Although controlled radical polymerizations (CRPs) has been extensively utilized to synthesize random copolymers to achieve desired properties for a number of applications, the fundamental studies such as kinetics and reactivity ratio in the copolymerizations, required for the expansion of the CRPs towards many different applications, have not been thoroughly investigated. In this work, we demonstrate detailed kinetic studies for the copolymerizations of two different simple model monomers, methyl methacrylate (MMA) and ethyl methacrylate (EMA) via single-electron transfer living radical polymerization (SET-LRP) which is well-established and versatile technique for controlled radical polymerization of a broad range of monomers including acrylates and methacrylates. Particularly, SET-LRP is beneficial in achieving a broad range of molecular weight (up to hundreds kg/mol), low dispersity (down to ~1.1), and tailored functionalities simultaneously under relatively mild conditions. In kinetic studies, apparent propagation rate constants were estimated with the variation of the feed ratio and polymerization temperature. Furthermore, reactivity ratio values were determined by the approach using Mayo-Lewis equation and other modified approaches, <i>i.e.</i> Finemann-Rose and Kelen-Tudos methods. We also explored the glass transition behaviors of resulting random copolymer samples in bulk and thin films as a function of composition. Our findings provide deeper understanding of the fundamental aspects in the copolymerization via the SET-LRP.

Random copolymers of simple methacrylates synthesized by Cu(0)-mediated single-electron transfer living radical polymerization: Copolymerization kinetics and thermal properties

256th National Meeting (2018)

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