NOVEL SYNTHESIS OF POLY(SILYL ETHER)S BY THE ADDITION-REACTION OF BIS(EPOXIDE)S WITH DICHLOROSILANES OR BIS(CHLOROSILANE)S

Certain new poly(silyl ether)s with reactive pendant chloromethyl grou ps were synthesized by the polyaddition of bis(epoxide)s with dichloro silanes or bis(chlorosilane)s. The polyaddition proceeded very smoothl y and regioselectively in toluene catalyzed by quaternary ammonium or phosphonium salts such as tetrabutylammonium chloride (TBAC) and tetra butylphosphonium chloride (TBPC) under mild reaction conditions to giv e the corresponding poly(silyl ether)s having high molecular weights, although the reaction did not occur without a catalyst nor with 4-(dim ethylamino)pyridine (DMAP) as the catalyst under the same reaction con ditions. The polyaddition also proceeded using either triphenylphosphi ne (TPP) or a complex of 18-crown-6 with potassium chloride as catalys ts to afford the poly(silyl ether), but with low molecular weights. Th at is; the catalytic activity-of the above quaternary onium salts such as TBAC and TBPC was higher than that of DMAP, TPP, or the crown ethe r complex. Furthermore, it was found that the resulting poly(silyl eth er)s with reactive pendant chloromethyl groups exhibited excellent sol ubility in common organic solvents.