Abstract
Initiation in cationic polymerization of phenyl-substituted 1,3-butadienes with triphenylmethylstannic pentachloride as catalyst was studied. The rates of consumption of Ph3CSnCl5 with 1-phenyl-substituted butadienes are represented by the following equation−d[Ph3CSnCl5]/dt=ki′[Ph3CSnCl5][M], where M means monomer.On the other hand, in the case of 2-phenyl-substituted butadienes the rate is represented as follows−d[Ph3CSnCl5]/dt=ki′[Ph3CSnCl5][M]+k[Ph3CSnCl5]([M]0−[M])and the formation of a π-complex between the monomer and a carbonium ion is suggested. The initiation rate constants decreased according to the following order:1-phenyl-1,3-butadiene>2-phenyl-1,3-butadiene>1,1-diphenyl-1,3-butadiene>1,2-diphenyl-1,3-butadiene>2,3-diphenyl-1,3-butadiene.1,4-Diphenyl-1,3-butadiene did not react with Ph3CSnCl5 at all. The high reactivity of phenylbutadienes toward Ph3CSnCl5 in comparison with that of vinyl monomers could be ascribed to the stabilization of allyl-type cations which were formed by an attack of a trityl cation onto the 4-position and the 1-position carbon for 1-phenylbutadienes and 2-phenylbutadiene, respectively.
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Asami, R., Hasegawa, Ki. Cationic Polymerization of Phenylbutadienes. II. Initiation Reaction in Cationic Polymerization of Phenylbutadienes Catalyzed by Triphenylmethylstannic Pentachloride. Polym J 8, 53–59 (1976). https://doi.org/10.1295/polymj.8.53
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DOI: https://doi.org/10.1295/polymj.8.53