Synthesis and properties of poly(1,1-diethynyl-1-silacyclopent-3-enes and -1-silacyclobutane)

Polycarbosilanes containing diacetylene and organosilacyclic groups, such as poly(1,1-diethynyl-1-silacyclopent-3-ene), poly(1,1-diethynyl-3-triethylsilyl-1-silacyclopent-3-ene), and poly(1,1-diethynyl-1-silacyclobutane), were synthesized by the Glaser oxidative coupling polymerization reactions of 1,1-diethynyl-1-silacyclopent-3-ene, 1,1-diethynyl-3-triethylsilyl-1-silacyclopent-3-ene, and 1,1-diethynyl-1-silacyclobutane, respectively. These materials are almost insoluble in usual organic solvents such as CHCl₃ and THF. The polymers were characterized by using several spectroscopic methods in solid state. FTIR spectra of all the polymeric materials show that the characteristic C≡C stretching frequencies appear at 2146-2170 cm^-1, in particular. The polymers in the solid state show that the strong maximum excitation peaks appear at 255-257 nm and the strong maximum fluorescence emission bands at 401-402 nm. About 71-87% of the initial polymer weights remain at 400°C in nitrogen according to thermogravimetric analysis.