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CN103740092B - 一种高导热石墨烯/尼龙复合材料及其制备方法 - Google Patents

一种高导热石墨烯/尼龙复合材料及其制备方法 Download PDF

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CN103740092B
CN103740092B CN201310699879.9A CN201310699879A CN103740092B CN 103740092 B CN103740092 B CN 103740092B CN 201310699879 A CN201310699879 A CN 201310699879A CN 103740092 B CN103740092 B CN 103740092B
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thermal conductivity
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CN103740092A (zh
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蔡铜祥
成文俊
杨玉晴
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Shanghai Yueda New Material Technology Co., Ltd.
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Abstract

本发明公开了一种高导热石墨烯/尼龙复合材料及其制备方法。按重量份数，包含尼龙30～80份、可膨石墨4～8份、双亲性芘类接枝物0.5～1.5份、高取向氮化硅纤维1～20份、碳纤维1～15份、氮化硼5～10份、耐高温助剂0.02～4份、抗氧剂0.02～0.8份、抗水解剂1～3份、增韧剂2～6份。本发明采用了新型的导热助剂用以提高尼龙的导热性能，这种导热助剂是可膨石墨与双亲性芘类接枝物通过液相超声剥离法制备出的石墨烯。这种新型的导热助剂的优势在于：使石墨烯均匀地分散在基体树脂中，又能够使石墨烯与尼龙之间的界面粘接力变强，相容性提高。

Description

一种高导热石墨烯/尼龙复合材料及其制备方法
技术领域
本发明涉及一种高导热石墨烯/尼龙复合材料及其制备方法，确切地说是涉及一种高导热石墨烯/尼龙6或者尼龙12或者尼龙66复合材料及其制备方法。
技术背景
尼龙具有良好的机械性能、较好的柔韧性、耐磨性、耐油性、自润滑性等优良的综合性能，被广泛应用于汽车行业、电子电器工业、机械设备、建筑业等领域。由于其具有加工周期短、生产成本低、使用寿命长且产品设计自由度高等优点得到越来越广泛的应用，近几年在导热高分子复合材料方面的应用尤为突出，例如帝斯曼公司生产的大功率LED散热器已得到市场的普遍认可。
导热材料广泛应用于换热工程、电子信息工程等领域。长期以来，大部分导热材料为金属材料，但是由于金属材料的抗腐蚀性能差以及加工性能不佳、产品设计自由度低等诸多因素，限制了其应用范围。
为了提高导热材料的表面抗腐蚀性，通常采用冶金、防腐涂层等手段，但是此方法在很大的程度上降低了材料的导热性能并且材料的其他性能没有得到根本性的改善。近年来，随着导热材料应用范围越来越广泛，对材料的综合性能要求也越来越高。比如不仅要求材料具有优良的导热性能，还要求材料具有良好的机械性能、耐高温使用性能、耐环境腐蚀性能等。
传统的导热复合材料一般以Si3N4、SiN、AlN和BN做为导热填料，但因其本身的导热率低，故需在高的添加量下才能取得较高的导热系数，然而这必然会降低高分子材料本身的其他性能。自从石墨烯2004年被发现以来，其作为一种新型的二维碳纳米材料，具有极好的热导率、电导率，是已知的机械强度最高的物质且具备化学性能稳定透光性好等优点。单层石墨烯的室温导热系数达到4840～5300W·（m·K）-1，是目前导热系数最高的材料。这些独特的性质能使石墨烯做为一种新型的纳米导热填料，从而使聚合物的导热性能得到很大的提高。
发明内容
本发明主要是解决现有导热高分子复合材料发展中的导热性能差的技术问题，提供一种具备优异导热性能、良好抗腐蚀性能、耐高温使用性能、综合机械强度高的复合材料及其制备方法。
本发明的技术解决方案是，由以下以重量份数配比的原料制成：尼龙30～80份、可膨石墨4～8份、双亲性芘类接枝物0.5～1.5份、高取向氮化硅纤维1～20份、碳纤维1～15份、氮化硼5～10份、耐高温助剂0.02～4份、抗氧剂0.02～0.8份、抗水解剂1～3份、增韧剂2～6份。
其中所述尼龙为特性粘度在1.6～3.8dL/g之间的尼龙6或者尼龙12或者尼龙66三种物质中的一种或者几种的混合物；
所述可膨石墨为粒度为60目可膨石墨或者70目可膨石墨或者80目可膨石墨三种物质中的一种或者几种的混合物；
所述双亲性芘类接枝物为芘与树枝状聚丙烯酸酯-聚乙二醇单甲醚嵌段共聚物或者树枝状聚丙烯酸酯-聚乙二醇乙醚嵌段共聚物或者树枝状聚乙二醇环氧甘油酯嵌段共聚物三者中的一种或者几种通过亲电取代反应所形成的物质；
所述高取向氮化硅纤维为经偶联剂处理后的高取向氮化硅纤维；所用偶联剂为：硅烷类偶联剂、钛酸酯类偶联剂或者络合物类偶联剂；
所述碳纤维为经偶联剂处理后的高取向碳纤维。所用偶联剂为：硅烷类偶联剂、钛酸酯类偶联剂或者络合物类偶联剂；
所述氮化硼为纯度＞99%，粒径范围为5～15μm的六方氮化硼；
所述耐高温助剂为烃基一硫代磷酸铜或烯基丁二酸铜或硫代氨基甲酸铜或以上几种复配；
所述抗氧剂为N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺和三[2,4-二叔丁基苯基]亚磷酸酯按照质量比为8:1~2:1复配而成；
所述抗水解剂为碳化二亚胺或者聚[次氮基甲烷四次氮基[2,4,6-三（1-甲乙基）-1,3-亚苯基]]或者三烯丙基异氰脲酸酯中的一种或几种复配；
所述增韧剂为POE-g-GMA或EPDM-g-GMA或EPR-g-MAH或SWR-3C或是以上几种复配使用。
本发明的具体制备方法步骤如下：
1）石墨烯的制备。先将可膨石墨与双亲性芘类接枝物一同放置在具有一定比例H2O/MeOH的混合溶剂中进行超声振荡3～5h，然后进行离心处理，离心转速为1200～1500rpm，时间为15～30min，上层清液即为分散的石墨烯溶液，其浓度达到1.5～2mg/ml，将上清液放置70～100℃烘箱中干燥15～20h得到干燥粉状石墨烯。
2）将上述步骤1）中所制得的石墨烯粉末与尼龙粒子混合均匀，三辊研磨机中研磨10～15min，备用。
3）将上述步骤2）中所得尼龙/石墨烯混合均匀的粒子与氮化硼、抗氧剂、抗水解剂、耐高温剂、增韧剂按配方比例在高混机中混合10～25min，混合均匀后加入双螺杆挤出机的料斗中，高取向氮化硅纤维与碳纤维按一定比例从螺杆的加纤口中加入，温度为230～260℃，主机频率为15～25Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高导热尼龙/石墨烯复合材料。
本发明与现有技术相比所具备的优点是：
1）采用可膨石墨与双亲性芘类接枝物通过液相超声剥离法制备出高浓度石墨烯。首先芘能够与二维结构的石墨烯通过π-π共轭双键的芳环堆积作用很好的结合，其次芘上接枝的双亲性基团既能够使石墨烯均匀地分散在基体树脂中，又能够使石墨烯与尼龙之间的界面粘接力变强，相容性提高；
2）三辊研磨法能够使石墨烯很好地包覆在尼龙粒子的表面，易于形成良好的“导热通道”；
3）采用的不同粒度大小的填料以及高度取向的氮化硅纤维填充在基体树脂中，填料之间能够形成最大的堆砌度并且与纤维相互作用形成优异的导热网链。
具体实施方式
下面对本发明的优选实施例进行详细阐述，以使本发明的内容特点易于被本领域中的研究人员理解，从而对本发明的保护范围做出更为详实的界定。
实施例1：
本发明的高导热石墨烯/尼龙复合材料，其组份按质量份数，选取尼龙40份，可膨石墨4份，双亲性芘类接枝物0.8份，高取向氮化硅纤维10份，碳纤维10份，氮化硼7份，耐高温剂0.1份，抗氧剂0.3份，抗水解剂1份，增韧剂4份，首先将可膨石墨与双亲性芘类接枝物一同放置在具有一定比例H2O/MeOH=6/4的混合溶剂中进行超声振荡3h，然后进行离心处理，离心转速为1200rpm，时间为16min，上层清液即为分散的石墨烯溶液，将上清液放置70℃烘箱中干燥15h得到干燥粉状石墨烯。然后将所制得的石墨烯粉末与尼龙粒子混合均匀，在三辊研磨机中研磨10min，备用。最后将尼龙/石墨烯混合均匀的粒子与氮化硼、抗氧剂、抗水解剂、耐高温剂、增韧剂按配方比例在高混机中混合12min，混合均匀后加入双螺杆挤出机的料斗中，高取向氮化硅纤维与碳纤维按一定比例从螺杆的加纤口中加入，温度为230～260℃，主机频率为15～25Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高导热尼龙/石墨烯复合材料。
实施例2：
本发明的高导热石墨烯/尼龙复合材料，其组份按质量份数，选取尼龙40份，可膨石墨5份，双亲性芘类接枝物1份，高取向氮化硅纤维15份，碳纤维5份，氮化硼5份，耐高温剂0.3份，抗氧剂0.2份，抗水解剂1份，增韧剂6份，首先将可膨石墨与双亲性芘类接枝物一同放置在具有一定比例H2O/MeOH=7/3的混合溶剂中进行超声振荡3h，然后进行离心处理，离心转速为1300rpm，时间为20min，上层清液即为分散的石墨烯溶液，将上清液放置90℃烘箱中干燥18h得到干燥粉状石墨烯。然后将所制得的石墨烯粉末与尼龙粒子混合均匀，在三辊研磨机中研磨12min，备用。最后将尼龙/石墨烯混合均匀的粒子与氮化硼、抗氧剂、抗水解剂、耐高温剂、增韧剂按配方比例在高混机中混合15min，混合均匀后加入双螺杆挤出机的料斗中，高取向氮化硅纤维与碳纤维按一定比例从螺杆的加纤口中加入，温度为230～260℃，主机频率为15～25Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高导热尼龙/石墨烯复合材料。
实施例3：
本发明的高导热石墨烯/尼龙复合材料，其组份按质量份数，选取尼龙50份，可膨石墨5份，双亲性芘类接枝物1.2份，高取向氮化硅纤维12份，碳纤维8份，氮化硼8份，耐高温剂0.5份，抗氧剂0.4份，抗水解剂1.2份，增韧剂8份，首先将可膨石墨与双亲性芘类接枝物一同放置在具有一定比例H2O/MeOH=7/5的混合溶剂中进行超声振荡3h，然后进行离心处理，离心转速为1400rpm，时间为20min，上层清液即为分散的石墨烯溶液，将上清液放置100℃烘箱中干燥18h得到干燥粉状石墨烯。然后将所制得的石墨烯粉末与尼龙粒子混合均匀，在三辊研磨机中研磨16min，备用。最后将尼龙/石墨烯混合均匀的粒子与氮化硼、抗氧剂、抗水解剂、耐高温剂、增韧剂按配方比例在高混机中混合10min，混合均匀后加入双螺杆挤出机的料斗中，高取向氮化硅纤维与碳纤维按一定比例从螺杆的加纤口中加入，温度为230～260℃，主机频率为15～25Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高导热尼龙/石墨烯复合材料。
实施例4：
本发明的高导热石墨烯/尼龙复合材料，其组份按质量份数，选取尼龙60份，可膨石墨6份，双亲性芘类接枝物1.4份，高取向氮化硅纤维16份，碳纤维4份，氮化硼10份，耐高温剂1份，抗氧剂0.8份，抗水解剂3份，增韧剂6份，首先将可膨石墨与双亲性芘类接枝物一同放置在具有一定比例H2O/MeOH=5/4的混合溶剂中进行超声振荡3h，然后进行离心处理，离心转速为1500rpm，时间为30min，上层清液即为分散的石墨烯溶液，将上清液放置85℃烘箱中干燥17h得到干燥粉状石墨烯。然后将所制得的石墨烯粉末与尼龙粒子混合均匀，在三辊研磨机中研磨12min，备用。最后将尼龙/石墨烯混合均匀的粒子与氮化硼、抗氧剂、抗水解剂、耐高温剂、增韧剂按配方比例在高混机中混合17min，混合均匀后加入双螺杆挤出机的料斗中，高取向氮化硅纤维与碳纤维按一定比例从螺杆的加纤口中加入，温度为230～260℃，主机频率为15～25Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高导热尼龙/石墨烯复合材料。
按照国家标准，对上述高导热石墨烯/尼龙复合材料进行各项性能测试：
结果见下表：
注：强度保持率是指所制得的复合材料在80℃恒温水浴中浸泡24干燥处理后拉伸强度相对于未处理的复合材料的变化率。

Claims (8)

1.一种高导热石墨烯/尼龙复合材料，其特征在于：由以下以重量份数配比的原料制成：尼龙30～80份、可膨石墨4～8份、双亲性芘类接枝物0.5～1.5份、高取向氮化硅纤维1～20份、碳纤维1～15份、氮化硼5～10份、耐高温助剂0.02～4份、抗氧剂0.02～0.8份、抗水解剂1～3份、增韧剂2～6份；所述可膨石墨为粒度为60目可膨石墨或者70目可膨石墨或者80目可膨石墨三种物质中的一种或者几种的混合物。
2.如权利要求1所述的一种高导热石墨烯/尼龙复合材料，其特征在于：所述尼龙为特性粘度在1.6～3.8dL/g之间的尼龙6或者尼龙12或者尼龙66三种物质中的一种或者几种的混合物。
3.如权利要求1所述的一种高导热石墨烯/尼龙复合材料，其特征在于：所述双亲性芘类接枝物为芘与树枝状聚丙烯酸酯-聚乙二醇单甲醚嵌段共聚物或者树枝状聚丙烯酸酯-聚乙二醇乙醚嵌段共聚物或者树枝状聚乙二醇环氧甘油酯嵌段共聚物三者中的一种或者几种通过亲电取代反应所形成的物质。
4.如权利要求1所述的一种高导热石墨烯/尼龙复合材料，其特征在于：所述高取向氮化硅纤维为经偶联剂处理后的高取向氮化硅纤维；所用偶联剂为硅烷类偶联剂、钛酸酯类偶联剂或者络合物类偶联剂；所述碳纤维为经偶联剂处理后的高取向碳纤维；所用偶联剂为硅烷类偶联剂、钛酸酯类偶联剂或者络合物类偶联剂。
5.如权利要求1所述的一种高导热石墨烯/尼龙复合材料，其特征在于：所述氮化硼为纯度＞99%，粒径范围为5～15μm的六方氮化硼。
6.如权利要求1所述的一种高导热石墨烯/尼龙复合材料，其特征在于：所述耐高温助剂为烃基一硫代磷酸铜或烯基丁二酸铜或硫代氨基甲酸铜或以上几种复配。
7.如权利要求1所述的一种高导热石墨烯/尼龙复合材料，其特征在于：所述抗氧剂为N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺和三[2,4-二叔丁基苯基]亚磷酸酯按照质量比为8:1~2:1复配而成；所述抗水解剂为碳化二亚胺或者聚[次氮基甲烷四次氮基[2,4,6-三（1-甲乙基）-1,3-亚苯基]]或者三烯丙基异氰脲酸酯中的一种或几种复配；所述增韧剂为POE-g-GMA或EPDM-g-GMA或EPR-g-MAH或SWR-3C或是以上几种复配使用。
8.一种如权利要求1所述的高导热石墨烯/尼龙复合材料的制备方法，其特征在于：具体制备方法步骤如下：
1）石墨烯的制备
先将可膨石墨与双亲性芘类接枝物一同放置在具有一定比例H2O/MeOH的混合溶剂中进行超声振荡3～5h，然后进行离心处理，离心转速为1200～1500rpm，时间为15～30min，上层清液即为分散的石墨烯溶液，其浓度达到1.5～2mg/ml，将上清液放置70～100℃烘箱中干燥15～20h得到干燥粉状石墨烯；
2）将步骤1）中所制得的石墨烯粉末与尼龙粒子混合均匀，三辊研磨机中研磨10～15min，备用；
3）将步骤2）中所得尼龙/石墨烯混合均匀的粒子与氮化硼、抗氧剂、抗水解剂、耐高温剂、增韧剂按配方比例在高混机中混合10～25min，混合均匀后加入双螺杆挤出机的料斗中，高取向氮化硅纤维与碳纤维按一定比例从螺杆的加纤口中加入，温度为230～260℃，主机频率为15～25Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高导热尼龙/石墨烯复合材料。
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