Pulsed‐laser radical polymerization and propagation kinetic parameters of some alkyl acrylates

Pulsed‐laser photoinitiated polymerization was used to determine, in toluene solution, the propagation kinetic parameters of a series of acrylates with increasing size of the alkyl side group. Transfer to monomer and to toluene did not occur significantly in our PLP conditions and our temperature range since no broadening of the MMD was observed, allowing generally to work with two inflection points. In contrast, depending on the nature of the acrylate and on the PLP conditions, transfer to polymer, and thus long chain branching, can critically interfere. Indeed, the Mark‐Houwink‐Sakurada parameters, which are used to calculate the absolute molar mass at the inflection point, strongly depend on the polymer structure and thus, should be carefully measured for each PLP sample. Although still preliminary, the results show that the k_ps measured in toluene solution present a tendency to continuously decrease when increasing the size of the side group. This observation is conflicting with the reported behaviour for PLP experiments in bulk, revealing a possible solvent effect.