Novel benzimidazole and pyridine-containing poly(ether ether ketone) s with good solubility, thermal properties and fluorescence

  • Hongyang Deng
  • Yewei XuEmail author
  • Hong Lei
  • Yonglin Lei
  • Jichuan Huo
  • Lin ZhangEmail author


3,5-bis(2-benzimidazolyl) pyridine (3,5-BP) is synthesized and a series of benzimidazolyl and pyridyl-containing poly (ether ether ketone) s (mPEEK-BPs) with precise structures and high yield are prepared through a nucleophilic displacement reaction of 3,5-BP, m-dihydroxybenzene and 4,4′-difluorobenzophenone. X-ray diffraction results show that mPEEK-BPs are amorphous. All the synthesized polymers posses high glass transition temperatures (Tg = 211~270 °C) and high thermal stability (Td5% = 506~549 °C in N2, 471~564 °C in air). The polymers have good solubilities in common organic solvents. With the increase of benzimidazole and pyridine units content, the thermal properties and solubility of the as-prepared polymers improved. Additionally, the resulted polymers exhibit excellent fluorescence performance and the fluorescence emission peak appears at 425 nm.


PEEKs Solubility Thermal properties Fluorescence properties Benzimidazole· pyridine 



This work was supported by the Scientific Research Fund of Sichuan Provincial Education Department (No. 16ZB0146), National Natural Science Foundation of China (No. 51602267) and Longshan academic talent research supporting program of SWUST (No. 18LZX552).


  1. 1.
    Panayotov IV, Orti V, Cuisinier F, Yachouh J (2016) Polyetheretherketone (PEEK) for medical applications. J Mater Sci Mater M 27:118–128CrossRefGoogle Scholar
  2. 2.
    Shekar RI, Kotresh TM, Rao PMD, Kumar K (2009) Properties of high modulus PEEK yarns for aerospace applications. J Appl Polym Sci 112:2497–2510CrossRefGoogle Scholar
  3. 3.
    Sun HD, Lv YX, Zhang CY, Zuo XD, Li MZ, Yue XG, Jiang ZH (2018) Materials with low dielectric constant and loss and good thermal properties prepared by introducing perfluorononenyl pendant groups onto poly(ether ether ketone). RSC Adv 28:7753–7760CrossRefGoogle Scholar
  4. 4.
    More AS, Pasale SK, Honkhambe PN, Wadgaonkar PP (2011) Synthesis and characterization of organo-soluble poly(ether ether ketone)s and poly(ether ether ketone ketone)s containing pendant pentadecyl chains. J Appl Polym Sci 121:3689–3695CrossRefGoogle Scholar
  5. 5.
    Ouellette ES, Gilbert JL (2015) Production and characterization of melt-spun Poly(Ether Ether Ketone) fibers for biomedical applications. Polymer 63:10–18CrossRefGoogle Scholar
  6. 6.
    Connell JW, Smith JG, Hergenrother PM, Criss JM (2003) High temperature transfer molding resins: laminate properties of PETI-298 and PETI-330. High Perform Polym 15:375–394CrossRefGoogle Scholar
  7. 7.
    Na RQ, Liu JY, Wang GB, Zhang SL (2018) Light weight and flexible poly(ether ether ketone) based composite film with excellent thermal stability and mechanical properties for wide-band electromagnetic interference shielding. RSC Adv 8:3296–3303CrossRefGoogle Scholar
  8. 8.
    Balaji V, Tiwari AN, Goyal RK (2011) Fabrication and properties of high performance PEEK/Si3N4 nanocomposites. J Appl Polym Sci 119:311–318CrossRefGoogle Scholar
  9. 9.
    Liu Z, Li XB, Shen KZ, Feng PJ, Zhang YN, Xu X, Hu W, Jiang ZH, Liu BJ, Guiver MD (2013) Naphthalene-based poly(arylene ether ketone) anion exchange membranes. J Mater Chem A 1:6481–6488CrossRefGoogle Scholar
  10. 10.
    Li D, Shi DQ, Feng K, Li XF, Zhang HM (2017) Poly(ether ether ketone) (PEEK) porous membranes with super high thermal stability and high rate capability for lithium-ion batteries. J Membr Sci 530:125–131CrossRefGoogle Scholar
  11. 11.
    Wang W, Lu XF, Li ZY, Lei JY, Liu XC, Wang ZJ, Zhang HN, Wang C (2011). One-dimensional polyelectrolyte/polymeric semiconductor core/shell structure: sulfonated poly(arylene ether ketone)/polyaniline nanofibers for organic field-effect transistors. Adv Mater 23:5109–5112CrossRefGoogle Scholar
  12. 12.
    Nag S, Castro M, Choudhary V, Feller JF (2017) Sulfonated poly(ether ether ketone) [SPEEK] nanocomposites based on hybrid nanocarbons for the detection and discrimination of some lung cancer VOC biomarkers. J Mater Chem B 5:348–359CrossRefGoogle Scholar
  13. 13.
    Gao CC, Wang Y, Han FX, Yuan ZQ, Li Q, Shi C, Cao WW, Zhou PH, Xing XD, Li B (2017) Antibacterial activity and osseointegration of silver-coated poly(ether ether ketone) prepared using the polydopamine-assisted deposition technique. J Mater Chem B 5:9326–9336CrossRefGoogle Scholar
  14. 14.
    Liaw DJ, Hsu CY, Liaw BY (2001) Synthesis and characterization of new highly organosoluble poly(ether imide)s derived from 1,1-bis[4-(4-dicarboxyphenoxy)phenyl]-4-tert-butylcyclohexane dianhydride. Polymer 42:7993–7998CrossRefGoogle Scholar
  15. 15.
    Hergenrother PM, Havens SJ (1994) Polyimides Containing Quinoxaline and Benzimidazole Units. Macromolecules 27:4659–4664CrossRefGoogle Scholar
  16. 16.
    Pramanik Kar SKK (2012) Functionalized poly(ether ether ketone): Improved mechanical property and acellular bioactivity. J Appl Polym Sci 123:1100–1111CrossRefGoogle Scholar
  17. 17.
    Wang CY, Tan JH, Peng WY, Li G, Jiang JM (2008) High glass transitions and fluorescence of novel organosoluble poly(arylene ether)s containing kink noncoplanar heterocyclic structures. Polym Bull 61:299–309CrossRefGoogle Scholar
  18. 18.
    Colquhoun HM, Hodge P, Paoloni FPV, McGrail PT, Cross P (2009) Reversible, nondegradative conversion of crystalline aromatic poly(ether ketone)s into organo-soluble poly(ether dithioketal)s. Macromolecules 42:1955–1963CrossRefGoogle Scholar
  19. 19.
    Liu YJ, Jian XG, Liu SJ (2001) Synthesis and properties of novel poly(phthalazinone ether ketone ketone). J Appl Polym Sci 82:823–826CrossRefGoogle Scholar
  20. 20.
    Xu YW, Feng JA, Ren HB, Bi YT, Zhu JY, Sun Y, Wen SY, Huo JC, Zhang L (2017) Thermal stability, solubility, and fluorescence property of poly(arylene ether ketone)s bearing N-arylenebenzimidazole units. J Polym Res 24:90–97CrossRefGoogle Scholar
  21. 21.
    Xu YW, Sun Y, Lei YL, Huo JC, Zhang L (2015) Synthesis of N-substituted poly(benzimidazole ketone ketone)s containing pyridine rings. High Perform Polym 27:326–331CrossRefGoogle Scholar
  22. 22.
    Xu YW, Cui XW, Zhu FH, Luo X, Yin Q, Zhang L (2014) Synthesis of soluble and thermally stable poly(N-arylenebenzimidazole)s. Polym Int 63:537–545CrossRefGoogle Scholar
  23. 23.
    Michalska ZM, Ostaszewski B, Zientarska J, Rynkowski JM (2002) Novel polymer-supported platinum catalyst for selective hydrogenation of crotonaldehyde. J Mol Catal A Chem 185:279–283CrossRefGoogle Scholar
  24. 24.
    Schubert US, Eschbaumer C (2002) Makromoleküle mit Bipyridin- und Terpyridinkomplexen als Verknüpfungsstellen: erste Schritte auf dem Weg zu metallo-supramolekularen Polymeren. Angew Chem Int Ed 114:3016–3050CrossRefGoogle Scholar
  25. 25.
    Tong L, Thummel RP (2016) Mononuclear ruthenium polypyridine complexes that catalyze water oxidation. Chem Sci 7:6591–6603CrossRefGoogle Scholar
  26. 26.
    Cheng W, Yang L, Chang GJ (2018) Recyclable Cu(II)-coordination crosslinked poly(benzimidazolyl pyridine)s as high performance polymers. Macromol Rapid Comm 39:1700573–1700578Google Scholar
  27. 27.
    Yang P, Yang L, Yang JX, Luo X, Chang GJ (2019) Synthesis of a metal-coordinated N-substituted polybenzimidazole pyridine sulfone and method for the nondestructive analysis of thermal stability. High Perform Polym 31:238–246CrossRefGoogle Scholar
  28. 28.
    Sannigrahi A, Arunbabu D, Sankar RM, Jana T (2007) Aggregation behavior of polybenzimidazole in aprotic polar solvent. Macromolecules 40:2844–2851CrossRefGoogle Scholar
  29. 29.
    Ghosh S, Sannigrahi A, Maity S, Jana T (2010) Role of solvent protic character on the aggregation behavior of polybenzimidazole in solution. J Phys Chem B 114:3122–3132CrossRefGoogle Scholar
  30. 30.
    Park J, Jeong YG (2015) Effects of chain orientation and packing on the photoluminescence and photothermal properties of polybenzimidazole fibers with meta-linkage. Macromolecules 48:8823–8830CrossRefGoogle Scholar

Copyright information

© The Polymer Society, Taipei 2019

Authors and Affiliations

  1. 1.Science and Technology on Plasma Physics Laboratory, Research Center of Laser FusionChina Academy of Engineering PhysicsMianyangPeople’s Republic of China
  2. 2.State Key Laboratory of Environmental Friendly Energy Materials & School of Material Science and EngineeringSouthwest University of Science and TechnologyMianyangPeople’s Republic of China

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