High molecular weight acrylonitrile-butadiene architectures via a combination of RAFT polymerization and orthogonal copper mediated azide-alkyne cycloaddition

Dürr, C. J., Emmerling, S. G. J., Lederhose, P., Kaiser, A., Brandau, S., Klimpel, M., & Barner-Kowollik, C. (2012) High molecular weight acrylonitrile-butadiene architectures via a combination of RAFT polymerization and orthogonal copper mediated azide-alkyne cycloaddition. Polymer Chemistry, 3(4).

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α-Functional nitrile butadiene rubber (NBR) building blocks were employed in the copper mediated 1,3-dipolar Huisgen coupling upon addition of 1,4-bis(azidomethyl)benzene (4). Polymer-polymer coupling afforded linear polymers with molecular weights ranging from 2500 g mol -1 to 97000 g mol -1 and polydispersities from 1.1 to 1.6. The α-functional NBR building blocks were obtained via the reversible addition-fragmentation chain transfer (RAFT) copolymerization of acrylonitrile (AN) and 1,3-butadiene (BD) at 100 °C, utilizing the high temperature azo initiator 1,1′-azobis(cyclohexane-1-carbonitrile) and chlorobenzene or acetone as solvents. A novel alkyne-functional trithiocarbonate 2 was synthesized in 64% yield via the N,N′-dicyclohexylcarbodiimide mediated coupling of 2-((dodecylsulfanyl)carbono-thioyl)sulfanyl propanoic acid (DoPAT, 1) and propargyl alcohol. 2 was shown to be an efficient controlling agent for the controlled/living radical copolymerization of acrylonitrile and 1,3-butadiene. The use of copper mediated azide-alkyne cycloaddition was extended towards the side-chain modification of acrylonitrile-butadiene rubbers as well as applied in the synthesis of branched and cross-linked NBR structures. For this purpose an acrylonitrile-1,3-butadiene-propargyl methacrylate (PMA) terpolymer of 3900 g mol -1 with a PDI of 1.3 was synthesized by a DoPAT-mediated RAFT polymerization. Herein, monomers were employed in the ratio of 56:35:9 (BD:AN:PMA). The ability of the terpolymer to undergo side-chain modification was demonstrated upon addition of 1-undecane azide. Cross-links were established via addition of 1,4-bis(azidomethyl)benzene. The current study provides the first successful approach to employ an orthogonal conjugation technique on this technically important class of synthetic rubbers. © 2012 The Royal Society of Chemistry.

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ID Code: 99307
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :16
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany; email: christopher.barner-kowollik@kit.edu
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Keywords: 1 ,3-butadiene, Acrylonitrile-butadiene rubber, Azide-alkyne cycloaddition, Azoinitiator, Building blockes, Controlling agent, Dicyclohexylcarbodiimide, High molecular weight, High temperature, Linear polymers, Nitrile butadiene rubber, Propanoic acid, Propargyl alcohol, Radical copolymerization, RAft polymerization, Reversible addition-fragmentation chain transfer, Side-chains, Trithiocarbonate, Acetone, Acetylene, Benzene, Butadiene, Copolymerization, Copolymers, Copper, Living polymerization, Molecular weight, Polydispersity, Polymer blends, Polymers, Cycloaddition
DOI: 10.1039/c2py00547f
ISSN: 17599954
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 04:25

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