Palladium-catalyzed silation of adamantanedi- and triol, leading to adamantane-siloxane alternating polymers with high heat resistance

Palladium-catalyzed dehydrocoupling reactions of 1,3-adamantanediol (Ad(OH)2) with excess amounts of PhMeSiH2 and PhSiH3 gave silated products, Ad(OSiPhMeH)2 and Ad(OSiPhH2)2, respectively, in good yield. 1,3,5-Adamantantriol (Ad(OH)3) also underwent silation with PhMeSiH2 under the same conditions. When silation of Ad(OH)2 was carried out with 1 equiv of PhSiH3, a polymer consisting of a repeating unit of -O-Ad-OSi(OH)Ph- was obtained. The polymer thus obtained showed high heat resistance and Td5 = 420 °C and Td10 = 512 °C were noted by its TGA in nitrogen. It was also found that thermal stability of the polymer was improved by using Ad(OH)3 as a comonomer.