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Electron spin resonance study on homogeneous catalysts derived from n-butyl titanate and triethylaluminum
Authors:Hidefumi Hirai  Katsuma Hiraki  Isamu Noguchi  Shoji Makishima
Abstract:ESR spectra of homogeneous catalyst systems derived from n-butyl titanate and triethylaluminum at Al/Ti molar ratios of 1.0–10 were observed in toluene solution at several temperatures from ?78°C to +25°C. In the whole range of Al/Ti molar ratios, a single signal with a g value of 1.951 was observed at ?78°C and was associated with the first reaction intermediate. With increasing temperature, the intensity of the signal decreased gradually, while two series of signals appeared, depending on the Al/Ti molar ratio. At an Al/Ti molar ratio of 1.7, seven kinds of signals with g values of 1.960, 1.946, 1.950, 1.959, 1.980, 1.977, and 1.978, respectively, were observed. On the other hand, four kinds of signals with g values of 1.934, 1.966, 1.952, and 1.979, respectively, were found at Al/Ti molar ratios larger than 3. The structures of the species corresponding to the signals were discussed on the basis of the ESR spectra, the order of their growth and their hyperfine structures being considered. Two series of ESR signal were correlated to two kinds of active species for polymerization of styrene and butadiene, respectively.
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