Synthesis of PMMA and PMMA block copolymers at elevated temperatures by phosphor ylide-mediated polymerizations

The MMA polymerization initiated by (l-naphthyl: triphenylphosphonium triph enylmethyl anion( TPM,NTPP) or the NTPF salt of the methylisobutyrate anion (MIB,NTPP) in THF at temperatures varying from 25 to 70 degrees C appears to be a living polymerization as indicatred by a linear M-n vs. MMA convers ion plot and by the narrow MW distributions. As indicated by the proton spe ctrum of MIB, NTPP ir THF d(8) the predominant polymerization intermediate appears to be the ylide formed exclusively by addition of the MIB anion to the 4-carbon ol the l-naphthyl group. This ylide shows upfield shifts for t he 3- proton ol the cyclohexadienyl ring and of the 6- and 8-protons of the remaining aromatic ring.