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Kinetic Studies of the Solution Polymerization of Trioxane Catalyzed by BF 3 ·O(C 2 H 5 ) 2 . I. The Effect of the Catalyst and the Water Concentration on the Rate of Polymerization

1965; Oxford University Press; Volume: 38; Issue: 12 Linguagem: Inglês

10.1246/bcsj.38.2067

1348-0634

Toshinobu Higashimura, Tetsuro Miki, Seizô Okamura,

Photopolymerization techniques and applications

In the solution polymerization of TO catalyzed by BF3·O(C2H5)2, water acted as a co-catalyst in n-hexane, a non-polar solvent; in ethylene dichloride, a polar solvent, water slightly accelerated the rate of polymerization, and in nitrobenzene, a more polar solvent, water did not affect the rate at all. The kinetic order of the catalyst concentration to the polymerization rate was 1.0 in benzene, 0.5 in ethylene dichloride, and zero in nitrobenzene. The induction period was very short when water was excluded as much as possible, but it increased with an increase in the water concentration and with a decrease in the catalyst concentration. On the basis of these results, it may be concluded that the polymerization of TO by BF3·O(C2H5)2 is initiated by the attack of the proton or the ethyl cation on the monomer.