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H(OEt2)2[P(1,2-O2C6Cl4)3]: Synthesis, Characterization, and Application as a Single-Component Initiator for the Carbocationic Polymerization of Olefins

H(OEt2)2[P(1,2-O2C6Cl4)3]: Synthesis, Characterization, and Application as a Single-Component Initiator for the Carbocationic Polymerization of Olefins

Paul W Siu, Khatera Hazin, Derek P Gates

Chemistry. 2013 Jul 1;19(27):9005-14.

PMID: 23677559

Abstract:

The development of novel Brønsted acids featuring the hexacoordinate phosphorus(V) anion [TRISPHAT](-) {[1](-)=[P(1,2-O2C6Cl4)3](-)} are reported. The title compound, H(OEt2)2[1], was synthesized from 1,2-(HO)2C6Cl4 (3 equiv) and PCl5 in the presence of diethyl ether. This compound was fully characterized by (1)H, (31)P and (13)C NMR spectroscopy, X-ray crystallography and elemental microanalysis. Dissolution of H(OEt2)2[1] in acetonitrile results in the slow precipitation of crystalline H(OEt2)(NCMe)[1], which was characterized by X-ray diffraction; however, in CD2Cl2 solution the [TRISPHAT](-) anion protonated and ring-opened. The weighable, solid H(OEt2)2[1] was found to be a competent initiator for the polymerization of n-butyl vinyl ether, α-methylstyrene, styrene and isoprene at a variety of temperatures and monomer-to-initiator ratios. At low temperatures, polymers with M(n) >10(5) were obtained for n-butyl vinyl ether and α-methylstyrene whereas slightly lower molecular weights were obtained with styrene and isoprene (10(4) < M(n) <10(5)). The poly(α-methylstyrene) synthesized at -78 °C is syndiotactic-rich (ca. 87% rr) whereas the polystyrene obtained at -50 °C is atactic. The polyisoprene obtained possessed all possible modes of enchainment as well as branched and/or cyclic structures that are often observed in polyisoprene.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP25014317	Poly(α-methylstyrene)		25014-31-7	Price

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