Reaction of α- (trifluoromethyl) Styrene With Anionic Initiators

α-(Trifluoromethyl)styrene (Q = 0.43, e = 0.90) does not undergo radical homopolymerization. Anionic polymerization fails to produce appreciable amounts of polymer even in bulk at -78 °C in spite of its high e value. The resistance to anionic polymerization is primarily due to side reactions involving addition-elimination sequences (SN2') when initiators are nucleophilic enough to add to the β-carbon of TFMST. Weaker anionic initiators such as pyridine and potassium tert-butoxide that effectively induce polymerization of methyl α-(trifluoromethyl)acrylate (Q = 0.74, e = 2.5) do not react with TFMST. Reactions of TFMST with several anionic initiators are described in detail. © 1989, American Chemical Society. All rights reserved.