Polymerization of Methyl α-(Trifluoromethyl)acrylate and α-(Trifluoromethyl)acrylonitrile and Copolymerization of These Monomers with Methyl Methacrylate

Methyl α-(trifluoromethyl)acrylate (MTFMA) and α-(trifluoromethyl)acrylonitrile (TFMAN) have been successfully anionically homopolymerized by pyridine initiation. Typical anionic initiators for methyl methacrylate (MMA) polymerizations gave rise to complications such as attack on the trifluoromethyl moiety. While radical polymerizations of these monomers failed, both of the monomers have been copolymerized with MMA (M2) by benzoyl peroxide (BPO) initiation, and monomer reactivity ratios have been determined: rMTFMA = 0 and rMTFMA = 2.36; rTFMAN = 0 and rMMA = 1.02. Mechanistic explanations of the monomer reactivities are presented. © 1982, American Chemical Society. All rights reserved.