Polymerization of vinyl chloride (VC) with titanium complexes containing Ti‐OPh bond in combination with methylaluminoxane (MAO) catalysts was investigated. Among the titanium complexes examined, Cp*Ti(OPh)3/MAO catalyst (Cp*; pentamethylcyclopentadienyl, Ph; C6H5) gave the highest activity for the polymerization of VC, but the polymerization rate was slow. From the kinetic study on the polymerization of VC with Cp*Ti(OPh)3/MAO catalyst, the relationship between the Mn of the polymer and the polymer yields gave a straight line, and the line passed through the origin. The Mw/Mn values of the polymer gradually decrease as a function of polymer yields, but the Mw/Mn values were somewhat broad. This may be explained by a slow initiation in the polymerization of VC with Cp*Ti(OPh)3/MAO catalyst. The results obtained in this study demonstrate that the molecular weight control of the polymers is possible in the polymerization of VC with the Cp*Ti(OPh)3/MAO catalyst. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3872–3876, 2007

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Polymerization of vinyl chloride (VC) with a Cp*Ti(OPh) 3 /MAO catalyst in toluene was investigated. The polymerization rate was lower than that in CH 2 Cl 2 , and the mm triad concentration of the PVC obtained in toluene was somewhat higher than that of the PVC obtained in CH 2 Cl 2 . As the polymerization in toluene proceeded at a considerable rate, a kinetic study of this polymerization was undertaken. The polymer yield increased with reaction time, and the molecular weight of the polymer increased with increasing polymer yield. The M w /M n ratio of the polymer decreased with increasing polymerization temperature. The initiator efficiency of the catalyst was low at the initial stage of the polymerization in toluene, but it reached nearly 100% when the polymerization was carried out for more than 30 h. The control of both the molecular weight of PVC and its main-chain structure was found to be possible in the polymerization of VC with the Cp*Ti(OPh) 3 /MAO catalyst in toluene.