Investigations into chain-length-dependent termination in bulk radical polymerization of 1H, 1H, 2H, 2H-Tridecafluorooctyl methacrylate
- 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.
