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Issue 4, 2012
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High molecular weight acrylonitrilebutadiene architectures via a combination of RAFT polymerization and orthogonal copper mediated azidealkyne cycloaddition

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Abstract

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). Polymerpolymer coupling afforded linear polymers with molecular weights ranging from 2500 g mol−1 to 97 000 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 azidealkyne cycloaddition was extended towards the side-chain modification of acrylonitrilebutadiene 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.

Graphical abstract: High molecular weight acrylonitrile–butadiene architectures via a combination of RAFT polymerization and orthogonal copper mediated azide–alkyne cycloaddition

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Publication details

The article was received on 15 Nov 2011, accepted on 08 Jan 2012 and first published on 07 Feb 2012


Article type: Paper
DOI: 10.1039/C2PY00547F
Citation: Polym. Chem., 2012,3, 1048-1060
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    High molecular weight acrylonitrilebutadiene architectures via a combination of RAFT polymerization and orthogonal copper mediated azidealkyne cycloaddition

    C. J. Dürr, S. G. J. Emmerling, P. Lederhose, A. Kaiser, S. Brandau, M. Klimpel and C. Barner-Kowollik, Polym. Chem., 2012, 3, 1048
    DOI: 10.1039/C2PY00547F

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