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Summary: The ring‐opening polymerization (ROP) of 1,5‐dioxepan‐2‐one (DXO) catalyzed by diphenyl phosphate (DPP) using 3‐phenyl‐1‐propanol (PPA) as an initiator has been studied. The polymerization in toluene at room temperature produced poly(1,5‐dioxepan‐2‐one) (PDXO) with a narrow polydispersity index. For the initial DXO 0 /PPA 0 /DPP 0 of 50/1/1, the molecular weight determined from 1 H NMR ( M n,NMR ) of 5670 g mol −1 agreed with the calculated one ( M n,calcd ) of 5680 g mol −1 . The obtained PDXO possessing a PPA residue at the α‐chain end was confirmed by the 1 H NMR and MALDI‐TOF MS measurements. The livingness of the ROP of DXO was supported by the kinetic and chain‐extension experiments. The diblock and random copolymerizations of DXO and ϵ ‐caprolactone (CL) afforded respective copolymers. The monomer reactivity ratios were obtained as r DXO = 0.59 and r CL = 1.19 using the Kelen–Tüdös method, and the random copolymers showed different thermal properties corresponding to copolymer compositions.
Makiguchi et al. (Sun,) studied this question.