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Epoxides are polymerized homogeneously by some metallocene halides. Cp2TiCl2 is ineffective, Cp2ZrCl2 and Cp2ZrI2 are active as catalysts (Cp denotes the cyclopentadienyl group). Epichlorohydrin is polymerized to high conversions. The resultant polymers are amorphous and of low mol. wt. because of transfer reactions. The bridged compound (Cp2ZrCl)2O is also active and gives higher mol. wt. Phenyl glycidyl ether polymerizes well. The formation of oligomers from propylene oxide is also catalyzed by Cp2ZrCl2. A cationic mechanism is suggested for the polymerizations.
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Kyoji Kaeriyama (1972) studied this question.
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