(Meth)Acrylate Vinyl Ester Hybrid Polymerizations

In this study, vinyl ester monomers were synthesized by an amine catalyzed Michael addition reaction between a multifunctional thiol and the acrylate double bond of vinyl acrylate. The copolymerization behavior of both methacrylate/vinyl ester and acrylate/vinyl ester systems was studied with near-infrared spectroscopy. In acrylate/vinyl ester systems, the acrylate groups polymerize faster than the vinyl ester groups resulting in an overall conversion of 80% for acrylate double bonds in the acrylate/vinyl ester system relative to only 50% in the bulk acrylate system. In the methacrylate/vinyl ester systems, the difference in reactivity is even more pronounced resulting in two distinguishable polymerization regimes, one dominated by methacrylate polymerization and a second dominated by vinyl ester polymerization. A faster polymerization rate and higher overall conversion of the methacrylate double bonds is thus achieved relative to polymerization of the pure metbacrylate System. The methacrylate conversion in the methacrylate/vinyl ester system is near 100% compared to only similar to 60% in the pure methacrylate system. Utilizing hydrophilic vinyl ester and hydrophobic metbacrylate monomers, polymerization-induced phase separation is observed. The phase separated domain size is in the order of similar to 1 mu m under the polymerization conditions. The phase separated domains become larger and more distinct with slower polymerization and correspondingly increased time for diffusion. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2509-2517, 2009