Journal article
Influence of the alkene structure on the mechanism and kinetics of thiol–alkene photopolymerizations with real‐time infrared spectroscopy
Journal of polymer science. Part A, Polymer chemistry, Vol.42(24), pp.6283-6298
12/15/2004
DOI: 10.1002/pola.20452
Abstract
The effect of the chemical structure on the reactivity of alkenes used in thiol–ene photopolymerizations has been investigated with real‐time infrared spectroscopy. Model studies of thiol–ene photoreactions with various monofunctional hydrocarbon alkenes and the monofunctional thiol ethyl‐3‐mercaptopropionate have been performed to identify and understand structure–reactivity relationships. The results demonstrate that terminal enes react very rapidly with thiol, achieve complete conversion, and are independent of the aliphatic hydrocarbon substituent length. Disubstitution on a single carbon of a terminal ene significantly reduces the reactivity, whereas substitution on the carbon α to the terminal ene has a minimal influence on the reactivity. Internal trans enes display reduced reactivity and a lower overall conversion and deviate from the standard thiol–ene reaction mechanism because of steric strain induced by 1,3‐interactions. The reactivity and conversion of internal trans enes decrease as the substituents on the ene become larger, reaching a minimum when the substituent size is greater than or equal to that of propyl groups. Internal cis enes react rapidly with thiol; however, they undergo a fast isomerization–elimination reaction sequence generating the trans ene, which proceeds to react at a reduced rate with thiol. The reactivity of cyclic enes is dictated by ring strain, stereoelectronic effects, and hydrogen ability. The reactivity trends in the model studies have been used to explain the photopolymerization mechanism and kinetics of a series of multifunctional thiol–ene systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6283–6298, 2004
The effect of chemical structure on the reactivity of alkenes utilized in thiol‐ene photopolymerizations was investigated using real‐time infrared spectroscopy (RTIR). The RTIR results from the photopolymerization of 4‐vinyl‐1‐cyclohexene with 1,6‐hexanedithiol indicate the rapid reactivity of the terminal vinyl ene (1640 cm‐1) with thiol as compared to the internal cyclic ene (1654 cm‐1), which reacts much slower. Understanding the reaction mechanism/kinetics enables the design of polymer morphologies and tailored physical properties.
Details
- Title: Subtitle
- Influence of the alkene structure on the mechanism and kinetics of thiol–alkene photopolymerizations with real‐time infrared spectroscopy
- Creators
- Todd M RoperC. A GuymonE. S JönssonC. E Hoyle
- Resource Type
- Journal article
- Publication Details
- Journal of polymer science. Part A, Polymer chemistry, Vol.42(24), pp.6283-6298
- Publisher
- Wiley Subscription Services, Inc., A Wiley Company; Hoboken
- DOI
- 10.1002/pola.20452
- ISSN
- 0887-624X
- eISSN
- 1099-0518
- Number of pages
- 16
- Grant note
- Fusion UV Systems, Inc. National Science Foundation (Tie Grant EEC‐0120965)
- Language
- English
- Date published
- 12/15/2004
- Academic Unit
- Chemical and Biochemical Engineering
- Record Identifier
- 9984003450202771
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