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Effects of ligand and cosolvent on oxidative coupling polymerization of 2,6-dimethylphenol catalyzed by chelating amine-copper(II) complexes

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Abstract

The influence of chelating amine ligands, copper precursors, and solvent composition on copper-catalyzed oxidative coupling of 2,6-dimethylphenol was investigated. The most efficient catalytic reaction was conducted with CuCl2-di-tert-butylethylenediamine (Dt-BEDA) complex in anisole or toluene with alcohol cosolvent. Slight structural changes in the N-substituent, backbone, or coordination atom of the ligand significantly dropped catalytic activities, leading to a low polymer yield. Alcohol cosolvent was necessary to synthesize a polymer of high molecular weight \(\left( {\overline {M_n } > 10,000} \right)\) with the copper(II) catalyst in toluene. With increasing alcohol ratios, the isolated yields and \(\overline {M_n }\) values of the resulting polymers gradually decreased. However, the use of sterically bulky t-butanol produced polymers of the desired molecular weight ranges with low polydispersity indexes (PDI, <2) and without a significant drop in isolated yield.

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Authors and Affiliations

  1. Department of Chemistry and Institute of Basic Science, Sungkyunkwan University, Gyeonggi, 440-746, Korea

    Mingu Kim, Xinhui Feng & Jaesook Yun

  2. Corporate Research Institute, Samsung Cheil Industries Inc, Gyeonggi, 437-711, Korea

    Yong Tae Kim & Joong-In Kim

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  1. Mingu Kim
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  2. Xinhui Feng
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  3. Yong Tae Kim
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  4. Joong-In Kim
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  5. Jaesook Yun
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Correspondence to Jaesook Yun.

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Kim, M., Feng, X., Kim, Y.T. et al. Effects of ligand and cosolvent on oxidative coupling polymerization of 2,6-dimethylphenol catalyzed by chelating amine-copper(II) complexes. Macromol. Res. 21, 1054–1058 (2013). https://doi.org/10.1007/s13233-013-1150-2

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  • DOI: https://doi.org/10.1007/s13233-013-1150-2

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