Trioxane was copolymerized with small amounts of dioxolane in benzene in the presence of a boron trifluoride:a crylonitrile complex as initiator. The kinetics of reactions was expressed in terms of topoenergetic principles. The copolymerizations had no induction periods and the maximum reaction rate was found proportional to the square of both the initiator and monomers concentrations. A zwitterionic mechanism is suggested for initiation. The activation energy for the system with 5% dioxolane was determined as 18.3 kcal/mol. The melting behavior of the copolymers is briefly discussed as a function of the dioxolane initial content, and is indicative of the amorphous-crystalline coupling phenomenon. The copolymers with ∼ 5% dioxolane are thermostable in air up to 250%deg; and are recommended for practical purposes.