The catalytic kinetics and synthesis of poly(styrene-co-chloromethylstyrene) resin of different degrees of crosslinkages and ring substitutions were investigated by copolymerizing styrene and chloromethylstyrene through crosslinking with divinylbenzene. Poly(styrene-co-chloromethylstyrene) quaternary ammonium salt was obtained with activating poly(styrene-co-chloromethylstyrene) resin with tertiary amine. More than 20 types of poly(styrene-co-chloromethylstyrene) quaternary ammonium catalyst were prepared, with reaction conditions including immobilized time (0.125 similar to 4 days), concentration of tertiary amine (0.1 similar to 2 kmol/m(3)), kinds of solvents in immobilization (methanol, ethyl alcohol, and DMF), and kinds of tertiary amines (trimethylamine, triethylamine, tripropylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, and tri-n-octylamine). These catalysts were used to achieve the optimum allylation of phenol The reactions were conducted and studied individually with either equal mole or equal weight of catalyst. The best reactivity for the allylation of phenol was obtained when the structure of the quaternary ammonium catalyst was 10% degree of ring substitution and 2% degree of crosslinkage activating with trihexylamine. The turnover number and the effectiveness factor were also calculated. (c) 2006 American Institute of Chemical Engineers.