基于多重动态键的自愈合聚肟氨酯弹性体-中国材料进展

文章信息/Info

Title:: Self-Healing Polyoxime-Urethane Elastomers Based on Multiple Dynamic Bonds

作者:: 金宇慧; 薛振华; 吴泽凯; 陈海龙; 晏雪生; 游正伟; 1. 东华大学材料科学与工程学院纤维材料改性国家重点实验室, 上海 201600 2. 浙江禾欣科技有限公司，浙江嘉兴 314000

Author(s):: JIN Yuhui; XUE Zhenhua; WU Zekai; CHEN Hailong; YAN Xuesheng; YOU Zhengwei; 1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201600, China 2. Zhejiang Hexin Science and Technology Co., Ltd., Jiaxing 314000, China

Keywords:: polyurethane; metal coordination; multiple dynamic bonds; self-healing; p-benzoquinone dioxime

摘要:: 利用两步法将对苯醌二肟（BQDO）、聚四氢呋喃二醇（PTMG）和异佛尔酮二异氰酸酯（IPDI）反应合成得到含有动态肟氨酯键（BQDU）的自愈合聚氨酯弹性体（BQDU-LPU）。进一步引入铜离子构筑了一系列具有氢键、肟氨酯键和金属配位键多重动态键的聚肟氨酯弹性体（Cu-BQDU-LPUs）。通过核磁共振氢谱仪和傅里叶变换红外光谱仪对弹性体的结构进行表征，并采用热重分析仪、动态热机械分析仪和电子万能材料试验机测试弹性体的热学性能、力学性能和愈合性能，系统研究了铜离子的引入对弹性体性能的影响规律。结果表明，铜离子的引入能同步提升弹性体的热稳定性与力学性能。在制备的一系列Cu-BQDU-LPUs（2.5% Cu-BQDULPU、5% Cu-BQDU-LPU、7.5% Cu-BQDU-LPU和10%Cu-BQDU-LPU）中，5% Cu-BQDU-LPU具有最佳的力学性能（拉伸强度为（15.8±2.7）MPa，韧性为（92.7±31.5）MJ/m3，杨氏模量为（5.0±0.4）MPa）；在70 ℃下加热2 h愈合效率可达（90.9±2.9）%。

Abstract:: In this study, we employed a two-step approach to synthesize self-healing polyurethane elastomers (BQDU-LPU) containing dynamic oxime-urethane bonds (BQDU) by reacting p-benzoquinone dioxime (BQDO),polytetramethylene ether glycol (PTMG) and isophorone diisocyanate (IPDI). Subsequently, a series of Cu-BQDU-LPUs elastomers possessing triple dynamic bonds, including hydrogen bonds, oxime-amide bonds and metal coordination bonds were constructed by introducing copper ions. The structure of elastomers was characterized by nuclear magnetic resonance spectroscopy and Fourier-transform infrared spectroscopy, while their thermal, mechanical and self-healing properties were evaluated using thermogravimetric analysis,dynamic mechanical analysis and electronic universal material testing machine, respectively. The influence of copper ions on the properties of elastomers was systematically investigated. The results demonstrated that the introduction of copper ions simultaneously enhance the thermal stability and mechanical properties of the elastomers. Among the series of Cu-BQDU-LPUs,the 5% Cu-BQDU-LPU exhibited optimal mechanical properties,characterized by a tensile strength of (15.8±2.7) MPa, toughness of (92.7±31.5) MJ/m3 and Young’s modulus of (5.0±0.4) MPa. When subjected to heating at 70 ℃ for 2 h, this particular composition displayed a healing efficiency up to (90.9±2.9)%.