CN110628020B - 一种聚合物弹性表面聚吡咯褶皱的制备方法 - Google Patents

一种聚合物弹性表面聚吡咯褶皱的制备方法 Download PDF

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CN110628020B
CN110628020B CN201910853579.9A CN201910853579A CN110628020B CN 110628020 B CN110628020 B CN 110628020B CN 201910853579 A CN201910853579 A CN 201910853579A CN 110628020 B CN110628020 B CN 110628020B
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polypyrrole
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刘岚
刘海州
邓智富
陈松
巫运辉
王萍萍
郑荣敏
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South China University of Technology SCUT
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Abstract

本发明公开了一种聚合物弹性体表面聚吡咯褶皱的制备方法，包括步骤：(1)将聚合物弹性基体置于具有吡咯的纯溶剂或与吡咯共溶的溶剂中进行溶胀；(2)将所得的溶胀聚合物弹性基体置入氧化剂的酸性水溶剂中进行反应；(3)将所得的聚合物弹性基体完全解溶胀。本发明的制备方法简单，成本低廉，制备得到的聚吡咯褶皱能够显著的改变聚合物基体表面的粗糙度等性质，在能源转化、能源储存以及传感器等领域具有重要的运用前景。

Description

一种聚合物弹性表面聚吡咯褶皱的制备方法
技术领域
本发明涉及柔性功能材料领域，尤其涉及一种聚合物弹性表面聚吡咯褶皱的制备方法。
背景技术
高性能功能材料是近年来新材料领域研究的核心，新兴产业发展需要前瞻布局前沿新材料研发，开发智能材料、仿生材料等功能材料。材料的性质除了由内在的属性决定以外，其组成结构或形式也是重要的影响因素之一。一般来说，材料内在的属性难以发生大的改变，因此研究者的研究重点主要集中在构筑独特的微纳结构来赋予材料新的功能化应用。
褶皱是自然界中普遍存在的刚性材料克服挠曲应力形成的结构。基于仿生构筑的微纳褶皱结构已经被广泛的运用在功能材料的制备当中。如超疏水材料、透明度可调光学薄膜材料、高效率光热转化材料以及柔性压阻材料等等。可见表面褶皱结构的存在能够显著改变材料的表面特性，同时带来特殊的电学、光学性能。
然而，上述现有技术都是在薄膜中实现二维褶皱的制备，在纤维等曲面表面上的制备依然存在困难。此前虽然采用预拉伸工艺实现了曲面纤维一维褶皱的制备，但目前曲表面如纤维表面的二维褶皱的制备依然是一个工艺难题。
发明内容
本发明的目的在于克服目前不同形式表面聚合物弹性体表面二维褶皱结构制备的难题，提供一种聚合物弹性体表面聚吡咯褶皱的制备方法。本发明利用吡咯作为溶胀剂和单体在多种形式表面制备了聚吡咯二维褶皱，提供了一种解决多形式表面制备二维褶皱的难题的思路，在能源、传感以及防污防腐等领域具有潜在的应用前景。
本发明的目的能够通过以下技术方案实现：
一种聚合物弹性体表面聚吡咯褶皱的制备方法，包括步骤：
(1)将聚合物弹性基体置于具有吡咯的纯溶剂或与吡咯共溶的溶剂中进行溶胀；
(2)将所得的溶胀聚合物弹性基体置入氧化剂的酸性水溶剂中进行反应；
(3)将反应后的聚合物弹性基体完全解溶胀后即可实现在其表面聚吡咯电褶皱的制备。
优选地，聚合物弹性基体为橡胶或热塑性弹性体，包括但不限于硅橡胶和热塑性聚氨酯。
优选地，聚合物弹性基体形状为纤维等曲面或薄膜等平面。
优选地，所述与吡咯共溶的溶剂包括但不限于三氯甲烷和二甲苯。
优选地，所述具有吡咯的纯溶剂或与吡咯共溶的溶剂，吡咯含量为5-100％。
优选地，溶胀时间为0.1-120h。
优选地，所述氧化剂为过硫酸铵，浓度为1-100mmol/L。
优选地，所述酸性水溶剂的酸为水溶性酸，可以为无机酸或有机酸，无机酸包括但不限于盐酸和硫酸，有机酸包括但不限于苯磺酸和柠檬酸。
优选地，所述水溶剂包括含水的互溶溶剂，如水/无水乙醇互溶溶剂体系。
优选地，所述反应的时间为0.01-1h。
根据所述方案，能够在纤维状以及薄膜状等各种形状的硅橡胶、热塑性聚氨酯等弹性基体表面制得聚吡咯褶皱，褶皱波长介于0.2-15μm之间。
本发明相较于现有技术，具有以下的有益效果：
1、本发明以吡咯作为溶剂及反应单体，无需额外的溶剂。
2、本发明能够在各种形式的弹性基体表面制备得到二维褶皱结构。
3、本发明能够通过调控氧化剂的浓度实现褶皱尺寸的调控。
附图说明
图1是本发明制备方法制备得到的聚氨酯纤维表面的聚吡咯褶皱结构的电镜照片(500倍)。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
将热塑性聚氨酯纤维放入吡咯溶剂(100％)中，溶胀0.1h，取出置入1mmol/L过硫酸铵盐酸溶液中，反应1h后，将聚氨酯纤维取出使用去离子水清洗干净，置于通风橱中自然风干。聚氨酯解溶胀后即能诱导表面聚吡咯薄膜形成二维褶皱，其褶皱波长为0.2μm。
实施例2
将热塑性聚氨酯薄膜放入吡咯溶剂(100％)中，溶胀0.1h，取出置入1mmol/L过硫酸铵盐酸溶液中，反应1h后，将聚氨酯薄膜取出使用去离子水清洗干净，置于通风橱中自然风干。聚氨酯解溶胀后即能诱导表面聚吡咯薄膜形成二维褶皱，其褶皱波长为0.3μm。
实施例3
将热塑性聚氨酯纤维放入吡咯溶剂(100％)中，溶胀120h，取出置入100mmol/L过硫酸铵盐酸溶液中，反应0.01h后，将聚氨酯纤维取出使用去离子水清洗干净，置于通风橱中自然风干。聚氨酯解溶胀后即能诱导表面聚吡咯薄膜形成二维褶皱，其褶皱波长为15μm。
实施例4
将硅橡胶薄膜放入吡咯(10％)-三氯甲烷混合溶剂中，溶胀8h，取出置入10mmol/L过硫酸铵盐酸溶液中，反应0.5h后，将硅橡胶薄膜取出使用去离子水清洗干净，置于通风橱中自然风干。硅橡胶解溶胀后即能诱导表面聚吡咯薄膜形成二维褶皱，其褶皱波长为3μm。
根据本发明制备方法制备得到的聚氨酯纤维表面的聚吡咯褶皱结构的电镜照片(500倍)如图1所示。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (5)

1.一种聚合物弹性体表面聚吡咯褶皱的制备方法，其特征在于，所述方法通过调控氧化剂的浓度实现褶皱尺寸的调控，包括步骤：
(1)将聚合物弹性基体置于具有吡咯的纯溶剂中进行溶胀；聚合物弹性基体为橡胶或热塑性弹性体，包括硅橡胶和热塑性聚氨酯；
(2)将所得的溶胀聚合物弹性基体置入氧化剂的酸性水溶液中进行反应；所述氧化剂为过硫酸铵，浓度为1-100mmol/L；
(3)将反应后的聚合物弹性基体完全解溶胀。
2.根据权利要求1所述的方法，其特征在于，聚合物弹性基体形状为纤维或薄膜。
3.根据权利要求1所述的方法，其特征在于，溶胀时间为0.1-120h。
4.根据权利要求1所述的方法，其特征在于，所述酸性水溶液的酸为水溶性酸，可以为无机酸或有机酸，无机酸包括盐酸和硫酸，有机酸包括苯磺酸和柠檬酸。
5.根据权利要求1所述的方法，其特征在于，所述反应的时间为0.01-1h。
CN201910853579.9A 2019-09-10 2019-09-10 一种聚合物弹性表面聚吡咯褶皱的制备方法 Expired - Fee Related CN110628020B (zh)

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EP1144728A1 (en) * 1998-12-02 2001-10-17 The Board Of Governors For Higher Education State Of Rhode Island And Providence Plantations Water-borne polymeric complex and anti-corrosive composition
CN105061731A (zh) * 2015-07-31 2015-11-18 天津大学 基于原位起皱与热膨胀构建多级形貌的聚吡咯膜的方法
CN107630390A (zh) * 2017-09-27 2018-01-26 华南理工大学 一种木质素磺酸增强聚吡咯导电纸及其制备方法

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EP1144728A1 (en) * 1998-12-02 2001-10-17 The Board Of Governors For Higher Education State Of Rhode Island And Providence Plantations Water-borne polymeric complex and anti-corrosive composition
CN105061731A (zh) * 2015-07-31 2015-11-18 天津大学 基于原位起皱与热膨胀构建多级形貌的聚吡咯膜的方法
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