Synthetic polymers aimed at biomedical applications must meet challenging criteria in terms of structure and properties, such as (i) uniformity in chain length, (ii) biocompatibility, (iii) biodegradability and (iii) functionalizability. Controlled/living radical polymerization (CLRP) techniques satisfy most of these requirements and enable the synthesis of well-defined and easy-to-functionalize macromolecular architectures but are still facing a lack of biodegradable approaches.Among the few strategies allowing the insertion of degradable units in the backbone of a vinyl polymer, radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) is thus far the most promising one.In this project, the nitroxide-mediated radical polymerization (NMP) of methacrylate derivatives has been combined to the radical ring-opening polymerization of various cyclic ketene acetals (CKAs), as a source of biodegradable ester functions.Three CKAs have been synthesized, the 2-methylene-1,3-dioxepane (MDO), the 5,6-benzo-2-methylene-1,3-dioxepane (BMDO) and the 2-methylene-4-phenyl-1,3-dioxolane (MPDL), and copolymerized with methyl methacrylate (MMA) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA), at 90�C. While the two first ones showed limited results, the controlled insertion of MPDL led to well-defined copolymers, with dispersities as low as 1,25. Chemical hydrolyses were then performed, with predictable molar mass reductions, from 25% to 90%, as function of the amount of CKA inserted. The innocuousness of the obtained copolymers was confirmed on three different cell lines (NIH/3T3, HUVEC and J774 cells), thus representing a promising approach for new tailor-made biodegradable and biocompatible polymers.

New biodegradable PEG-based copolymers synthesized by nitroxide-mediated radical ring-opening polymerization, for biomedical applications

248th National Meeting (2014)

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