New silane monomers, which contain the 4-(dialkylamino)pyridine (DAAP) function, have been synthesized by hydrosilylation of 4-(N-methylallylamino)pyridine with Me,Si(OEt),H (n = 0,l) and 4-(diallylamino)pyridine with Me,Si(OEt)s-,H (n = 0-2) usingH2PtCbas a catalyst. Only @-addition products were observed. The products were characterized by elemental analysis, infrared and lH and l3C NMR spectroscopy, and gas chromatography-mass spectrometry. Hydrolysis-polycondensation of the respective difunctional monomers with a basic catalyst gave a mixture of linear homopolymer and cyclic oligomers from the monomer with a pendant DAAP residue and only the linear homopolymer from the monomer with the in-chain DAAP residue. The linear homopolymers were trimethylsiloxy end-blocked by reaction with (Me3-Si)*NH or bis(trimethylsily1)acetamide. The end-blocked homopolymers were characterized by spectroscopic and thermal analytical methods. Thermal analysis (TGA) of the linear homopolymers indicates remarkable thermal stability (Td > 400 "C) comparable to that of poly(dimethylsi1oxane). Molecular weights for the pendant and in-chain polymers were determined by end-group analysis from the lH NMR spectra and exclusion chromatography. The mass spectra of the homopolymers above the degradation temperature indicate depolymerization, giving rise to a cyclic monomer and cyclic oligomeric products. The two linear homopolymers have different and unusual solubility properties in immiscible H*O/CH2C12 medium. The effect of pH on solubility and partition behavior of both polymers is discussed. Cross-linked homopolymers were prepared by established procedures.
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