[HL2][P(1,2-O2C6Cl4)3] (L = THF, DMF): Br?nsted acid initiators for the polymerization of n-butyl vinyl ether and p-methoxystyrene?

Dalton Transactions Pub Date: 2017-04-12 DOI: 10.1039/C6DT04820J

Abstract

The development of solid, weighable Br?nsted 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 1H, 31P, 13C 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 °C where high molecular weight polymers were isolated in high yield. 1H 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.

Graphical abstract: [HL2][P(1,2-O2C6Cl4)3] (L = THF, DMF): Br?nsted acid initiators for the polymerization of n-butyl vinyl ether and p-methoxystyrene
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