Influence of methyl‐modified silyl groups on the properties of polymers and Si/B/N/C ceramics derived from N‐silylated borazine derivatives

Abstract

Thermal silazane cleavage of dichloroboryldisilylamines (SiClmMe3−m)N(SiMe3)(BCl2) (1: m = 1; 2: m = 2) at 196 °C leads to the borazine derivates [(SiClmMe3−m)NB(ClnMe1−n)]3 (3: m = 1, n = 0.185; 4: m = 2, n = 0.111) characterized by NMR and IR spectroscopy and mass spectrometry. Single‐crystal X‐ray diffraction structure analyses reveal (BN)3 units with unusual twisted boat conformations in both compounds. Additionally, more detailed studies are done to clear up the function of the by‐products (SiClmMe3−m)N(SiClMe2)(BClMe) formed during the cyclization step leading to asymmetrically boron substituted borazine derivatives. The single‐source precursors 3 and 4 were cross‐linked with methylamine producing polymers 3P and 4P, which were transformed into black amorphous materials with ceramic yields of 20.8 % and 50.3 %, respectively. Ceramic 4C (Si1.00B0.98 N2.55 C1.37O0.05) was further investigated by 11B and 29Si magic angle spinning (MAS) NMR spectroscopy. A combined study of high‐temperature TG analyses and X‐ray powder diffraction analyses confirms the thermal stability of 4C up to 1670 °C. Copyright © 2012 John Wiley & Sons, Ltd.