The radical copolymerization of vinyl and cyclic ketene acetal (CKA) monomers is a promising way to prepare degradable vinyl polymers. The reactivity of the comonomer pair is known to be dependent of the vinyl monomer structure that requires to play with experimental conditions (feed ratio, overall monomer conversion, etc.) to target a desired cumulative (average) copolymer composition. Even if the materials are completely degradable, the degradability of such materials is in the literature only roughly investigated and the homogeneity of the degradation product not characterized in detail.<br/><br/>By matrix based kinetic Monte Carlo simulations, it is nevertheless possible to completely describe the composition of the original copolymer and the derived degradation product on the molecular level and to investigate the key parameters that could influence the complete molar mass distribution of the residual oligomers.<br/><br/>In this work, we simulated the degradation at the molecular level and investigated the homogeneity of the incorporation of degradable ester units through vinyl-based polymer backbones via the radical copolymerization of vinyl and cyclic ketene acetal monomers. At the view of this study, the radical technique of polymerization (FRP or RDRP) does not influence the material properties after degradation, whereas the presence or not of a drift of composition during the synthesis and the values of the comonomer reactivity ratios are on the contrary of prime importance. When targeting a given final cumulative copolymer composition, a system with no or limited drift of composition and with monomers of reactivity ratios both close to 1 gives shorter and more homogeneous chains after degradation. Such properties could be of high importance when targeting biomedical applications.

Simulation of the degradation of cyclic ketene acetal and vinyl-based copolymers synthesized via a radical process

2019 Spring National Meeting

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