Jg. Deng et Yx. Peng, CATIONIC POLYMERIZATION OF 1,3-PENTADIENE INITIATED BY (CH3)(3)SIOSO2CF3 TICL4 SYSTEM/, Huaxue xuebao, 56(10), 1998, pp. 1032-1036
The polymerization of 1, 3 - pentadiene initiated by TMSOTf/TiCl4 init
iating system is reported. The results showed that, the initiating sys
tem has an higher activity than TiCl4 alone. It can increase the molec
ular weight and raise reaction rate of polymerization. The polymer yie
ld increases with the [TMSOTf]/TiCl4 ratio,and then keeps constantly w
hen the [TMSOTf]/[TiCl4] ratio is not less than 0.5, The molecular wei
ght reaches a maximum when [TMSOTf]/[TiCl4] = 1. The reaction kinetic
and reaction mechanism are studied. In our study, the polymerization o
f PD is initiated by the TiCl4 in complexation with HOTf released by h
ydrolysis of TMSOTf. The yield and the molecular weight increase with
steric hindrance of kentone.