基于二硫键和氢键的自修复聚氨酯弹性体的制备、改性及其应用

doi:10.16085/j.issn.1000-6613.2022-0743

化工进展 ›› 2023, Vol. 42 ›› Issue (2): 934-943.DOI: 10.16085/j.issn.1000-6613.2022-0743

基于二硫键和氢键的自修复聚氨酯弹性体的制备、改性及其应用

席慧敏¹(), 钱坤¹, 俞科静¹(), 李杰², 张中威², 熊自明², 张耀良³

^1.江南大学生态纺织教育部重点实验室，江苏无锡 214122
^2.陆军工程大学爆炸冲击防灾减灾国家重点实验室，江苏南京 210007
^3.江苏长江爆破工程有限公司研发部，江苏镇江 212011

收稿日期:2022-04-25 修回日期:2022-06-20 出版日期:2023-02-25 发布日期:2023-03-13
通讯作者: 俞科静
作者简介:席慧敏（1997—），女，硕士研究生，研究方向为自修复材料。E-mail：1132752394@qq.com。
基金资助:
连云港市重大技术攻关-揭榜挂帅项目(CGJBGS2104);镇江市重点研发计划(GY2021009)

Preparation, modification and application of self-healing polyurethane elastomers based on disulfide and hydrogen bonds

XI Huimin¹(), QIAN Kun¹, YU Kejing¹(), LI Jie², ZHANG Zhongwei², XIONG Ziming², ZHANG Yaoliang³

^1.Key Laboratory of Eco-Textiles, Ministry of Education, Jiangnan University, Wuxi 214122, Jiangsu, China
^2.State Key Laboratory of Blast Impact Disaster Prevention and Mitigation, Army Engineering University, Nanjing 210007, Jiangsu, China
^3.R&D Department of Jiangsu Changjiang Blasting Engineering Co. , Ltd. , Zhenjiang 212011, Jiangsu, China

Received:2022-04-25 Revised:2022-06-20 Online:2023-02-25 Published:2023-03-13
Contact: YU Kejing

摘要/Abstract

摘要：

以聚丙二醇（PPG）为软段，异佛尔酮二异氰酸酯（IPDI）为硬段构建聚氨酯主链，然后将1,4-丁二醇（BDO）和2,2′-二氨基二苯二硫醚（DTDA）作为扩链剂嵌入聚氨酯主链中，制备一种具有高强度、刺激条件温和且能快速修复的基于二硫键和氢键协同作用的聚氨酯（PU）弹性体。采用红外光谱、拉曼光谱、热分析、力学测试及光学显微观察对其结构和性能进行表征，研究了软硬段比、修复时间和修复温度对PU力学性能和自修复性能的影响。实验结果发现，所制备的PU具有很高的断裂伸长率（2398%）、断裂强度（8.84MPa）以及抗穿刺性能。同时PU在温和的刺激条件下具有优异的自修复性能，其修复效率与修复时间和修复温度呈正比，硬段质量分数为44.26%的试样经70℃加热3h后，断裂强度可恢复到原始试样的92.7%。再处理试验的结果表明，该PU可以通过热压实现循环利用，回收率高达98.8%。此外，该自修复PU弹性体可作为柔性基底应用于可穿戴传感器来监测人体肢体运动。

关键词: 聚氨酯, 二硫键, 氢键, 自修复, 可穿戴传感器

Abstract:

The polyurethane (PU) elastomer with high strength, mild irritation conditions and rapid repair based on the synergistic action of disulfide and hydrogen bonds was prepared. Starting from molecular structure design, poly(propylene glycol) (PPG) was used as a soft segment and isophorone diisocyanate (IPDI) as a hard segment to construct a polyurethane backbone, and then 1,4-butanediol (BDO) and 2,‍2'-diaminodiphenyl disulfide (DTDA) were embedded in the polyurethane backbone as chain extenders. The structure and properties were characterized by infrared spectroscopy, Raman spectroscopy, thermal analysis, mechanical testing and optical microscopy. The effects of the ratio of soft to hard segments, repair time and repair temperature on the mechanical properties and self-healing properties of PU were studied. The results showed that the self-healing polyurethane had high elongation at break of 2398%, fracture strength of 8.84MPa and puncture resistance. At the same time, the PU had excellent self-healing properties under mild stimulation conditions, and its repair efficiency was directly proportional to the repair time and repair temperature. The fracture strength of the specimen with 44.26% mass fraction of hard segment content could be recovered to 92.7% of the original specimen by heating at 70℃ for 3h. Reprocessing tests indicated that PU could also be recycled by hot pressing with a recovery rate of 98.8%. Furthermore, the self-healing PU elastomer could be used as a flexible substrate for wearable sensors to monitor human limb movements.

Key words: polyurethane, disulfide bond, hydrogen bond, self-healing, wearable sensor

中图分类号:

TQ334

席慧敏, 钱坤, 俞科静, 李杰, 张中威, 熊自明, 张耀良. 基于二硫键和氢键的自修复聚氨酯弹性体的制备、改性及其应用[J]. 化工进展, 2023, 42(2): 934-943.

XI Huimin, QIAN Kun, YU Kejing, LI Jie, ZHANG Zhongwei, XIONG Ziming, ZHANG Yaoliang. Preparation, modification and application of self-healing polyurethane elastomers based on disulfide and hydrogen bonds[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 934-943.

图/表 12

参考文献 25

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样品	IPDI/PPG（摩尔比）	DTDA 质量分数/%	BDO 质量分数/%	ODA 质量分数/%	硬段质量分数/%
PU0	5.1∶1	0	4.74	16.43	48.59
PU1	5.1∶1	17.66	4.58	0	50.35
PU2	4.1∶1	15.01	3.89	0	44.26
PU3	3.5∶1	13.05	3.42	0	39.84
PU4	3.1∶1	11.58	3.01	0	36.45

样品	IPDI/PPG（摩尔比）	DTDA 质量分数/%	BDO 质量分数/%	ODA 质量分数/%	硬段质量分数/%
PU0	5.1∶1	0	4.74	16.43	48.59
PU1	5.1∶1	17.66	4.58	0	50.35
PU2	4.1∶1	15.01	3.89	0	44.26
PU3	3.5∶1	13.05	3.42	0	39.84
PU4	3.1∶1	11.58	3.01	0	36.45

序号	断裂强度/MPa	断裂伸长率/%	修复时间/h	修复温度/℃	修复效率/%	动态键	参考文献
1	6.23	105	24	25	91	二硫键	[21]
2	0.8	3000	24	25	97	二硫键、氢键	[22]
3	7.7	580	24	60	97.4	二硫键	[14]
4	3.64	372	24	60	89.8	二硫键	[23]
5	2.6	551	8	60	80.8	二硫键	[24]
6	2.64	551.7	12	70	87.1	二硫键、氢键	[25]
7	13.6	531.3	2	80	97.1	二硫键、氢键	[26]
8	1.45	212.5	24	80	84.8	二硫键	[10]
9	7.48	2223	3	70	92.7	二硫键、氢键	本文工作

序号	断裂强度/MPa	断裂伸长率/%	修复时间/h	修复温度/℃	修复效率/%	动态键	参考文献
1	6.23	105	24	25	91	二硫键	[21]
2	0.8	3000	24	25	97	二硫键、氢键	[22]
3	7.7	580	24	60	97.4	二硫键	[14]
4	3.64	372	24	60	89.8	二硫键	[23]
5	2.6	551	8	60	80.8	二硫键	[24]
6	2.64	551.7	12	70	87.1	二硫键、氢键	[25]
7	13.6	531.3	2	80	97.1	二硫键、氢键	[26]
8	1.45	212.5	24	80	84.8	二硫键	[10]
9	7.48	2223	3	70	92.7	二硫键、氢键	本文工作

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基于二硫键和氢键的自修复聚氨酯弹性体的制备、改性及其应用

Preparation, modification and application of self-healing polyurethane elastomers based on disulfide and hydrogen bonds

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