Abstract
Tetraoxane, tetramer of formaldehyde, was polymerized in solid state in n-heptane using BF3O (C2H5) 2 as catalyst. The polymerization proceeded without a change in a shape of crystal particles of tetraoxane. The rateof polymerization was proportional to the catalyst concentration, and it was independent of the monomer concentration.The rate of polymerization and the molecular weight of polymer increased with increasing polymerizationtemperature. These features are quite similar to those observed for trioxane. Since the molecular weight ofthe polymer increased with increasing conversion and the molecular weight of the polymer decreased by the additionof a small amount of benzene and ethylene chloride, the good solvent for tetraoxane, a high molecular weightpolymer does not seem to be formed on a surface of the monomer crystals. The above results suggest that thepolymerization proceeds in solid state.
