Thioketone-mediated polymerization with dithiobenzoates: Proof for the existence of stable radical intermediates in RAFT polymerization

Junkers, T., Delaittre, G., Chapman, R., Günzler, F., Chernikova, E., & Barner-Kowollik, C. (2012) Thioketone-mediated polymerization with dithiobenzoates: Proof for the existence of stable radical intermediates in RAFT polymerization. Macromolecular Rapid Communications, 33(11).

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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. Living characteristics are observed in acrylate radical polymerization in the presence of a dithiobenzoate possessing a nonleaving R group. These observations account for the presence of dormant radicals-which are analogous to RAFT intermediate radicals-and corroborate the compatibly between slow fragmentation and intermediate radical termination. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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ID Code: 99314
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :8
Export Date: 5 September 2016
Correspondence Address: Junkers, T.; Preparative Macromolecular Chemistry, Institut für Technische und Polymerchemie, Karlsruhe Institute of Technology, Engesserstr. 18, 76131 Karlsruhe, Germany; email:
Chemicals/CAS: acrylic acid butyl ester, 141-32-2; Acrylates; Polymers; n-butyl acrylate, 141-32-2
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Keywords: controlled/living radical polymerization, dithiobenzoate, radical stability, reversible addition-fragmentation transfer, thioketone, Control agent, Dispersity, Dithiobenzoates, Dithioesters, Dormant radicals, Intermediate radical terminations, Molar mass distribution, Monomer conversions, N-butyl acrylate, RAft polymerization, Rate of polymerization, Reversible addition-fragmentation transfers, Stable radicals, Atom transfer radical polymerization, Molar mass, Polymethyl methacrylates, Living polymerization, acrylic acid butyl ester, acrylic acid derivative, polymer, article, chemistry, synthesis, Acrylates, Polymers
DOI: 10.1002/marc.201200128
ISSN: 10221336
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 04 Oct 2016 05:15

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