TY  - JOUR
A1  - Siegmann, Rebekka
A1  - Möller, Eleonore
A1  - Beuermann, Sabine
T1  - Propagation rate coefficients for homogeneous phase VDF-HFP copolymerization in supercritical CO2
JF  - Macromolecular rapid communications
N2  - 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.
KW  - copolymerization
KW  - fluorinated olefins
KW  - kinetics (polym)
KW  - pulse laser initiated polymerization
KW  - radical polymerization
Y1  - 2012
U6  - https://doi.org/10.1002/marc.201200115
SN  - 1022-1336
VL  - 33
IS  - 14
SP  - 1208
EP  - 1213
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Jelicic, Aleksandra
A1  - Yasin, Muttaqin
A1  - Beuermann, Sabine
T1  - Toward the description and prediction of solvent induced variations in Methacrylate Propagation Rate Coefficients on the basis of Solvatochromic Parameters
JF  - Macromolecular reaction engineering
N2  - Benzyl methacrylate (BzMA) propagation rate coefficients, k(p), were determined in ionic liquids and common organic solvents via pulsed-laser polymerizations with subsequent polymer analysis by size-exclusion chromatography (PLP-SEC). The aim of the work is to gain a deeper understanding of the solvent influence on k(p) and to develop a general correlation between solvent-induced variations in k(p) and solvent properties. Applying a linear solvation energy relationship (LSER), which correlates k(p) to solvent solvatochromic parameters, suggests that dipolarity/polarizability determines the solvent influence on k(p). To compare the solvent influence on BzMA k(p) with data for methyl methacrylate, hydroxypropyl methacrylate, and 2-ethoxyethyl methacrylate normalized k(p) data were treated by a single LSER, providing a universal treatment of the solvent influence on the propagation kinetics of the four monomers. Further, the predictive capabilities of this universal correlation were tested with additional monomers from the methacrylate family.
KW  - ionic liquid
KW  - kinetics (polym.)
KW  - radical polymerization
KW  - solvent influence
Y1  - 2011
U6  - https://doi.org/10.1002/mren.201000058
SN  - 1862-832X
VL  - 5
IS  - 5-6
SP  - 232
EP  - 242
PB  - Wiley-Blackwell
CY  - Malden
ER  - 
TY  - JOUR
A1  - Barth, Johannes
A1  - Siegmann, Rebekka
A1  - Beuermann, Sabine
A1  - Russell, Gregory T.
A1  - Buback, Michael
T1  - Investigations into chain-length-dependent termination in bulk radical polymerization of 1H, 1H, 2H, 2H-Tridecafluorooctyl methacrylate
JF  - Macromolecular chemistry and physics
N2  - 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.
KW  - ESR
KW  - EPR
KW  - kinetics (polym
KW  - )
KW  - methacrylates
KW  - radical polymerization
KW  - termination
Y1  - 2012
U6  - https://doi.org/10.1002/macp.201100479
SN  - 1022-1352
VL  - 213
IS  - 1
SP  - 19
EP  - 28
PB  - Wiley-Blackwell
CY  - Malden
ER  -