CN112409734B - 一种具备形状记忆与可修复功能的pva/ptmg-paa共混薄膜 - Google Patents

一种具备形状记忆与可修复功能的pva/ptmg-paa共混薄膜 Download PDF

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CN112409734B
CN112409734B CN202011305561.4A CN202011305561A CN112409734B CN 112409734 B CN112409734 B CN 112409734B CN 202011305561 A CN202011305561 A CN 202011305561A CN 112409734 B CN112409734 B CN 112409734B
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宋晓峰
任亚君
周琦锋
夏文龙
张转转
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Changchun University of Technology
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Abstract

本发明涉及一种具备形状记忆与可修复功能的PVA/PTMG‑PAA共混薄膜，合成一种以PTMG(Tg＝‑76℃)为软段和PAA为亲水段的聚合物，通过AGE一端的环氧开环与PTMG脱水，使PTMG两端被双键功能化，然后合成的PTMG‑AGE引发AA自由基聚合，最终产物共混PVA，获得PVA/PTMG‑PAA共混薄膜。因为合成的聚合物具有软段，并且亲水段PAA含有大量羧基，可以与PVA羟基形成稳定氢键，PVA自身分子间氢键较弱，遇水氢键断裂，脱水形成氢键，合成产物极大增加PVA吸水溶胀率，使形状恢复和修复取得优异效果。

Description

一种具备形状记忆与可修复功能的PVA/PTMG-PAA共混薄膜
技术领域
本发明属于高分子功能化领域，涉及一种具备形状记忆与可修复功能的PVA/PTMG-PAA共混薄膜。
背景技术
一定形状的固体材料在某种外界条件刺激下发生塑性形变，经过特定环境刺激，材料又完全恢复到变形前形状的现象被称为形状记忆效应。根据实现记忆功能的环境条件不同，可分为感温型、感水型、感光型和感酸碱型等多种记忆材料，目前应用研究最多的是热致形状记忆和水诱导形状记忆聚合物材料。
将可修复功能集成到人造材料中，不但可以减少原材料消耗，而且可以提高其耐用性和可靠性。目前，人们应用可逆共价键相互作用(或氢键)制造出可修复材料。例如，PVA是一种理想的绿色聚合物，通过重复的冻融方法可以制备出PVA水凝胶，在冷冻过程中PVA微晶和PVA链之间的氢键形成物理交联。PVA晶体容易熔化，加热到50～60℃时氢键断裂，降温氢键可以恢复。但是普通PVA水凝胶修复缓慢。如果设计出一种聚合物不但可以使PVA具备形状记忆，而且能够增强自恢复损伤，那么这种材料将在更尖端的领域获得应用。
发明内容
为了达到上述目的，本发明提供了一种具备形状记忆与可修复功能的PVA/PTMG-PAA共混薄膜，形状恢复条件简单，裂口修复时间短，效率高。
本发明的技术方案：合成一种以PTMG(Tg＝-76℃)为软段和PAA为亲水段的聚合物，通过AGE一端的环氧开环与PTMG脱水，使PTMG两端被双键功能化，然后合成的PTMG-AGE引发AA自由基聚合，最终产物共混PVA，获得PVA/PTMG-PAA共混薄膜。因为合成的聚合物具有软段，并且亲水段PAA含有大量羧基，可以与PVA羟基形成稳定氢键，PVA自身分子间氢键较弱，遇水氢键断裂，脱水形成氢键，合成产物极大增加PVA吸水溶胀率，使形状恢复和修复取得优异效果。
所述的聚合物，其分子链上PTMG软段的结构如下：
Figure GDA0003644257440000011
n为大于1的整数。
所述的聚合物，其分子链AGE中间段的结构如下：
Figure GDA0003644257440000012
所述的聚合物，其分子链上PAA的结构如下：
Figure GDA0003644257440000021
m为大于1的整数。
附图说明
图1为聚合物的核磁共振氢谱图。
如图1所示，核磁谱图中，A图中1.6～1.7ppm、3.5ppm均为PTMG中-CH2-中氢的化学位移，B图中5.5ppm左右乙烯基上氢的化学位移出现说明PTMG与AGE脱水结合成功。C图中12.25ppm左右出现的-COOH峰，5.5ppm左右乙烯基上氢的化学位移消失，表明PAA已经通过AGE与PTMG聚合。采用1H-NMR表征的结果说明一种PTMG软段和PAA为亲水段的聚合物已经合成。
图2为本发明制备的聚合物和PVA共混薄膜形状记忆过程。
图3为本发明制备的聚合物与PVA共混薄膜修复的过程。
具体实施方式
下面通过实施例对本发明进行具体描述。
实施例1：
称重适量PTMG和AGE放入250ml三口烧瓶中通氮气，防止环氧高温氧化，40min后加热使PTMG融化，并搅拌；将催化剂浓硫酸缓慢滴加到一定量的四氢呋喃当中，混合均匀，然后滴加到反应体系，冷凝回流，升温到125℃，停止通氮气，改成抽真空进行反应。4h后向体系中加50ml去离子水，终止反应，并回流1h，然后用Ca(OH)2中和催化剂并进行分液水洗，减压蒸馏除去低沸物。将适量上述产物与甲醇加入装有磁力搅拌棒的250ml三口烧瓶中通氮气30min，加入适量偶氮二异丁腈催化剂，65℃下边搅拌边滴加AA。反应5h。产物通过去离子水沉降，真空干燥12h。
将PVA、PTMG-PAA按质量比8:2加入去离子水溶剂当中，其中PVA/PTMG-PAA的浓度为10wt％，95℃搅拌3h。将搅拌后的溶液倒到玻璃板上，让溶液在玻璃板上自由流延。在常温真空干燥3天，待膜完全干燥后备用。
将样条加热到50℃时加工成临时形状后，放置于室温中一段时间，固定临时形状。临时形状再次置于50℃氛围或者浸水后，迅速恢复初始形状，说明PTMG-PAA可以赋予PVA形状记忆功能。将样条人为从中间断开后，断裂处接触水，当再次把水蒸发后，样条重新接触良好，并且时间迅速，说明PTMG-PAA可以赋予PVA优异恢复功能。

Claims (1)

1.一种具备形状记忆与可修复功能的PVA/PTMG-PAA共混薄膜，其制备方法如下：
称重适量PTMG和AGE放入250ml三口烧瓶中通氮气，防止环氧高温氧化，40min后加热使PTMG融化，并搅拌；将催化剂浓硫酸缓慢滴加到一定量的四氢呋喃当中，混合均匀，然后滴加到反应体系，冷凝回流，升温到125℃，停止通氮气，改成抽真空进行反应；4h后向体系中加50ml去离子水，终止反应，并回流1h，然后用Ca(OH)2中和催化剂并进行分液水洗，减压蒸馏除去低沸物；将适量上述产物与甲醇加入装有磁力搅拌棒的250ml三口烧瓶中通氮气30min，加入适量偶氮二异丁腈催化剂，65℃下边搅拌边滴加AA，反应5h，产物通过去离子水沉降，真空干燥12h；
将PVA、PTMG-PAA按质量比8:2加入去离子水溶剂当中，其中PVA/PTMG-PAA的浓度为10wt％，95℃搅拌3h；将搅拌后的溶液倒到玻璃板上，让溶液在玻璃板上自由流延，在常温真空干燥3天，待膜完全干燥后备用。
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