Towards continuous processes for the synthesis of precursors of amorphous Si/B/N/C ceramics

The development of a process for the continuous synthesis of Cl3SiNMeBCl2 (DMTA) as a single-source precursor of highly durable Si/B/N/C ceramics is reported. The process is based on a series of gas phase reactions starting from silicon tetrachloride and methylamine. Cl3SiNHMe (TSMA), which is initially formed, is subsequently reacted with BCl3 to yield DMTA as a colorless, highly air-sensitive liquid. Amine hydrochloride byproducts are removed by filtration through ceramic filters. DMTA crystallizes in the monoclinic system, space groupP21/m, with a = 709.96(13) pm, b = 685.61(12) pm, c = 897.28(16) pm, and Z = 2. Polymerization of DMTA by aminolysis in n-hexane at −78 °C releases a polyborosilazane, SiBN2.4C2.5H8.8, which upon thermolysis releases amorphous SiBN2.3C1.7 ceramic in 56% yield. The latter resists thermal degradation by crystallization in Ar atmosphere up to at least 1700 °C.

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