Abstract This work describes the effect of zirconium(IV) acetylacetonate (Zr(acac)4) on the self-healing and thermomechanical properties of urethane–acrylate copolymers, and which were compared with dibutyltin dilaurate (DBTDL). For prepolymer synthesis, glyceryl methacrylate (GlyMA) and 2-hydroxyethyl methacrylate (HEMA) were chosen and copolymerized with methyl methacrylate (MMA) and butyl acrylate (BA) at a concentration of 8 mol%. The prepolymers (G8 and H8) were then crosslinked with HDI trimer to prepare self-healing copolymers, and DBTDL or Zr(acac)4 was used as both crosslinking and self-healing catalysts. The self-healing performance of new carbonate bond formation by DBTDL and transesterification by Zr(acac)4 were studied and compared using single scratch test with atomic force microscopy (AFM). Owing to the secondary hydroxyl groups of GlyMA, DBTDL shows scratch-healing capability only in the GlyMA-based copolymer (G8) within 1 h at 55 and 75 °C. On the other hand, Zr(acac)4 shows scratch-healing capability in both copolymers (G8 and H8) within 1 h at 55 and 75 °C; however, transesterification may result in the changes of storage modulus and glass-transition temperature (Tg). This was confirmed from dynamic mechanical analysis (DMA) that a low temperature (∼55 °C) exhibited excellent self-healing performance with minimal hardness change by transesterification.

中文翻译：

---

锆对聚氨酯-丙烯酸酯汽车清漆划痕修复和力学性能的催化作用

摘要 本工作描述了乙酰丙酮锆 (IV) (Zr(acac)4) 对氨基甲酸酯-丙烯酸酯共聚物自修复和热机械性能的影响，并与二月桂酸二丁基锡 (DBTDL) 进行了比较。对于预聚物合成，选择甲基丙烯酸甘油酯 (GlyMA) 和甲基丙烯酸 2-羟乙酯 (HEMA) 并以 8 mol% 的浓度与甲基丙烯酸甲酯 (MMA) 和丙烯酸丁酯 (BA) 共聚。然后将预聚物（G8 和 H8）与 HDI 三聚体交联以制备自修复共聚物，并使用 DBTDL 或 Zr(acac)4 作为交联和自修复催化剂。使用单划痕试验和原子力显微镜 (AFM) 研究并比较了 DBTDL 形成新碳酸酯键和 Zr(acac)4 酯交换的自修复性能。由于 GlyMA 的仲羟基，DBTDL 仅在基于 GlyMA 的共聚物（G8）中在 55 和 75°C 下 1 小时内显示出划痕愈合能力。另一方面，Zr(acac)4 在两种共聚物（G8 和 H8）中在 55 和 75°C 下 1 小时内显示出划痕修复能力；然而，酯交换可能导致储能模量和玻璃化转变温度（Tg）的变化。动态力学分析（DMA）证实了这一点，低温（~55°C）表现出优异的自愈性能，酯交换引起的硬度变化最小。酯交换可能导致储能模量和玻璃化转变温度 (Tg) 的变化。动态力学分析（DMA）证实了这一点，低温（~55°C）表现出优异的自愈性能，酯交换引起的硬度变化最小。酯交换可能导致储能模量和玻璃化转变温度 (Tg) 的变化。动态力学分析（DMA）证实了这一点，低温（~55°C）表现出优异的自愈性能，酯交换引起的硬度变化最小。