Biodegradable synthetic polymers for biomedical applications are mainly limited to polyesters, polypeptides and poly(alkyl cyanoacrylate); three polymer families with important constraints in terms of chemistry. Conversely, controlled/living radical polymerization (CLRP) techniques enable the design of functional polymers and complex macromolecular architectures, but developing a strategy affording the degradability of such materials is still challenging.Although known for more than thirty years, radical ring-opening polymerization (rROP) has been scarcely studied in combination with CLRP techniques. Copolymerizing traditional vinyl monomers by CLRP with cyclic ketene acetals (CKAs), as a source of biodegradable ester functions that polymerize through radical ring-opening polymerization (rROP), should open new perspectives. Figure 1. <img src='https://acs-archive-assets2.s3.amazonaws.com/241nm/uploads/62997_acs_abstract_figure_2.jpg' alt='' />Herein is reported the nitroxide-mediated radical ring opening copolymerization of three different CKAs [2-methylene-1,3-dioxepane (MDO), 5,6-benzo-2-methylene-1,3-dioxepane (BMDO) and 2-methylene-4-phenyl-1,3-dioxolane (MPDL)] with methyl methacrylate (MMA) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA), at 90�C. The resulting copolymers were qualitatively and quantitatively characterized by 1H and 31P NMR spectroscopy, as well as by size exclusion chromatography. Among the tested CKAs, MPDL was the best candidate as it enabled the synthesis of well-defined architectures with a high degree of livingness and a tunable amount of ester functions in the main chain, leading to complete chemical hydrolysis. The high degree of livingness was illustrated by the synthesis of various diblock copolymers containing a degradable block. Finally, the innocuousness of the obtained copolymers was confirmed on three different cell lines (NIH/3T3, HUVEC and J774 cells) by cell viability assays.

Toward radical ring-opening living polymerization via NMP: End-chain characterization, livingness, and control

248th National Meeting (2014)

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