Synthesis of novel macromonomeric peroxy initiators of styrene with the cationic copolymerization and the quantum chemically investigation of the initiation system effects

Abstract

AbstractCationic polymerization of styrene (S) was performed with peroxy initiators synthesized from bis(4,4′‐bromomethyl benzoyl peroxide) (BBP) or bromomethyl benzoyl t‐butyl peroxy ester (t‐BuBP) and AgSbF6 or ZnCl2 system at 0 and −10°C to obtain macromonomeric peroxy initiators (poly‐S initiators). Kinetic studies were accomplished for poly‐S initiators. Poly(styrene‐block‐methyl methacrylate) block copolymers [poly(S‐b‐MMA)] were synthesized by bulk polymerization of methyl methacrylate (MMA) with poly‐S initiators. The quantum chemical calculations for the initiating systems of the cationic polymerization of S and poly(S‐b‐MMA) block copolymers were achieved using Hyperchem 7.5 program. The optimized geometries of the polymers were investigated with the quantum chemical calculations. Poly(S‐b‐MMA) block copolymers containing undecomposed peroxide groups were used to initiate thermal copolymerization of acrylic acid (AA) to obtain crosslinked poly(S‐b‐MMA‐b‐AA) multicomponent copolymers. The crosslinked multicomponent copolymers were investigated by sol–gel analysis. Swelling ratio values of the crosslinked multicomponent copolymers in CHCl3 were calculated. Poly‐S initiators having undecomposed peroxygen groups were used for graft copolymerization of polybutadien (PBd) to obtain crosslinked poly(S‐graft‐polybutadien) graft copolymers [poly(S‐g‐PBd)]. The characterizations of the polymers were achieved by FTIR, 1H‐NMR, GPC, SEM, and DSC techniques. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 348–357, 2006