CN110172149A - 一种石墨烯掺杂聚酰亚胺薄膜 - Google Patents

一种石墨烯掺杂聚酰亚胺薄膜 Download PDF

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CN110172149A
CN110172149A CN201910503013.3A CN201910503013A CN110172149A CN 110172149 A CN110172149 A CN 110172149A CN 201910503013 A CN201910503013 A CN 201910503013A CN 110172149 A CN110172149 A CN 110172149A
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闵永刚
饶秋实
刘屹东
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Huimai Material Technology (guangdong) Co Ltd
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Abstract

本发明公开了一种石墨烯掺杂聚酰亚胺薄膜的制造方法。其具体制造方法为采取溶液混合的方法将石墨烯与二胺、二酐反应所得的聚酰胺酸充分混合，然后利用涂膜机将混合后聚酰胺酸均匀的涂布在平面板材上，再将其放入高温烘箱中进行亚胺化生成所需的聚酰亚胺。最后取出产品放入水中冷却半小时后将板材上的聚酰亚胺薄膜剥离后即可制得所需的材料。本方法制得的聚酰亚胺薄膜具有机械强度高，导电率提升显著的特点，是一种新型石墨烯掺杂聚酰亚胺薄膜。

Description

一种石墨烯掺杂聚酰亚胺薄膜
技术领域
本发明涉及一种薄膜制造方法，具体涉及一种石墨烯掺杂聚酰亚胺薄膜制造方法。
背景技术
聚酰亚胺(PI)是指主链上含有酰亚胺环的一类聚合物材料，是目前已经实现工业化的特殊高分子材料，具有优越的物理机械综合性能，优良的电气与化学稳定性，广泛的应用于高新技术领域。而聚酰亚胺薄膜是其中最早的商品之一同时又是用量最大的一种。这种新型耐高温有机聚合物薄膜是目前世界上性能最好的薄膜类绝缘材料和最贵的薄膜材料之一，被称为“黄金薄膜”。聚酰亚胺薄膜优良的性能使得其在诸多领域发挥着越来越重要的作用。聚酰亚胺薄膜与碳纤维、芳纶纤维一起，被认为是目前制约我国发展高技术产业的三大瓶颈性关键高分子材料。
目前，国内聚酰亚胺薄膜存在着产品质量差、综合性能不稳定、产品精细化程度不够、品种少等缺点，影响了其应用。石墨烯作为迄今为止最薄的二维材料，具有优异的机械性能、电学性能、光学性能及热学性能，已成为当今新材料研究的热点。聚合物材料具有易成型及成本低等特点而具有广泛的应用。然而，由于聚合物材料较低的力学性能、固有的绝缘性等特点不能满足一些领域的应用。利用炭纳米材料改性及增强聚合物被认为是十分有效的途径。本发明提供了一种石墨烯掺杂的聚酰亚胺薄膜的制造方法，生产出的聚酰亚胺薄膜机械性能好且导电，可应用在许多特殊领域。
发明内容
本发明目的在于提供一种石墨烯掺杂聚酰亚胺薄膜的制作方法。
对于一种石墨烯掺杂聚酰亚胺薄膜的制造方法，本发明所采取的技术方案为：一种石墨烯掺杂聚酰亚胺薄膜的制造方法。其具体制造方法为采取溶液混合的方法将石墨烯与二胺、二酐反应所得的聚酰胺酸充分混合，然后利用涂膜机将混合后聚酰胺酸均匀的涂布在平面板材上，再将其放入高温烘箱中进行亚胺化生成所需的聚酰亚胺。最后取出产品放入水中冷却半小时后将板材上的聚酰亚胺薄膜剥离后即可制得所需的材料。
作为优选，所采用的石墨烯可以是石墨烯粉末，也可以是氧化石墨烯，氧化还原石墨烯等，石墨烯作为一种填料，可以有效改善聚酰亚胺性能。
作为优选，所采用制造聚酰胺酸的方法为先将二氨基二苯醚溶入二甲基乙酰胺中，而后再缓慢加入均苯四甲酸二酐，当二氨基二苯醚与均苯四甲酸二酐摩尔数相等时体系黏度会快速增大，此时停止加入均苯四甲酸二酐。
作为优选，所采用的溶液混合法是先将石墨烯溶入二甲基乙酰胺中，而后再将其与制好的聚酰胺酸充分搅拌混合，再抽真空去除气泡，即可制得混有石墨烯的聚酰亚胺溶液。
作为优选，所采用的平面板材可以是钢化玻璃板，所采用薄膜厚度可以是20微米。
作为优选，生成聚酰胺酸在高温烘箱中进行亚胺化的温度开始可以是80℃保温1H，接着100℃,150℃,200℃,250℃，300℃各保温30分钟。
与现有技术相比所具有的优势是：
1：本发明采用溶液聚合将石墨烯溶入聚酰胺酸中，而后再进行亚胺化生产聚酰亚胺，制作方法简便，纳米颗粒在聚酰亚胺中分散良好。
2：本发明生产的聚酰亚胺具有高机械强度高导电率的特性，可应用在一些特殊的领域。
具体实施方式
下面将结合本发明的方法进行实例描述，对本发明实例中的技术方案进行描述，显然，所述的实例仅仅是本发明一部分实例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。
例1：称取50g二氨基二苯醚，将其溶于400g二甲基乙酰胺溶液中，边搅拌边缓慢加入63.2g均苯四甲酸二酐中，搅拌直至溶液黏度变大出现爬杆现象。称取200g石墨烯粉末，溶入250g的二甲基乙酰胺溶液中，搅拌混合均匀，再将其与聚酰胺酸溶液混合，搅拌3H，抽真空去除气泡。将上述液体取出利用自动涂膜机将其均匀的涂覆在钢化玻璃板上，使其膜厚为20微米，接着将覆有聚酰胺酸溶液的钢化玻璃板放入高温烘箱中，控制升温保温速度，使其进行亚胺化，温度调控开始可以是80℃保温1H，接着在100℃、150℃、200℃、250℃、300℃各保温30分钟。最后等烘箱温度降低取出板材，放入水中冷却30分钟，将上面的聚酰亚胺薄膜剥落即可制得具有石墨烯掺杂的聚酰亚胺薄膜。
在室温下测试聚酰亚胺与石墨烯复合膜的机械强度如下表所示：

Claims (7)

1.一种石墨烯掺杂聚酰亚胺薄膜的制造方法。其特征在于具体制造方法为采取溶液混合的方法将石墨烯与二胺、二酐反应所得的聚酰胺酸充分混合，然后利用涂膜机将混合后聚酰胺酸均匀的涂布在平面板材上，再将其放入高温烘箱中进行亚胺化生成所需的聚酰亚胺。最后取出产品放入水中冷却半小时后将板材上的聚酰亚胺薄膜剥离后即可制得所需的材料。
2.根据权利要求1所述的一种石墨烯掺杂聚酰亚胺薄膜的制造方法，其特征在于所述的制造聚酰胺酸的方法为先将二胺溶入溶剂中，而后再缓慢加入二酐，当二胺与二酐摩尔数相等时体系黏度会快速增大，此时停止加入二酐。
3.根据权利要求2所述的一种石墨烯掺杂聚酰亚胺薄膜的制造方法，其特征在于所述的二胺可以是44-二氨基二苯醚与对苯二胺等，所述的二酐可以是均苯四甲酸二酐与联苯四甲酸二酐，所述的溶剂可以是二甲基乙酰胺与二甲基甲酰胺。
4.根据权利要求1所述的一种石墨烯掺杂聚酰亚胺薄膜的制造方法，其特征在于所述的溶液混合法是指讲石墨烯先溶入溶剂中，溶剂可以是二甲基乙酰胺或二甲基甲酰胺，再将其与聚酰胺酸混合，搅拌均匀，抽真空去除气泡即可制得混有石墨烯的聚酰胺酸溶液。
5.根据权利要求1所述的一种石墨烯掺杂聚酰亚胺薄膜的制造方法，其特征在于所述的平面板材可以是钢化玻璃板材，也可以是不锈钢板材，涂在平面板材上薄膜的厚度可以是5-200微米。
6.根据权利要求1所述的一种石墨烯掺杂聚酰亚胺薄膜的制造方法，其特征在于高温烘箱中进行亚胺化的温度开始可以是80℃保温1H，接着100℃,150℃,200℃,250℃，300℃各保温30分钟。
7.根据权利要求1所述的一种石墨烯掺杂聚酰亚胺薄膜的制造方法，其特征在于二酐与二胺的质量总和可以占溶剂质量的10％到30％，所述的石墨烯填料可以占二酐与二胺质量总和的1％到200％。
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