Amine activators for the ?cool? peroxide initiated polymerization of acrylic monomers

Abstract

Two tertiary amines with a chemical structure rather similar to dimethyl-4-toluidine have been prepared and tested as activators for the free radical polymerization of methyl methacrylate. 4-Dimethylaminobenzyl alcohol, DMOH, was synthesized by reduction of the corresponding benzaldehyde. 4-Dimethylaminobenzyl methacrylate, DMMO, was synthesized by condensation of methacryloyl chloride with DMOH in the presence of triethylamine as catalyst. Kinetic studies of the bulk polymerization of methyl methacrylate initiated by the redox system BPO–amine have been carried out by differential scanning calorimetry at different temperatures in the interval 30–40°C. An increase of the overall rate constant, k, with increasing temperature was observed for all redox systems. The system BPO/DMT gave the highest values of k. The polymerizations catalyzed by DMOH and DMMO respectively gave lower values of the overall Arrhenius activation than that obtained with DMT. DMMO may participate in the polymerization not only as activator but also as an acrylic derivative which can be incorporated into the polymeric growing chains during the propagation step of the free radical polymerization. © 1996 John Wiley & Sons, Inc.