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    Highly Orthogonal Functionalization of ADMET Polymers via Photo-Induced Diels–Alder Reactions
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    † Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76128 Karlsruhe, Germany
    ‡ Laboratory of Applied Chemistry, Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe
    *E-mail: (C.B.-K.) [email protected]; (M.A.R.M.): [email protected]
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    Macromolecules

    Cite this: Macromolecules 2012, 45, 12, 5012–5019
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    https://doi.org/10.1021/ma3007043
    Published June 7, 2012
    Copyright © 2012 American Chemical Society
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    Abstract

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    Within the current contribution, we introduce two strategies for the catalyst-free, modular, ambient temperature synthesis of ABC triblock copolymers via photoinduced Diels–Alder reactions. On the one hand, the 2-formyl-3-methylphenoxy (FMP) moiety (a second generation photoenol precursor) was employed for orthogonal polymer–polymer conjugations using terminal acrylates of diblock copolymers synthesized via acyclic-diene-metathesis (ADMET) polymerizations to directly prepare triblock copolymers. On the other hand, the disparate reactivity of 2,5-dimethylbenzophenone (first generation photoenol) and the FMP moiety was exploited to selectively synthesize complex triblock copolymers (6.5 kDa≤ Mn ≤11.5 kDa, 1.16≤ PDI ≤ 1.30) via a sequential one pot approach utilizing the extraordinary orthogonality of the photoinduced Diels–Alder reaction. Polymers functionalized with a photoenol (second generation) moiety were employed for conjugation reactions with polymers featuring an acrylate terminus, while polymers having a photoenol (first generation) end group were employed for selective conjugations of maleimide functional polymers. In this context, the selective head-to-tail ADMET polymerization was employed as a straightforward methodology for the preparation of bifunctional polymers having a terminal acrylate and a photoenol end-group.

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    Additional NMR spectra, SEC analyses, and ESI–MS spectra/analyses related to the present investigation. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Macromolecules

    Cite this: Macromolecules 2012, 45, 12, 5012–5019
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ma3007043
    Published June 7, 2012
    Copyright © 2012 American Chemical Society
    Request reuse permissions

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