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Abstract: The quantum chemical method was employed to study the anionic polymerization mechanism of propylene oxide. All the structures are optimized completely at the HF/6-31G+(d) level. The calculated results showed that the ring-opening reaction between the anionic nucleophiles and propylene oxide is feasible, and that the products are mainly secondary alcohols. The anionic ring-opening polymerization of propylene oxide proceeds by nucleophilic attack of the secondary alcohol propagating anion on monomer. The calculated results satisfactorily agree with the experimental facts.

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