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

Pulsed-laser photoinitiated polymerization was used to determine, in toluen e solution, the propagation kinetic parameters of a series of acrylates wit h increasing size of the alkyl side group. Transfer to monomer and to tolue ne did not occur significantly in our PLP conditions and our temperature ra nge since no broadening of the MMD was observed, allowing generally to work with two inflection points. In contrast, depending on the nature of the ac rylate and on the PLP conditions, transfer to polymer, and thus long chain branching, can critically interfere. Indeed, the Mark-Houwink-Sakurada para meters, which are used to calculate the absolute molar mass at the inflecti on point, strongly depend on the polymer structure and thus, should be care fully measured for each PLP sample. Although still preliminary, the results show that the ks measured in toluene solution present a tendency to contin uously decrease when increasing the size of the side group. This observatio n is conflicting with the reported behaviour for PLP experiments in bulk, r evealing a possible solvent effect.