Racemic and optically active protected glycidols (as 1‐ethoxyethyl ethers) are readily polymerized with anionic initiators (e.g., CsOH). Polymers with molecular weights up to 30 000 are obtained without cleavage of the protective group. Oligomers (degree of polymerization [DPn] 5 to 10) are prepared using an aluminium complex derived from a Schiff's base. The protected thioglycidol (synthesized from the protected glycidol) leads to very high‐molecular‐weight polymers (150 000–320 000) using anionic or anionic coordinated initiators. Copolymers of protected glycidol with ethylene oxide are obtained with KOH as initiator. Regeneration of hydroxyl groups in polymers is carried out with acidic cleavage. Treatment of protected polyglycidol with formic acid leads first to the formate of polyglycidol. Then, after saponification, pure polyglycidol is obtained. The use of aqueous hydrochloric acid leads directly to the free polymer.

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A general reexamination of the configurational statistics of polymers obtained by ringopening polymerization of heterocyclic monomers is presented. The polymers under study involve one or two asymmetric centres in the main chain per monomeric unit. Sequence probabilities are calculated for Bernoullian, and first-and second-order Markov propagation models. The analyses of two polymers [poly(styrene oxide) and poly(tert-butyloxirane)] for which tacticity data are available in the literature are given as examples.0025-1 16X/88/%03.00