Highly orthogonal functionalization of ADMET polymers via photo-induced Diels-Alder reactions

Winkler, M., Mueller, J. O., Oehlenschlaeger, K. K., Montero De Espinosa, L., Meier, M. A. R., & Barner-Kowollik, C. (2012) Highly orthogonal functionalization of ADMET polymers via photo-induced Diels-Alder reactions. Macromolecules, 45(12).

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Abstract

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≥ M n ≥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. © 2012 American Chemical Society.

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40 citations in Web of Science®
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ID Code: 99331
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :33
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Meier, M.A.R.; Laboratory of Applied Chemistry, Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany; email: m.a.r.meier@kit.edu
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Keywords: ABC triblock copolymers, Bifunctional, Catalyst-free, Diels-Alder reaction, End groups, Functionalizations, Functionalized, Maleimides, One pot, Orthogonality, Photo-induced, Photoenol, Second generation, Temperature synthesis, Functional polymers, Olefins, Polymerization, Block copolymers
DOI: 10.1021/ma3007043
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: 30 Sep 2016 03:08

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