Synthesis of trimethylene carbonate/ϵ‐caprolactone copolymers initiated with zinc alkoxide: influence of copolymer chain microstructure on thermal and mechanical properties

Ethylzinc(II ) ethoxide is a highly active and efficient initiator for the bulk polymerization of 1,3‐trimethylene carbonate and its copolymerization with ? ‐caprolactone. This initiator allows one to obtain (co)polymers with high molar masses in quite a short time. Significant difference in co‐monomer reactivity and relatively low participation of intermolecular transesterification processes lead to the obtained copolymers being characterized by a gradient chain microstructure. In ¹³C NMR spectra, in all regions, we observed the presence of triads which were distinctly represented by four peaks for the carbonyl signal. Mechanical tests showed that copolymers containing 70% and more of ? ‐caprolactone presented a relatively high Young's modulus and a very high maximum elongation factor; therefore these materials are promising in many biomedical applications. Due to the high reaction rate, we also made an attempt at copolymerization using reactive extrusion which gave promising results. © 2017 Society of Chemical Industry