Abstract

The promise of ultrapermeable polymers, such as poly(trimethylsilylpropyne) (PTMSP), for reducing the size and increasing the efficiency of membranes for gas separations remains unfulfilled due to their poor selectivity. We report an ultrapermeable polymer of intrinsic microporosity (PIM-TMN-Trip) that is substantially more selective than PTMSP. From molecular simulations and experimental measurement we find that the inefficient packing of the two-dimensional (2D) chains of PIM-TMN-Trip generates a high concentration of both small (<0.7 nm) and large (0.7–1.0 nm) micropores, the former enhancing selectivity and the latter permeability. Gas permeability data for PIM-TMN-Trip surpass the 2008 Robeson upper bounds for O2/N2, H2/N2, CO2/N2, H2/CH4 and CO2/CH4, with the potential for biogas purification and carbon capture demonstrated for relevant gas mixtures. Comparisons between PIM-TMN-Trip and structurally similar polymers with three-dimensional (3D) contorted chains confirm that its additional intrinsic microporosity is generated from the awkward packing of its 2D polymer chains in a 3D amorphous solid. This strategy of shape-directed packing of chains of microporous polymers may be applied to other rigid polymers for gas separations.

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References

  1. 1.

    & Gas separation membrane materials: a perspective. Macromolecules 47, 6999–7013 (2014).

  2. 2.

    , & Membrane gas separation: a review/state of the art. Ind. Eng. Chem. Res. 48, 4638–4663 (2009).

  3. 3.

    , , & Advances in high permeability polymeric membrane materials for CO2 separations. Energy Envron. Sci. 5, 7306–7322 (2012).

  4. 4.

    & Highly permeable polymers for gas separation membranes. Polym. Chem. 1, 63–68 (2010).

  5. 5.

    et al. Advances in high permeability polymer-based membrane materials for CO2 separations. Energy Envron. Sci. 9, 1863–1890 (2016).

  6. 6.

    , , & Poly 1-(trimethylsilyl)-1-propyne—a new high polymer synthesized with transition-metal catalysts and characterized by extremely high gas-permeability. J. Am. Chem. Soc. 105, 7473–7474 (1983).

  7. 7.

    , , , & Synthesis and properties of indan-based polyacetylenes that feature the highest gas permeability among all the existing polymers. Macromolecules 41, 8525–8532 (2008).

  8. 8.

    , & Polymerization of substituted acetylenes and features of the formed polymers. Polym. Chem. 2, 1044–1058 (2011).

  9. 9.

    , , & Structural, sorption and transport characteristics of an ultrapermeable polymer. J. Membr. Sci. 314, 15–23 (2008).

  10. 10.

    et al. Polymers of intrinsic microporosity (PIMs): robust, solution-processable, organic nanoporous materials. Chem. Commun.230–231 (2004).

  11. 11.

    et al. Gas permeation parameters and other physicochemical properties of a polymer of intrinsic microporosity: polybenzodioxane PIM-1. J. Membr. Sci. 325, 851–860 (2008).

  12. 12.

    et al. Gas separation membranes from polymers of intrinsic microporosity. J. Membr. Sci. 251, 263–269 (2005).

  13. 13.

    & Rigid and microporous polymers for gas separation membranes. Prog. Polym. Sci. 43, 1–32 (2015).

  14. 14.

    et al. Highly permeable benzotriptycene-based polymer of intrinsic microporosity. ACS Macro Lett. 4, 912–915 (2015).

  15. 15.

    et al. The enhancement of chain rigidity and gas transport performance of polymers of intrinsic microporosity via intramolecular locking of the spiro-carbon. Chem. Commun. 52, 6553–6556 (2016).

  16. 16.

    et al. Triptycene induced enhancement of membrane gas selectivity for microporous Troger’s base polymers. Adv. Mater. 26, 3526–3531 (2014).

  17. 17.

    , , & Ultra-microporous triptycene-based polyimide membranes for high-performance gas separation. Adv. Mater. 26, 3688–3692 (2014).

  18. 18.

    , , , & Energy-efficient hydrogen separation by AB-type ladder-polymer molecular sieves. Adv. Mater. 26, 6696–6700 (2014).

  19. 19.

    et al. An efficient polymer molecular sieve for membrane gas separations. Science 339, 303–307 (2013).

  20. 20.

    , & Fine-tuned intrinsically ultramicroporous polymers redefine the permeability/selectivity upper bounds of membrane-based air and hydrogen separations. ACS Macro Lett. 4, 947–951 (2015).

  21. 21.

    , , , & Targeted synthesis of a mesoporous triptycene-derived covalent organic framework. CrystEngComm 15, 1524–1527 (2013).

  22. 22.

    , , , & A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization. Nat. Chem. 6, 774–778 (2014).

  23. 23.

    et al. Large area synthesis of a nanoporous two-dimensional polymer at the air/water interface. J. Am. Chem. Soc. 137, 3450–3453 (2015).

  24. 24.

    et al. A triptycene-based polymer of intrinsic microposity that displays enhanced surface area and hydrogen adsorption. Chem. Commun.67–69 (2007).

  25. 25.

    et al. Triptycene-based polymers of intrinsic microporosity: organic materials that can be tailored for gas adsorption. Macromolecules 43, 5287–5294 (2010).

  26. 26.

    et al. Perpendicular organization of macromolecules: synthesis and alignment studies of a soluble poly(iptycene). J. Am. Chem. Soc. 127, 17976–17977 (2005).

  27. 27.

    et al. Two-dimensional and related polymers: concepts, synthesis, and their potential application as separation membrane materials. Polym. Rev. 55, 57–89 (2015).

  28. 28.

    & Rationally synthesized two-dimensional polymers. Nat. Chem. 5, 453–465 (2013).

  29. 29.

    , , & Two-dimensional polymers: concepts and perspectives. Chem. Commun. 52, 18–34 (2016).

  30. 30.

    , , , & Two-dimensional soft nanomaterials: a fascinating world of materials. Adv. Mater. 27, 403–427 (2015).

  31. 31.

    et al. The synthesis of organic molecules of intrinsic microporosity designed to frustrate efficient molecular packing. Chem. Eur. J. 22, 2466–2472 (2016).

  32. 32.

    , & Polymatic: a generalized simulated polymerization algorithm for amorphous polymers. Theor. Chem. Acc. 132, 1334 (2013).

  33. 33.

    , , & Molecular simulations of PIM-1-like polymers of intrinsic microporosity. Macromolecules 44, 6944–6951 (2011).

  34. 34.

    , & Elucidating the mechanism(s) of gas-transport in poly 1-(trimethylsilyl)-1-propyne (PTMSP) membranes. J. Membr. Sci. 86, 67–86 (1994).

  35. 35.

    , & An investigation of the high gas-permeability of poly (1-trimethylsilyl-1-propyne). J. Membr. Sci. 34, 5–18 (1987).

  36. 36.

    , , & Sorption and transport of hydrocarbon and perfluorocarbon gases in poly(1-trimethylsilyl-1-propyne). J. Polym. Sci. B 38, 273–296 (2000).

  37. 37.

    , , & Polyacetylene derivatives as membranes for gas separation. Gas Sep. Purif. 2, 3–8 (1988).

  38. 38.

    The upper bound revisited. J. Membr. Sci. 320, 390–400 (2008).

  39. 39.

    , & Defect-free PIM-1 hollow fiber membranes. J. Membr. Sci. 530, 33–41 (2017).

  40. 40.

    , , & Physical aging, plasticization and their effects on gas permeation in ‘rigid’ polymers of intrinsic microporosity. Macromolecules 48, 6553–6561 (2015).

  41. 41.

    , , , & Poly 1-(trimethylsilyl)-1-propyne and related polymers: synthesis, properties and functions. Prog. Polym. Sci. 26, 721–798 (2001).

  42. 42.

    , , & Mixed-gas permeation of syngas components in poly(dimethylsiloxane) and poly(1-trimethylsilyl-1-propyne) at elevated temperatures. J. Membr. Sci. 191, 85–94 (2001).

  43. 43.

    , , & Gas-permeability of polyacetylenes carrying substituents. J. Appl. Polym. Sci. 30, 1605–1616 (1985).

  44. 44.

    , , & Impact of thermal ageing on sorption and diffusion properties of PTMSP. J. Membr. Sci. 270, 123–131 (2006).

  45. 45.

    , & Polymerization of silicon-containing diphenylacetylenes and high gas-permeability of the product polymers. Macromolecules 25, 5816–5820 (1992).

  46. 46.

    et al. A dense membrane contactor for intensified CO2 gas/liquid absorption in post-combustion capture. J. Membr. Sci. 377, 261–272 (2011).

  47. 47.

    et al. Robust high-permeance PTMSP composite membranes for CO2 membrane gas desorption at elevated temperatures and pressures. J. Membr. Sci. 470, 439–450 (2014).

  48. 48.

    & Transport of organic vapors through poly(1-trimethylsilyl-1-propyne). J. Membr. Sci. 116, 199–209 (1996).

  49. 49.

    , , & Pure and mixed gas CH4 and n-C4H10 permeability and diffusivity in poly(1-trimethylsilyl-1-propyne). Polymer 48, 7329–7344 (2007).

  50. 50.

    et al. Extraction of butanol from aqueous solutions by pervaporation through poly(1-trimethylsilyl-1-propyne). J. Membr. Sci. 186, 205–217 (2001).

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Acknowledgements

The research leading to these results has received funding from the Horizon 2020/FP7 Framework Program under grant agreement no. 608490, project M4CO2 and from the EPSRC (UK) grant numbers EP/M01486X/1 and EP/K008102/2. This work was also supported by the US National Science Foundation (DMR-1604376) and the Leverhulme Trust, UK (RPG-2014-308). High-performance computational resources were provided by the University of Florida Research Computing and the Research Computing and Cyberinfrastructure unit at Pennsylvania State University.

Author information

Affiliations

  1. EastChem, School of Chemistry, University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK

    • Ian Rose
    • , C. Grazia Bezzu
    • , Mariolino Carta
    • , Bibiana Comesaña-Gándara
    •  & Neil B. McKeown
  2. School of Engineering, University of Edinburgh, Robert Stevenson Road, Edinburgh EH9 3FB, UK

    • Elsa Lasseuguette
    •  & M. Chiara Ferrari
  3. Institute on Membrane Technology, ITM-CNR, Via P. Bucci 17/C, 87036 Rende (CS), Italy

    • Paola Bernardo
    • , Gabriele Clarizia
    • , Alessio Fuoco
    •  & Johannes C. Jansen
  4. Department of Materials Science and Engineering, Pennsylvania State University, University Park, Pennsylvania 16802, USA

    • Kyle E. Hart
  5. Department of Chemistry, University of Florida, 318 Leigh Hall, PO Box 117200, Gainesville, Florida 32611-7200, USA

    • Thilanga P. Liyana-Arachchi
    •  & Coray M. Colina

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Contributions

I.R. prepared PIM-TMN-Trip. C.G.B. prepared PIM-TMN-SBI and performed the crystallographic study of the monomers. M.C. prepared the films for gas permeability and coordinated the experimental part of the project. B.C.G. verified the synthesis of PIM-TMN-Trip and performed the WAXS analysis. E.L. performed the high-temperature gas permeability measurements. M.C.F. performed the gas adsorption measurements and Horvath–Kawazoe analysis of pore-size distribution and designed the high-temperature gas permeability experiments. P.B. designed and performed the film conditioning protocol and carried out the elaboration of the single-gas permeability data to evaluate the transport parameters (Table 1: data series 1–5, 8–10). C.G. performed the single gas permeability measurements (Table 1: data series 1–5, 8–10), A.F. performed the single gas permeability measurements (Table 1: data series 6) and the elaboration of the data. J.C.J. performed the mixed gas experiments, the density and tensile strength analysis and supervised the gas permeability work and data elaboration. K.E.H. devised the methodology for simulation and analysis of the chain packing of PIMs related to PIM-TMN-SBI. T.P.L.A. performed the simulation and analysis of the chain packing of PIM-TMN-Trip. C.M.C. designed and supervised the chain-packing simulation work. N.B.M. designed the polymers and prepared the manuscript with input from all of the other authors.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Neil B. McKeown.

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