Synthesis and characterization of bis(phenyl)fluorene-based cardo polyimide membranes for H2/CH4 separation

  • Caili ZhangEmail author


Three bis(phenyl)fluorene-based cardo diamine monomers with different side groups (–CF3, –H, and –CH3) were synthesized and used to synthesize three 6FDA-based polyimides (6FDA-FBPF, 6FDA-BPF, and 6FDA-MBPF). The influence of bis(phenyl)fluorene cardo moiety and different side groups on the glass transition temperature (Tg), thermal stabilities, and chain packing of the synthesized polyimides were systematically studied. The gas permeabilities and selectivities of three bis(phenyl)fluorene-based polyimide membranes were studied and correlated with their fractional free volumes and chain packing conditions. As a result, the obtained polyimides showed promising performance for hydrogen separation. Among the three polyimides, 6FDA-FBPF had the highest gas permeabilities which exhibited H2 permeability of 151.12 Barrer and H2/CH4 selectivity of 62.19. The high gas separation performance of 6FDA-FBPF mainly attributed to the ineffective chain packing via the incorporation of bi(phenyl)fluorene cardo moiety and introduction of bulky CF3 side groups into the polyimide backbones that is favorable to formation hourglass-shaped pores.



The author acknowledges the financial support of this work by the Natural Science Foundation of Beijing Municipality (2194071).

Compliance with ethical standards

Conflict of interest

The author declares no competing financial interest.

Supplementary material

10853_2019_3609_MOESM1_ESM.docx (1012 kb)
Characterizations. FTIR and HRMS spectra of bis(phenyl)fluorene-based diamine monomers. ATR-FTIR spectra, DSC curves, optical images, thermal properties, and organic solvents solubility of the synthesized bis(phenyl)fluorene-based polyimides (DOCX 1011 kb)


  1. 1.
    Koros W, Fleming G (1993) Membrane-based gas separation. J Membr Sci 83:1–80CrossRefGoogle Scholar
  2. 2.
    Sridhar S, Smitha B, Mayor S (2007) Gas permeation properties of polyamide membrane prepared by interfacial polymerization. J Mater Sci 42:9392–9401CrossRefGoogle Scholar
  3. 3.
    Li L, Wang C, Wang N, Gao Y, Wang T (2015) The preparation and gas separation properties of zeolite/carbon hybrid membranes. J Mater Sci 50:2561–2570. CrossRefGoogle Scholar
  4. 4.
    Zhang CL, Li P, Cao B (2017) Effects of the side groups of the spirobichroman-based diamines on the chain packing and gas separation properties of the polyimides. J Membr Sci 530:176–184. CrossRefGoogle Scholar
  5. 5.
    Zhang CL, Li P, Cao B (2017) Decarboxylation crosslinking of polyimides with high CO2/CH4 separation performance and plasticization resistance. J Membr Sci 528:206–216CrossRefGoogle Scholar
  6. 6.
    Zhang CL, Li P (2018) Preparation and gas separation properties of spirobichroman-based polyimides. Macromol Chem Phys 219:1800157CrossRefGoogle Scholar
  7. 7.
    Ghanem BS, Swaidan R, Litwiller E, Pinnau I (2014) Ultra-microporous triptycene-based polyimide membranes for high-performance gas separation. Adv Mater 26:3688–3692CrossRefGoogle Scholar
  8. 8.
    Rogan Y, Malpass-Evans R, Carta M, Lee M, Jansen JC, Bernardo P, Clarizia G, Tocci E, Friess K, Lanč M (2014) A highly permeable polyimide with enhanced selectivity for membrane gas separations. J Mater Chem A 2:4874–4877CrossRefGoogle Scholar
  9. 9.
    Wang Z, Wang D, Jin J (2014) Microporous polyimides with rationally designed chain structure achieving high performance for gas separation. Macromolecules 47:7477–7483CrossRefGoogle Scholar
  10. 10.
    Santiago-García JL, Álvarez C, Sánchez F, José G (2015) Gas transport properties of new aromatic polyimides based on 3, 8-diphenylpyrene-1, 2, 6, 7-tetracarboxylic dianhydride. J Membr Sci 476:442–448CrossRefGoogle Scholar
  11. 11.
    Weidman JR, Luo S, Zhang Q, Guo R (2017) Structure manipulation in triptycene-based polyimides through main chain geometry variation and its effect on gas transport properties. Ind Eng Chem Res 56:1868–1879CrossRefGoogle Scholar
  12. 12.
    Shrimant B, Dangat Y, Kharul UK, Wadgaonkar PP (2018) Intrinsically microporous polyimides containing spirobisindane and phenazine units: synthesis, characterization and gas permeation properties. J Polym Sci Pol Chem 56:766–775CrossRefGoogle Scholar
  13. 13.
    Ghanem BS, McKeown NB, Budd PM, Selbie JD, Fritsch D (2008) High-performance membranes from polyimides with intrinsic microporosity. Adv Mater 20:2766–2771CrossRefGoogle Scholar
  14. 14.
    Freeman BD (1999) Basis of permeability/selectivity tradeoff relations in polymeric gas separation membranes. Macromolecules 32:375–380CrossRefGoogle Scholar
  15. 15.
    Zhang CL, Yan J, Tian ZK, Liu XB, Cao B, Li P (2017) Molecular design of Troger’s base-based polymers containing spirobichroman structure for gas separation. Ind Eng Chem Res 56:12783–12788CrossRefGoogle Scholar
  16. 16.
    Budd PM, Elabas ES, Ghanem BS, Makhseed S, McKeown NB, Msayib KJ, Tattershall CE, Wang D (2004) Solution-processed, organophilic membrane derived from a polymer of intrinsic microporosity. Adv Mater 16:56–459CrossRefGoogle Scholar
  17. 17.
    Chen G, Zhang X, Zhang S, Chen T, Wu Y (2007) Synthesis, properties, and gas permeation performance of cardo poly (arylene ether sulfone)s containing phthalimide side groups. J Appl Polym Sci 106:2808–2816CrossRefGoogle Scholar
  18. 18.
    Xu Z, Dannenberg C, Springer J, Banerjee S, Maier G (2002) Gas separation properties of polymers containing fluorene moieties. Chem Mater 14:3271–3276CrossRefGoogle Scholar
  19. 19.
    Camacho-Zuniga C, Ruiz-Trevino F, Zolotukhin M, Del Castillo L, Guzman J, Chavez J, Torres G, Gileva N, Sedova E (2006) Gas transport properties of new aromatic cardo poly (aryl ether ketone)s. J Membr Sci 283:393–398CrossRefGoogle Scholar
  20. 20.
    Ghosh S, Banerjee S (2014) Fluorinated poly (arylene ether)s with aliphatic chain appended cardo moiety: synthesis and gas transport properties. J Membr Sci 470:535–546CrossRefGoogle Scholar
  21. 21.
    Lu Y, Hao J, Li L, Song J, Xiao G, Zhao H, Hu Z, Wang T (2017) Preparation and gas transport properties of thermally induced rigid membranes of copolyimide containing cardo moieties. React Funct Polym 119:134–144CrossRefGoogle Scholar
  22. 22.
    Yahaya GO, Mokhtari I, Alghannam AA, Choi SH, Maab H, Bahamdan AA (2017) Cardo-type random co-polyimide membranes for high pressure pure and mixed sour gas feed separations. J Membr Sci 550:526–535CrossRefGoogle Scholar
  23. 23.
    Hernández-Martínez H, Ruiz-Treviño FA, Ortiz-Espinoza J, Aguilar-Vega MJ, Zolotukhin MG, Marcial-Hernandez R, Olvera LI (2018) Simultaneous thermal cross-linking and decomposition of side groups to mitigate physical aging in poly (oxyindole biphenylylene) gas separation membranes. Ind Eng Chem Res 57:4640–4650CrossRefGoogle Scholar
  24. 24.
    Zhang CL, Cao B, Li P (2018) Thermal oxidative crosslinking of phenolphthalein-based cardo polyimides with enhanced gas permeability and selectivity. J Membr Sci 546:90–99CrossRefGoogle Scholar
  25. 25.
    Bos A, Pünt I, Wessling M, Strathmann H (1998) Plasticization-resistant glassy polyimide membranes for CO2/CH4 separations. Sep Purif Technol 14:27–39CrossRefGoogle Scholar
  26. 26.
    Qiu W, Chen CC, Xu L, Cui L, Paul DR, Koros WJ (2011) Sub-Tg cross-linking of a polyimide membrane for enhanced CO2 plasticization resistance for natural gas separation. Macromolecules 44:6046–6056CrossRefGoogle Scholar
  27. 27.
    Puleo AC, Paul DR, Kelley SS (1989) The effect of degree of acetylation on gas sorption and transport behavior in cellulose acetate. J Membr Sci 47:301–332CrossRefGoogle Scholar
  28. 28.
    Aitken CL, Koros WJ, Paul DR (1992) Effect of structural symmetry on gas transport properties of polysulfones. Macromolecules 25:17–42Google Scholar
  29. 29.
    Sanders DF, Smith ZP, Guo R, Robeson LM, Mcgrath JE, Paul DR, Freeman BD (2013) Energy-efficient polymeric gas separation membranes for a sustainable future: a review. Polymer 54:4729–4761CrossRefGoogle Scholar
  30. 30.
    Huang Y, Paul DR (2007) Effect of film thickness on the gas-permeation characteristics of glassy polymer membranes. Ind Eng Chem Res 46:2342–2347CrossRefGoogle Scholar
  31. 31.
    Bernardo P, Bazzarelli F, Tasselli F, Clarizia G, Mason C, Maynard-Atem L, Budd P, Lanč M, Pilnáček K, Vopička O (2017) Effect of physical aging on the gas transport and sorption in PIM-1 membranes. Polymer 113:283–294CrossRefGoogle Scholar
  32. 32.
    Tiwari RR, Jin J, Freeman B, Paul D (2017) Physical aging, CO2 sorption and plasticization in thin films of polymer with intrinsic microporosity (PIM-1). J Membr Sci 537:362–371CrossRefGoogle Scholar
  33. 33.
    Wiegand JR, Smith ZP, Liu Q, Patterson CT, Freeman BD, Guo R (2014) Synthesis and characterization of triptycene-based polyimides with tunable high fractional free volume for gas separation membranes. J Mater Chem A 2:13309–13320CrossRefGoogle Scholar
  34. 34.
    Robeson LM (2008) The upper bound revisited. J Membr Sci 320:390–400CrossRefGoogle Scholar
  35. 35.
    Robeson LM (1991) Correlation of separation factor versus permeability for polymeric membranes. J Membr Sci 62:165–185CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Materials Science and Mechanical EngineeringBeijing Technology and Business UniversityBeijingChina

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