MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 310027, China.
College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, 314001, China.
Angew Chem Int Ed Engl. 2022 Nov 14;61(46):e202213028. doi: 10.1002/anie.202213028. Epub 2022 Oct 17.
It is significant and challenging to use CO to produce polymeric materials, especially with olefins. Here, a novel strategy named "scrambling polymerizations" is designed and performed for the copolymerization of a CO -and-1,3-butadiene-derived valerolactone, 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVL), with ϵ-caprolactone (CL) to prepare polyesters. Anionic ring-opening polymerization of CL and conjugated addition oligomerization of EVL take place individually to form PCL and EVL oligomers, respectively. Then EVL oligomers insert into PCL by transesterification resulting in polyester P(CL-co-EVL) with a tunable topology and composition. The non-cytotoxic and degradable polyester network with elongation at break of >600 % can be used as an elastomer. We propose a method to provide polyester elastomers from CO and olefins for the first time, and expand the potential of transformation from sustainable feedstocks to polymeric materials.
使用 CO 来生产聚合材料，尤其是与烯烃共聚，是一项具有重要意义和挑战性的工作。在这里，我们设计并实施了一种名为“ scrambling 聚合”的新策略，用于 CO 和 1,3-丁二烯衍生的戊内酯、3-亚乙基-6-乙烯基四氢-2H-吡喃-2-酮（EVL）与 ε-己内酯（CL）的共聚，以制备聚酯。CL 的阴离子开环聚合和 EVL 的共轭加成聚合分别进行，分别形成 PCL 和 EVL 低聚物。然后，EVL 低聚物通过酯交换插入 PCL 中，形成拓扑结构和组成可调的聚酯 P（CL-co-EVL）。具有断裂伸长率>600%的非细胞毒性和可降解聚酯网络可用作弹性体。我们首次提出了一种从 CO 和烯烃制备聚酯弹性体的方法，拓展了从可持续原料转化为聚合材料的潜力。
