6-Trimethylsilyl-3,5-hexadiyn-2-one was synthesized and selectively 1,2-pyropolymerized under vacuum to give a black polymer, poly(6-trimethylsilyl-3,5-hexadiyn-2-one) [PATA]. Desilylation of PATA by KOH/MeOH afforded a highly crystalline polymer [PAEA] which turned into graphite-like materials on heat treatment in vacuo. The polymers were characterized by GPC, FT-IR, NMR, and X-ray diffraction studies. 1,4-Bis(trimethylsilyl)-1,3-butadiyne and 1,4-bis(t-butyldimethylsilyl) -1,3-butadiyne were thermally polymerized in sealed ampoules respectively to give ceramic materials containing silicon carbide and free carbon. Spectroscopic studies revealed that the polymerization of these butadiynes proceeds by 1,4-polymerizaion. The polymers were characterized by FT-IR, NMR, elemental analysis, and X-ray diffraction.
