Thioketone‐Mediated Polymerization with Dithiobenzoates: Proof for the Existence of Stable Radical Intermediates in RAFT Polymerization
Abstract
A novel dithioester control agent [dimethyltetrathioterephtalate (DMTTT)] is presented for the thioketone‐mediated radical polymerization (TKMP) of n‐butyl acrylate. The rate of polymerization is significantly decreased in the presence of DMTTT indicating formation of dormant radical species. During polymerization, molar masses increase linearly with monomer conversion with reasonably narrow initial molar mass distributions (PDI between 1.3 and 1.8), whereas the dispersity increases during the course of the polymerization due to irreversible termination of both propagating and dormant radicals. The present results thus highlight the possibility of a mixed mechanism operating in RAFT polymerization, which combines slow fragmentation (long‐lived intermediates) and intermediate radical termination.
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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 [10]
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- Authors
- Junkers, T., Delaittre, G., Chapman, R., Günzler, F., Chernikova, E., & Barner‐Kowollik, C.
- Affiliations
- Karlsruhe Institute of Technology (DE)
- The University of Sydney (AU)
- Lomonosov Moscow State University (RU)
- Corresponding author
- Junkers, Tanja
- Barner‐Kowollik, Christopher
- Venue
- Macromolecular Rapid Communications
- Publisher
- Wiley
- Published
- 2012-05-03
- Volume
- 33
- Issue
- 11
- Pages
- 984-990
- ISSN
- 1022-1336 (ISSN-L)
- 1521-3927
- OpenAlex
- W2112804153
- Cited by
- 24
- References
- 33
- Citations by year
- 2026: 1 · 2024: 1 · 2023: 2 · 2022: 1 · 2021: 3 · 2020: 1 · 2019: 1 · 2018: 3 · 2017: 2 · 2016: 2 · 2015: 2 · 2014: 3 · 2013: 1 · 2012: 1
- FWCI
- 1.03
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecular Rapid Communications (publishedVersion)
- PubMed (publishedVersion)
- Document Server@UHasselt (UHasselt) (submittedVersion)
- QUT ePrints (Queensland University of Technology) (submittedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer Synthesis and Characterization
- Keywords
- RAFT polymerization, dithiobenzoate, radical intermediates, butyl acrylate, polymerization rate, molecular weight distribution, radical termination
- MeSH terms
- Acrylates, Polymers
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