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Thiol–norbornene materials: Approaches to develop high Tg thiol–ene polymers
Authors:Jacquelyn A Carioscia  Lauren Schneidewind  Casey O'Brien  Robert Ely  Caitlin Feeser  Neil Cramer  Christopher N Bowman
Institution:1. Department of Chemical and Biological Engineering, Engineering Center, ECCH 111, University of Colorado, Boulder, Colorado 80309‐0424;2. Department of Chemical Engineering, Widener University, Chester, Pennsylvania 19013‐4059;3. Department of Chemical and Biological Engineering, Engineering Center, ECCH 111, University of Colorado, Boulder, Colorado 80309‐0424Department of Chemical and Biological Engineering, Engineering Center, ECCH 111, University of Colorado, Boulder, Colorado 80309‐0424
Abstract:The ability to prepare high Tg low shrinkage thiol–ene materials is attractive for applications such as coatings and dental restoratives. However, thiol and nonacrylated vinyl materials typically consist of a flexible backbone, limiting the utility of these polymers. Hence, it is of importance to synthesize and investigate thiol and vinyl materials of varying backbone chemistry and stiffness. Here, we investigate the effect of backbone chemistry and functionality of norbornene resins on polymerization kinetics and glass transition temperature (Tg) for several thiol–norbornene materials. Results indicate that Tgs as high as 94 °C are achievable in thiol–norbornene resins of appropriately controlled chemistry. Furthermore, both the backbone chemistry and the norbornene moiety are important factors in the development of high Tg materials. In particular, as much as a 70 °C increase in Tg was observed in a norbornene–thiol specimen when compared with a sample prepared using allyl ether monomer of analogous backbone chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5686–5696, 2007
Keywords:step‐growth polymerization  glass transition  structure–  property relations
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