Study of the telomerization of dimethylaminoethyl methacrylate (DMAEMA) with mercaptoethanol. Application to the synthesis of a new macromonomer

The telomerization of dimethylaminoethyl methacrylate (DMAEMA) with mercaptoethanol initiated by 2,2'-azobisisobutyronitrile was first investigated at 70 degreesC and the influence of the type of solvent was studied. The results showed that well-defined telomers of DMAEMA could not be synthetized via telomerization of DMAEMA in water or water/acetonitrile mixture since the telomerization reaction is in competition with the nucleophilic addition of thiol onto the monomer. Transfer constants for mercaptoethanol in benzene and acetonitrile were determined by Mayo's and O'Brien's methods. The transfer constant obtained in acetonitrile (0,6) was higher than that obtained in benzene. This difference can be explained by the fact that the thiol was consumed by two reactions: nucleophilic addition and telomerization. The influence of solvents on the polymerization kinetics was enlightened. These results were applied to the synthesis of macromonomers of DMAEMA with isocyanatoethyl methacrylate (IEM). These macromonomers were copolymerized with styrene. (C) 2004 Elsevier Ltd. All rights reserved.