The (CH3)3SiOSO2CF3/SbCl3 initiating system for cationic polymerization of 1, 3-pentadiene

Cationic polymerization of I, 3-pentadiene (PD) by trimethylsilyl trifluoromethanesulfonate ((CH3)(3)SiOSO2CF3) in combination with SbCl3 were carried out in n-hexance at 30 degrees C. Addition of SbCl3 into the (CH3)(3)SiOSO2CF3 induced PD polymerization. The polymer yield increases from 55% to 80%, the polymerization is accelerated 2.4 times and the molecular weight of polymer is 1.7 times. Various ketones were used to mediate the initiating system (CH3)(3)SiOSO2CF3/SbCl3, the more bulky the ketone-is, the higher yield and molecular weight are obtained. The H-1-NMR and the IR show that the polymerization of PD was initiated by the SbCl3 in complexation with trific acid (HOTf) resulting from hydrolysis of (CH3)(3)SiOSO2CF3 by adventitious water.