1,3-Dioxolan-4-one (DOX) chemistry was explored for production of “one-pot” biobased polyester thermosets. DOX monomer was first functionalized by naturally occurring eugenol to introduce a structural element, which could induce cross-linking reaction through cationic polymerization of the double bond. The feasibility of polymerizing DOX monomers bearing bulky side groups was proven by model phenol-substituted DOX monomer (PhDOX). Once the reaction was shown to be effective, the same protocol was applied to eugenol-substituted monomer (EuDOX). A brief screening of the optimal catalyst concentration was performed, to obtain a highly cross-linked product. The synthesized thermoset showed good thermal resistance and high mechanical strength probably due to the rich aromatic content. The obtained thermoset was further subjected to microwave-assisted hydrothermal degradation test, which demonstrated complete recyclability to water or methanol soluble products. NMR and matrix-assisted laser desorption/ionization-mass spectroscopy analyses of the obtained degradation products unveiled the structure of the thermoset, strongly indicating that the polymerization of eugenol-functionalized DOX monomer resulted in polylactide-like chains connected with aromatic–aliphatic segments resulting from the reaction of the eugenol double bonds. The presence of free hydroxyl and carboxyl groups sheds light on the mechanism behind the observed shape-memory and self-healing properties.

中文翻译：

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利用丁香酚官能化的1,3-二氧戊环-4-一酮一锅合成可持续的高性能热固性塑料

探索了1,3-二氧戊环-4-酮（DOX）化学方法以生产“一锅”生物基聚酯热固性塑料。首先通过天然存在的丁子香酚将DOX单体官能化，以引入结构元素，该结构元素可通过双键的阳离子聚合反应引发交联反应。通过模型苯酚取代的DOX单体（PhDOX）证明了聚合带有庞大侧基的DOX单体的可行性。一旦证明该反应是有效的，则将相同的方案应用于丁子香酚取代的单体（EuDOX）。对最佳催化剂浓度进行简短筛选，以​​获得高度交联的产物。合成的热固性塑料表现出良好的耐热性和较高的机械强度，这可能是由于其芳族化合物含量较高。将获得的热固性塑料进一步进行微波辅助的水热降解试验，该试验证明了其对水或甲醇可溶产品的完全可回收性。所得降解产物的NMR和基质辅助激光解吸/电离质谱分析揭示了热固性化合物的结构，强烈表明丁香酚官能化的DOX单体的聚合导致聚丙交酯样链与由丁子香酚双键的反应。游离羟基和羧基的存在阐明了观察到的形状记忆和自我修复特性的机理。所得降解产物的NMR和基质辅助激光解吸/电离质谱分析揭示了热固性化合物的结构，强烈表明丁香酚官能化的DOX单体的聚合导致聚丙交酯样链与由丁子香酚双键的反应。游离羟基和羧基的存在阐明了观察到的形状记忆和自我修复特性的机理。所得降解产物的NMR和基质辅助激光解吸/电离质谱分析揭示了热固性化合物的结构，强烈表明丁香酚官能化的DOX单体的聚合导致聚丙交酯样链与由丁子香酚双键的反应。游离羟基和羧基的存在阐明了观察到的形状记忆和自我修复特性的机理。