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Investigations Into Chain‐Length‐Dependent Termination in Bulk Radical Polymerization of 1 H , 1 H , 2 H , 2 H ‐Tridecafluorooctyl Methacrylate
Author(s) -
Barth Johannes,
Siegmann Rebekka,
Beuermann Sabine,
Russell Gregory T.,
Buback Michael
Publication year - 2012
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.201100479
Subject(s) - monomer , polymer chemistry , acrylate , methacrylate , polymerization , radical polymerization , kinetics , chain (unit) , chemistry , chain termination , polymer , electron paramagnetic resonance , materials science , physics , organic chemistry , nuclear magnetic resonance , quantum mechanics , astronomy
The SP‐PLP‐EPR technique is used to carry out a detailed investigation of the radical termination kinetics of 1 H , 1 H , 2 H , 2 H ‐tridecafluorooctyl methacrylate (TDFOMA) in bulk at relatively low conversion. Composite‐model behavior for chain‐length‐dependent termination rate coefficients, k t i,i , is observed. It is found that for TDFOMA, i c ≈ 60 independent of temperature, and α s ≈ 0.65 and α l ≈ 0.2 at 80 °C and above. However, at lower temperatures the situation is strikingly different, with the significantly higher average values of α s = 0.89 ± 0.15 and α l = 0.32 ± 0.10 being obtained at 50 °C and below. This makes TDFOMA the first monomer to be found that exhibits clearly different exponent values, α s and α l , at lower and higher temperature, and that has both a high α s , like an acrylate, and a high i c , like a methacrylate.