CO2/生物基环氧化合物共聚制备绿色聚碳酸酯材料

Green Polycarbonates Prepared by CO2 and Bio-Based Epoxides

以CO2为原料合成脂肪族聚碳酸酯材料不仅利用了廉价、可再生的CO2资源,而且可以实现全生物降解高分子材料的制备,是一条绿色可持续的高分子材料合成路线。但长期以来,该领域研究多集中在利用CO2与一些石油来源的环氧烷烃(如环氧丙烷、环氧环己烷等)共聚方面,未能完全摆脱对石油资源的依赖。因此,发展基于生物基的环氧单体制备全生物基高分子材料逐渐成为CO2基高分子材料研究的热点。生物基来源化合物的引入有助于丰富CO2基高分子材料的结构和性能,拓展其应用领域。本文综述了近年来利用生物基环氧化合物与CO2共聚合成全生物基高分子材料的研究进展,并对未来该领域发展的趋势进行了展望。

The synthesis of aliphatic polycarbonates from carbon dioxide(CO2) not only utilizes cheap and renewable CO2 resources, but also enables the preparation of fully biodegradable polymer materials, providing us a promising green and sustainable polymer material synthetic route. However, the researches in this field have mainly focused on the copolymerization of CO2 with some petroleum-derived alkylene oxides(such as propylene oxide, cyclohexene oxide, etc.),and have not completely shed the dependence on petroleum resources. In 2004, Coates developed a non-petroleum route towards CO2-based copolymer for the first time via the copolymerization of CO2 and limonene epoxide(LO) usingβ-diiminate zinc complexes. Afterwards, the use of bio-based epoxides combined with CO2 to achieve fully bio-based polymer materials has gradually turned to be a research focus in this area. The structural diversity of bio-based products and their derivatives also provides more possibilities for enriching the divercities of CO2-based polymer family, as well as for expending the properties and the application ranges of the materials. However, due to the feature of the copolymerization of CO2 and epoxide, the structure and the purity of epoxides are crucial to the activity and selectivity of the reaction. Many biobased epoxides exhibit very low copolymerization activity with CO2, or only forming cyclic carbonates. In current stage, the main bio-based monomers which can copolymerize with CO2 include limonene epoxides, furfural-based epoxides, and vegetable oil-derived epoxides. Herein, recent advances in the copolymerization of CO2 and bio-based epoxides are reviewed,and the future development trends in this field are also prospected.