Propagation and Termination Kinetics of PEGylated Methacrylate Radical Polymerizations

Propagation and chain‐length averaged termination rate coefficients, kp and , for radical polymerizations of methacrylates carrying poly(ethylene glycol) (PEG) units are reported. kp derived from pulsed laser initiated polymerizations in bulk, in organic solvents, and in ionic liquids follows the methacrylate‐type family behavior. Contrary, diffusion controlled kt values obtained from chemically initiated polymerizations with in‐line FT‐NIR monitoring of monomer conversion are strongly affected by the PEG units in the ester group. Compared to alkyl methacrylates is unexpectedly high. Moreover, of poly(ethylene glycol) ethyl ether methacrylate shows a significant reduction in kt already at 15% conversion, whereas dodecyl methacrylate is constant up to at least 70% conversion. Propagation and termination rate coefficients of PEGylated monomers are presented. For both coefficients methacrylate‐type behavior is seen. Long PEG ester groups lead to significant differences in chain‐length averaged termination rate coefficients and their conversion dependence compared to alkyl methacrylates of similar size.