CN113773544B - 一种含原位聚合绝缘涂层的碳纳米管电热膜的制备方法 - Google Patents
一种含原位聚合绝缘涂层的碳纳米管电热膜的制备方法 Download PDFInfo
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Abstract
本发明涉及高分子材料领域，公开了一种含原位聚合绝缘涂层的碳纳米管电热膜的制备方法。本发明首先通过将碳纳米管强制分散在有机溶剂中，然后加入正硅酸四乙酯、硅烷偶联剂和羟基树脂对其进行改性，避免团聚，再将改性后的碳纳米管分散液置于聚四氟乙烯滤膜表面抽滤、干燥、剥离，得到改性碳纳米管薄膜，再将偏苯三酸酐和二异氰酸酯制备得到的聚酰胺酰亚胺预聚体加入，在改性碳纳米管薄膜表面原位聚合得到聚酰胺酰亚胺绝缘层；实现了聚酰胺酰亚胺绝缘材料在电热膜上的应用。该绝缘层耐热性能好，不易老化，且通过原位聚合的方式与电热膜复合，贴合度好，无需外加胶黏剂。
Description
技术领域
本发明涉及高分子材料领域，尤其涉及一种含原位聚合绝缘涂层的碳纳米管电热膜的制备方法。
背景技术
电热膜是近年来发展很快的新型电加热技术，以电热膜为发热元件，通电后能够产生热能，热量以辐射的形式进入周围空间中。与传统的利用电热丝为电阻元件的通电散发热量方式相比，电热膜在使用时无需二次传、导热，加热快速、均匀，使用安全、方便，热能利用率能达到95％以上，是一种清洁高效的加热方式。根据电热膜使用的材料可以将电热膜分为金属材料电热膜和非金属材料电热膜，其中碳系电热薄膜为最常见的非金属材料电热膜。
纳米碳管是一种由单层或多层石墨片层围绕同一中心轴按特定的螺旋角缠绕而成的无缝纳米材料。碳纳米管具有低密度、高长径比、高石墨化程度等结构特点，机械强度高、导电性和导热性良好，可作为复合材料增强材料，同时由于其良好的导电性和成膜后的高可见光透射率，因此可用于透明导电膜。碳纳米管的柔韧性优越、重量轻、加热快、易于加工，已成为电热膜领域的研究热点；可以说碳纳米管几乎是一种理想的电加热材料。但碳纳米管具有较大的比表面积，容易发生团聚，与其他材料结合的界面效应差，几乎不能均匀分散到任何溶剂中，制备的薄膜均匀性差。
电热膜两侧分别为绝缘层和装饰层，其中装饰层作为电热膜的最外层由电热膜加热，将热量直接以辐射热方式散发，绝缘层可以防止热量以热传导的方式向另一侧散失，同时也防止漏电危险性。常用的绝缘层采用阻燃聚酯薄膜，耐热性能有限容易老化，且需要通过黏结剂才能和电热膜进行复合，而传统黏结剂也容易受热老化，因此容易导致绝缘层脱落。
聚酰胺酰亚胺是由柔性酰胺基团和耐热酰亚胺环有规则排列的一种热塑性树脂，具有一定的柔性和优良的耐高温性、介电性、绝缘性，对金属及其他材料有很突出的粘结性能，作为耐高温绝缘涂层已广泛应用于航空航天、电子、消防、漆包线漆等领域。聚酰胺酰亚胺是一种理想的绝缘层材料，但由于聚酰胺酰亚胺无法和PET聚酯一样作为基体膜材料，贴合碳材料膜来形成电热膜，因此将聚酰胺酰亚胺应用到电热膜中尚未见文献报道。
发明内容
为了解决上述技术问题，本发明提供了一种含原位聚合绝缘涂层的碳纳米管电热膜的制备方法。本发明首先通过将碳纳米管强制分散在有机溶剂中，然后加入正硅酸四乙酯和硅烷偶联剂对其进行改性，避免团聚，再将改性后的碳纳米管分散液置于聚四氟乙烯滤膜表面抽滤、干燥、剥离，得到改性碳纳米管薄膜，再将偏苯三酸酐和二异氰酸酯制备得到的聚酰胺酰亚胺预聚体加入，在改性碳纳米管薄膜表面原位聚合得到聚酰胺酰亚胺绝缘层；实现了聚酰胺酰亚胺绝缘材料在电热膜上的应用。该绝缘层耐热性能好，不易老化，且通过原位聚合的方式与电热膜复合，贴合度好，无需外加胶黏剂。
本发明的具体技术方案为：
一种含原位聚合绝缘涂层的碳纳米管电热膜的制备方法，包括以下步骤：
1)碳纳米管薄膜的制备：将碳纳米管加入到有机溶剂中，高速剪切搅拌20-40min，转速4000-6000rpm，然后加入氨水和水，再缓慢滴加正硅酸四乙酯、硅烷偶联剂和羟基树脂的混合液，经1-2h滴加结束，继续搅拌反应1-2h；然后将改性后的碳纳米管分散液置于含聚四氟乙烯滤膜的抽滤装置中，真空抽滤3-4h，然后在70-90℃干燥3-4h，将聚四氟乙烯滤膜取出，浸泡在无水乙醇中，通过机械剥离，室温干燥后，得到改性碳纳米管薄膜。
2)绝缘涂层的制备：将偏苯三酸酐溶于N-甲基吡咯烷酮，然后加入二异氰酸酯，升温至120-140℃，保温反应2-3h，加入封闭剂，继续保温反应1-2h，得到聚酰胺酰亚胺预聚体，均匀涂布在改性碳纳米管薄膜上，升温至180-200℃，保温反应1-2h，使聚酰胺酰亚胺预聚体解封，在改性碳纳米管薄膜表层发生原位聚合反应，得到含原位聚合绝缘涂层的碳纳米管电热膜。
本发明的技术原理如下：
步骤1)中，本发明采用正硅酸四乙酯和硅烷偶联剂对碳纳米管进行改性，使其在有机溶剂中均匀分散，避免发生团聚，然后通过真空抽滤法制备碳纳米管薄膜，将改性的碳纳米管分散液沉积在聚四氟乙烯微孔滤膜上，干燥后剥离得到，制备方法简单，薄膜均匀缺陷少。本发明通过将正硅酸四乙酯和硅烷偶联剂在氨水的催化下，发生水解-缩合反应，既可以改善碳纳米管的分散性，同时由于具有丰富的硅羟基和氨基/环氧基官能团，可以起到黏结剂的效果，可在后续的原位聚合过程中，与异氰酸酯基反应，将聚酰胺酰亚胺绝缘层均匀牢固的粘结到碳纳米管薄膜上。
步骤2)中，本发明通过封闭剂对偏苯三酸酐和二异氰酸酯反应的产物进行封闭，得到的聚酰胺酰亚胺预聚体分子量低，在原位聚合的过程中，升温至解封温度，脱去封闭剂，重新生成异氰酸酯基，自身发生交联固化反应，同时和碳纳米管表面的硅羟基和氨基/环氧基官能团进行反应，牢固的结合在碳纳米管薄膜表面。
作为优选，所述改性碳纳米管薄膜的厚度为35-50μm；所述聚酰胺酰亚胺绝缘层厚度为10-25μm。
作为优选，步骤1)中：所述有机溶剂选自无水乙醇、异丙醇和仲丁醇中的一种或多种。
作为优选，步骤1)中：所述羟基树脂选自羟值为80-120mg KOH/g的羟基聚酯树脂和羟基丙烯酸树脂中的一种或多种。
作为优选，步骤1)中：所述硅烷偶联剂选自γ-(2，3-环氧丙氧)丙基三甲氧基硅烷、β-(3、4环氧环己基)-乙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷和N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷中的一种或多种。
作为优选，步骤1)中：所述碳纳米管、有机溶剂、氨水、水、正硅酸四乙酯、硅烷偶联剂和羟基树脂的质量比为2-5∶20-40∶2-5∶20-40∶10-20∶1-5∶10-20。
作为优选，步骤2)中：所述二异氰酸酯选自二苯基甲烷-4,3’-二异氰酸酯、甲苯二异氰酸酯、对苯二异氰酸酯和3,3′-二甲基-4,3’-联苯二异氰酸酯中的一种或多种。
作为优选，步骤2)中：所述封闭剂选自苯酚、对氯苯酚。
作为优选，步骤2)中：所述偏苯三酸酐和二异氰酸酯的摩尔比为1∶1-1.02。
作为优选，步骤2)中：所述N-甲基吡咯烷酮的质量为偏苯三酸酐和二异氰酸酯的质量总和的2-3倍。
作为优选，步骤2)中：所述封闭剂的质量为二异氰酸酯的2-5wt％。
与现有技术相比，本发明具有以下技术效果：
1、本发明通过正硅酸四乙酯和硅烷偶联剂对碳纳米管进行改性，避免了碳纳米管的团聚，然后通过真空抽滤法制备碳纳米管薄膜，薄膜厚度可控，均匀缺陷少。
2、本发明加入的正硅酸四乙酯和硅烷偶联剂水解-缩合后，仍具有丰富的硅羟基和氨基/环氧基活性官能团，同时引入高羟基树脂，赋予碳纳米管优异的柔韧性。
3、本发明通过苯酚类封闭剂对聚酰胺酰亚胺的异氰酸酯基进行封闭，得到的聚酰胺酰亚胺预聚体，在达到解封温度后，重新生成异氰酸酯基，发生原位聚合反应时，和碳纳米管表面的羟基、硅羟基和氨基/环氧基活性官能团进行反应，无需外加胶黏剂，贴合度好。
4、本发明的合成方法简单、易于工业化，制备得到的碳纳米管电热膜可应用于低电压电热产品。
具体实施方式
下面结合实施例对本发明作进一步的描述。
总实施例
一种含原位聚合绝缘涂层的碳纳米管电热膜的制备方法，包括以下步骤：
1)碳纳米管薄膜的制备：将碳纳米管加入到有机溶剂中，高速剪切搅拌20-40min，转速4000-6000rpm，然后加入氨水和水，再缓慢滴加正硅酸四乙酯、硅烷偶联剂和羟基树脂的混合液，经1-2h滴加结束，继续搅拌反应1-2h，然后将改性后的碳纳米管分散液置于聚四氟乙烯滤膜的布氏漏斗中，抽滤3-4h，然后在70-90℃干燥3-4h，将聚四氟乙烯滤膜取出，浸泡在无水乙醇中，通过机械剥离，室温干燥后，得到改性碳纳米管薄膜(厚度为35-50μm)。
其中，有机溶剂选自无水乙醇、异丙醇、仲丁醇。羟基树脂选自羟基聚酯树脂、羟基丙烯酸树脂，羟值为80-120mg KOH/g。硅烷偶联剂选自γ-(2，3-环氧丙氧)丙基三甲氧基硅烷、β-(3、4环氧环己基)-乙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷。碳纳米管、有机溶剂、氨水、水、正硅酸四乙酯、硅烷偶联剂和羟基树脂的质量比为2-5∶20-40∶2-5∶20-40∶10-20∶1-5∶10-20。
2)绝缘涂层的制备：将偏苯三酸酐溶于N-甲基吡咯烷酮，然后加入二异氰酸酯，升温至120-140℃，保温反应2-3h，加入封闭剂，继续保温反应1-2h，得到聚酰胺酰亚胺预聚体，均匀涂布在改性碳纳米管薄膜上，升温至180-200℃，保温反应1-2h，使聚酰胺酰亚胺预聚体解封，在改性碳纳米管薄膜表层发生原位聚合反应，得到碳纳米管电热膜表面原位聚合的绝缘涂层，聚酰胺酰亚胺绝缘层的厚度为10-25μm。
其中，二异氰酸酯选自二苯基甲烷-4,3’-二异氰酸酯、甲苯二异氰酸酯、对苯二异氰酸酯、3，3′-二甲基-4,3’-联苯二异氰酸酯。封闭剂选自苯酚、对氯苯酚。偏苯三酸酐和二异氰酸酯的摩尔比为1∶1-1.02。N-甲基吡咯烷酮的质量为偏苯三酸酐和二异氰酸酯的质量总和的2-3倍。封闭剂的质量为二异氰酸酯的2-5wt％。
实施例1
1)碳纳米管薄膜的制备：将碳纳米管加入到异丙醇中，高速剪切搅拌20min，转速4000rpm，然后加入氨水和水，再缓慢滴加正硅酸四乙酯、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷和羟值为80mg KOH/g的羟基聚酯树脂混合液，经1h滴加结束，继续搅拌反应2h，然后将改性后的碳纳米管分散液置于聚四氟乙烯滤膜的布氏漏斗中，抽滤3h，然后在70℃干燥4h，将聚四氟乙烯滤膜取出，浸泡在无水乙醇中，通过机械剥离，室温干燥后，得到厚度为35μm的改性碳纳米管薄膜；碳纳米管、异丙醇、氨水、水、正硅酸四乙酯、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷和羟基聚酯树脂的质量比为2∶20∶3∶20∶10∶1∶10；
2)绝缘涂层的制备：将偏苯三酸酐溶于N-甲基吡咯烷酮，然后加入二苯基甲烷-4,3’-二异氰酸酯，升温至120℃，保温反应3h，加入苯酚，继续保温反应1h，得到聚酰胺酰亚胺预聚体，均匀涂布在改性碳纳米管薄膜上，升温至180℃，保温反应2h，使聚酰胺酰亚胺预聚体解封，在改性碳纳米管薄膜表层发生原位聚合反应，得到碳纳米管电热膜表面原位聚合的绝缘涂层，绝缘涂层厚度为25μm；偏苯三酸酐和二苯基甲烷-4,4’-二异氰酸酯的摩尔比为1∶1，N-甲基吡咯烷酮的质量为偏苯三酸酐和二苯基甲烷-4,4’-二异氰酸酯的质量总和的3倍，苯酚的质量为二苯基甲烷-4,4’-二异氰酸酯的2wt％。
实施例2
1)碳纳米管薄膜的制备：将碳纳米管加入到无水乙醇中，高速剪切搅拌40min，转速6000rpm，然后加入氨水和水，再缓慢滴加正硅酸四乙酯、β-(3、4环氧环己基)-乙基三甲氧基硅烷和羟值为120mg KOH/g的羟基丙烯酸树脂的混合液，经2h滴加结束，继续搅拌反应1h，然后将改性后的碳纳米管分散液置于聚四氟乙烯滤膜的布氏漏斗中，抽滤4h，然后在90℃干燥3h，将聚四氟乙烯滤膜取出，浸泡在无水乙醇中，通过机械剥离，室温干燥后，得到厚度为50μm的改性碳纳米管薄膜；碳纳米管、无水乙醇、氨水、水、正硅酸四乙酯、β-(3、4环氧环己基)-乙基三甲氧基硅烷羟值和羟基丙烯酸树脂的质量比为5∶40∶5∶40∶20∶3∶20；
2)绝缘涂层的制备：将偏苯三酸酐溶于N-甲基吡咯烷酮，然后加入甲苯二异氰酸酯，升温至140℃，保温反应2h，加入对氯苯酚，继续保温反应2h，得到聚酰胺酰亚胺预聚体，均匀涂布在改性碳纳米管薄膜上，升温至200℃，保温反应1h，使聚酰胺酰亚胺预聚体解封，在改性碳纳米管薄膜表层发生原位聚合反应，得到碳纳米管电热膜表面原位聚合的绝缘涂层，绝缘涂层厚度为10μm；偏苯三酸酐和甲苯二异氰酸酯的摩尔比为1∶1.02，N-甲基吡咯烷酮的质量为偏苯三酸酐和甲苯二异氰酸酯的质量总和的2倍，对氯苯酚的质量为甲苯二异氰酸酯的5wt％。
实施例3
1)碳纳米管薄膜的制备：将碳纳米管加入到仲丁醇中，高速剪切搅拌30min，转速5000rpm，然后加入氨水和水，再缓慢滴加正硅酸四乙酯、γ-氨丙基三乙氧基硅烷和羟值为100mg KOH/g的羟基丙烯酸树脂的混合液，经1h滴加结束，继续搅拌反应2h，然后将改性后的碳纳米管分散液置于聚四氟乙烯滤膜的布氏漏斗中，抽滤3h，然后在80℃干燥3h，将聚四氟乙烯滤膜取出，浸泡在无水乙醇中，通过机械剥离，室温干燥后，得到厚度为40μm的改性碳纳米管薄膜；碳纳米管、仲丁醇、氨水、水、正硅酸四乙酯、γ-氨丙基三乙氧基硅烷和羟基丙烯酸树脂的质量比为3∶40∶5∶40∶20∶5∶15。
2)绝缘涂层的制备：将偏苯三酸酐溶于N-甲基吡咯烷酮，然后加入对苯二异氰酸酯，升温至130℃，保温反应3h，加入苯酚，继续保温反应1h，得到聚酰胺酰亚胺预聚体，均匀涂布在改性碳纳米管薄膜上，升温至180℃，保温反应2h，使聚酰胺酰亚胺预聚体解封，在改性碳纳米管薄膜表层发生原位聚合反应，得到碳纳米管电热膜表面原位聚合的绝缘涂层，绝缘涂层厚度为20μm；偏苯三酸酐和对苯二异氰酸酯的摩尔比为1∶1.01，N-甲基吡咯烷酮的质量为偏苯三酸酐和对苯二异氰酸酯的质量总和的2倍，苯酚的质量为对苯二异氰酸酯的3wt％。
实施例4
1)碳纳米管薄膜的制备：将碳纳米管加入到异丙醇中，高速剪切搅拌40min，转速4000rpm，然后加入氨水和水，再缓慢滴加正硅酸四乙酯、N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷和羟值为100mg KOH/g的羟基聚酯树脂的混合液，经2h滴加结束，继续搅拌反应1h，然后将改性后的碳纳米管分散液置于聚四氟乙烯滤膜的布氏漏斗中，抽滤4h，然后在70℃干燥4h，将聚四氟乙烯滤膜取出，浸泡在无水乙醇中，通过机械剥离，室温干燥后，得到厚度为45μm的改性碳纳米管薄膜；碳纳米管、异丙醇、氨水、水、正硅酸四乙酯、N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷和羟基聚酯树脂的质量比为2∶30∶3∶30∶15∶2∶15。
2)绝缘涂层的制备：将偏苯三酸酐溶于N-甲基吡咯烷酮，然后加入3，3′-二甲基-4,3’-联苯二异氰酸酯，升温至140℃，保温反应2h，加入对氯苯酚，继续保温反应1h，得到聚酰胺酰亚胺预聚体，均匀涂布在改性碳纳米管薄膜上，升温至200℃，保温反应1h，使聚酰胺酰亚胺预聚体解封，在改性碳纳米管薄膜表层发生原位聚合反应，得到碳纳米管电热膜表面原位聚合的绝缘涂层，绝缘涂层厚度为15μ m；偏苯三酸酐和3，3′-二甲基-4,4′-联苯二异氰酸酯的摩尔比为1∶1，N-甲基吡咯烷酮的质量为偏苯三酸酐和3，3′-二甲基-4,4′-联苯二异氰酸酯的质量总和的3倍，对氯苯酚的质量为3，3′-二甲基-4,4′-联苯二异氰酸酯的5wt％。
对比例1
与实施例1的区别仅在于，步骤1)中不添加羟基树脂，其余步骤以及物料与组成与实施例1一致。
对比例2
与实施例1的区别仅在于，步骤2)中不添加封闭剂苯酚，其余步骤以及物料与组成与实施例1一致。
对比例3
采用实施例1步骤1)制备的碳纳米管薄膜为电热膜，以市售的PET为绝缘层通过耐热胶黏剂粘贴在碳纳米管薄膜上。
实施例1-4及对比例1-3制备的电热膜膜厚控制在60μm，对其拉伸强度、热稳定性、电热转换效率、温度均匀性及电热稳定性进行检测，其中拉升强度通过将电热膜裁剪成60*20mm的样品，两端加固后，采用电子万能试验机对其进行拉升性能测试，拉升速度为0.5mm/min；热稳定性通过热重分析测试得到的初始热分解温度进行判定；电热转换效率通过测量升高单位温度需要消耗的电功率计算得到，计算公式为hr+c＝Ic·Vi/(Tm-Ti)，hr+c为电热转换效率(mW/℃)，Ic为稳态电流(mA)，Vi为施加电压(V)，测试电压设定为36V，Ti为初始温度(℃)，Tm为稳定最高温度(℃)；温度均匀性通过红外热成像仪测试电热膜通电后3个不同位置的样品温度，温差≤1℃，温度均匀性为优，温差在1-3℃为良，温差＞3℃为差；电热稳定性通过循环测试30次升降温变化后，测定升温相同时间同一位置的温差来判定，温差≤1℃，温度均匀性为优，温差在1-3℃为良，温差＞3℃为差；检测结果如表1。
表1实施例1-4以及对比例1-3产品性能测试结果：
经检验，对比例1以正硅酸四乙酯和硅烷偶联剂作为改性剂，可以使碳纳米管稳定分散，但不添加羟基树脂，虽有活性官能基团可以连接聚酰胺酰亚胺层和碳纳米管薄膜，但缺少柔性有机树脂，复合层的柔韧性较差，电热膜的柔性不足，拉伸强度和电热转换效率也有一定程度的下降；对比例2未添加封闭剂苯酚，涂布在改性碳纳米管薄膜上的聚酰胺酰亚胺已经聚合完成，无法做到原位聚合，粘结力不佳，绝缘层不均一，有空鼓现象，拉伸强度、电热转换效率、温度均匀性和电热稳定性都较差；对比例3常用常规的聚酯绝缘层，通过胶黏剂和碳纳米管薄膜复合，拉伸强度、电热转换效率和温度均匀性好，但初始热分解温度下降较多，电热稳定性也不佳，说明聚酯绝缘层的耐热性和耐老化性不佳。
实施例1-4制备的碳纳米管电热膜的电热转换效率高、温度均匀性好，且热稳定性和电热稳定性优于常规的聚酯绝缘层，说明通过硅羟基和氨基/环氧基的连接，解封后原位聚合的聚酰胺酰亚胺可以在碳纳米管薄膜表面生成牢固结合的绝缘层，无需外加胶黏剂，贴合度好。
本发明中所用原料、设备，若无特别说明，均为本领域的常用原料、设备；本发明中所用方法，若无特别说明，均为本领域的常规方法。
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变换，均仍属于本发明技术方案的保护范围。
Claims (8)
1.一种含原位聚合绝缘涂层的碳纳米管电热膜的制备方法，其特征在于包括以下步骤：
1）碳纳米管薄膜的制备：将碳纳米管加入到有机溶剂中，高速剪切搅拌20-40min，转速4000-6000rpm，然后加入氨水和水，再缓慢滴加正硅酸四乙酯、硅烷偶联剂和羟基树脂的混合液，经1-2h滴加结束，继续搅拌反应1-2h；然后将改性后的碳纳米管分散液置于含聚四氟乙烯滤膜的抽滤装置中，真空抽滤3-4h，然后在70-90℃干燥3-4h，将聚四氟乙烯滤膜取出，浸泡在无水乙醇中，通过机械剥离，室温干燥后，得到改性碳纳米管薄膜；
所述硅烷偶联剂选自γ-(2,3-环氧丙氧) 丙基三甲氧基硅烷、β-(3、4环氧环己基)-乙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷和N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷中的一种或多种；
所述碳纳米管、有机溶剂、氨水、水、正硅酸四乙酯、硅烷偶联剂和羟基树脂的质量比为2-5:20-40:2-5:20-40:10-20:1-5:10-20；
2）绝缘涂层的制备：将偏苯三酸酐溶于N-甲基吡咯烷酮，然后加入二异氰酸酯，升温至120-140℃，保温反应2-3h，加入封闭剂，继续保温反应1-2h，得到聚酰胺酰亚胺预聚体，均匀涂布在改性碳纳米管薄膜上，升温至180-200℃，保温反应1-2h，使聚酰胺酰亚胺预聚体解封，在改性碳纳米管薄膜表层发生原位聚合反应，得到含原位聚合绝缘涂层的碳纳米管电热膜。
2.如权利要求1所述的制备方法，其特征在于：所述改性碳纳米管薄膜的厚度为35-50μm；所述原位聚合绝缘涂层的厚度为10-25μm。
3.如权利要求1所述的制备方法，其特征在于：步骤1）中：所述有机溶剂选自无水乙醇、异丙醇和仲丁醇中的一种或多种；所述羟基树脂选自羟值为80-120mg KOH/g的羟基聚酯树脂和羟基丙烯酸树脂中的一种或多种。
4.如权利要求1所述的制备方法，其特征在于：步骤2）中：所述二异氰酸酯选自二苯基甲烷-4,3’-二异氰酸酯、甲苯二异氰酸酯、对苯二异氰酸酯和3,3'-二甲基-4,3’-联苯二异氰酸酯中的一种或多种。
5.如权利要求1所述的制备方法，其特征在于：步骤2）中：所述封闭剂选自苯酚、对氯苯酚。
6.如权利要求4或5所述的制备方法，其特征在于：步骤2）中：所述偏苯三酸酐和二异氰酸酯的摩尔比为1:1-1.02。
7.如权利要求6所述的制备方法，其特征在于：步骤2）中：所述N-甲基吡咯烷酮的质量为偏苯三酸酐和二异氰酸酯的质量总和的2-3倍。
8.如权利要求5所述的制备方法，其特征在于：步骤2）中：所述封闭剂的质量为二异氰酸酯的2-5wt%。
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