TY - JOUR A1 - Siegmann, Rebekka A1 - Beuermann, Sabine T1 - Individual rate coefficients for 1H,1H,2H,2H-tridecafluorooctyl methacrylate radical polymerizations N2 - Kinetic data for radical polymerizations of 1H,1H,2H,2H-tridecafluorooctyl methacrylate (TDFOMA) in bulk is reported. Pulsed laser initiated polymerizations yield propagation rate coefficients, k(p), which are by a factor of 1.9 higher than methyl methacrylate k(p). The activation energy of TDFOMA k(p) is not significantly different from that of alkyl methacrylates. Chain-length averaged termination rate coefficients were estimated from chemically initiated polymerizations with in-line FT-NIR spectroscopic monitoring of monomer conversion. Up to 30% of monomer conversion TDFOMA termination rate coefficients are only slightly below MMA low conversion values. The result is suggested to be due to less interactions between the macroradicals compared to nonfluorinated systems. Y1 - 2010 UR - http://pubs.acs.org/journal/mamobx U6 - https://doi.org/10.1021/Ma902653b SN - 0024-9297 ER - TY - JOUR A1 - Siegmann, Rebekka A1 - Jelicic, Aleksandra T1 - Propagation and termination kinetics of PEGylated methacrylate radical polymerizations N2 - Propagation and chain-length averaged termination rate coefficients, k(p) 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 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 is unexpectedly high. Moreover, of poly(ethylene glycol) ethyl ether methacrylate shows a significant reduction in k(t) already at 15% conversion, whereas dodecyl methacrylate is constant up to at least 70% conversion. Y1 - 2010 UR - http://www3.interscience.wiley.com/journal/10003495/home U6 - https://doi.org/10.1002/macp.200900527 SN - 1022-1352 ER -