In this work we propose an approach for obtaining of polydimethylsiloxanes of various structures, both linear and branched, by a ring-opening polymerization (ROP) of hexamethylcyclotrisiloxane initiated by silanols in liquid ammonia. In this case, ammonia acts both as a solvent and as a catalyst. Such hydroxy-containing compounds as Ph3SiOH, Ph2Si(OH)2, PhSi(OH)3 and cis-[PhSi(O)OH]4 are used as initiators.

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