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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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3544487A (en) * 1967-06-16 1970-12-01 Quaker Oats Co Cross-linked polytetrahydrofuran polymers
CN1552748A (zh) * 2003-05-30 2004-12-08 北京化工大学 一种降低丙烯酸酯橡胶玻璃化转变温度的方法
WO2007116946A1 (en) * 2006-03-31 2007-10-18 Nippon Shokubai Co., Ltd. Polyalkylene glycol copolymer, polyalkylene glycol monomer, and production method thereof
CN101273078A (zh) * 2005-09-29 2008-09-24 株式会社日本触媒 聚亚烷基二醇单体、含有该聚亚烷基二醇单体的聚亚烷基二醇聚合物及其用途
CN105778079A (zh) * 2016-03-23 2016-07-20 联泓(江苏)新材料研究院有限公司 一种不饱和聚醚单体及其制备方法和应用
CN106188416A (zh) * 2015-05-06 2016-12-07 天津大学 一种具有氢键增强离子驱动的高强度形状记忆水凝胶及其制备方法及其应用
CN107257816A (zh) * 2014-12-16 2017-10-17 巴斯夫欧洲公司 用环氧化物改性烷基聚亚烷基二醇

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5939505A (en) * 1997-12-16 1999-08-17 National Starch And Chemical Investment Holding Corporation High solids ethylene vinyl acetate emulsions
EP1992646A4 (en) * 2006-02-14 2010-02-24 Kaneka Corp VINYL POLYMER HAVING POLAR FUNCTIONAL GROUP AND PROCESS FOR PRODUCTION THEREOF

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3544487A (en) * 1967-06-16 1970-12-01 Quaker Oats Co Cross-linked polytetrahydrofuran polymers
CN1552748A (zh) * 2003-05-30 2004-12-08 北京化工大学 一种降低丙烯酸酯橡胶玻璃化转变温度的方法
CN101273078A (zh) * 2005-09-29 2008-09-24 株式会社日本触媒 聚亚烷基二醇单体、含有该聚亚烷基二醇单体的聚亚烷基二醇聚合物及其用途
WO2007116946A1 (en) * 2006-03-31 2007-10-18 Nippon Shokubai Co., Ltd. Polyalkylene glycol copolymer, polyalkylene glycol monomer, and production method thereof
CN107257816A (zh) * 2014-12-16 2017-10-17 巴斯夫欧洲公司 用环氧化物改性烷基聚亚烷基二醇
CN106188416A (zh) * 2015-05-06 2016-12-07 天津大学 一种具有氢键增强离子驱动的高强度形状记忆水凝胶及其制备方法及其应用
CN105778079A (zh) * 2016-03-23 2016-07-20 联泓(江苏)新材料研究院有限公司 一种不饱和聚醚单体及其制备方法和应用

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Synthesis and thermal properties of poly(acrylonitrile-co-allyl glycidyl ether)-graft-methoxypoly(ethylene glycol) copolymers as novel solid–solid phase-change materials for thermal energy storage;Xuelin Huang等;《Journal or applied polymer》;20180915;第135卷(第35期);第1-8页 *
异丁烯基聚乙二醇醚与丙烯酸共聚物结构形成过程;王子明等;《化学反应工程与工艺》;20190625;第35卷(第03期);第234-241页 *
端羟基PAGE⁃PTMEG⁃PAGE 嵌段共聚醚的合成及表征;莫洪昌等;《chinese journal or energetic materials》;20180928;第26卷(第9期);第749-752页 *
聚丙烯酸水凝胶自修复性能及溶胀行为的研究;洪浩群等;《功能材料》;20160930;第47卷(第09期);第9012-9016页 *

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