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Propagation and Termination Kinetics of PEGylated Methacrylate Radical Polymerizations
Author(s) -
Siegmann Rebekka,
Jeličić Aleksandra,
Beuermann Sabine
Publication year - 2010
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200900527
Subject(s) - methacrylate , polymer chemistry , ethylene glycol , monomer , chemistry , kinetics , alkyl , ether , radical polymerization , polymer , organic chemistry , physics , quantum mechanics
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.