Electrochemically initiated bulk polymerization of trioxane

Abstract

S U M M A R Y :The electroinitiated bulk polymerization of trioxane containing tetrabutylammonium perchlorate as background electrolyte has been investigated at the temperature of 66,5"C.The polymerization can be started by a very small charge initially supplied and does not present significant termination features.The resulting polymers have high molecular weights, which are dependent on the current amounts, and show satisfactory thermal stability. The species initiating the polymerization is perchloric acid, which is produced by anodic oxidation of the perchlorate ion, followed by hydrogen atom abstraction from trioxane.Bulk trioxane polymerizations catalyzed by added perchloric acid, show in fact similar features as to kinetic chain length, molecular weight of the polymers and polymerization rate, with respect to the electroinitiated trioxane polymerizations. Z U S A M M E N F A S S U N G :Die elektroinitiierte Polymerisation yon Trioxan in Substanz mit Tetrabutylammoniumperchlorat als Leitsalz wurde bei 66,5"C untersucht.Die Polymerisation kann durch sehr geringe Mengen, die man anfanglich zugibt, eingeleitet werden und zeigt keine besonderen Abbruchsmerkmale.Die resultierenden Polymere besitzen hohe Molekulargewichte, die von der Strommenge abhangen, und sie zeigen befriedigende thermische Stabilitat. Perchlorsaure ist die initiierende Spezies. Sie wird bei der anodischen Oxidation des Perchlorat-Ions, der eine Abspaltung eines Wasserstoffatoms vom Trioxan folgt, gebildet.Polymerisationen von Trioxan in Substanz durch zugefiigte Perchlorsaure zeigen in der Tat ahnliche Merkmale im Hinblick auf die kinetische Kettenlange, das Molekulargewicht der Polymere und die Polymerisationsgeschwindigkeit im Vergleich zu den elektro-initiierten Trioxan-Polymerisationen.

Kinetics of 1,3,5‐trioxacycloheptane formation in the electro‐initiated copolymerization of 1,3‐dioxolane with trioxane

“…The present work, retaking the study of the electroinitiated copolymerization of 2 with 48, 9), investigates mainly the kinetics and mechanism of the formation of 1 in 1,2-dichloroethane as solvent, using tetrabutylammonium perchlorate as base electrolyte. As the electrochemical initiation generally involves the formation of perchloric acid lo), the results here obtained, could be likely extensible to the copolymerization chemically promoted by every acid catalyst.…”