Solvent effects on acrylate kp in organic media?-A systematic PLP-SEC study

The Arrhenius parameters of the propagation rate coefficient, kp , are determined employing high-frequency pulsed laser polymerization-size exclusion chromatography (PLP-SEC) for the homologous series of five linear alkyl acrylates (i.e., methyl acrylate (MA), butyl acrylate (BA), dodecyl acrylate (DA), stearyl acrylate (SA), and behenyl acrylate (BeA)) in 1 m solution in butyl acetate (BuAc) as well as in toluene. The comparison of the obtained kp values with the literature known values for bulk demonstrates that no significant solvent influence neither in BuAc nor in toluene on the propagation reaction compared to bulk is detectable. Concomitantly, the kp values in toluene and in BuAc solution display a similar increase with increasing number of C-atoms in the ester side chain as was previously reported for the bulk systems. These findings are in clear contrast to earlier studies, which report a decrease of kp with increasing ester side chain length in toluene. The additional investigation of the longest and shortest ester side chain acrylate (i.e., BeA and MA) over the entire experimentally available concentration range at one temperature (i.e., 50 °C) does not reveal any general concentration dependence and all observed differences in the kp are within the experimental error.