美国明尼苏达大学Tonks Ian A.团队报道了基于二氧化碳和丁二烯制备可调、可回收聚酯。相关研究成果发表在2022年6月27日出版的《自然—化学》。
二氧化碳价格低廉且储量丰富，其作为废物的普遍性使其成为一种具有吸引力的可持续化工原料。虽然有CO2与高能单体共聚的例子，但CO2与烯烃的直接共聚尚未报道。
该文描述了通过中间内酯3-乙基-6-乙烯基四氢-2H-吡喃-2-酮从CO2、丁二烯和氢衍生的可功能化、可回收聚酯的替代路线。内酯通过1,5,7-三氮杂二环[4.4.0]dec-5-烯的催化开环聚合，生成摩尔质量高达13.6kgmol-1的聚酯和可进行聚合后功能化的悬垂乙烯基侧链。该聚合物的最高温度较低，为138°C，便于化学回收，并且在好氧含水条件下具有固有的可生物降解性（OECD-301B协议）。这些结果表明，可以从二氧化碳、烯烃和氢气中衍生出定义明确的聚酯，从而扩大了对曾经被认为不可行的新聚合物原料的获取。
附：英文原文
Title: Tunable and recyclable polyesters from CO2 and butadiene
Author: Rapagnani, Rachel M., Dunscomb, Rachel J., Fresh, Alexandra A., Tonks, Ian A.
Issue&Volume: 2022-06-27
Abstract: Carbon dioxide is inexpensive and abundant, and its prevalence as waste makes it attractive as a sustainable chemical feedstock. Although there are examples of copolymerizations of CO2 with high-energy monomers, the direct copolymerization of CO2 with olefins has not been reported. Here an alternative route to functionalizable, recyclable polyesters derived from CO2, butadiene and hydrogen via an intermediary lactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one, is described. Catalytic ring-opening polymerization of the lactone by 1,5,7-triazabicyclo[4.4.0]dec-5-ene yields polyesters with molar masses up to 13.6kgmol1 and pendent vinyl side chains that can undergo post-polymerization functionalization. The polymer has a low ceiling temperature of 138°C, allowing for facile chemical recycling, and is inherently biodegradable under aerobic aqueous conditions (OECD-301B protocol). These results show that a well-defined polyester can be derived from CO2, olefins and hydrogen, expanding access to new polymer feedstocks that were once considered unfeasible.
DOI: 10.1038/s41557-022-00969-2
