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2,6-Bis-benzimidazolylpyridines as new catalyst in copper-based ATRP

Abstract

The ligands, 2,6-bis(NH-benzimidazol-2-yl)pyridine (L1) and 2,6-bis(N-methyl-benzimidazol-2-yl)pyridine (L2), were synthesized by a one-step reaction of 2,6-pyridinedicarboxylic acid with a diamine (o-phenylenediamine or N-methyl-1,2-phenylenediamine), respectively, in syrupy phosphoric acid at ca. 200 °C. Their efficiency as a catalyst in Cu-based atom transfer radical polymerizations (ATRP) of methylmethacrylate (MMA) was investigated. The linear first-order kinetic plots were observed; indicating that the number of active species is constant during the polymerization and termination reactions are limited. The apparent rate constant values of ATRP of MMA with CuCl/L1 catalyst system at 90 °C in acetonitrile were found to be between 3.83 × 10−5 and 1.33 × 10−4 s−1, while they were between 1.86 × 10−4 and 4.40 × 10−4 s−1 in the case of CuCl/L2 catalyst, indicating the presence of lower radical concentration throughout the polymerization of MMA using CuCl/L1 catalyst system. In both the cases, low apparent rate constant values are obtained. This indicates that ATRP proceeded at reasonable rates and a good control over ATRP in general. Apparent rate constant vs [ligand]/[catalyst] ratio plots showed a maximum at the [ligand]/[catalyst] ratio of two. M n,GPC values increased slightly linearly with conversion and molecular weight values were closer to M n,th in the case of ATRP of MMA using CuCl/L2 catalyst complex. Cyclic voltammetry measurements confirmed that CuCl/L1 and CuCl/L2 complexes in acetonitrile give reversible redox couples and copper(I) centers in CuCl/L1 and CuCl/L2 catalyst complexes that are readily oxidized and they potentially suit to facile ATRP.

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Acknowledgments

This work was supported by Bülent Ecevit University Research Fund, Turkey (BAP Project No: 2015-72118496-06 and BAP Project No: 2012-10-03-02).

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Arslan, H., Avcı, Ç., Tutkun, B. et al. 2,6-Bis-benzimidazolylpyridines as new catalyst in copper-based ATRP. Polym. Bull. 74, 931–948 (2017). https://doi.org/10.1007/s00289-016-1754-8

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  • DOI: https://doi.org/10.1007/s00289-016-1754-8

Keywords

  • 2,6-Bis(NH-benzimidazol-2-yl)pyridine
  • 2,6-Bis(N-methyl-benzimidazol-2-yl)pyridine
  • Cu-based atom transfer radical polymerization
  • Cyclic voltametry measurements