@article{BarthSiegmannBeuermannetal.2012, author = {Barth, Johannes and Siegmann, Rebekka and Beuermann, Sabine and Russell, Gregory T. and Buback, Michael}, title = {Investigations into chain-length-dependent termination in bulk radical polymerization of 1H, 1H, 2H, 2H-Tridecafluorooctyl methacrylate}, series = {Macromolecular chemistry and physics}, volume = {213}, journal = {Macromolecular chemistry and physics}, number = {1}, publisher = {Wiley-Blackwell}, address = {Malden}, issn = {1022-1352}, doi = {10.1002/macp.201100479}, pages = {19 -- 28}, year = {2012}, abstract = {The SP-PLP-EPR technique is used to carry out a detailed investigation of the radical termination kinetics of 1H, 1H, 2H, 2H-tridecafluorooctyl methacrylate (TDFOMA) in bulk at relatively low conversion. Composite-model behavior for chain-length-dependent termination rate coefficients, kti,i, is observed. It is found that for TDFOMA, ic approximate to 60 independent of temperature, and as approximate to 0.65 and al approximate to 0.2 at 80 degrees C and above. However, at lower temperatures the situation is strikingly different, with the significantly higher average values of as = 0.89 +/- 0.15 and al = 0.32 +/- 0.10 being obtained at 50 degrees C and below. This makes TDFOMA the first monomer to be found that exhibits clearly different exponent values, as and al, at lower and higher temperature, and that has both a high as, like an acrylate, and a high ic, like a methacrylate.}, language = {en} } @article{CockburnSiegmannPayneetal.2011, author = {Cockburn, Robert A. and Siegmann, Rebekka and Payne, Kevin A. and Beuermann, Sabine and McKenna, Timothy F. L. and Hutchinson, Robin A.}, title = {Free Radical Copolymerization Kinetics of gamma-Methyl-alpha-methylene-gamma-butyrolactone (MeMBL)}, series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, volume = {12}, journal = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, number = {6}, publisher = {American Chemical Society}, address = {Washington}, issn = {1525-7797}, doi = {10.1021/bm200400s}, pages = {2319 -- 2326}, year = {2011}, abstract = {The propagation kinetics and copolymerization behavior of the biorenewable monomer gamma-methyl-alpha-methylene-gamma-butyrolactone (MeMBL) are studied using the Pulsed laser polymerization (PLP)/size exclusion chromatography (SEC) technique. The propagation rate coefficent for MeMBL is 15\% higher than that of its structural analogue, methyl methacrylate (MMA), with a similar activation energy of 21.8 kJ . mol(-1). When compared to MMA, MeMBL is preferentially incorporated into copolymers when reacted with styrene (ST), MMA, and n-butyl acrylate (BA); the monomer reactivity ratios fit from bulk MeMBL/ST, MeMBL/MMA, and MeMBL/BA copolymerizations are r(MeMBL) = 0.80 +/- 0.04 and r(ST) = 0.34 +/- 0.04, r(MeMBL), = 3.0 +/- 0.3 and r(MMA) = 0.33 +/- 0.01, and r(MeMBL) = 7.0 +/- 2.0 and r(BA) = 0.16 +/- 0.03, respectively. In all cases, no significant variation with temperature was found between 50 and 90 degrees C. The implicit penultimate unit effect (IPUE) model was found to adequately fit the composition-averaged copolymerization propagation rate coefficient, k(p,cop), for the three systems.}, language = {en} } @article{SiegmannBeuermann2010, author = {Siegmann, Rebekka and Beuermann, Sabine}, title = {Individual rate coefficients for 1H,1H,2H,2H-tridecafluorooctyl methacrylate radical polymerizations}, issn = {0024-9297}, doi = {10.1021/Ma902653b}, year = {2010}, abstract = {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.}, language = {en} } @article{SiegmannJelicic2010, author = {Siegmann, Rebekka and Jelicic, Aleksandra}, title = {Propagation and termination kinetics of PEGylated methacrylate radical polymerizations}, issn = {1022-1352}, doi = {10.1002/macp.200900527}, year = {2010}, abstract = {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.}, language = {en} } @article{SiegmannMoellerBeuermann2012, author = {Siegmann, Rebekka and M{\"o}ller, Eleonore and Beuermann, Sabine}, title = {Propagation rate coefficients for homogeneous phase VDF-HFP copolymerization in supercritical CO2}, series = {Macromolecular rapid communications}, volume = {33}, journal = {Macromolecular rapid communications}, number = {14}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201200115}, pages = {1208 -- 1213}, year = {2012}, abstract = {For the first time, propagation rate coefficients, kp,COPO, for the copolymerizations of vinylidene fluoride and hexafluoropropene have been determined. The kinetic data was determined via pulsed-laser polymerization in conjunction with polymer analysis via size-exclusion chromatography, the PLP-SEC technique. The experiments were carried out in homogeneous phase with supercritical CO2 as solvent for temperatures ranging from 45 to 90 degrees C. Absolute polymer molecular weights were calculated on the basis of experimentally determined MarkHouwink constants. The Arrhenius parameters of kp,COPO vary significantly compared with ethene, which is explained by the high electronegativity of fluorine and less intra- and intermolecular interactions between the partially fluorinated macroradicals.}, language = {en} }