CN106939518A - 具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法 - Google Patents

具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法 Download PDF

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CN106939518A
CN106939518A CN201710245984.3A CN201710245984A CN106939518A CN 106939518 A CN106939518 A CN 106939518A CN 201710245984 A CN201710245984 A CN 201710245984A CN 106939518 A CN106939518 A CN 106939518A
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巩桂芬
王磊
徐阿文
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Harbin University of Science and Technology
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Abstract

一种具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法。采用碳纳米管对聚酰亚胺薄膜进行改性，能有效降低聚酰亚胺薄膜的电阻率，但随着碳纳米管含量的增加，碳纳米管在聚酰亚胺中会产生严重的团聚现象，使得聚酰亚胺薄膜的力学性能急剧下降。本发明的方法包括如下步骤：（1）碳纳米管改性聚酰胺酸溶液的制备；（2）静电纺丝法制备碳纳米管改性聚酰胺酸微孔膜；（3）聚酰胺酸溶液的制备；（4）在微孔膜两侧涂覆聚酰胺酸溶液；（5）对碳纳米管改性聚酰胺酸三层复合薄膜进行热亚胺化。本发明主要应用于扩展聚酰亚胺薄膜在电磁屏蔽材料的应用。

Description

具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法
技术领域：
本发明涉及一种具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法。
背景技术：
聚酰亚胺(PI)是一类以酰亚胺环为结构特征的高性能聚合物材料，具有较高的耐热性及优异的力学性能、电性能、耐辐照性能、耐溶剂性能等，作为介电空间层，金属薄膜保护层广泛用于微电子领域，但聚酰亚胺的绝缘性能优良，电阻率较高，需要加入导电填料进行改性，降低其电阻率再能作为电磁屏蔽材料而使用。近年来，银纳米线、碳纳米管、碳纤维、聚苯胺等导电填料被作为填料广泛填充到聚酰亚胺基体中，制备具有电磁屏蔽功能的聚酰亚胺薄膜，并且聚酰亚胺薄膜的导电性随着填料含量的增加而增加。但是随着填料含量的不断增加，聚酰亚胺薄膜的力学性能也急剧下降。因此如何在提高聚酰亚胺薄膜导电性使其作为电磁屏蔽材料的同时阻止力学性能的下降，成为扩展聚酰亚胺薄膜在电磁屏蔽材料领域应用的关键。
发明内容：
本发明的目的是提供一种具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，具体涉及一种碳纳米管改性聚酰胺酸微孔膜的制备、微孔膜两侧聚酰胺酸的涂覆以及三层复合薄膜的热亚胺化工艺。
上述的目的通过以下的技术方案实现：
一种具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：该方法包括如下步骤：
（1）碳纳米管改性聚酰胺酸溶液的制备；
（2）静电纺丝法制备碳纳米管改性聚酰胺酸微孔膜；
（3）聚酰胺酸溶液的制备；
（4）在微孔膜两侧涂覆聚酰胺酸溶液；
（5）对碳纳米管改性聚酰胺酸三层复合薄膜进行热亚胺化。
所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：碳纳米管改性均苯型聚酰胺酸溶液的制备，按摩尔比1：1.02称取4，4-二氨基二苯基醚和均苯四甲酸二酐，将4，4-二氨基二苯基醚和0-10wt%的单壁碳纳米管倒入三口瓶，并按照聚酰胺酸固含量为26wt%加入N，N-二甲基乙酰胺，通入氮气进行保护，在10℃冷水浴下超声搅拌1 h后，撤除超声，将称取的均苯四甲酸二酐分批逐步加入到溶液中，加料时间控制在120min，待出现爬竿现象后继续搅拌24小时，将粘稠状的碳纳米管改性聚酰胺酸液体倒入小烧杯中密封备用。
所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的静电纺丝法制备碳纳米管/聚酰胺酸微孔膜，取10ml所述的碳纳米管改性聚酰胺酸液体于静电纺丝装置的注射泵中，调节纺丝电压为10kV，注射速度为0.3ml/h，接收距离为15cm，纺丝5 h制得厚度为20μm的碳纳米管改性聚酰胺酸微孔膜。
所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的聚酰胺酸溶液的制备，按摩尔比1：1.02称取4，4-二氨基二苯基醚和均苯四甲酸二酐，将4，4-二氨基二苯基醚倒入三口瓶，按溶液中聚酰胺酸固含量为20wt%加入N，N-二甲基乙酰胺，通入氮气进行保护，在10℃冷水浴下搅拌1h后，将称取的均苯四甲酸二酐分批逐步加入到溶液中，加料时间控制在120min，待出现爬竿现象后继续搅拌24小时，将粘稠状的聚酰胺酸液体倒入小烧杯中密封备用。
所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的在微孔膜两侧涂覆聚酰胺酸溶液，将碳纳米管改性聚酰胺酸微孔膜在80℃和120℃下分别预处理1h，使溶剂挥发后，采用自制的铺膜机在碳纳米管改性聚酰胺酸微孔膜两侧进行铺膜，首先在玻璃板上铺一层所述的聚酰胺酸溶液，然后将预处理后的碳纳米管改性聚酰胺酸微孔膜铺在该溶液上，待所述的微孔膜内部微孔完全浸入胶液后，再利用铺膜机在碳纳米管改性聚酰胺酸微孔膜上铺一层所述的聚酰胺酸胶液并静置一段时间，待聚酰胺酸溶液充分浸入微孔膜后，放入烘箱以备亚胺化。
所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的对碳纳米管改性聚酰胺酸三层复合薄膜进行热亚胺化，采用梯度升温法对碳纳米管改性聚酰胺酸三层复合薄膜进行热亚胺化，所采用的温度与时间依次如下：1）80℃条件下1h；2）120℃条件下1h；3）150℃条件下1h；4）200℃条件下1h；5）250℃条件下1h；6）300℃条件下1h，然后待自然冷却后得具有电磁屏蔽功能的碳纳米管/聚酰亚胺三层复合薄膜。
本发明的有益效果：
1.本发明将将4，4-二氨基二苯基醚和单壁碳纳米管加入N，N-二甲基乙酰胺，在氮气保护和10℃冷水浴下超声搅拌1h后，加入均苯四甲酸二酐，得到碳纳米管改性聚酰胺酸纺丝液，并通过高压静电纺丝制备碳纳米管改性聚酰胺酸微孔膜。然后将4，4-二氨基二苯基醚加入到N，N-二甲基乙酰胺，在氮气保护和10℃冷水浴下溶解后，加入均苯四甲酸二酐，得到聚酰胺酸溶液，利用铺膜机将其铺在碳纳米管改性聚酰胺酸微孔膜两侧，待胶液完全渗入微孔膜后，通过梯度升温法进行热亚胺化处理，得到具有电磁屏蔽功能的碳纳米管/聚酰亚胺三层复合薄膜。
本发明利用高压静电纺丝将具有导电功能的碳纳米管引入到聚酰亚胺中，可以减小碳纳米管的团聚效应，同时由于经电纺得到的微孔膜为三维网状结构，使得碳纳米管容易构成导电通道，能在聚酰亚胺薄膜中以较小的填量构建具有较好电磁屏蔽功能的导电网络。同时，由于碳纳米管通过聚酰亚胺纤维引入到聚酰亚胺薄膜中，聚酰亚胺纤维的取向以及其与聚酰亚胺胶液的相容性，使得其形成的复合材料具有较好的界面相容性，从而达到增韧的目的，有效改善由于填料的引入导致薄膜力学性能下降的缺陷，实现了在添加碳纳米管改善聚酰亚胺薄膜电磁屏蔽性能的同时提升其力学等性能。
具体实施方式：
实施例1：
一种具有具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：该方法包括如下步骤：
（1）碳纳米管改性聚酰胺酸溶液的制备；
（2）静电纺丝法制备碳纳米管改性聚酰胺酸微孔膜；
（3）聚酰胺酸溶液的制备；
（4）在微孔膜两侧涂覆聚酰胺酸溶液；
（5）对碳纳米管改性聚酰胺酸三层复合薄膜进行热亚胺化。
实施例2：
根据实施例1所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：碳纳米管改性均苯型聚酰胺酸溶液的制备，按摩尔比1：1.02称取4，4-二氨基二苯基醚和均苯四甲酸二酐，将4，4-二氨基二苯基醚和0-10wt%的单壁碳纳米管倒入三口瓶，并按照聚酰胺酸固含量为26wt%加入N，N-二甲基乙酰胺，通入氮气进行保护，在10℃冷水浴下超声搅拌1 h后，撤除超声，将称取的均苯四甲酸二酐分批逐步加入到溶液中，加料时间控制在120min，待出现爬竿现象后继续搅拌24小时，将粘稠状的碳纳米管改性聚酰胺酸液体倒入小烧杯中密封备用。
实施例3：
根据实施例1或2所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的静电纺丝法制备碳纳米管/聚酰胺酸微孔膜，取一定量所述的碳纳米管改性聚酰胺酸液体于静电纺丝装置的注射泵中，调节纺丝电压为10kV，注射速度为0.3ml/h，接收距离为15cm，纺丝5 h制得厚度为20μm的碳纳米管改性聚酰胺酸微孔膜。
实施例4：
根据实施例1或2或3所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的聚酰胺酸溶液的制备，按摩尔比1：1.02称取4，4-二氨基二苯基醚和均苯四甲酸二酐，将4，4-二氨基二苯基醚倒入三口瓶，按溶液中聚酰胺酸固含量为20wt%加入N，N-二甲基乙酰胺，通入氮气进行保护，在10℃冷水浴下搅拌1h后，将称取的均苯四甲酸二酐分批逐步加入到溶液中，加料时间控制在120min，待出现爬竿现象后继续搅拌24小时，将粘稠状的聚酰胺酸液体倒入小烧杯中密封备用。
实施例5：
根据实施例1或2或3或4所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的在微孔膜两侧涂覆聚酰胺酸溶液，将碳纳米管改性聚酰胺酸微孔膜在80℃和120℃下分别预处理1h，使溶剂挥发后，采用自制的铺膜机在碳纳米管改性聚酰胺酸微孔膜两侧进行铺膜，首先在玻璃板上铺一层所述的聚酰胺酸溶液，然后将预处理后的碳纳米管改性聚酰胺酸微孔膜铺在该溶液上，待所述的微孔膜内部微孔完全浸入胶液后，再利用铺膜机在碳纳米管改性聚酰胺酸微孔膜上铺一层所述的聚酰胺酸胶液并静置一段时间，待聚酰胺酸溶液充分浸入微孔膜后，放入烘箱以备亚胺化。
实施例6：
根据实施例1或2或3或4或5所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的对碳纳米管改性聚酰胺酸三层复合薄膜进行热亚胺化，采用梯度升温法对碳纳米管改性聚酰胺酸三层复合薄膜进行热亚胺化，所采用的温度与时间依次如下：1）80℃条件下1h；2）120℃条件下1h；3）150℃条件下1h；4）200℃条件下1h；5）250℃条件下1h；6）300℃条件下1h，然后待自然冷却后得具有电磁屏蔽功能的碳纳米管/聚酰亚胺三层复合薄膜。

Claims (6)

1.一种具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：该方法包括如下步骤：
（1）碳纳米管改性聚酰胺酸溶液的制备；
（2）静电纺丝法制备碳纳米管改性聚酰胺酸微孔膜；
（3）聚酰胺酸溶液的制备；
（4）在微孔膜两侧涂覆聚酰胺酸溶液；
（5）对碳纳米管改性聚酰胺酸三层复合薄膜进行热亚胺化。
2.根据权利要求1所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的碳纳米管改性均苯型聚酰胺酸溶液的制备：
按摩尔比1：1.02称取4，4-二氨基二苯基醚和均苯四甲酸二酐，将4，4-二氨基二苯基醚和0-10wt%的单壁碳纳米管倒入三口瓶，并按照聚酰胺酸固含量为26wt%加入N，N-二甲基乙酰胺，通入氮气进行保护，在10℃冷水浴下超声搅拌1h后，撤除超声，将称取的均苯四甲酸二酐分批逐步加入到溶液中，加料时间控制在120min，待出现爬竿现象后继续搅拌24小时，将粘稠状的碳纳米管改性聚酰胺酸液体倒入小烧杯中密封备用。
3.根据权利要求1或2所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的静电纺丝法制备碳纳米管/聚酰胺酸微孔膜：
取10 ml所述的碳纳米管改性聚酰胺酸液体于静电纺丝装置的注射泵中，调节纺丝电压为10kV，注射速度为0.3ml/h，接收距离为15cm，纺丝5 h制得厚度为20μm的碳纳米管改性聚酰胺酸微孔膜。
4.根据权利要求1或2或3所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的聚酰胺酸溶液的制备：
按摩尔比1：1.02称取4，4-二氨基二苯基醚和均苯四甲酸二酐，将4，4-二氨基二苯基醚倒入三口瓶，按溶液中聚酰胺酸固含量为20 wt%加入N，N-二甲基乙酰胺，通入氮气进行保护，在10℃冷水浴下搅拌1h后，将称取的均苯四甲酸二酐分批逐步加入到溶液中，加料时间控制在120min，待出现爬竿现象后继续搅拌24小时，将粘稠状的聚酰胺酸液体倒入小烧杯中密封备用。
5.根据权利要求1或2或3或4所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的在微孔膜两侧涂覆聚酰胺酸溶液：
将碳纳米管改性聚酰胺酸微孔膜在80℃和120℃下分别预处理1h，使溶剂挥发后，采用自制的铺膜机在碳纳米管改性聚酰胺酸微孔膜两侧进行铺膜，首先在玻璃板上铺一层所述的聚酰胺酸溶液，然后将预处理后的碳纳米管改性聚酰胺酸微孔膜铺在该溶液上，待所述的微孔膜内部微孔完全浸入胶液后，再利用铺膜机在碳纳米管改性聚酰胺酸微孔膜上铺一层所述的聚酰胺酸胶液并静置一段时间，待聚酰胺酸溶液充分浸入微孔膜后，放入烘箱以备亚胺化。
6.根据权利要求1或2或3或4或5所述的具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法，其特征是：所述的对碳纳米管改性聚酰胺酸三层复合薄膜进行热亚胺化：
采用梯度升温法对碳纳米管改性聚酰胺酸三层复合薄膜进行热亚胺化，所采用的温度与时间依次如下：
（1）80℃条件下1h；
（2）120℃条件下1h；
（3）150℃条件下1h；
（4）200℃条件下1h；
（5）250℃条件下1h；
（6）300℃条件下1h。
然后待自然冷却后得具有电磁屏蔽功能的碳纳米管/聚酰亚胺三层复合薄膜。
CN201710245984.3A 2017-04-14 2017-04-14 具有电磁屏蔽功能的聚酰亚胺三层复合薄膜的制备方法 Pending CN106939518A (zh)

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Application publication date: 20170711