onr:"swepub:oai:DiVA.org:kth-124738"
Search: onr:"swepub:oai:DiVA.org:kth-124738" > Thiol-ene coupling ...
- 1 of 1
- Previous record
- Next record
- To hitlist
- Claudino, MauroKTH,Ytbehandlingsteknik (author)
Thiol-ene coupling kinetics of D-limonene : a versatile 'non-click' free-radical reaction involving a natural terpene
- Article/chapterEnglish2013
Publisher, publication year, extent ...
- RSC Publishing,2013
- printrdacarrier
Numbers
- LIBRIS-ID:oai:DiVA.org:kth-124738
- https://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-124738URI
- https://doi.org/10.1039/c3ra40696bDOI
Supplementary language notes
- Language:English
- Summary in:English
Part of subdatabase
- SwePubSwePub
Classification
Notes
- QC 20130730
- The free-radical photoinduced thiol-ene reaction between D-limonene, as renewable diolefinic substrate, and two mono-/tri-functional thiols (iso-tridecyl 3-mercaptopropionate and trimethylolpropane tris(3-mercaptopropionate)), has been investigated kinetically to define a relationship between alkene structure and reactivity. Separate thiol-ene solutions of the appropriate thiol in d-chloroform, supplemented with 1.0 wt% of DMPA (Irgacure 651), were subjected to polychromatic UV-irradiation and the chemical changes monitored discontinuously via H-1 NMR spectroscopy to quantify double bond conversion. The kinetic concentration profiles were modeled analytically and simulated in the application software COPASI for parameter estimation and to verify if the experimental data explained a suggested mechanistic scheme. Empirical results demonstrate that the external vinylidene bond of limonene reacts about 6.5 times faster with thiol than the internal trisubstituted 1-methyl-cyclohexene unsaturation. The selectivity observed for the two unsaturations was successfully explained by means of a simplified steady-state equation derived from the sequential reaction mechanism accounting for propagation and chain-transfer elementary steps with estimated rate coefficients. Kinetic modeling results attribute the difference in selectivity partially to steric impediments controlling thiyl-radical insertion onto the double bonds and predominantly to differences in relative energy between the two tertiary insertion carbon radical intermediates. The rate-limiting step was identified as the third chain-transfer hydrogen-abstraction reaction promoted by the second insertion carbon radical intermediate. High thiol-ene conversions were obtained in a timely fashion without major influence of secondary reactions demonstrating the suitability of this reaction for network forming purposes. The mechanistic and kinetic information collected can be used as a quantitative predictive tool to assess the potential use of D-limonene in thiol-ene network forming systems involving multifunctional alkyl ester 3-mercaptopropionates.
Subject headings and genre
- NATURVETENSKAP Kemi hsv//swe
- NATURAL SCIENCES Chemical Sciences hsv//eng
- Carbon-Centered Radicals
- Acrylate Photopolymerizations
- Unsaturated-Compounds
- Vinyl Mechanisms
- Thiyl Radicals
- Cross-Linking
- Chemistry
- Polymerization
- Termination
- Copolymers
Added entries (persons, corporate bodies, meetings, titles ...)
- Jonsson, MatsKTH,Tillämpad fysikalisk kemi(Swepub:kth)u11mc94v (author)
- Johansson, MatsKTH,Ytbehandlingsteknik(Swepub:kth)u1oqmcv9 (author)
- KTHYtbehandlingsteknik (creator_code:org_t)
Related titles
- In:RSC Advances: RSC Publishing3:27, s. 11021-110342046-2069
Internet link
- 1 of 1
- Previous record
- Next record
- To hitlist
Find more in SwePub
- By the author/editor
- Claudino, Mauro
- Jonsson, Mats
- Johansson, Mats
- About the subject
-
- NATURAL SCIENCES
- NATURAL SCIENCES
- and Chemical Science ...
- Articles in the publication
- RSC Advances
- By the university
- Royal Institute of Technology
Search outside SwePub
- Extend your search to:
- Google Book Search
- Google Scholar
Kungliga biblioteket hanterar dina personuppgifter i enlighet med EU:s dataskyddsförordning (2018), GDPR. Läs mer om hur det funkar här.
Så här hanterar KB dina uppgifter vid användning av denna tjänst.
- Copyright © LIBRIS - National Library Systems
- LIBRIS.kb.se
