CN103772926A - 高性能阻燃pla/石墨烯纳米片复合材料及其制备方法 - Google Patents

高性能阻燃pla/石墨烯纳米片复合材料及其制备方法 Download PDF

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CN103772926A
CN103772926A CN201310700056.3A CN201310700056A CN103772926A CN 103772926 A CN103772926 A CN 103772926A CN 201310700056 A CN201310700056 A CN 201310700056A CN 103772926 A CN103772926 A CN 103772926A
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nanometer sheet
pla
graphene nanometer
silane coupling
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虞小波
杨玉晴
蔡铜祥
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Jiangsu Yueda Novel Material Science And Technology Ltd
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Abstract

本发明公开了一种高性能阻燃PLA/石墨烯纳米片复合材料的制备方法。按重量份数，包含：PLA30～100份、阻燃剂10～30份、阻燃协效剂5～10份、成核促进剂1～5份、增韧剂2～6份、石墨烯纳米片1～6份、碳纤维5～15份、玻璃纤维10～20份、滑石粉5～25份。本发明采用经硅烷偶联剂表面处理过的石墨烯纳米片用以提高PLA的机械性能。其优点在于：提高石墨烯纳米片与PLA的相容性，能够使石墨烯纳米片很好地分散在基体树脂中，并且能够起到协效阻燃的效果。

Description

高性能阻燃PLA/石墨烯纳米片复合材料及其制备方法
技术领域
本发明涉及一种PLA/石墨烯纳米片复合材料，具体涉及一种高性能阻燃PLA/石墨烯纳米片复合材料及其制备方法。 
背景技术
PLA（聚乳酸）是一种热塑性脂肪族聚酯，生产聚乳酸所需要的乳酸和丙交酯可以通过可再生资源发酵、脱水、纯化后得到，所得到的聚乳酸一般具有良好的机械和加工性能，而聚乳酸产品废弃后又可以通过各种方式快速降解，是一种具备良好使用性能的绿色塑料。但PLA材料本身较脆，不具有阻燃性且耐热性较差，这极大的限制了其应用。 
石墨烯纳米片，简称GNSs（Graphene nanosheets）或GNFs(Graphene Nano Flakes)，也称为碳纳米片CNFs(Carbon nanoflakes)或碳纳米壁CNWs(Carbon nanowalls)，是由单层碳原子平面结构石墨烯堆垛而成，厚度为纳米尺度的两维石墨纳米材料，其极端情况是单层石墨烯，其具有较大的比表面积和层状结构，能够在基体中形成很好的支撑网络结构，对于提高PLA各项性能具有深远的研究意义。 
发明内容
本发明的目的是为了克服现有技术的不足，提供一种优异阻燃性能、良好韧性、耐高温性能好、综合机械强度高的PLA/石墨烯纳米片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：PLA（聚乳酸）30～100份，阻燃剂10～30份，阻燃协效剂5～10份，成核促进剂1～5份，增韧剂2～6份，石墨烯纳米片1～6份，碳纤维5～15份，玻璃纤维10～20份，滑石粉5～25份；其中，所述石墨烯纳米片的比表面积达到80～100m2/g，并且经过硅烷偶联剂KH792处理过。 
所述PLA（聚乳酸）的重均分子量为6万～80万，熔点为60℃。 
所述阻燃剂为膨胀型阻燃剂，酸源为聚磷酸铵，碳源为木质素，气源为三聚氰胺。 
所述阻燃协效剂为α-磷酸锆与有机蒙脱土或者凹凸棒土或者埃洛石中的一种或者两种的组合物；所述成核促进剂为碳酸钙或者硫酸钡或者云母中的一种或者两种的组合物；所述增韧剂为HBP（超支化聚酰胺）。 
所述碳纤维经硅烷偶联剂KH550或者硅烷偶联剂KH560或者硅烷偶联剂KH570处理过；所述玻璃纤维经硅烷偶联剂KH550或者硅烷偶联剂KH560或者硅烷偶联剂KH570处理过。 
所述滑石粉的粒径小于40μm。 
具体制备方法步骤如下： 
1）石墨烯纳米片的处理 
将石墨烯纳米片与硅烷偶联剂KH792一起放置于DMF溶剂中，机械搅拌持续1～3小时，转速500rpm～1500rpm，混合均匀后，放置于干燥烘箱中，温度控制在45℃～55，℃持续烘干6小时，得到表面改性的石墨烯纳米片； 
2）将步骤1）中所制得的石墨烯纳米片与聚乳酸粒子混合均匀，三辊研磨机中研磨20～30min，备用； 
3）将步骤2）中所得PLA/石墨烯纳米片混合均匀的粒子与阻燃剂、阻燃协效剂、增韧剂、成核促进剂、滑石粉按配方比例在高混机中混合10～30min，混合均匀后加入双螺杆挤出机的料斗中，碳纤维以及玻璃纤维按一定比例从螺杆的加纤口中加入，温度为170～220℃，主机频率为10～20Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高性能PLA/石墨烯纳米片复合材料。 
本发明与现有技术相比，所具备的优点是： 
1）采用溶液共混法制备出硅烷偶联剂表面处理的石墨烯纳米片，能够使石墨烯纳米片与基体树脂具有很好的相容性。 
2）超支化聚合物(HBP)是由小分子通过倍增方式合成的一类具有三维结构的聚合物。HBP拥有较大的相对分子质量，却显示出很低的黏度，因此被用来降低聚合物的熔体黏度，改善聚合物的熔体流动性。尤其是HBP表面拥有大量活性基团，如羟基和羰基等，通过与其它基团反应或与基体产生相互作用，增韧效果极佳。 
3）采用膨胀型阻燃剂与层状硅酸盐纳米材料复配阻燃，能够在基体表面形成连续且致密的炭层，并且不会产生融滴。 
具体实施方式
实施例1： 
本发明的高性能阻燃PLA/石墨烯纳米片复合材料，其组份按质量份数，选取PLA30份，膨胀型阻燃剂12份，阻燃协效剂5份，成核促进剂2份，增韧剂3份，石墨烯纳米片2份，碳纤维6份，玻璃纤维10份，滑石粉5份，首先将石墨烯纳米片与硅烷偶联剂KH792一起放置于四氢呋喃（DMF）溶剂中，机械搅拌持续1小时，转速800rpm，混合均匀后，放置于干燥烘箱中，温度控制在45，℃持续烘干6小时，得到表面改性的石墨烯纳米片。再将所制得的石墨烯纳米片与聚乳酸粒子混合均匀，三辊研磨机中研磨20min，备 用。最后将所得PLA/石墨烯纳米片混合均匀的粒子与阻燃剂、阻燃协效剂、增韧剂、成核促进剂、滑石粉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，碳纤维以及玻璃纤维按一定比例从螺杆的加纤口中加入，温度为170～220℃，主机频率为10～20Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高性能PLA/石墨烯纳米片复合材料。 
实施例2： 
本发明的高性能阻燃PLA/石墨烯纳米片复合材料，其组份按质量份数，选取PLA50份，膨胀型阻燃剂15份，阻燃协效剂7份，成核促进剂3份，增韧剂5份，石墨烯纳米片3份，碳纤维10份，玻璃纤维15份，滑石粉10份，首先将石墨烯纳米片与硅烷偶联剂KH792一起放置于DMF溶剂中，机械搅拌持续3小时，转速1000rpm，混合均匀后，放置于干燥烘箱中，温度控制在55，℃持续烘干6小时，得到表面改性的石墨烯纳米片。再将所制得的石墨烯纳米片与聚乳酸粒子混合均匀，三辊研磨机中研磨20min，备用。最后将所得PLA/石墨烯纳米片混合均匀的粒子与阻燃剂、阻燃协效剂、增韧剂、成核促进剂、滑石粉按配方比例在高混机中混合20min，混合均匀后加入双螺杆挤出机的料斗中，碳纤维以及玻璃纤维按一定比例从螺杆的加纤口中加入，温度为170～220℃，主机频率为10～20Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高性能PLA/石墨烯纳米片复合材料。 
实施例3： 
本发明的高性能阻燃PLA/石墨烯纳米片复合材料，其组份按质量份数，选取PLA70份，膨胀型阻燃剂25份，阻燃协效剂10份，成核促进剂4份，增韧剂5份，石墨烯纳米片5份，碳纤维15份，玻璃纤维15份，滑石粉17份，首先将石墨烯纳米片与硅烷偶联剂KH792一起放置于DMF溶剂中，机械搅拌持续1～3小时，转速1500rpm，混合均匀后，放置于干燥烘箱中，温度控制在55，℃持续烘干6小时，得到表面改性的石墨烯纳米片。再将所制得的石墨烯纳米片与聚乳酸粒子混合均匀，三辊研磨机中研磨30min，备用。最后将所得PLA/石墨烯纳米片混合均匀的粒子与阻燃剂、阻燃协效剂、增韧剂、成核促进剂、滑石粉按配方比例在高混机中混合30min，混合均匀后加入双螺杆挤出机的料斗中，碳纤维以及玻璃纤维按一定比例从螺杆的加纤口中加入，温度为170～220℃，主机频率为10～20Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高性能PLA/石墨烯纳米片复合材料。 
实施例4： 
本发明的高性能阻燃PLA/石墨烯纳米片复合材料，其组份按质量份数，选取PLA100 份，膨胀型阻燃剂30份，阻燃协效剂10份，成核促进剂5份，增韧剂6份，石墨烯纳米片6份，碳纤维15份，玻璃纤维20份，滑石粉25份，首先将石墨烯纳米片与硅烷偶联剂KH792一起放置于DMF溶剂中，机械搅拌持续3小时，转速1500rpm，混合均匀后，放置于干燥烘箱中，温度控制在50℃，持续烘干6小时，得到表面改性的石墨烯纳米片。再将所制得的石墨烯纳米片与聚乳酸粒子混合均匀，三辊研磨机中研磨30min，备用。最后将所得PLA/石墨烯纳米片混合均匀的粒子与阻燃剂、阻燃协效剂、增韧剂、成核促进剂、滑石粉按配方比例在高混机中混合25min，混合均匀后加入双螺杆挤出机的料斗中，碳纤维以及玻璃纤维按一定比例从螺杆的加纤口中加入，温度为170～220℃，主机频率为10～20Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高性能PLA/石墨烯纳米片复合材料。 
按照国家标准，对上述高性能阻燃PLA/石墨烯纳米片复合材料进行各项性能测试： 
结果见下表： 
Figure BDA0000440840750000041
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 (7)

1.一种高性能阻燃PLA/石墨烯纳米片复合材料，其特征在于：由以下以重量份数配比的原料制成：PLA（聚乳酸）30～100份，阻燃剂10～30份，阻燃协效剂5～10份，成核促进剂1～5份，增韧剂2～6份，石墨烯纳米片1～6份，碳纤维5～15份，玻璃纤维10～20份，滑石粉5～25份；其中，所述石墨烯纳米片的比表面积达到80～100m2/g，并且经过硅烷偶联剂KH792处理过。
2.如权利要求1所述的一种高性能阻燃PLA/石墨烯纳米片复合材料，其特征在于：所述PLA（聚乳酸）的重均分子量为6万～80万，熔点为60℃。
3.如权利要求1所述的一种高性能阻燃PLA/石墨烯纳米片复合材料，其特征在于：所述阻燃剂为膨胀型阻燃剂，酸源为聚磷酸铵，碳源为木质素，气源为三聚氰胺。
4.如权利要求1所述的一种高性能阻燃PLA/石墨烯纳米片复合材料，其特征在于：所述阻燃协效剂为α-磷酸锆与有机蒙脱土或者凹凸棒土或者埃洛石中的一种或者两种的组合物；所述成核促进剂为碳酸钙或者硫酸钡或者云母中的一种或者两种的组合物；所述增韧剂为HBP（超支化聚酰胺）。
5.如权利要求1所述的一种高性能阻燃PLA/石墨烯纳米片复合材料，其特征在于：所述碳纤维经硅烷偶联剂KH550或者硅烷偶联剂KH560或者硅烷偶联剂KH570处理过；所述玻璃纤维经硅烷偶联剂KH550或者硅烷偶联剂KH560或者硅烷偶联剂KH570处理过。
6.如权利要求1所述的一种高性能阻燃PLA/石墨烯纳米片复合材料，其特征在于：所述滑石粉的粒径小于40μm。
7.一种高性能阻燃PLA/石墨烯纳米片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）石墨烯纳米片的处理
将石墨烯纳米片与硅烷偶联剂KH792一起放置于DMF溶剂中，机械搅拌持续1～3小时，转速500rpm～1500rpm，混合均匀后，放置于干燥烘箱中，温度控制在45℃～55，℃持续烘干6小时，得到表面改性的石墨烯纳米片；
（2）将步骤（1）中所制得的石墨烯纳米片与聚乳酸粒子混合均匀，三辊研磨机中研磨20～30min，备用；
（3）将步骤（2）中所得PLA/石墨烯纳米片混合均匀的粒子与阻燃剂、阻燃协效剂、增韧剂、成核促进剂、滑石粉按配方比例在高混机中混合10～30min，混合均匀后加入双螺杆挤出机的料斗中，碳纤维以及玻璃纤维按一定比例从螺杆的加纤口中加入，温度为170～220℃，主机频率为10～20Hz，经熔融共混挤出，挤出物料经冷去后吹干切粒，制得高性能PLA/石墨烯纳米片复合材料。
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Application publication date: 20140507