Preparation of polymers with substituted allyl end group using dimer of α-methylvinyl monomer as addition fragmentation chain transfer agent at high temperatures

The dimerization of methyl methacrylate, ethyl methacrylate, methacrylonitrile, and α-methylstyrene to 2-substituted-1-allylic compounds CH₂?C(X)CH₂C(CH₃)₂X] (X = COOR, C₆H₅, or CN), and methyl α-ethylacrylate to a 3-substituted-2-allylic compound CH₃CH?C(COOCH₃)CH₂C(CH₃)(C₂H₅) COOCH₃] was carried out by catalytic chain transfer using benzylbis (dimethylglyoximato) (pyridine) cobalt (III). These dimers were then used as addition-fragmentation chain transfer agents in the polymerizations of methyl methacrylate and styrene at 80⁰C or above. Cross-dimers from methacrylic ester-α-methylstyrene and methacrylonitrile-α-methylstyrene mixtures were similarly prepared. Except for those from methyl α-ethylacrylate and methacrylonitrile, all the dimers participated in the addition-fragmentation and the copolymerization to different extents. The dimer of methyl α-ethylacrylate was actually inactive during the styrene and methyl methacrylate polymerizations. The methacrylonitrile dimer was primarily incorporated in the polymer chain through copolymerization. Among the dimer and the cross-dimers from α-methylstyrene with the other monomers, those bearing the α-methylstyrene moiety in the α-substituent CH₂?C(X)CH₂C(CH₃)₂C₆H₅, X?COOCH₃, COOC₂H₅, and CN] are noted as highly reactive chain transfer agents. © 1994 John Wiley & Sons, Inc.