Photo-induced ligation of acrylonitrile-butadiene rubber: Selective tetrazole-ene coupling of chain-end-functionalized copolymers of 1,3-butadiene

Dürr, C. J., Lederhose, P., Hlalele, L., Abt, D., Kaiser, A., Brandau, S., & Barner-Kowollik, C. (2013) Photo-induced ligation of acrylonitrile-butadiene rubber: Selective tetrazole-ene coupling of chain-end-functionalized copolymers of 1,3-butadiene. Macromolecules, 46(15).

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A highly selective photo-induced nitrile imine mediated tetrazole-ene coupling (NITEC) of chain-end-functionalized nitrile-butadiene rubber (NBR) is reported, providing nitrile rubbers with molar masses of up to 48 000 g·mol-1. NBR was obtained via the reversible addition-fragmentation chain transfer (RAFT) mediated copolymerization of acrylonitrile and 1,3-butadiene employing a novel photoreactive tetrazole-functionalized trithiocarbonate. The herein reported tetrazole-functionalized trithiocarbonate represents - to the best of our knowledge - the first ever reported photoreactive RAFT agent capable of undergoing light-induced ligations with enes. Molar masses of the tetrazole-functionalized NBRs were in the range of 1000 to 38 000 g·mol-1 with dispersities between 1.1 to 1.6. By an appropriate choice of the tetrazole substituents, a reaction of the in situ formed enophile with the double bonds or the nitrile moieties of the incorporated monomer units within the polymer backbone - present in high excess relative to the dipolarophile linker molecule - was not observed. Underpinned by DFT calculations, the selectivity was identified to originate from a reduced LUMO energy level of the maleimide linker compared to the nonactivated backbone olefins when employing a nitrile-imine of moderate reactivity. © 2013 American Chemical Society.

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ID Code: 99345
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :11
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76128 Karlsruhe, Germany; email:
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Keywords: Acrylonitrile-butadiene rubber, DFT calculation, Linker molecules, LUMO energy levels, Nitrile butadiene rubber, Polymer backbones, Reversible addition fragmentation chain transfer (RAFT), Trithiocarbonate, Butadiene, Copolymers, Cyanides, Photoreactivity, Sulfur compounds, Surgical equipment, Polymer blends
DOI: 10.1021/ma401154k
ISSN: 00249297
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: 29 Sep 2016 03:49

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