The copolymerization behavior and the dark polymerization kinetics of highly reactive novel acrylic monomers were compared to traditional acrylate monomers. Copolymerization of thiol functionalities with novel acrylic monomers was characterized, and it was observed that the inclusion of secondary functionalities such as carbarnates, carbonates, and cyclic carbonates, in acrylic monomers significantly alters the relative reactivity of the novel acrylates with thiols. While traditional aliphatic acrylates exhibited propagation to chain transfer ratios ranging between 0.8 (+/- 0.1) and 1.5 (+/- 0.2), the novel acrylates characterized by secondary functionalities exhibited much higher propagation to chain transfer ratios ranging from 2.8 (+/- 0.2) to 4 (+/- 0.2). In the dark polymerization studies, the kinetics of the novel acrylates were evaluated following cessation of the UV light. The novel acrylates exhibited extensive polymerization in the dark compared to most traditional acrylates and diacrylates. For instance, cyclic carbonate acrylate was observed to attain 35% additional conversion in the dark when the UV light was extinguished at 35% conversion, whereas traditional acrylates such as hexyl acrylate attained only 3% additional conversion when the UV light was extinguished at 35%, and a diacrylate such as HDDA attained 15% additional conversion when the UV light was extinguished at 40% conversion. Also, through choice of appropriate monomers, the dark polymerization studies were performed such that the polymerization rate was approximately the same at the point the light was extinguished for all these monomers. The copolymerization and dark polymerization studies support the hypothesis that the nature of the propagating species in the novel acrylates is altered as compared to traditional acrylic monomers and polymerizations. (c) 2007 Elsevier Ltd. All rights reserved.