[Hl2][P(1,2-O2c6cl4)(3)] (L = Thf, Dmf): Bronsted Acid Initiators For The Polymerization Of N-Butyl Vinyl Ether And P-Methoxystyrene

The development of solid, weighable Bronsted acids featuring the hexacoordinated phosphorous(V) anion [TRISPHAT](-)are reported. H(DMF)(2)[1] and H(THF)(2)[1] {[1](-) = [P(1,2- O2C6Cl4)(3)](-)} were synthesized and fully characterized by H-1, P-31, C-13 and 2D- NOESY NMR spectroscopy, X-ray crystallography, mass spectrometry and elemental analysis. Both, H(DMF)(2)[1] and H(THF)(2)[1] are found to be suitable initiators for the polymerization of n-butyl vinyl ether and p-methoxystyrene. Optimal polymerization results for these single-component initiators were generally obtained at -50 degrees C where high molecular weight polymers were isolated in high yield. H-1 NMR spectroscopic analysis and dynamic light scattering of solutions of the isolated polymers provide evidence for a branched structure which presumably arises from chain transfer.