Add time:08/02/2019         Source:sciencedirect.com

Poly(diarylsiloxane)s are highly crystalline, high-melting polymers with excellent high-temperature properties. As a consequence of the rigid polymer backbone, they show crystal-liquid-crystal transitions, and both nematic and smectic states have been observed by optical microscopy. The polymers of greatest interest in this investigation have been those containing phenyl and p-tolyl substituents on the siloxane backbone. We have prepared a series of polymers with various combinations of these substituents, as well as the end members of the series, poly(diphenylsiloxane) and poly(di(p-tolyl)siloxane). The polymers are prepared with controlled molecular weights and distribution by ring-opening anionic polymerization of the cyclic trimers in solution. The crystal-liquid-crystal transition temperatures, T1c, for poly(diphenylsiloxane) and poly(di(p-tolyl)siloxane) are very high (265 and 300°C, respectively) and the polymers are only soluble in a few solvents at temperatures above 150°C. However, the T1c values are reduced for the mixed poly((phenylp-tolyl)siloxane)s and the polymers become soluble at lower temperatures. The symmetric poly((phenylp-tolyl)siloxane) is of particular interest since T1c is reduced to 150–160°C, and the polymer is soluble at room temperature in common solvents such as toluene, tetrahydrofuran and chloroform. In contrast to the retention of the crystalline and liquid-crystalline character in the mixed diarylsiloxanes, the replacement of a single phenyl group by a methyl group in the repeat hexaphenyl triad sequence of poly(diphenylsiloxane) is sufficient to destroy both the crystalline and liquid crystalline character of the polymer.

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