Backbone-assisted reactions of polymers. . Poly[(chloromethyl)thiirane]

The conversion of (chloromethy1)thiirane to poly[(chloromethyl)thiirane] of molecular weight ca. 20 000 was accomplished by using boron trifluoride etherate as initiator. Initiators based on cadmium, , or aluminum were less effective, and the anionic initiators KOH and NaNH2 produced no polymer. [(chloromethyl)thiirane] was found to undergo an unusual structural rearrangement at room temperature the absence of solvent and to hydrolyze in a dioxane/water mixture at a rate much greater than that observed poly(epichlorohydrin). These results suggest important anchimeric assistance by the backbone sulfur atom the reactions of poly[ (chloromethyl)thiirane].