Synthesis, characterization, and catalytic properties of polysiloxanes with pendant 4-(3-pyridinyl)butyl and 4-(1-oxypyridin-3-yl)butyl groups

Synthesis, characterization, and catalytic properties of polysiloxanes with pendant 4-(3-pyridinyl)butyl and 4-(1-oxypyridin-3-yl)butyl groups

Zeldin, Martel and Granger, Eric and Fife, Wilmer K.

Journal of Inorganic and Organometallic Polymers 1993

Abstract : New silane monomers with the pendant 4-(3-pyridine)butyl group have been synthesized by hydrosilation of 3-(3-butenyl)pyridine with MenSi(OEt)3-nH (n=0, 1) using a platinum catalyst. Only $β$-addition products were observed. The products were characterized by elemental analysis, infrared,1H- and13C-NMR spectroscopy, and gas chromatography-mass spectrometry. Hydrolysis-polycondensation of the difunctional monomer with a basic catalyst, Me4NOH, gave a mixture of cyclic oligomers, principally cyclic tetramer, and linear homopolymer. Under similar reaction conditions, the trifunctional monomer gave crosslinked material which was soluble in common organic solvents. The linear homopolymer and crosslinked polymer were trimethylsilyl end-blocked with hexamethyldisilazane. The cyclic and end-blocked polymers were characterized by elemental analysis and spectroscopic methods. Molecular weights of the polymers were obtained by end-group analysis using1H-NMR spectral data, size exclusion chromatography, and direct insertion-probe mass spectrometry. The cyclic, linear, and crosslinked materials were N-oxidized with m-chloroperoxybenzoic acid and characterized by spectroscopic methods. The polymeric N-oxide derivatives were shown to be effective transacylation catalysts in the synthesis of mixed carboxylic acid anhydrides in immiscible solvents (H2O/CH2Cl2) under phase-transfer conditions. The implications of the results on the mechanism of catalysis are discussed. © 1993 Plenum Publishing Corporation.