度和弯曲强度，是一种力学性能优良的复合材料。 
实施例2 
(1)用浓硫酸和浓硝酸(3：1)进行对1.5重量份碳纳米管进行处理，先在50℃、60HZ下超声2小时，接着在100℃条件下回流2小时；酸化后用10倍蒸馏水洗涤，利用微孔滤膜减压抽滤，直至滤液pH值达到7。 
(2)将5重量份尼龙6加入100ml甲酸中，80℃油浴机械搅拌溶解，同时将步骤(1)得到的改性碳纳米管加入到甲酸溶液中超声，待尼龙6完全溶解后将改性碳纳米管甲酸混合液倒入溶有尼龙6的甲酸溶液中，机械搅拌100分钟，用蒸馏水冲洗，多次洗涤，最后鼓风烘干24小时，直至甲酸全部挥发，得到尼龙6和改性碳纳米管母料。 
(3)将剩余份数尼龙6(即，70重量份)在100℃条件下烘10小时，25重量份热塑性弹性体在60℃条件下烘6小时。 
(4)将步骤(3)中烘干的70重量份尼龙6、25重量份热塑性弹性体、0.5重量份抗氧剂以及步骤(2)得到的尼龙6与改性碳纳米管母料混合进行双螺杆挤出，各段温度为245～255℃，螺杆转速为60转/分钟，挤出切粒，得到性能优良的复合材料。 
(5)利用注塑机注塑用于力学测试的样条，注塑机各段温度为235～245℃。 
对于得到的注塑样条根据国标要求进行力学测试。 
按照GB/T1040-92进行样条拉伸试验。试验样品为哑铃型样品，样品总长150mm，夹距间距离115mm，标距50mm，拉伸速度50mm/min。 
按照GB/T9341-2000进行弯曲性嫩测试。样品长80mm，宽10mm，厚度4mm。 
按照GB/T1043-93进行冲击强度测试。样品长度80mm，宽度10mm，缺口为I性缺口0.25mm。 
所有样品在测试前，在25℃恒温条件下恒温24小时。测试温度为25℃。 
对于上述样品配比条件下，得到复合材料的冲击强度为58.32KJ/m2，相对于尼龙6原样，性能有将近6倍的显著提高。这样的结果远远高于一般无极填充颗粒和纤维的作用结果，不但改善了尼龙6的缺点，而且改善明显，使尼龙6的应用范围进一步扩大。 
材料的弯曲强度为110.51MPa，对于尼龙纯样与近19％的提高，拉伸强度为72.276MPa，较尼龙6纯样有20％的提高。 
实施例3 
(1)用浓硫酸和浓硝酸(3：1)对1.5重量份碳纳米管进行处理，先在50℃，60HZ下超声2小时，接着在100℃条件下回流2小时；酸化后用10倍蒸馏水洗涤，利用微孔滤膜减压抽滤，直至滤液pH值达到7。 
(2)将5重量份尼龙6加入100ml甲酸中，80℃油浴机械搅拌溶解，同时将步骤(1)得到的改性碳纳米管加入到甲酸溶液中超声，待尼龙6完全溶解后将改性碳纳米管甲酸混合液倒入溶有尼龙6的甲酸溶液中，机械搅拌100分钟，用蒸馏水冲洗，多次洗涤，最后鼓风烘干24小时，直至甲酸全部挥发。得到尼龙6和改性碳纳米管母料。 
(3)将剩余份数尼龙6(即，75份)在100℃条件下烘10小时，20重量份热塑性弹性体在60℃条件下烘6小时。 
(4)将步骤(3)中烘干的75重量份尼龙6、20重量份热塑性弹性体、0.5份抗氧剂以及步骤(2)得到的尼龙6与改性碳纳米管母料混合进行双螺杆挤出，各段温度为245～255℃，螺杆转速为60转/分钟，挤出切粒，得到性能优良的复合材料。 
(5)利用注塑机注塑用于力学测试的样条，注塑机各段温度为235～245℃。 
对于得到的注塑样条根据国标要求进行力学测试。 
按照GB/T1040-92进行样条拉伸试验。试验样品为哑铃型样品，样品总长150mm，夹距间距离115mm，标距50mm，拉伸速度50mm/min。 
按照GB/T9341-2000进行弯曲性嫩测试。样品长80mm，宽10mm，厚度4mm。 
按照GB/T1043-93进行冲击强度测试。样品长度80mm，宽度10mm，缺口为I性缺口0.25mm。 
所有样品在测试前，在25℃恒温条件下恒温24小时。测试温度为25℃。 
对于上述样品配比条件下，得到复合材料的冲击强度为55.32KJ/m2，相对于尼龙6原样，性能有将近6倍的显著提高。这样的结果远远高于一般无极填充颗粒和纤维的作用结果，不但改善了尼龙6的缺点，而且改善明显，使尼龙6的应用范围进一步扩大。 
材料的弯曲强度为116.09MPa，对于尼龙纯样与近25％的提高，拉伸强度为73.48MPa，较尼龙6纯样有22％的提高。 
综上所述仅为本发明的较佳实施例而已，并非用来限制本发明的实施范围。即凡依本发明申请专利范围的内容所做的等效变化与修饰，都应为本发明的技术范畴。 

Claims (9)

1.一种增韧增强尼龙6三元复合材料，其特在在于，所述复合材料包括如下重量分数的组分：
其中，尼龙6和热塑性弹性体的重量份数之和为100。
2.根据权利要求1所述的复合材料，其特征在于，所述尼龙6的密度为1.1～1.17g/cm3，相对粘度为2.7～3，熔点为215～220℃。
3.根据权利要求1所述的复合材料，其特征在于，所述热塑性弹性体为马来酸酐接枝聚乙烯-辛烯嵌段共聚物，其中马来酸酐的接枝率为0.8～1.2；所述热塑性弹性体的熔融指数为3～7g/min。
4.根据权利要求1所述的复合材料，其特征在于，所述热塑性弹性体为马来酸酐接枝的三元乙丙橡胶，其中马来酸酐的接枝率为0.5～1，三元乙丙橡胶中乙烯链段的重量百分含量为45～60％。
5.根据权利要求1所述的复合材料，其特征在于，所述碳纳米管为多壁碳纳米管，直径为10～40nm，长度5～50μm，比表面积为50～160m2/g。
6.根据权利要求1或5所述的三元复合材料，其特征在于，所述碳纳米管是接枝羧基或羟基极性基团的改性碳纳米管。
7.根据权利要求1所述的复合材料，其特征在于，所述抗氧剂选自抗氧剂2246、抗氧剂1010、抗氧剂4426、抗氧剂1076、抗氧剂300。
8.权利要求1至7任一所述的增韧增强尼龙6三元复合材料的制备方法，其特征在于，包含如下步骤：
(1)用浓硫酸和浓硝酸的重量比为3：1的混合液对0.5～1.5重量份碳纳米管进行回流处理，在所述碳纳米管上接枝羧基和羟基极性基团得到改性碳纳米管；
(2)用100ml甲酸作溶剂，加入5重量份的尼龙6在80℃下油浴搅拌溶解；
(3)用50ml甲酸做溶剂加入步骤(1)得到的改性碳纳米管，在80℃下油浴搅拌溶解；
(4)将步骤(2)和步骤(3)得到的溶液混合均匀，用蒸馏水冲洗，多次洗涤，最后鼓风烘干直至甲酸全部挥发，得到尼龙6和改性碳纳米管母料；
(5)将65～75重量份尼龙6、20～30重量份热塑性弹性体、0.1～0.5重量份抗氧剂以及步骤(4)得到的尼龙6与改性碳纳米管母料混合进行双螺杆挤出，各段温度为245～255℃，螺杆转速为60转/分钟，挤出切粒，得到所述复合材料；
其中，尼龙6的总量和热塑性弹性体的重量份数之和为100。
9.根据权利要求8所述的制备方法，其特征在于，所述回流处理的过程如下：先在40～50℃、50～60Hz下超声2～4小时，接着在80～100℃条件下回流2小时；酸化后用10～20倍蒸馏水洗涤，利用微孔滤膜减压抽滤，直至滤液pH值达到6～7。
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