Dynamic combinatorial chemistry (DCC) involves reversible reactions which can be controlled by thermodynamics method. Transesterification is one of the most widely explored DCC reactions. In this paper, transesterification was used to synthesize self-healing network. First, a three-arm star-shaped hydroxyl-terminated polyglycolide (HTPG) was fabricated though the ring-opening polymerization (ROP) of glycolide by using triethanolamine (TEA) as initiator and tetrabutyl titanate (TBT) as catalyst. Then the self-healing network i.e. isocyanate-based crosslinked star-shaped polyglycolide (ICSPG) was prepared through the crosslink between hexamethylene diisocyanate trimer (HDIT) and HTPG. In order to explore the mechanism of the self-healing, a polyurethane based on a tri-functional polyether polyol (PPPU)was synthesized. The structures of HTPG, ICSPG and PPPU were characterized by fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹H NMR). The mechanical properties and self-healing properties were characterized by dynamic mechanical thermal analysis (DMTA) and polarizing optical microscopy (POM). And the welding test was used to further characterize the self-healing properties of ICSPG. It was found that mechanical recovery is about 70%. The POM results showed that ICSPG exhibited self-healing properties at high temperature.

动态组合化学（DCC）涉及可逆反应，可通过热力学方法进行控制。酯交换反应是开发最广泛的DCC反应之一。本文采用酯交换反应合成自愈网络。首先，通过使用三乙醇胺（TEA）作为引发剂和钛酸四丁酯（TBT）作为催化剂，通过乙交酯的开环聚合（ROP）来制备三臂星形羟基封端的聚乙交酯（HTPG）。然后是自我修复网络，即基于异氰酸酯的交联星通过六亚甲基二异氰酸酯三聚体（HDIT）和HTPG之间的交联制备了异型聚乙交酯（ICSPG）。为了探索自修复的机理，合成了基于三官能聚醚多元醇（PPPU）的聚氨酯。HTPG，ICSPG和PPPU的结构通过傅里叶变换红外光谱（FTIR）和核磁共振光谱（¹ H NMR）进行表征。通过动态机械热分析（DMTA）和偏振光学显微镜（POM）对机械性能和自愈性能进行了表征。并使用焊接测试进一步表征了ICSPG的自愈性能。发现机械回复率约为70％。POM结果表明，ICSPG在高温下表现出自愈特性。