Anionic ring‐opening polymerization behavior of trans‐cyclohexene carbonate using metal tert‐butoxides: Construction of living anionic ring‐opening polymerization by lithium tert‐butoxide

Abstract Anionic ring‐opening polymerization (ROP) behavior of trans ‐cyclohexene carbonate (CHC) using metal alkoxides as initiators was investigated. As a result, lithium tert ‐butoxide‐initiated ROP of CHC with a high‐monomer concentration (10 M) at low temperature (−15 to −10°C) proceeded to afford a poly( trans ‐cyclohexene carbonate) (PCHC) without undesired side reactions such as mainly backbiting. The suppression of side reactions enables the control of the molecular weight ( M n = 2400–6100) of PCHC with low molar‐mass dispersity values ( M w / M n = 1.16–1.22). Furthermore, by increasing the feed ratio of the monomer to the initiator, the molecular weight increases proportionally, indicating a controllable polymerization. The results of a matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis, a kinetic study, and a chain extension experiment suggested a living nature of this ROP using lithium tert ‐butoxide.