摘要
由于其独特的可降解性和生物相容性,脂肪族聚酯被广泛地应用于生物医药、组织工程、包装等领域,环内酯(如ε-己内酯,丙交酯等)的开环聚合是制备高分子量脂肪族聚酯的有效方法,但受到环内酯单体种类的限制.γ-丁内酯(γ-BL)可由生物质转化合成得到,具有可再生的绿色来源,价格低廉,是非常有潜力的环内酯单体,然而由于其五元环的热力学稳定性,在以往的教科书和文献中通常把γ-BL称为是"不可聚合的"单体. 2016年,Hong和Chen通过控制热力学和动力学等条件首次实现了γ-BL在温和条件下的高效开环聚合,并为制备绿色可回收高分子材料提供了新思路,该突破性工作迅速地引起了科研界的关注,并由此发展出了可进行γ-BL高效可控开环聚合的催化剂,单体范围也扩展到了γ-BL的衍生物,合成得到了结构新颖的高性能高分子材料.本文系统地综述近3年来这一领域的研究进展,侧重于讨论其催化剂结构与聚合行为、聚合物结构与聚合物性能之间的关系,以及后续的回收行为,并提出该领域存在的挑战以及未来的发展方向.
Aliphatic polyesters are a class of technologically important biodegradable and/or biocompatible polymers and have realized wide applications in biological medicine, temporary implants for tissue engineering,and packaging. Ring-opening polymerization(ROP) has proven to be a powerful methodology to prepare largescale polyesters with different structures and properties. However, up to date, the monomers suitable for ROP are only restricted to the cyclic esters or lactones with a relatively high strain energy, which greatly limits the development and application of this methodology. Biomass-derived γ-butyrolactone(γ-BL), commercially available at a low price, would be a desirable monomer for ROP, but it is commonly referred as "nonpolymerizable" in textbooks and the literature due to low strain energy of its five-membered ring. In 2016, Hong and Chen et al. established the first efficient ROP of γ-BL under mild conditions by controlling thermodynamics and kinetic conditions, which also provided a new approach for recyclable polymers. This breakthrough work attracted the attention of the scientific researchers in a short time, and a series of new catalysts have been developed for the ROP of γ-BL and its derivatives. In this context, this review article systematically summarizes the progress of the emerging area in the past three years by focusing on the discussion of the relationship between the catalyst structure and polymerization behavior, the structure-dependent polymer properties, as well as the recyclability of the resultant polymers. The currently unmet challenges in this field, and thus the suggested corresponding future research directions, are also presented.
引文
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