基于双硫键和氢键协效的高性能自修复聚氨酯脲的研制

doi:10.16085/j.issn.1000-6613.2020-0512

化工进展 ›› 2021, Vol. 40 ›› Issue (1): 324-331.DOI: 10.16085/j.issn.1000-6613.2020-0512

基于双硫键和氢键协效的高性能自修复聚氨酯脲的研制

王玉龙¹^,²(), 胡国胜¹(), 张静婷¹, 白静静¹^,², 吕秦牛², 李振中²

^1.中北大学高分子与生物工程研究所，山西太原 030051
^2.太原工业学院材料工程系，山西太原 030008

收稿日期:2020-04-03 出版日期:2021-01-05 发布日期:2021-01-12
通讯作者: 胡国胜
作者简介:王玉龙（1989—），男，博士研究生，主要研究自修复聚氨酯的开发。E-mail：Vi12342019@163.com。
基金资助:
西安近代化学研究所开放合作创新基金(204-J-2019-0387-1/6-18);山西省“1331工程”重点学科建设项目(2017-6-02-17)

Development of self-healing poly(urethane urea) with high performances based on the synergistic effect of disulfide bonds and hydrogen bonds

Yulong WANG¹^,²(), Guosheng HU¹(), Jingting ZHANG¹, Jingjing BAI¹^,², Qinniu LYU², Zhenzhong LI²

^1.Institute of Macromolecules and Bioengineering, North University of China, Taiyuan 030051, Shanxi, China
^2.Department of Materials Engineering, Taiyuan Institute of Technology, Taiyuan 030051, Shanxi, China

Received:2020-04-03 Online:2021-01-05 Published:2021-01-12
Contact: Guosheng HU

摘要/Abstract

摘要：

为解决自修复弹性体同时具有优异的力学性能和自修复性能的矛盾，首先将原料胱氨酸（CYS）进行甲酯化得到含双硫键的二胺扩链剂胱氨酸二甲酯（CDE），然后以聚四氢呋喃醚二醇（PTMG）为软段，异佛尔酮二异氰酸酯（IPDI）和CDE为硬段，固定摩尔比为1∶3∶2，采用两步法制备了自修复聚氨酯脲（SH-PUU）弹性体，并对SH-PUU进行了红外光谱测试、拉曼光谱测试、力学性能测试、自修复性能测试、划痕修复微观形貌观察、应力松弛和动态力学性能测试。实验结果表明：SH-PUU的软段和硬段的玻璃化转变温度分别为-38.5℃和77.6℃，微相分离程度较高，SH-PUU具有良好的力学性能，拉伸强度为13.6MPa，断裂伸长率达531.3%；同时SH-PUU具有高效的自修复能力，试样在经过80℃修复2h后，基于拉伸强度的自修复效率达到97.1%，SH-PUU的力学性能和自修复性能达到较好的平衡。SH-PUU的高自修复能力是由动态双硫键和氢键协效增强引起的，其通过加热方式的自修复机理为：SH-PUU中的动态双硫键在80℃发生可逆交换反应，SH-PUU中的氢键在低于100℃时会重新形成。

关键词: 双硫键, 氢键, 聚氨酯脲, 自修复, 胱氨酸二甲酯

Abstract:

In order to solve the contradiction between excellent mechanical properties and self-healing properties of self-healing elastomers, a diamine chain extender cystine dimethyl ester (CDE) containing disulfide bond was obtained by methyl esterification of cysteine (CYS). The self-healing poly (urethane urea) (SH-PUU) elastomer was prepared through two-step approach by using polytetramethylene ether glycol (PTMG) as the soft segments and isophorone diisocyanate (IPDI) and CDE as the hard segments, with the molar ratio of 1︰3︰2. The SH-PUU was characterized by infrared spectrum, Raman spectrum, mechanical property test, self-healing property test, micromorphology observation of scratch healing, stress relaxation and dynamic mechanical property analysis. The results showed that the glass transition temperature of soft segments and hard segments was -38.5℃ and 77.6℃, respectively, indicating that SH-PUU had a high degree of microphase separation. SH-PUU had outstanding mechanical properties, which tensile strength and elongation at break was 13.6MPa and 531.3%, respectively. The self-healing efficiency of 97.1% after healing at 80℃ for 2h based on tensile strength indicated the performance of SH-PUU got a good balance between mechanical properties and self-healing properties. The high self-healing ability of SH-PUU was caused by the enhancement of the synergistic effect of dynamic disulfide bonds and hydrogen bonds. The self-healing mechanism of SH-PUU is that the dynamic disulfide bonds in SH-PUU occur exchange reaction reversibly at 80℃, and the hydrogen bonds in SH-PUU regenerate at less than 100℃.

Key words: disulfide bonds, hydrogen bonds, poly(urethane urea), self-healing, cystine dimethyl ester

中图分类号:

TQ334.1

王玉龙, 胡国胜, 张静婷, 白静静, 吕秦牛, 李振中. 基于双硫键和氢键协效的高性能自修复聚氨酯脲的研制[J]. 化工进展, 2021, 40(1): 324-331.

Yulong WANG, Guosheng HU, Jingting ZHANG, Jingjing BAI, Qinniu LYU, Zhenzhong LI. Development of self-healing poly(urethane urea) with high performances based on the synergistic effect of disulfide bonds and hydrogen bonds[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 324-331.

图/表 13

图1 合成CDE的化学反应式

图2 合成SH-PUU的化学反应式

图3 CDE的对比FTIR光谱图

图4 CDE的1H NMR光谱图

图5 SH-PUU的对比FTIR光谱图

图6 SH-PUU的对比Raman光谱图

图7 SH-PUU的自修复效果图

图8 SH-PUU的应力-应变曲线

图9 HA-PUU的应力-应变曲线

图10 SH-PUU的划痕修复SEM图

图11 SH-PUU的应力松弛曲线

图12 SH-PUU的DMA曲线

图13 SH-PUU的自修复机理

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基于双硫键和氢键协效的高性能自修复聚氨酯脲的研制

Development of self-healing poly(urethane urea) with high performances based on the synergistic effect of disulfide bonds and hydrogen bonds

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