【摘要】 ε-己内酯（ε-CL）的开环聚合及共聚可生成生物降解高分子材料，具有广阔的应用前景，关键是高性能催化体系的研发。针对ε-己内酯的开环聚合及共聚中催化体系的结构设计与性能优化，综述了近年来有机铝化合物催化剂的发展现状。通过调控配体类型（如双核、螺-菲单酮衍生物）、金属中心几何构型（协同双核、刚性桥联）及取代基效应（空间位阻、电子供体/受体），显著提升催化活性与聚合物结构可控性。双核铝配合物因金属间距缩短增强协同效应，促进单体交替插入，实现无规共聚物链段分布接近理想状态；大体积取代基通过空间位阻优化活性位点可及性，抑制副反应并缩小相对分子质量分布。反应条件（温度、加料策略）的精细调控则进一步提升了单体转化率和丰富的聚合物结构的实现。酯交换反应通过调控单体序列分布，使共聚物呈现单一玻璃化转变温度，验证无规微观结构。手性催化剂设计则通过平衡单体反应活性差异，实现高规整度交替共聚并提升聚合物力学性能。这些进展为开发高效、可调控的生物可降解聚酯合成技术提供了理论支撑，推动了其在包装、医疗等领域的应用潜力。更多还原

【Abstract】 The ring opening polymerization and copolymerization of ε-caprolactone can generate biodegradable polymer materials with broad application prospects, and the key is the development of high-performance catalytic systems. Focusing on the structural design and performance optimization of the catalytic systems for the ring-opening polymerization and copolymerization of ε-caprolactone( ε-CL), this review summarizes recent advances in aluminum-based catalytic systems with optimized structure-performance relationships. By tailoring ligand types(e.g., dinuclear and spiro-phenanthrenequinone derivatives), metal center geometries(synergistic dinuclear, rigid bridged), and substituent effects(steric hindrance, electron-donating/withdrawing groups),catalytic activity and polymer structural controllability have been significantly enhanced. Dinuclear aluminum complexes exhibit shortened metal-metal distances, strengthening synergistic effects that promote alternating monomer insertion, achieving near-ideal chain-segment distribution in amorphous copolymers. Bulky substituents optimize active site accessibility via steric regulation, suppressing side reactions and narrowing molecular weight distributions. Precise control of reaction conditions(temperature, feeding strategies) further improves monomer conversion rates and enables diverse polymer architectures. Transesterification reactions modulate monomer sequence distribution, yielding copolymers with a single glass transition temperature,confirming their amorphous nature. Chiral catalyst design balances reactivity differences between monomers,enabling highly regular alternating copolymerization and enhanced mechanical properties. These advancements provide theoretical support for developing efficient, tunable biodegradable polyester synthesis technologies,advancing their potential applications in packaging, medical devices, and related fields.更多还原