Abstract
Kinetics for homogeneous aldol condensation-type of group transfer polymerization (aldol-GTP) of 1-butadienyloxytrimethylsilane (BdTMS) were investigated at −78°C in toluene, employing benzaldehyde as an initiator and a solution of ZnBr2 in diethyl ether (Et2O) as a catalyst. The polymerization rate (Rp) was the first order function of concentration of the catalyst as well as initiator. The kinetic order with respect to the concentration of BdTMS depended on the molar ratio of Et2O and ZnBr2. The influence of Et2O on Rp could be explained in terms of interaction between Et2O and the carbocationic propagating center produced by coordination of a formyl group with ZnBr2. The equilibrium constant for complexation between the formyl groups and ZnBr2 Was determined by 13C NMR. The concentration of the activated formyl groups is considerably low compared with the total concentration of the formyl groups. On the assumption that the concentration of the activated formyl group is very low and constant, the rate equation for the homogeneous aldol-GTP was derived and the most probable kinetic scheme was formulated based on the experimental results.
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Sumi, H., Suzuki, A., Hirabayashi, T. et al. Kinetic Study on the Group Transfer Polymerization of 1-Butadienyloxytrimethylsilane. Polym J 26, 705–714 (1994). https://doi.org/10.1295/polymj.26.705
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DOI: https://doi.org/10.1295/polymj.26.705