Chemical modification of poly(vinyltrimethylsilane) and poly(1-trimethylsilyl-1-propyne) using highly reactive metallating systems

Abstract

Poly(vinyltrimethylsilane) and poly(1-trimethylsilyl-1-propyne) are metallated using normal and secondary butyllithium chelate complexes with tetramethylethylenediamine and superbases based on complexes of normal and secondary butyllithium with potassium tert-pentoxide as metallating agents. Optimal conditions ensuring metallation of poly(vinyltrimethylsilane) and poly(1-trimethylsilyl-1-propyne) with a high yield without degradation of macrochains are determined. Poly(vinyltrimethylsilane) and poly(1-trimethylsilyl-1-propyne) are functionalized via reactions of metallated polymers with CO2, trimethylsilyl chlorosulfone, diethyl disulfide, and ethylene oxide. COOH, SO3H, OH, and thioester groups are introduced into poly(vinyltrimethylsilane), and SO3H and COOH groups are incorporated into poly(1-trimethylsilyl-1-propyne). Upon introduction of carboxyl groups into poly(vinyltrimethylsilane), its hydrophilicity and permselectivity with respect to H2O/N2, H2O/H2, and H2O/CH4 pairs increase. The introduction of SO3H groups into poly(1-trimethylsilyl-1-propyne) and poly(vinyltrimethylsilane) leads to the appearance of proton conductivity of these polymers.