ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 36, Number 2
JKCSEZ 36(2)
April 20, 1992 

The cationic polymerization of cyclic acetals are investigated theoretically using the semiempirical MINDO/3, MNDO, and AM1, methods. The nucleophilicity and basicity of cyclic acetals can be explained by the negative charge on oxygen atom of cyclic acetals. The reactivity of propagation in the polymerization of cyclic acetals can be represented by the positive charge on C2 atom and the low LUMO energy of active species of cyclic acetals. The reactivity of 2-buthyl-1,3-dioxepane(2-Bu-DOP) of cyclic oxonium and opening carbenium ion form is expected computational stability of the oxonium ion by 5∼7kcal/mole favoring the carbenium ion. Owing to the rapid equilibrium of these cation forms and the reaction coordinate based on calculation that the reaction coordinate based on calculation that the chain growth SN1 mechanism will be at least as fast as that for SN2 mechanism.