Radical Copolymerization of Allylbenzene in the Presence of Zinc Chloride

Abstract

Allylbenzene (AB) was radically copolymerized with methyl acrylate, methacrylonitrile, acrylonitrile (AN), methyl methacrylate (MMA), and fumaronitrile (FN) in the presence of zinc chloride. The copolymerization with last two monomers did not take place unless zinc chloride was added. The AB-FN system gave an alternating copolymer. In the AB-AN and AB-MMA systems, apparent monomer reactivity ratio decreased with increasing concentration of zinc chloride added. The significance of the apparent monomer reactivity ratio for these copolymerization systems was studied from a kinetic point of view, and absolute monomer reactivity ratios were evaluated from the values of the apparent monomer reactivity ratio obtained experimentally: k11/k12=0.13, k11k13 = 5.1, k12/k13=39.4, k22/k21=1.05, k22/k23=0.85, and k21/k23=0.81 for the AB-AN system, and k11k/k12=0.024, k22/k21=0.91, k22/k28=8.57, and k21/k23=9.42 for the AM-MMA system, where M1, M2, and M3 represent free AN (or MMA), complexed AN (or MMA), and AB, respectively. Q and e values of AN and MMA complexed with zinc chloride were QAN ⋅ZuCl2=25; eAN⋅znCl2 = 2.61, QMMA⋅ZnCl2=68, and eMMA⋅ZnC12=2.36, respectively. The copolymerizations in the presence of other metal salts were also studied.