Investigations Into Chain‐Length‐Dependent Termination in Bulk Radical Polymerization of 1 H , 1 H , 2 H , 2 H ‐Tridecafluorooctyl Methacrylate

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.