Abstract: | A novel class of platinum-based initiating systems for the ring-opening polymerization of a wide variety of heterocyclic compounds including epoxides, oxetanes, and 1,3,5-trioxane have been discovered. In addition to a platinum complex as a catalyst, a cocatalyst, consisting of a compound or polymer containing silicon-hydrogen bonds must also be present. This article reports on a preliminary survey of the scope and limitations of these new initiator systems. Particular emphasis in this article has been placed on the ring-opening polymerization of epoxides which have been studied in some detail and which proceed rapidly and exothermically at room temperature. A number of mechanistic studies have been conducted and the best current evidence suggests that polymerization proceeds by a cationic mechanism. Evidence is also presented which suggests that platinum metal colloids may function as the active initiating species. |