Thioketone‐Mediated Polymerization of Butyl Acrylate: Controlling Free‐Radical Polymerization via a Dormant Radical Species
Abstract
It is demonstrated by experiment and simulation that the commercially available thioketone 4,4‐bis(dimethylamino)thiobenzophenone is capable of controlling AIBN‐initiated bulk butyl acrylate polymerization at 80 °C. On the basis of molecular weight data and from monomer conversion versus time curves, the associated rate parameters are estimated. The addition rate coefficient, kad, for the reaction of a propagating chain with the thioketone is close to 10 6 L · mol−1 · s−1 and the fragmentation rate coefficient, kfrag, is around 10−2 s−1 giving rise to large equilibrium constants in the order of 10 8 L · mol−1. Furthermore, cross‐ and self‐termination of the dormant radical species are identified to be operational. magnified image
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Direct radical addition reactions of thiocarbonyl (C=S) groups unaccompanied by β-scission have rarely been reported.
“Direct radical addition reactions of thiocarbonyl (C=S) groups unaccompanied by β-scission have rarely been reported despite their potential for constructing various sulfur-containing compounds.”
From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [9]
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- Authors
- Junkers, T., Stenzel, M. H., Davis, T. P., & Barner‐Kowollik, C.
- Affiliations
- UNSW Sydney (AU)
- Corresponding author
- Barner‐Kowollik, Christopher
- Venue
- Macromolecular Rapid Communications
- Publisher
- Wiley
- Published
- 2007-03-16
- Volume
- 28
- Issue
- 6
- Pages
- 746-753
- ISSN
- 1022-1336 (ISSN-L)
- 1521-3927
- OpenAlex
- W2095523926
- Cited by
- 41
- References
- 24
- Citations by year
- 2026: 1 · 2025: 1 · 2023: 2 · 2022: 1 · 2021: 1 · 2020: 1 · 2018: 4 · 2017: 1 · 2014: 1 · 2013: 2 · 2012: 3
- FWCI
- 2.88
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecular Rapid Communications (publishedVersion)
- QUT ePrints (Queensland University of Technology) (submittedVersion)
- Institute for Future Environments; Science & Engineering Faculty
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Chemistry › Organic Chemistry › Photopolymerization techniques and applications
- Physical Sciences › Chemistry › Organic Chemistry › Radical Photochemical Reactions
- Keywords
- butyl acrylate, AIBN initiation, cross-termination, self-termination, equilibrium constants
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