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Synthesis and property of polyimines containing 2,2,4,4-tetramethyl-1,3-cyclobutadiimine moiety

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Abstract

Although 2,2,4,4-tetramethyl-1,3-cyclobutadione (TMCBDI) has been known for more than 50 years, it has never been used for synthesis of polymer primarily due to its inefficiency in direct polycondensation reaction. We report the first synthesis of high molecular weight polyimines prepared from TMCBDI using Pd-catalyzed Suzuki coupling polymerization. To overcome sluggish condensation polymerization of TMCBDI, it was first converted to diimine monomer containing phenyl bromide on both sides (compound 1) via condensation reaction and polymerized with three different examples aryl diboronate compounds (2a, 2b, 2c). The resulting polyimines (3a, 3b, 3c) were found to exist in a mixture of E and Z isomers in a ratio of 2:1. The number and weight average molecular weights of polyimines were high considering the rigidity of the backbone structure: 20,000 and 44,300 g/mol and 23,100 and 40,500 g/mol for 3a and 3b, respectively. They also showed good thermal stability over 340 °C and a high glass transition temperature over 220 °C. There was no observable photoluminescence from the polyimines in the range of 800 to 300 nm. Apparently, the TMCBDI moiety disrupts electron delocalization in conjugated backbone of polymer chains.

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References

  1. R. Adams, J. E. Bullock, and W. C. Wilson, J. Am. Chem. Soc., 45, 512 (1923).

    Google Scholar 

  2. G. F. D'lelio, J. V. Crivello, R. K. Schoenig, and T. F. Huemmer, J. Macromol. Sci., Part A: Chem., A1, 1161 (1967).

    Article  Google Scholar 

  3. P. W. Morgan, S. L. Kwolek, and T. C. Pletcher, Macromolecules, 20, 729 (1987).

    Article  CAS  Google Scholar 

  4. K. S. Lee, J. C. Won, and J. C. Jung, Makromol. Chem., 190, 1547 (1989).

    Article  CAS  Google Scholar 

  5. K. S. Lee and M. Samoc, Polym. Commun., 32, 361 (1991).

    Article  CAS  Google Scholar 

  6. C. J. Yang and S. A. Jenekhe, Chem. Mater., 3, 878 (1991).

    Article  CAS  Google Scholar 

  7. C. J. Yang and S. A. Jenekhe, Macromolecules, 28, 1180 (1995).

    Article  CAS  Google Scholar 

  8. S. Barik and W. G. Skene, Polym. Chem., 2, 1091 (2011).

    Article  CAS  Google Scholar 

  9. C. I. Simionescu, M. Grigoras, I. Cianga, and N. Olaru, Eur. Polym. J., 34, 891 (1998).

    Article  CAS  Google Scholar 

  10. M. Grigoras, I. Cianga, A. Farcas, G. Nastase, and M. Ivanoiu, Rev. Roum. Chim., 45, 703 (2000).

    CAS  Google Scholar 

  11. R. Gauderon, C. J. G. Plummer, J. G. Hilborn, and D. M. Knauss, Macromolecules 31, 501 (1998).

    Article  CAS  Google Scholar 

  12. M. Grigoras and N. C. Antonoaia, Polym. Int., 54, 1641 (2005).

    Article  CAS  Google Scholar 

  13. I. Mihai, M. Ivanoiu, L. Vacareanu, and M. Grigoras, Des. Monomers Polym., 15, 41 (2012).

    Article  CAS  Google Scholar 

  14. F. R. Diaz, J. Moreno, L. H. Tagle, G. A. East, and D. Radic, Synth. Met., 100, 187 (1999).

    Article  CAS  Google Scholar 

  15. R. H. Hasek, E. U. Elam, and J. C. Martin, J. Org. Chem., 26, 4340 (1961).

    Article  CAS  Google Scholar 

  16. J. J. Worman and E. A. Schmidt, J. Org. Chem., 35, 2463 (1970).

    Article  CAS  Google Scholar 

  17. J. M. Behan, R. A. W. Johnstone, J. J. Worman, and T. P. Fehlner, J. Mol. Struct., 40, 151 (1977).

    Article  CAS  Google Scholar 

  18. A. Naik, M. Ferro, and J. Worman, Org. Lett., 4, 1059 (2002).

    Article  CAS  Google Scholar 

  19. N. Miyaura and A. Suzuki, Chem. Rev., 95, 2457 (1995).

    Article  CAS  Google Scholar 

  20. M.-J. Park, J. Lee, I. H. Jung, J.-H. Park, H. Kong, J.-Y. Oh, D.-H. Hwang, and H.-K. Shim, J. Polym. Sci., Part A: Polym. Chem., 48, 82 (2010).

    Article  CAS  Google Scholar 

  21. A. Iwan and D. Sek, Prog. Polym. Sci., 33, 289 (2008).

    Article  CAS  Google Scholar 

  22. R. Tanoue, R. Higuchi, N. Enoki, Y. Miyasato, S. Uemura, N. Kimizuka, A. Z. Stieg, J. K. Gimzewski, and M. Kunitake, ACS Nano, 5, 3923 (2011).

    Article  CAS  Google Scholar 

  23. B. J. Landi, C. M. Evans, J. J. Worman, S. L. Castro, S. G. Bailey, and R. P. Raffaelle, Mater. Lett., 60, 3502 (2006).

    Article  CAS  Google Scholar 

  24. M. K. Choi, H. L. Kim, and D. H. Suh, J. Appl. Polym. Sci., 101, 1228 (2006).

    Article  CAS  Google Scholar 

  25. H. J. Kim, J. H. Lee, M. Lee, and T. S. Lee, React. Funct. Polym., 68, 1696 (2008).

    Article  CAS  Google Scholar 

  26. S. Clavaguera et al., J. Polym. Sci., Part A: Polym. Chem., 47, 4141 (2009).

    Article  CAS  Google Scholar 

  27. D. Urselmann, D. Antovic, and T. J. J. Muller, Beilstein J. Org. Chem., 7, 1499 (2011).

    Article  CAS  Google Scholar 

  28. U. Rant, U. Scherf, M. Rehahn, P. Galda, J. L. Brédas, and E. Zojer, Synth. Met., 127, 241 (2002).

    Article  CAS  Google Scholar 

  29. S. H. Jung, T. W. Lee, Y. C. Kim, D. H. Suh, and H. N. Cho, Opt. Mater., 21, 169 (2002).

    Article  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, University of Nevada Las Vegas, 4505 Maryland Parkway, Box 454003, Las Vegas, NV, 89154-4003, USA

    Yeong-Beom Lee, James J. Worman & Chulsung Bae

  2. Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, 110 8th Street, Troy, NY, 12180, USA

    Woo-Hyung Lee & Chulsung Bae

  3. Department of Chemical Engineering, Rochester Institute of Technology, 160 Lomb Memorial Drive, Rochester, NY, 14623, USA

    Annick Anctil & Brian Landi

Authors
  1. Yeong-Beom Lee
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  2. Woo-Hyung Lee
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  3. James J. Worman
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  4. Annick Anctil
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  5. Brian Landi
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  6. Chulsung Bae
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Correspondence to Chulsung Bae.

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Acknowledgments: The authors gratefully acknowledge NSF grant (DMR-0747667) and Rensselaer Polytechnic Institute (start-up) for generous support and Prof. James C. Selser (Department of Physics and Astronomy, University of Nevada Las Vegas) for use of DSC/TGA instruments.

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Lee, YB., Lee, WH., Worman, J.J. et al. Synthesis and property of polyimines containing 2,2,4,4-tetramethyl-1,3-cyclobutadiimine moiety. Macromol. Res. 25, 578–583 (2017). https://doi.org/10.1007/s13233-017-5119-4

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  • DOI: https://doi.org/10.1007/s13233-017-5119-4

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