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Ternary Molecular Complex in the Alternating Copolymerization of Methyl Methacrylate with Styrene Using Stannic Chloride
Authors:Hidefumi Hirai
Affiliation:Department of Industrial Chemistry Faculty of Engineering , The University of Tokyo , Hongo-7, Bunkyo-ku, Tokyo, 113, Japan
Abstract:The equimolar alternating copolymerization of methyl methacrylate (MMA) with styrene (St) in the presence of stannic chloride in toluene (Tl) is investigated kinetically. The concentrations of the ternary molecular complexes, [SnCl4-MMA … St] and [SnCl4-MMA … T1], are calculated by use of the formation constants of the ternary molecular complexes. The rates of copolymerization under photo-irradiation and with tri-n-butyl boron-benzoyl peroxide as an initiator are proportional to the 1.5th order and 1. Oth order, respectively, of the concentration of the ternary molecular complex [SnCl4 · MMA … St]. The alternating copolymerization precedes the homopolymerization of the methyl methacrylate charged in excess. The alternating regulation of the copolymerization is ascribed to the homopolymerization of the ternary molecular complex from the kinetic results. The magnitudes of the shifts for
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