Studies on the laser degradation of the CHCl3 solution of polysilane

In this paper, the XeCl excimer laser was used to irradiate the CHCl₃ solution of polymethylphenethylsilane (PMPES) and that of poly(dimethylsilane-co-methylphenethylsilane) (PDM-MPES). The laser energy absorbed by the polysilane macromolecules was measured, the gel permeation chromatography molecular weights of the polysilane macromolecules both before and after irradiation were determined, and their corresponding apparent quantum yields under the irradiation were calculated. The apparent quantum yield of laser degradation of the CHCl₃ solution of PMPES is two orders of magnitude larger than that of the CHCl₃ solution of PDM-MPES, indicating that the spatial obstruction of the substituents attached to the polysilane chains has great effect on its apparent quantum yield of laser degradation. For the polysilane photodegradation under a rather low laser energy, with the increase of the laser energy absorbed by the polysilane macromolecules, the average molecular weight after irradiation decreases gradually while the average scissions per macromolecule and the apparent quantum yield increase. The concentration of the CHCl₃ solution of polysilane has only small effect on its apparent quantum yield of laser degradation. According to the X-ray photoelectron spectroscopy analysis, the CHCl₃ solvent is involved in the photoreaction and combined into the dissociated product. In light of the references, it is preliminarily proposed that the laser degradation of the CHCl₃ solution of polysilane may result from the comprehensive action of such factors as homolytic cleavage, silylene extrusion, chain cleavage by reductive elimination, the radical chain transfer process, the fluorescence quenching of polysilane by CHCl₃, etc. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1515–1519, 1997