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The Azide–para-Fluoro Substitution on Polymers: Multi-purpose Precursors for Efficient Sequential Postpolymerization Modification

Noy, Janina-Miriam, Li, Yuman, Smolan, Willi and Roth, Peter J. (2019) The Azide–para-Fluoro Substitution on Polymers: Multi-purpose Precursors for Efficient Sequential Postpolymerization Modification Macromolecules, 52 (8). pp. 3083-3091.

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Abstract

The 2,3,4,5,6-pentafluorobenzyl group has become a popular reactive functionality in polymer chemistry because of its high susceptibility to para-fluoro substitution with thiols. Herein, it is demonstrated postpolymerization that the para-fluoride can be substituted using sodium azide and that the resulting 4-azido-2,3,5,6-tetrafluorobenzyl-functional polymers are versatile precursors for a multitude of onward modifications with click-like efficiencies. Quantitative azide–para-fluoro substitution was found for poly(2,3,4,5,6-pentafluorobenzyl methacrylate) and the related Passerini ester–amide (meth)acrylic (co)polymers when heated in DMF with sodium azide to 80 °C for 60–90 min. Conversely, the azidation of poly(2,3,4,5,6-pentafluorostyrene) under similar conditions resulted in ~90% substitution efficiency. Azide-functional (co-)polymers were thermally stable below 100 °C and were subsequently modified with (i) four different alkynes (CuBr, triethylamine, DMF, 55 °C, overnight) to give 1,4-substituted 1,2,3-triazoles in >95% conversions; (ii) potassium thioacetate (DMF, RT, 15 min) with quantitative amidation to the acetanilide derivative; and (iii) DL-dithiothreitol (methanol/DMF, RT, 90 min) resulting in complete reduction of the azides to primary amines, which were subsequently acylated with two different acyl chlorides. Products were characterized by 1H NMR, 19F NMR, and FT-IR spectroscopies, and size exclusion chromatography. Given their adaptability, perfluorophenylazides have large potential as multi-purpose intermediates in polymer and materials chemistry.

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
NameEmailORCID
Noy, Janina-Miriam
Li, Yumanyuman.li@surrey.ac.uk
Smolan, Willi
Roth, Peter J.p.roth@surrey.ac.uk
Date : 10 April 2019
DOI : 10.1021/acs.macromol.9b00109
Copyright Disclaimer : Copyright © 2019 American Chemical Society
Uncontrolled Keywords : Post-polymerization modification; Click Chemistry; CuAAC; Functional Polymers; Amide Bond
Depositing User : Clive Harris
Date Deposited : 26 Apr 2019 07:46
Last Modified : 11 Apr 2020 02:08
URI: http://epubs.surrey.ac.uk/id/eprint/851695

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