(Meth)acrylate vinyl ester hybrid polymerizations
- 9 April 2009
- journal article
- research article
- Published by Wiley in Journal of Polymer Science Part A: Polymer Chemistry
- Vol. 47 (10) , 2509-2517
- https://doi.org/10.1002/pola.23327
Abstract
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 methacrylate system. The methacrylate conversion in the methacrylate/vinyl ester system is near 100% compared to only ∼60% in the pure methacrylate system. Utilizing hydrophilic vinyl ester and hydrophobic methacrylate monomers, polymerization‐induced phase separation is observed. The phase separated domain size is in the order of ∼1 μm under the polymerization conditions. The phase separated domains become larger and more distinct with slower polymerization and correspondingly increased time for diffusion. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2509–2517, 2009Keywords
Funding Information
- NSF Fundamentals and Applications of Photopolymerizations I/UCRC
- NIH (#DE10959)
This publication has 41 references indexed in Scilit:
- CONSUMPTION OF THE MOLECULAR OXYGEN IN POLYMERIZATION SYSTEMS USING PHOTOSENSITIZED OXIDATION OF DIMETHYLANTHRACENEChemical Engineering Communications, 2006
- Thiol–enes: Chemistry of the past with promise for the futureJournal of Polymer Science Part A: Polymer Chemistry, 2004
- Synthesis and photopolymerization of novel multifunctional vinyl estersJournal of Polymer Science Part A: Polymer Chemistry, 2004
- Thiol−Ene Photopolymerization Kinetics of Vinyl Acrylate/Multifunctional Thiol MixturesMacromolecules, 2004
- Thiol−Ene Photopolymerization Mechanism and Rate Limiting Step Changes for Various Vinyl Functional Group ChemistriesMacromolecules, 2003
- N-Vinylamides and Reduction of Oxygen Inhibition in Photopolymerization of Simple Acrylate FormulationsPublished by American Chemical Society (ACS) ,2003
- Photopolymerizations of Thiol−Ene Polymers without PhotoinitiatorsMacromolecules, 2002
- Kinetics of thiol–ene and thiol–acrylate photopolymerizations with real‐time fourier transform infraredJournal of Polymer Science Part A: Polymer Chemistry, 2001
- Photopolymerization of 1,6-hexanediol diacrylate: The effect of functionalized aminesPolymer, 1988
- The effect of aromatic amines on the photopolymerization of 1,6-hexanediol diacrylateJournal of Applied Polymer Science, 1987