Abstract2‐Phenylheptamethyltrisilane as a model compound of polysilastyrene was irradiated at a high dose (1440 kGy) of γ‐rays without any additive. The trisilane was found to be resistant to γ‐rays, while it gave small amounts of Me6Si2, Me3SiSiMe2Ph, Me3SiH, Me3SiSiHMePh and (Me3Si)2SiMeC6H4SiMe3. These products can be interpreted as being due to a chain contraction of the trisilane with the extrusion of methylphenylsilylene, a methyl migration with the extrusion of dimethylsilylene, a scission of an Si–Si bond due to an attack by hydrogen atoms, and a substitution of a hydrogen atom on the phenyl group by a trimethylsilyl radical. The same reactions, except the chain contraction, are observed in the cases of pentamethylphenyldisilane and 1,2‐diphenyltetramethyldisilane. On the basis of the data obtained, the chemical behavior of polysilastyrene during the irradiation i
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