Abstract

The polymerization of o-trimethylsilylphenylacetylene (o-Me3SiPA) initiated by tungsten carbene complex (I) was investigated under various conditions. Both a larger molar mass and larger yield of polymer were obtained in CCl4 and CHCl3 and in the presence of a Lewis acid such as AlCl3. The higher the temperature and the lower the initiator concentration, the larger was the molar mass of the polymer. The molar mass increases with concentration of cocatalyst SnCl4 and shows a maximum value for a ratio [SnCl4]/[I] =1. Moreover, when a solution of tungsten carbene complex in CCl4 was irradiated with UV light, the molar mass was remarkably enhanced. Kinetic orders and apparent rate constants were determined by gas chromatography. According to thermogravimetric results for poly(o-Me3SiPA), there is no significant interaction between the polymer and oxygen below 260°C. Above 260°C, the loss of mass in the presence of oxygen follows a two-step process. X-Ray diffraction measurements show that poly(o-Me3SiPA) has an amorphous structure.

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