Propagation and Termination Kinetics of PEGylated Methacrylate Radical Polymerizations

Propagation and chain‐length averaged termination rate coefficients, k p and < k t >, for radical polymerizations of methacrylates carrying poly(ethylene glycol) (PEG) units are reported. k p derived from pulsed laser initiated polymerizations in bulk, in organic solvents, and in ionic liquids follows the methacrylate‐type family behavior. Contrary, diffusion controlled k t 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 < k t > is unexpectedly high. Moreover, < k t > of poly(ethylene glycol) ethyl ether methacrylate shows a significant reduction in k t already at 15% conversion, whereas dodecyl methacrylate < k t > is constant up to at least 70% conversion.