Anionic and Cationic Ring-Opening Polymerization of 2,2-Divinyl-4,4,6,6-tetramethylcyclotrisiloxane. Synthesis of Regular Poly[2,2-bis(perfluoroalkyl-1‘H,1‘H,2‘H,2‘H-dimethylsilylethyl)-4,4,6,6- tetramethyltrisiloxanes] by Chemical Modification of Regular Poly(2,2-divinyl-4,4,6,6-tetramethyltrisiloxane)

Anionic ring-opening polymerization of 2,2-divinyl-4,4,6,6-tetramethylcyclotrisiloxane yields regular poly(2,2-divinyl-4,4,6,6-tetramethyltrisiloxane), while cationic ring-opening polymerization of 2,2-divinyl-4,4,6,6-tetramethylcyclotrisiloxane yields copoly(dimethylsiloxane/divinylsiloxane). The mechanisms of both anionic and cationic ring-opening polymerizations are discussed. Chemical modification of poly(2,2-divinyl-4,4,6,6-tetramethyltrisiloxane) has been achieved by platinum-catalyzed hydrosilylation reactions with both 3,3,3-trifluoropropyldimethylsilane and perfluorooctyl-1‘ H,1‘ H,2‘ H,2‘ H -dimethylsilane. Polymers and monomer have been characterized by 1 H, 13 C, 19 F, and 29 Si NMR as appropriate. Molecular weight distributions of polymers have been determined by GPC and their thermal properties measured by DSC and TGA.