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Conjugated block copolymers

Conjugated block copolymers: A new approach to synthesize rod-coil block copolymers via consecutive Kumada catalyst-transfer polycondensation and nitroxide-mediated free radical polymerization performed from a bifunctional initiator, TIPNO­–Ph–Ni(dppp)–Br was developed. The utility of the method was exemplified in a preparation of a model block copolymer, P3HT–b–PS with a narrow molecular weight distribution.

Figure 1. Preparation of P3HT-PS block copolymer using bifunctional initiator.
Figure 2. Preparation of donor-acceptor block copolymers with covalently bonded fullerene C60. In the first step, styrene-based copolymers with either hydroxystyrene or hydroxyethyl methacrylate as comonomers were prepared. These polymers were reacted with bromine functionalized fullerene derivatives that had been prepared by the Bingel reaction.

References

  • Kaul, E. ; Senkovsky, V. ; Tkachov, R. ; Bocharova, V. ; Komber, H. ; Stamm, M. ; Kiriy, A. Synthesis of a bifunctional initiator for controlled kumada catalyst-transfer polycondensation/Nitroxide-mediated polymerization and preparation of poly(3-hexylthiophene)-polystyrene block copolymer therefrom Macromolecules 43 (2010) 77-81.
  • Heuken, M. ; Komber, H. ; Erdmann, T. ; Senkovskyy, V. ; Kiriy, A. ; Voit, B. Fullerene-Functionalized Donor–Acceptor Block Copolymers through Etherification as Stabilizers for Bulk Heterojunction Solar Cellsheterojunction solar cells more Macromolecules 45 (2012) 4101-4114.
  • T. Erdmann, R. Tkachov, A. Kiriy, J. Back, S. Ludwigs, and B. Voit, Synthesis of Dithienosilole-Based All-Conjugated Block Copolymers Quasi-Living Kumada Followed by Negishi Catalyst-Transfer Polycondensations, Polym. Chem. 5 (2014) 5383-5390.
  • Tkachov, R.; Komber, H.; Rauch, S.; Lederer, A.; Oertel, U.; Häußler, L.;, Voit, B.; Kiriy, A. A One-Pot Synthesis of All-Conjugated Block-Like Bisthiophene-Naphthalenediimide/Fluorene Copolymer. Macromolecules 47 (2014) 4994.