Skip to main content
SpringerLink
Log in

Synthesis and Pyrolysis of Soluble Cyclic Hf-Schiff Base Polymers

  • Rapid Communication
  • Published:
Chinese Journal of Polymer Science Aims and scope Submit manuscript

Abstract

Soluble Hf-containing polymers are significant processable precursors for the fabrication of ultra-high temperature ceramics. In this work, cyclic Hf-Schiff base polymers were synthesized via direct polymerization of hafnium alkoxide and bis-salen monomers. The defined structure and molecular weight of the polymers were characterized by NMR spectroscopy, gel permeation chromatography and MALDI-TOF mass spectroscopy. The feed ratio of monomers regulated the molecular weight and solubility of the polymers. This synthetic strategy features simple operation under ambient conditions, efficient reaction with high yield and cyclic polymers as the main products. The Hf-Schiff base polymers were converted to HfC/C materials after pyrolysis under argon at 1600 °C, which was identified by XRD measurements, elemental analyses and Raman spectroscopy. This work will inspire more precise and efficient synthesis and applications of metallopolymers.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

References

  1. Abd-El-Aziz, A. S.; Shipman, P. O.; Boden, B. N.; McNeil, W. S. Synthetic methodologies and properties of organometallic and coordination macromolecules. Prog. Polym. Sci. 2010, 35, 714–836.

    Article  CAS  Google Scholar 

  2. Winter, A.; Schubert, U. S. Synthesis and characterization of metallo-supramolecular polymers. Chem. Soc. Rev. 2016, 45, 5311–5357.

    Article  CAS  Google Scholar 

  3. Wang, Y.; Astruc, D.; Abd-El-Aziz, A. S. Metallopolymers for advanced sustainable applications. Chem. Soc. Rev. 2019, 48, 558–636.

    Article  CAS  Google Scholar 

  4. Schwizer, F.; Okamoto, Y.; Heinisch, T.; Gu, Y.; Pellizzoni, M. M.; Lebrun, V.; Reuter, R.; Kohler, V.; Lewis, J. C.; Ward, T. R. Artificial metalloenzymes: reaction scope and optimization strategies. Chem. Rev. 2018, 118, 142–231.

    Article  CAS  Google Scholar 

  5. Gu, H.; Mu, S.; Qiu, G.; Liu, X.; Zhang, L.; Yuan, Y.; Astruc, D. Redox-stimuli-responsive drug delivery systems with supramolecular ferrocenyl-containing polymers for controlled release. Coordin. Chem. Rev. 2018, 364, 51–85.

    Article  CAS  Google Scholar 

  6. Zaheer, M.; Schmalz, T.; Motz, G.; Kempe, R. Polymer derived nonoxide ceramics modified with late transition metals. Chem. Soc. Rev. 2012, 41, 5102–5116.

    Article  CAS  Google Scholar 

  7. Foucher, D. A.; Tang, B. Z.; Manners, I. Ring-opening polymerization of strained, ring-tilted ferrocenophanes: a route to high molecular weight poly(ferrocenylsilanes). J. Am. Chem. Soc. 1992, 114, 6246–6248.

    Article  CAS  Google Scholar 

  8. Hailes, R. L. N.; Oliver, A. M.; Gwyther, J.; Whittell, G. R.; Manners, I. Polyferrocenylsilanes: synthesis, properties, and applications. Chem. Soc. Rev. 2016, 45, 5358–5407.

    Article  CAS  Google Scholar 

  9. Du, J.; Yuan, W.; Zhang, H.; Li, H.; Li, Y.; Tang, B. Z. Ferrocene-based hyperbranched poly(phenyltriazolylcarboxylate)s: synthesis by phenylpropiolate-azide polycycloaddition and use as precursors to nanostructured magnetoceramics. Polym. Chem. 2019, 10, 5931–5938.

    Article  CAS  Google Scholar 

  10. Bouzat, F.; Darsy, G.; Foucaud, S.; Lucas, R. Group 4 metal-containing polymers: an overview. Polym. Rev. 2016, 56, 187–224.

    Article  CAS  Google Scholar 

  11. Ionescu, E.; Bernard, S.; Lucas, R.; Kroll, P.; Ushakov, S.; Navrotsky, A.; Riedel, R. Polymer-derived ultra-high temperature ceramics (UHTCs) and related materials. Adv. Eng. Mater. 2019, 21, 1900269.

    Article  CAS  Google Scholar 

  12. Wuchina, E.; Opeka, M.; Causey, S.; Buesking, K.; Spain, J.; Cull, A.; Routbort, J.; Guitierrez-Mora, F. Designing for ultrahigh-temperature applications: the mechanical and thermal properties of HfB2, HfCx, HfNx, and aHf(N). J. Mater. Sci. 2004, 39, 5939–5949.

    Article  CAS  Google Scholar 

  13. Padture, N. P. Advanced structural ceramics in aerospace propulsion. Nat. Mater. 2016, 15, 804–809.

    Article  CAS  Google Scholar 

  14. Carraher, C. E. Synthesis and thermal analysis of hafnium polyesters. Angew. Makromol. Chem. 1973, 28, 145–151.

    Article  CAS  Google Scholar 

  15. Carraher, C. E.; Jambaya, L. M. Initial synthesis and thermal characterization of hafnium polyethers. Angew. Makromol. Chem. 1976, 52, 111–116.

    Article  CAS  Google Scholar 

  16. Matsui, H.; Okada, A.; Kuroda, T.; Seguchi, Y.; Kawahara, T.; Yoshihara, M. Syntheses and electronic behaviors of net-worked, alternating hafnium-organic moiety hybrid copolymers. J. Mater. Sci. 2007, 42, 3964–3968.

    Article  CAS  Google Scholar 

  17. Pomogailo, A. D.; Rozenberg, A. S.; Dzhardimalieva, G. I.; Bochkin, A. M.; Pomogailo, S. I.; Golubeva, N. D.; Grishchenko, V. M. Hafnium-containing nanocomposites. Inorg. Mater. 2006, 42, 128–143.

    Article  CAS  Google Scholar 

  18. Inzenhofer, K.; Schmalz, T.; Wrackmeyer, B.; Motz, G. The preparation of HfC/C ceramics via molecular design. Dalton. Trans. 2011, 40, 4741–4745.

    Article  CAS  Google Scholar 

  19. Cheng, J.; Wang, X.; Wang, H.; Shao, C.; Wang, J. Preparation and high-temperature behavior of HfC-SiC nanocomposites derived from a non-oxygen single-source-precursor. J. Am. Ceram. Soc. 2017, 100, 5044–5055.

    Article  CAS  Google Scholar 

  20. Newkome, G. R.; Cho, T. J.; Moorefield, C. N.; Baker, G. R.; Cush, R.; Russo, P. S. Self- and directed assembly of hexaruthenium macrocycles. Angew. Chem. Int. Ed. 1999, 38, 3717–3721.

    Article  CAS  Google Scholar 

  21. Taylor, P. N.; Anderson, H. L. Cooperative self-assembly of double-strand conjugated porphyrin ladders. J. Am. Chem. Soc. 1999, 121, 11538–11545.

    Article  CAS  Google Scholar 

  22. Jiang, P.; Huang, W.; Li, J.; Zhuang, D.; Shi, J. A soluble coordination polymer and its sol-gel-derived amorphous films: synthesis and third-order nonlinear optical properties. J. Mater. Chem. 2008, 18, 3688–3693.

    Article  CAS  Google Scholar 

  23. Leung, A. C. W.; MacLachlan, M. J. Schiff base complexes in macromolecules. J. Inorg. Organomet. Polym. Mater. 2007, 17, 57–89.

    Article  CAS  Google Scholar 

  24. Whiteoak, C. J.; Salassa, G.; Kleij, A. W. Recent advances with π-conjugated salen systems. Chem. Soc. Rev. 2012, 41, 622–631.

    Article  CAS  Google Scholar 

  25. Liang, Y.; Duan, R. L.; Hu, C. Y.; Li, L. L.; Pang, X.; Zhang, W. X.; Chen, X. S. Salen-iron complexes: synthesis, characterization and their reactivity with lactide. Chinese J. Polym. Sci. 2018, 36, 185–189.

    Article  CAS  Google Scholar 

  26. Saha, T. K.; Ramkumar, V.; Chakraborty, D. Salen complexes of zirconium and hafnium: synthesis, structural characterization, controlled hydrolysis, and solvent-free ring-opening polymerization of cyclic esters and lactides. Inorg. Chem. 2011, 50, 2720–2722.

    Article  CAS  Google Scholar 

  27. Mandal, M.; Chakraborty, D. Group 4 complexes bearing bis(salphen) ligands: synthesis, characterization, and polymerization studies. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 809–824.

    Article  CAS  Google Scholar 

  28. Mandal, M.; Ramkumar, V.; Chakraborty, D. Salen complexes of zirconium and hafnium: synthesis, structural characterization and polymerization studies. Polym. Chem. 2019, 10, 3444–3460.

    Article  CAS  Google Scholar 

  29. Archer, R. D.; Illingsworth, M. L.; Rau, D. N.; Hardiman, C. J. A Soluble linear Schiff-base coordination polymer containing eight-coordinate zirconium(IV). Macromolecules 1985, 18, 1371–1376.

    Article  CAS  Google Scholar 

  30. Archer, R. D.; Wang, B. Synthesis and characterization of the thermally stable copolymer of tetrakis(salicylaldehydato-O,O′)zirconium(IV) and 3,3′-diaminobenzidine. Inorg. Chem. 1990, 29, 39–43.

    Article  CAS  Google Scholar 

  31. Sun, Y.; Chen, F.; Qiu, W.; Ye, L.; Han, W.; Zhao, W.; Zhou, H.; Zhao, T. Synthesis of rare earth containing single-phase multicomponent metal carbides via liquid polymer precursor route. J. Am. Ceram. Soc. 2020, 103, 6081–6087.

    Article  CAS  Google Scholar 

  32. Curreli, S.; Escudero-Adan, E. C.; Benet-Buchholz, J.; Kleij, A. W. A modular approach towards nonsymmetrical bis(metallosalen) building blocks. Eur. J. Inorg. Chem. 2008, 2008, 2863–2873.

    Article  CAS  Google Scholar 

  33. Solari, E.; Maltese, C.; Franceschi, F.; Floriani, C.; Chiesi-Villa, A.; Rizzoli, C. Geometrical isomerism and redox behaviour in zirconium-Schiff base complexes: the formation of C-C bonds functioning as two-electron reservoirs. J. Chem. Soc., Dalton. Trans. 1997, 2903–2910.

  34. Haque, F. M.; Grayson, S. M. The synthesis, properties and potential applications of cyclic polymers. Nat. Chem. 2020, 12, 433–444.

    Article  CAS  Google Scholar 

  35. Li, X.; Chan, Y. T.; Casiano-Maldonado, M.; Yu, J.; Carri, G. A.; Newkome, G. R.; Wesdemiotis, C. Separation and characterization of metallosupramolecular libraries by ion mobility mass spectrometry. Anal. Chem. 2011, 83, 6667–6674.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 21604090). The authors are grateful for helpful advices from Lianjun Zheng and Pingxia Zhang on the manuscript.

Author information

Authors and Affiliations

  1. Key Laboratory of Science and Technology on High-tech Polymer Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Yu-Huan Wu, Li Ye, Ya-Nan Sun, Wei-Jian Han & Tong Zhao

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Ya-Nan Sun & Tong Zhao

Authors
  1. Yu-Huan Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Li Ye
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ya-Nan Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Wei-Jian Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Tong Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Tong Zhao.

Electronic Supplementary Information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wu, YH., Ye, L., Sun, YN. et al. Synthesis and Pyrolysis of Soluble Cyclic Hf-Schiff Base Polymers. Chin J Polym Sci 39, 659–664 (2021). https://doi.org/10.1007/s10118-021-2566-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10118-021-2566-3

Keywords

Search

Navigation