The ring-opening polymerization of cyclic ketene acetals (CKA) by free radical mechanism attracts considerable research interest since it presents an alternative route for the synthesis of aliphatic polyesters.1 These monomers can indeed undergo radical addition on their C=C double bond that subsequently leads to propagation by ring opening. By a theoretical approach based on DFT calculations combined with PREDICI modelings, the radical copolymerization of CKA and commun vinyl monomers was studied to find optimized CKA/vinyl monomer couples to obtain functionalized polyesters. Indeed, whereas polyesters based on lactones are widely used, such materials nevertheless exhibit severe limitations due to the absence of functionality on the polymer backbone, which could otherwise be used either for tuning their physical properties or for coupling various molecules of interest. Recently a few authors developed an elegant approach to prepare functionalized polyester-like structures based on the radical ring-opening copolymerization of CKA with traditional vinyl monomers.2 Whereas this approach is promising, severe limitations still remain: the unfavorable reactivity ratios of CKA compared to those of traditional vinyl monomers lead to a considerable difference between the fraction of 2-methylene-1,3-dioxepane (MDO) incorporated and the initial fraction in the co-monomer feed.2 Optimized vinyl monomer/CKA couples are highly desired. Once this vinyl monomer/CKA couple has been selected, this system was further used to prepare interesting materials for biomedical applications such as antibacterial surfaces and bioelastomers.3

Radical (Co)polymerization of cyclic ketene acetals

254th National Meeting (2017)

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