Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Kinetic Studies of the Solution Polymerization of Trioxane Catalyzed by BF3·O(C2H5)2. I. The Effect of the Catalyst and the Water Concentration on the Rate of Polymerization
Toshinobu HigashimuraTetsuro MikiSeizo Okamura
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1965 Volume 38 Issue 12 Pages 2067-2073


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.

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