AbstractFree‐radical polymerizations of several aliphatic and aromaticN‐substituted vinyl carbonates are described. The bulk polymerization was initiated at 35°C with di‐tert‐butylcylohexyl peroxydicarbonate yielding high‐molecular‐weight poly(vinyl carbonate)s. The structure of these polymers was examined by FTIR spectroscopy and the molecular weight by GPC. The effects of the substituents on the physical properties of the resulting polymers were studied. A comparison of the properties with those of similar compounds described in the literat