Electroinitiated polymerization of trioxane in chlorinated hydrocarbons

The electroinitiated polymerization of trioxane in chlorinated hydrocarbons, with tetrabutyl-ammonium perchlorate as background electrolyte, has been investigated. The initiation always involves perchlorate oxidation but the polymerization exhibits different features in the various solvents. It has been found that in 1–2 dichloroethane the polymerization, once started by a short pulse of current, proceeds without any induction period to moderate conversion of monomer to polymer. The initial rate of polymerization depends linearly on the monomer cone, and on the initiating charge, so allowing determination of some kinetic parameters. On the other hand, the electroinitiated polymerization of trioxane in dichloromethane requires continuous current to give reasonable conversions; it exhibits induction periods and acceleration which cannot be simply related to the current.