A styrene-based monomer having a five-membered cyclic carbonate structure, 4-vinylbenzyl 2,5-dioxoran-3-ylmethyl ether (VBCE), was prepared by lithium bromide-catalyzed addition of carbon dioxide to 4-vinylbenxyl glycidyl ether (VBGE). Radical polymerization of the obtained VBCE was carried out using 2,2'-azobisisobutyronitrile as an initiator. PolyVBCE with number-averaged molecular weight higher than 13,800 was obtained by a solution polymerization in N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and methyl ethyl ketone. The glass transition temperature and 5 wt % decomposition temperature of the polyVBCE were determined to be 52 and 305 degrees C by differential scanning calorimetry and thermal gravimetry analysis, respectively. It was confirmed that a polymer consisting of the same VBCE repeating unit can be also obtained via chemical modification of polyVBGE, that is, a lithium-bromide-catalyzed addition of carbon dioxide to a polyVBGE prepared from a radical polymerization of VBGE. Further copolymerization of VBCE with styrene gave the corresponding copolymer in a high yield. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012