CN108822317B - 一种石墨烯聚酰亚胺发热膜的制备方法 - Google Patents

一种石墨烯聚酰亚胺发热膜的制备方法 Download PDF

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CN108822317B
CN108822317B CN201810526763.8A CN201810526763A CN108822317B CN 108822317 B CN108822317 B CN 108822317B CN 201810526763 A CN201810526763 A CN 201810526763A CN 108822317 B CN108822317 B CN 108822317B
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杨新
汪丰礼
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Hangzhou New More Technology Co ltd
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Abstract

本发明采用多层复合结构制备石墨烯聚酰亚胺发热膜，通过的二酐和二胺单体进行预聚，并在聚酰胺溶液中加入石墨烯改性剂，加热局限亚胺化得到表层与底层，在中间加入石墨烯发热层，并在底层半干时进行表层涂敷，再涂覆表层，进行加热进行复合材料的酰亚胺化，使石墨烯聚酰亚胺发热膜各层间具有良好的结合性，同时兼具石墨烯与聚酰亚胺的优点，具有良好的导电和发热性能。同时花状氧化石墨烯褶皱化的独特结构，使得其活性增加，有益于氧化石墨烯在原料中的分散，并提高了石墨烯聚酰亚胺发热膜的力学性能。

Description

一种石墨烯聚酰亚胺发热膜的制备方法
技术领域
本发明属于复合材料领域，具体涉及一种石墨烯聚酰亚胺发热膜的制备方法。
背景技术
石墨烯是由碳原子组成的二维单层层状材料。石墨烯具有优异的光学、电学、力学特性，在材料学、微纳加工、能源、生物医学和药物传递等方面具有重要的应用前景，被认为是一种未来革命性的材料。石墨烯自身拥有高强度、高导热率以及良好的气体阻隔性等特性，是一种理想的层状纳米填料。聚酰亚胺具有良好的机械性能、热稳定性、耐溶剂性、耐化学腐蚀性等其他优异性能，几十年的应用研究表明，聚酰亚胺的高机械性能与耐化学腐蚀性可以适应各种苛刻的环境对材料性能的要求。因而被广泛应用于国民经济的诸多领域，比如载人航天、大型飞机、核电站、电子通讯、汽车等高科技产业。但是随着应用的拓展，对聚酰亚胺相关产品的要求不断提高。发热膜的发热材料和产品结构形态是决定发热膜产品性能的主要因素，其中发热材料起决定性作用。依据发热材料的不同把发热膜分为高分子、印刷油墨、碳纤维、金属丝(片)四种类型，这四种类型的发热膜因为同属于电加热元件，所以有共同或相似的特点，但是不同发热材料先天的物理、化学、电化学、电热等性质不同，又决定了不同类型发热膜性能有差异，本发明对聚酰亚胺的发热膜进行研究，加入石墨烯，增大添加剂的添加量提高了复合膜的性能。
发明内容
本发明的目的是克服现有技术的不足，提供了一种石墨烯聚酰亚胺发热膜的制备方法。所述的发热膜具有优异的发热和力学性能。
本发明的目的是通过以下技术方案实现的：一种石墨烯聚酰亚胺发热膜的制备方法，包括如下步骤：
(1)先将二胺溶解于有机溶剂中，在氮气保护下搅拌，再加入二酐和有机溶剂，在脱氧环境下进行缩聚反应，加入封端剂进行封端，得到固含量在18-24wt％的聚酰胺溶液，然后加入氧化石墨烯原料，搅拌得到复合溶液，过滤后通过涂刮得到初膜，加热干燥至半干得到膜A，其中，氧化石墨烯的质量为聚酰胺酸和氧化石墨烯总量的0.5wt％-5wt％；
(2)将石墨烯粉末与粘结剂混合涂于初膜A表面形成增强层C；
(3)采用步骤(1)的制备方法制备得到复合溶液，在增强层上刮涂得到初膜B，得到复合初膜；
(4)将步骤(3)所得复合初膜完全热处理进行酰亚胺化，得到石墨烯‐聚酰亚胺发热膜。
进一步的，步骤(2)中所采用的粘结剂为聚酰亚胺粘结剂。
进一步的，二酐单体包括三苯二醚四甲酸二酐，4,4’-(六氟异丙烯)二酞酸酐，二胺单体包括2,2’-双(三氟甲基)-4,4’-二氨基苯基醚，4,4’-双三氟甲基联苯。
进一步地，所述氧化石墨烯原料可以是花状氧化石墨烯粉末、花状氧化石墨烯溶液等。
进一步地，所述步骤1中的溶剂可以是水、DMF、DMAc、NMP、DMSO、甲醇、乙醇等溶剂。
进一步的，二酐和二胺的料比为45-60:50-55。
本发明的有益效果在于：本发明采用多层复合结构制备石墨烯聚酰亚胺发热膜，通过的二酐和二胺单体进行预聚，并在聚酰胺溶液中加入石墨烯改性剂，加热局限亚胺化得到表层与底层，在中间加入石墨烯发热层，并在底层半干时进行表层涂敷，再涂覆表层，进行加热进行复合材料的酰亚胺化，使石墨烯聚酰亚胺发热膜各层间具有良好的结合性，同时兼具石墨烯与聚酰亚胺的优点，具有良好的导电和发热性能。同时花状氧化石墨烯褶皱化的独特结构，使得其活性增加，有益于氧化石墨烯在原料中的分散，并提高了石墨烯聚酰亚胺发热膜的力学性能。
附图说明
图1为发热膜结构示意图。
具体实施方式
实施例1：
(1)先将二胺溶解于DMF中，在氮气保护下搅拌，再加入二酐和有机溶剂，在脱氧环境下进行缩聚反应，加入封端剂进行封端，得到固含量在18wt％的聚酰胺溶液，然后加入花状氧化石墨烯粉末，搅拌得到复合溶液，过滤后通过涂刮得到初膜，加热干燥至半干得到膜A，其中，氧化石墨烯的质量为聚酰胺酸和氧化石墨烯总量的1.5wt％-5wt％，二胺和二酐的加料比为45:45；
(2)将石墨烯粉末与聚酰亚胺粘结剂混合涂于初膜A表面形成增强层C；
(3)采用步骤(1)的制备方法制备得到复合溶液，在增强层上刮涂得到初膜B，得到复合初膜；
(4)将步骤(3)所得复合初膜完全热处理进行酰亚胺化，得到石墨烯‐聚酰亚胺发热膜。
其中，二酐单体为三苯二醚四甲酸二酐，二胺单体为2,2’-双(三氟甲基)-4,4’-二氨基苯基醚。
利用拉力机测定上述薄膜机械性能，拉伸强度为73.5MPa，杨氏模量为5.12GPa。
实施例2
(1)先将二胺溶解于DMAc中，在氮气保护下搅拌，再加入二酐和有机溶剂，在脱氧环境下进行缩聚反应，加入封端剂进行封端，得到固含量在20wt％的聚酰胺溶液，然后加入花状氧化石墨烯粉末，搅拌得到复合溶液，过滤后通过涂刮得到初膜，加热干燥至半干得到膜A，其中，氧化石墨烯的质量为聚酰胺酸和氧化石墨烯总量的3wt％，二胺和二酐的加料比为45:50；
(2)将石墨烯粉末与聚酰亚胺粘结剂混合涂于初膜A表面形成增强层C；
(3)采用步骤(1)的制备方法制备得到复合溶液，在增强层上刮涂得到初膜B，得到复合初膜；
(4)将步骤(3)所得复合初膜完全热处理进行酰亚胺化，得到石墨烯‐聚酰亚胺发热膜。
其中，二酐单体为4,4’-(六氟异丙烯)二酞酸酐，二胺单体为4,4’-双三氟甲基联苯。
利用拉力机测定上述薄膜机械性能，拉伸强度为70.1MPa，杨氏模量为5.10GPa。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。

Claims (6)

1.一种石墨烯聚酰亚胺发热膜的制备方法，包括如下步骤：
(1)先将二胺溶解于有机溶剂中，在氮气保护下搅拌，再加入二酐和有机溶剂，在脱氧环境下进行缩聚反应，加入封端剂进行封端，得到固含量在18-24wt％的聚酰胺溶液，然后加入氧化石墨烯原料，搅拌得到复合溶液，过滤后通过涂刮得到初膜，加热干燥至半干得到膜A，其中，氧化石墨烯的质量为聚酰胺酸和氧化石墨烯总量的0.5wt％-5wt％；
(2)将石墨烯粉末与粘结剂混合涂于初膜A表面形成增强层C；
(3)采用步骤(1)的制备方法制备得到复合溶液，在增强层上刮涂得到初膜B，得到复合初膜；
(4)将步骤(3)所得复合初膜完全热处理进行酰亚胺化，得到石墨烯-聚酰亚胺发热膜。
2.根据权利要求1所述的制备方法，步骤(2)中所采用的粘结剂为聚酰亚胺粘结剂。
3.根据权利要求1所述的制备方法，二酐单体包括三苯二醚四甲酸二酐，4,4’-(六氟异丙烯)二酞酸酐，二胺单体包括2,2’-双(三氟甲基)-4,4’-二氨基苯基醚，4,4’-双三氟甲基联苯。
4.根据权利要求1所述的制备方法，所述氧化石墨烯原料选用花状氧化石墨烯粉末或花状氧化石墨烯溶液。
5.根据权利要求1所述的制备方法，所述步骤(1)中的溶剂选用水、DMF、DMAc、NMP、DMSO、甲醇或乙醇。
6.根据权利要求1所述的制备方法，二酐和二胺的料比为45-60:50-55。
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