Effect of backbone structures of polysilanes on the photooxidation reaction

• Published in: Polymer (Guilford) 1996, Vol.37 (19), p.4327-4331
• Main Authors: Kabeta, Keiji, Shuto, Kiyoaki, Sugi, Shin-ichiro, Imai, Takafumi
• Format: Article
• Language: English
• Subjects: Applied sciences; Crosslinking and degradation; Exact sciences and technology; photooxidation; Physicochemistry of polymers; Polymers and radiations; polysilane; structure
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/0032-3861(96)00276-5

Photooxidation reactions of linear polysilanes [poly(cyclohexylmethylsilylene) and poly(methylphenylsilylene)], a network polysilane [poly(hexylsilyne)] and branched polysilanes [poly(cyclohexylmethylsilylene-co-phenylsilyne) and poly(cyclohexylmethylsilylene-co-hexylsilyne)] were investigated both in solution and in the solid state in the presence of oxygen. The reactions were monitored by u.v. and i.r. spectroscopies and size exclusion chromatography. Polysilanes containing a greater number of silyne units, i.e. highly branched polysilanes, required a greater dose of u.v. exposure for the completion of the photooxidation, which was determined by a decrease in the intensity of the polysilane's characteristic u.v. absorption and an increase in the intensity of the siloxane's i.r. absorption. The molecular weight change of the polymers also depended on the backbone structure. The degradation of the network and branched polysilanes was slower and smaller than that of linear polymers during the reactions.