Journal article
Synthesis and photopolymerization of novel multifunctional vinyl esters
Journal of polymer science. Part A, Polymer chemistry, Vol.42(17), pp.4424-4436
09/01/2004
DOI: 10.1002/pola.20181
Abstract
Novel mono‐ and multifunctional vinyl ester monomers containing thioether groups were synthesized via an amine‐catalyzed Michael addition reaction between vinyl acrylate and multifunctional thiols. Using photo‐differential scanning calorimetry and real‐time Fourier transform infrared (RTIR) spectroscopy, the polymerization kinetics and oxygen inhibition of the homopolymerizations of the vinyl ester monomers were investigated. The effect of the vinyl ester and thioether group on acrylate/vinyl ester and thiol/vinyl ester copolymerizations was determined using real‐time IR spectroscopy to monitor polymerization rates of acrylate, vinyl, and thiol groups simultaneously. Polymerization of the vinyl esters used was found to be relatively insensitive to oxygen inhibition. We propose that the thioether group is responsible for reducing oxygen inhibition by a series of chain transfer/oxygen‐scavenging reactions. In polymerization of a acrylate/vinyl ester mixture both in nitrogen and in air, the vinyl ester monomer significantly enhances the polymerization rates and the conversion of the acrylate double bonds via plasticization of the crosslinked matrix and reduction of inhibition by oxygen. Ultimately, the vinyl ester monomer is incorporated into the polymer network. Thiol/vinyl ester free‐radical copolymerization is much faster than either thiol/allylether copolymerization or vinyl ester homopolymerization. The electron‐rich vinyl ester double bonds ensure rapid copolymerization with thiol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4424–4436, 2004
Multifunctional vinyl ester monomers were synthesized via an amine catalyzed Michael addition of thiols to vinyl acrylate. The vinyl ester monomers contain thioether linkages, which are effective in reducing oxygen inhibition of the free‐radical homopolymerization and copolymerization processes with acrylates. The vinyl ester monomer not only enhances the polymerization rates of multifunctional acrylates, it also acts as a plasticizer leading to much higher acrylate conversions than obtained in the absence of the vinyl ester.
Details
- Title: Subtitle
- Synthesis and photopolymerization of novel multifunctional vinyl esters
- Creators
- Tai Y LeeW KaungE. Sonny JönssonK LoweryC. A GuymonC. E Hoyle
- Resource Type
- Journal article
- Publication Details
- Journal of polymer science. Part A, Polymer chemistry, Vol.42(17), pp.4424-4436
- Publisher
- Wiley Subscription Services, Inc., A Wiley Company; Hoboken
- DOI
- 10.1002/pola.20181
- ISSN
- 0887-624X
- eISSN
- 1099-0518
- Number of pages
- 13
- Grant note
- Fusion UV Curing Systems NSF (EEC‐0120965)
- Language
- English
- Date published
- 09/01/2004
- Academic Unit
- Chemical and Biochemical Engineering
- Record Identifier
- 9984003411102771
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