New Highly Heat-Resistant Polymers Containing Silicon:  Poly(silyleneethynylenephenyleneethynylene)s

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Six kinds of poly(silyleneethynylenephenyleneethynylene)s [−Si(R)H−C⋮C−C 6 H 4 −C⋮C−], wherein the phenylene group was the meta-, para- or ortho-form and R represents a phenyl, methyl, or hydrogen atom, were prepared, and the properties of the resulting polymers were investigated. The polymers, especially poly[(phenylsilylene)ethynylene-1,3-phenyleneethynylene] (R = Ph), which were thermosetting, soluble in solvent, fusible, and moldable, showed high heat-resistant and burning-resistant properties. A cross-linking reaction mechanism concerning the Si−H and C⋮C bonds was proposed, and the correlation between the molecular structures and the thermal properties was discussed. Fiber-reinforced polymers prepared using glass, carbon, or SiC fibers showed sufficient mechanical strength even at 400 °C under air. A black, hard, and glassy material (C−SiC) was obtained when poly[(phenylsilylene)ethynylene-1,3-phenyleneethynylene] was heated above 1000 °C under argon.