Kinetic Studies of the Solution Polymerization of Trioxane Catalyzed by BF3·O(C2H5)2. III. The Effect of the Monomer Concentration

Abstract In the solution polymerization of trioxane catalyzed by BF3·O(C2H5)2, the dependence of the monomer concentration on the polymerization reaction has been studied. The kinetic order of the monomer concentration as determined from the course of polymerization is close to 2 (except in a non-polar solvent). The kinetic order of the initial monomer concentration is extraordinarily large in the polar solvent. On the other hand, the molecular weight of the polymers formed increases with an increase in the initial monomer concentration. In the polymerization of trioxane in a polar solvent such as nitrobenzene at a low monomer concentration, the molecular weight of the polymers does not increase in the course of polymerization, even at the initial stage of polymerization. The reason for this has been discussed in terms of the nature of the chain carrier.