Radical ring-opening polymerization of cyclic ketene acetals is a means to achieve novel types of aliphatic polyesters. 2-methylene-1,3-dioxe-5-pene is a seven-membered cyclic ketene acetal containing an unsaturation in the 5-position in the ring structure. The double bond functionality enables further reactions subsequent to polymerization. The monomer 2-methylene-1,3-dioxe-5-pene was synthesized and polymerized in bulk by free radical polymerization at different temperatures, to determine the structure of the products and propose a reaction mechanism. The reaction mechanism is dependent on the reaction temperature. At higher temperatures, ring-opening takes place to a great extent followed by a new cyclization process to form the stable five-membered cyclic ester 3-vinyl-1,4-butyrolactone as the main reaction product. Thereby, propagation is suppressed and only small amounts of other oligomeric products are formed. At lower temperatures, the cyclic ester formation is reduced and oligomeric products containing both ring-opened and ring-retained repeating units are produced at higher yield. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4587-4601, 2009