

FOLLOWUS
a.State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin 300387, China
b.School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China
c.Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science & Technology Normal University, Nanchang 330013, China
mzjnju@jxstnu.edu.cn (Z.J.M.)
xhuama@tiangong.edu.cn (X.H.M.)
Received:19 April 2023,
Revised:2023-5-27,
Accepted:28 May 2023,
Online First:05 July 2023,
Published:01 October 2023
Scan QR Code
Huang, L. J.; Weng, Y. T.; Raiz, A.; Mao, Z. J.; Ma, X. H. Remarkably improved gas separation performance of polyimides by forming “bent and battered” main chain using paracyclophane as building block. Chinese J. Polym. Sci. 2023, 41, 1617–1628
Lu-Jun Huang, Ya-Tao Weng, Aqib Raiz, et al. Remarkably Improved Gas Separation Performance of Polyimides by Forming “Bent and Battered” Main Chain Using Paracyclophane as Building Block[J]. Chinese Journal of Polymer Science, 2023, 41(10): 1617-1628.
Huang, L. J.; Weng, Y. T.; Raiz, A.; Mao, Z. J.; Ma, X. H. Remarkably improved gas separation performance of polyimides by forming “bent and battered” main chain using paracyclophane as building block. Chinese J. Polym. Sci. 2023, 41, 1617–1628 DOI: 10.1007/s10118-023-3012-5.
Lu-Jun Huang, Ya-Tao Weng, Aqib Raiz, et al. Remarkably Improved Gas Separation Performance of Polyimides by Forming “Bent and Battered” Main Chain Using Paracyclophane as Building Block[J]. Chinese Journal of Polymer Science, 2023, 41(10): 1617-1628. DOI: 10.1007/s10118-023-3012-5.
A huge improvement of microporosity
solubility and gas separation properties for two intrinsic microporous polyimides were reported by incorporating of the paracyclophane with topological ultra-micropore (3.09 Å) into the polyimide backbone. This strategy of using topological ultra-micropore subunit to construct polymers paves a new way to search for advanced membranes for gas separation applications.
The design and development of highly permeable
selective and stable polymer membranes are great challenges in the gas separation industry. Herein
we constructed two intrinsic microporous polyimides (6FPCA and 6FMCA) derived from two isometric diamines (PCA and MCA)
which were synthesized by palladium catalyzed C―N coupling reaction. The PCA and MCA diamines contain a hollow beaded structure of 2
2’-paracyclophane as a building block with a specified window size of 3.09 Å. The chemical structures of monomers
polyimides were confirmed by NMR
FTIR
and elementary analysis. 6FPCA and 6FMCA exhibit good solubility
excellent thermal stability
and mechanical properties. 6FPCA exhibits much larger microporosity (434 versus 120 m
2
·g
−1
)
FFV (0.22 versus 0.15)
d
-spacing (6.9 versus 5.9 Å)
and over 10 times higher permeability with a very little decrease in selectivity than the corresponding polyimide (6FpA) with a plane structure
which remarkably increased their separation performance from far below the 2008 Robeson Upper bounds to reach these limitations for O
2
/N
2
and CO
2
/CH
4
. Additionally
the 6FPCA also demonstrates good plasticization resistance
moderate aging properties
and high CO
2
/CH
4
mixed-gas separation performance. These results indicate that paracyclophane subunit can be successfully incorporated into polymers to enhance their ultra-microporosity and separation properties
which open a new avenue for developing high performance gas separation membranes with topological ultra-micropores.
Sholl,D.S.;Lively,R.P.Sevenchemicalseparationstochangetheworld. Nature 2016 , 532 ,435−437..
Galizia,M.;Chi,W.S.;Smith,Z.P.;Merkel,T.C.;Baker,R.W.;Freeman,B.D.50 th Anniversaryperspective:polymersandmixedmatrixmembranesforgasandvaporseparation:areviewandprospectiveopportunities. Macromolecules 2017 , 50 ,7809−7843..
Sandru,M.;Sandru,E.M.;Ingram,W.F.;Deng,J.;Stenstad,P.M.;Deng,L.;Spontak,R.J.AnintegratedmaterialsapproachtoultrapermeableandultraselectiveCO 2 polymermembranes. Science 2022 , 376 ,90−94..
Park,H.B.;Kamcev,J.;Robeson,L.M.;Elimelech,M.;Freeman,B.D.Maximizingtherightstuff:thetrade-offbetweenmembranepermeabilityandselectivity. Science 2017 , 356 ,eaab0530..
Zhu,B.;He,S.;Yang,Y.;Li,S.;Lau,C.H.;Liu,S.;Shao,L.Boostingmembranecarboncapture via multifacetedpolyphenol-mediatedsoldering. Nat. Commun. 2023 , 14 ,1697..
Zhu,B.;He,S.;Wu,Y.;Li,S.;Shao,L.One-stepsynthesisofstructurallystableCO 2 -philicmembraneswithultra-highPEOloadingforenhancedcarboncapture. Engineering 2022 .doi:10.1016/j.eng.2022.03.016..
Robeson,L.M.Theupperboundrevisited. J. Membr. Sci. 2008 , 320 ,390−400..
Swaidan,R.;Ghanem,B.;Pinnau,I.Fine-tunedintrinsicallyultramicroporouspolymersredefinethepermeability/selectivityupperboundsofmembrane-basedairandhydrogenseparations. ACS Macro Lett. 2015 , 4 ,947−951..
Freeman,B.D.Basisofpermeability/selectivitytradeoffrelationsinpolymericgasseparationmembranes. Macromolecules 1999 , 32 ,375−380..
Comesaña-Gándara,B.;Chen,J.;Bezzu,C.G.;Carta,M.;Rose,I.;Ferrari,M.C.;Esposito,E.;Fuoco,A.;Jansen,J.C.;McKeown,N.B.RedefiningtheRobesonupperboundsforCO 2 /CH 4 andCO 2 /N 2 separationsusingaseriesofultrapermeablebenzotriptycene-basedpolymersofintrinsicmicroporosity. Energy Environ. Sci. 2019 , 12 ,2733−2740..
Du,N.;Park,H.B.;Robertson,G.P.;Dal-Cin,M.M.;Visser,T.;Scoles,L.;Guiver,M.D.PolymernanosievemembranesforCO 2 -captureapplications. Nat. Mater. 2011 , 10 ,372−375..
Yin,Y.;Guiver,M.D.Microporouspolymers:ultrapermeablemembranes. Nat. Mater. 2017 , 16 ,880−881..
Guiver,M.D.;Lee,Y.M.Polymerrigidityimprovesmicroporousmembranes. Science 2013 , 339 ,284−285..
Budd,P.M.;Ghanem,B.S.;Makhseed,S.;McKeown,N.B.;Msayib,K.J.;Tattershall,C.E.Polymersofintrinsicmicroporosity(PIMs):robust,solution-processable,organicnanoporousmaterials. Chem. Commun. 2004 ,230−231..
Budd,P.M.;McKeown,N.B.;Fritsch,D.Freevolumeandintrinsicmicroporosityinpolymers. J. Mater. Chem. 2005 , 15 ,1977−1986..
Budd,P.M.;Msayib,K.J.;Tattershall,C.E.;Ghanem,B.S.;Reynolds,K.J.;McKeown,N.B.;Fritsch,D.Gasseparationmembranesfrompolymersofintrinsicmicroporosity. J. Membr. Sci. 2005 , 251 ,263−269..
Li,P.;Chung,T.S.;Paul,D.R.GassorptionandpermeationinPIM-1. J. Membr. Sci. 2013 , 432 ,50−57..
Ghanem,B.S.;McKeown,N.B.;Budd,P.M.;Selbie,J.D.;Fritsch,D.High-performancemembranesfrompolyimideswithintrinsicmicroporosity. Adv. Mater. 2008 , 20 ,2766−2771..
Bezzu,C.G.;Carta,M.;Tonkins,A.;Jansen,J.C.;Bernardo,P.;Bazzarelli,F.;McKeown,N.B.Aspirobifluorene-basedpolymerofintrinsicmicroporositywithimprovedperformanceforgasseparation. Adv. Mater. 2012 , 24 ,5930−5933..
Carta,M.;Malpass-Evans,R.;Croad,M.;Rogan,Y.;Jansen,J.C.;Bernardo,P.;Bazzarelli,F.;McKeown,N.B.Anefficientpolymermolecularsieveformembranegasseparations. Science 2013 , 339 ,303−307..
Carta,M.;Croad,M.;Malpass-Evans,R.;Jansen,J.C.;Bernardo,P.;Clarizia,G.;Friess,K.;Lanc,M.;McKeown,N.B.TriptyceneinducedenhancementofmembranegasselectivityformicroporousTroger'sbasepolymers. Adv. Mater. 2014 , 26 ,3526−3531..
Rose,I.;Bezzu,C.G.;Carta,M.;Comesana-Gandara,B.;Lasseuguette,E.;Ferrari,M.C.;Bernardo,P.;Clarizia,G.;Fuoco,A.;Jansen,J.C.;Hart,K.E.;Liyana-Arachchi,T.P.;Colina,C.M.;McKeown,N.B.Polymerultrapermeabilityfromtheinefficientpackingof2Dchains. Nat. Mater. 2017 , 16 ,932−937..
Lai,H.W.H.;Benedetti,F.M.;Ahn,J.M.;Robinson,A.M.;Wang,Y.;Pinnau,I.;Smith,Z.P.;Xia,Y.Hydrocarbonladderpolymerswithultrahighpermselectivityformembranegasseparations. Science 2022 , 375 ,1390−1392..
Budd,P.M.;Elabas,E.S.;Ghanem,B.S.;Makhseed,S.;McKeown,N.B.;Msayib,K.J.;Tattershall,C.E.;Wang,D.Solution-processed,organophilicmembranederivedfromapolymerofintrinsicmicroporosity. Adv. Mater. 2004 , 16 ,456−459..
Yi,S.;Ghanem,B.;Liu,Y.;Pinnau,I.;Koros,W.J.Ultraselectiveglassypolymermembraneswithunprecedentedperformanceforenergy-efficientsourgasseparation. Sci. Adv. 2019 , 5 ,eaaw5459..
Ma,X.;Lai,H.W.H.;Wang,Y.;Alhazmi,A.;Xia,Y.;Pinnau,I.Facilesynthesisandstudyofmicroporouscatalyticarene-norborneneannulation-Tröger’sbaseladderpolymersformembraneairseparation. ACS Macro Lett. 2020 , 9 ,680−685..
Ma,X.H.;Abdulhamid,M.A.;Pinnau,I.Designandsynthesisofpolyimidesbasedoncarbocyclicpseudo-Troger'sbase-deriveddianhydridesformembranegasseparationapplications. Macromolecules 2017 , 50 ,5850−5857..
Ma,X.H.;Ghanem,B.;Salinas,O.;Litwiller,E.;Pinnau,I.Synthesisandeffectofphysicalagingongastransportpropertiesofamicroporouspolyimidederivedfromanovelspirobifluorene-baseddianhydride. ACS Macro Lett. 2015 , 4 ,231−235..
Ma,X.H.;Salinas,O.;Litwiller,E.;Pinnau,I.Novelspirobifluorene-anddibromospirobifluorene-basedpolyimidesofintrinsicmicroporosityforgasseparationapplications. Macromolecules 2013 , 46 ,9618−9624..
Ghanem,B.S.;Swaidan,R.;Litwiller,E.;Pinnau,I.Ultra-Microporoustriptycene-basedpolyimidemembranesforhigh-performancegasseparation. Adv. Mater. 2014 , 26 ,3688−3692..
Ghanem,B.S.;Swaidan,R.;Ma,X.;Litwiller,E.;Pinnau,I.Energy-efficienthydrogenseparationbyAB-typeladder-polymermolecularsieves. Adv. Mater. 2014 , 26 ,6696−6700..
Bezzu,C.G.;Fuoco,A.;Esposito,E.;Monteleone,M.;Longo,M.;Jansen,J.C.;Nichol,G.S.;McKeown,N.B.Ultrapermeablepolymersofintrinsicmicroporositycontainingspirocyclicunitswithfusedtriptycenes. Adv. Funct. Mater. 2021 , 31 ,2104474..
Williams,R.;Burt,L.A.;Esposito,E.;Jansen,J.C.;Tocci,E.;Rizzuto,C.;Lanc,M.;Carta,M.;McKeown,N.B.Ahighlyrigidandgasselectivemethanopentacene-basedpolymerofintrinsicmicroporosityderivedfromTroger'sbasepolymerization. J. Mater. Chem. A 2018 , 6 ,5661−5667..
Rose,I.;Carta,M.;Malpass-Evans,R.;Ferrari,M.C.;Bernardo,P.;Clarizia,G.;Jansen,J.C.;McKeown,N.B.Highlypermeablebenzotriptycene-basedpolymerofintrinsicmicroporosity. ACS Macro Lett. 2015 , 4 ,912−915..
Liu,J.;Xiao,Y.;Liao,K.S.;Chung,T.S.Highlypermeableandagingresistant3Darchitecturefrompolymersofintrinsicmicroporosityincorporatedwithbeta-cyclodextrin. J. Membr. Sci. 2017 , 523 ,92−102..
Liang,C.Z.;Liu,J.T.;Lai,J.Y.;Chung,T.S.High-performancemultiple-layerPIMcompositehollowfibermembranesforgasseparation. J. Membr. Sci. 2018 , 563 ,93−106..
Villalobos,L.F.;Huang,T.;Peinemann,K.V.Cyclodextrinfilmswithfastsolventtransportandshape-selectivepermeability. Adv. Mater. 2017 , 29 ,1606641..
Liu,J.;Hua,D.;Zhang,Y.;Japip,S.;Chung,T.S.PrecisemolecularsievingarchitectureswithJanuspathwaysforbothpolarandnonpolarmolecules. Adv. Mater. 2018 , 30 ,1705933..
Huang,T.;Puspasari,T.;Nunes,S.P.;Peinemann,K.V.Ultrathin2D-layeredcyclodextrinmembranesforhigh-performanceorganicsolventnanofiltration. Adv. Funct. Mater. 2019 , 30 ,1906797..
Huang,T.;Moosa,B.A.;Hoang,P.;Liu,J.;Chisca,S.;Zhang,G.;AlYami,M.;Khashab,N.M.;Nunes,S.P.Molecularly-porousultrathinmembranesforhighlyselectiveorganicsolventnanofiltration. Nat. Commun. 2020 , 11 ,5882..
Li,B.;Japip,S.;Chung,T.S.Molecularlytunablethin-filmnanocompositemembraneswithenhancedmolecularsievingfororganicsolventforwardosmosis. Nat. Commun. 2020 , 11 ,1198..
Jiang,Z.;Dong,R.;Evans,A.M.;Biere,N.;Ebrahim,M.A.;Li,S.;Anselmetti,D.;Dichtel,W.R.;Livingston,A.G.Alignedmacrocycleporesinultrathinfilmsforaccuratemolecularsieving. Nature 2022 , 609 ,58−64..
Cram,D.J.;Steinberg,H.MacroRings.I.Preparationandspectraoftheparacyclophanes. J. Am. Chem. Soc. 1951 , 73 ,5691−5704..
Hassan,Z.;Spuling,E.;Knoll,D.M.;Brase,S.Regioselectivefunctionalizationof[2.2]paracyclophanes:recentsynthet icprogressandperspectives. Angew. Chem. Int. Ed. 2020 , 59 ,2156−2170..
Hassan,Z.;Varadharajan,D.;Zippel,C.;Begum,S.;Lahann,J.;Brase,S.Designstrategiesforstructurallycontrolledpolymersurfaces via cyclophane-basedCVDpolymerizationandpost-CVDfabrication. Adv. Mater. 2022 , 34 ,e2201761..
Kumar,S.V.;Guiry,P.J.Zinc-catalyzedenantioselective[3+2]cycloadditionofazomethineylidesusingplanarchiral[2.2] paracyclophane-imidazolineN,O-ligands. Angew. Chem. Int. Ed. 2022 , 61 ,e202205516..
Liao,X.J.;Pu,D.;Yuan,L.;Tong,J.;Xing,S.;Tu,Z.L.;Zuo,J.L.;Zheng,W.H.;Zheng,Y.X.Planarchiralmultipleresonancethermallyactivateddelayedfluorescencematerialsforefficientcircularlypolarizedelectroluminescence. Angew. Chem. Int. Ed. 2023 , 62 ,e202217045..
Pye,D.G.;Hoehn,H.H.;Panar,M.Measurementofgaspermeabilityofpolymers.I.Permeabilitiesinconstantvolume/variablepressureapparatus. J. Appl. Polym. Sci. 1976 , 20 ,1921−1931..
Ye,C.;Luo,C.;Ji,W.;Weng,Y.;Li,J.;Yi,S.;Ma,X.Significantlyenhancedgasseparationpropertiesofmicroporousmembranesbypreciselytailoringtheirultra-microporositythroughbromination/debromination. Chem. Eng. J. 2023 , 451 ,138513..
Yeh,Y.L.;Gorham,W.F.Preparationandreactionsofsome[2.2]paracyclophanederivatives. J. Org. Chem. 2002 , 34 ,2366−2370..
Ruiz-Castillo,P.;Buchwald,S.L.Applicationsofpalladium-catalyzedC-Ncross-couplingreactions. Chem. Rev. 2016 , 116 ,12564−12649..
Snyder,R.W.;Thomson,B.;Bartges,B.;Czerniawski,D.;Painter,P.C.FTIRstudiesofpolyimides:thermalcuring. Macromolecules 2002 , 22 ,4166−4172..
Mi,Y.;Stern,S.A.;Trohalaki,S.Dependenceofthegas-permeabilityofsomepolyimideisomersontheirintrasegmentalmobility. J. Membr. Sci. 1993 , 77 ,41−48..
McKeown,N.B.;Budd,P.M.Polymersofintrinsicmicroporosity(PIMs):organicmaterialsformembraneseparations,heterogeneouscatalysisandhydrogenstorage. Chem. Soc. Rev. 2006 , 35 ,675−683..
Alghunaimi,F.;Ghanem,B.;Alaslai,N.;Swaidan,R.;Litwiller,E.;Pinnau,I.Gaspermeationandphysicalagingpropertiesofiptycenediamine-basedmicroporouspolyimides. J. Membr. Sci. 2015 , 490 ,321−327..
Li,K.;Zhu,Z.;Dong,H.;Li,Q.;Ji,W.;Li,J.;Cheng,B.;Ma,X.BottomupapproachtostudythegasseparationpropertiesofPIM-PIsanditsderivedCMSMsbyisomermonomers. J. Membr. Sci. 2021 , 635 ,119519..
Ma,X.H.;Swaidan,R.;Belmabkhout,Y.;Zhu,Y.H.;Litwiller,E.;Jouiad,M.;Pinnau,I.;Han,Y.Synthesisandgastransportpropertiesofhydroxyl-functionalizedpolyimideswithintrinsicmicroporosity. Macromolecules 2012 , 45 ,3841−3849..
Bondi,A.vanderWaalsvolumesandradii. J. Phys. Chem. 1964 , 68 ,441−451..
Nuhnen,A.;Klopotowski,M.;TanhJeazet,H.B.;Sorribas,S.;Zornoza,B.;Tellez,C.;Coronas,J.;Janiak,C.HighperformanceMIL-101(Cr)@6FDA-mPDandMOF-199@6FDA-mPDmixed-matrixmembranesforCO 2 /CH 4 separation. Dalton Trans. 2020 , 49 ,1822−1829..
Alaslai,N.;Ghanem,B.;Alghunaimi,F.;Litwiller,E.;Pinnau,I.Pure-andmixed-gaspermeationpropertiesofhighlyselectiveandplasticizationresistanthydroxyl-diamine-based6FDApolyimidesforCO 2 /CH 4 separation. J. Membr. Sci. 2016 , 505 ,100−107..
Ma,X.H.;Salinas,O.;Litwiller,E.;Pinnau,I.Pristineandthermally-rearrangedgasseparationmembranesfromnovel o -hydroxyl-functionalizedspirobifluorene-basedpolyimides. Polym. Chem. 2014 , 5 ,6914−6922..
Swaidan,R.;Ghanem,B.;Litwiller,E.;Pinnau,I.Effectsofhydroxyl-functionalizationandsub- T g thermalannealingonhighpressurepure-andmixed-gasCO 2 /CH 4 separationbypolyimidemembranesbasedon6FDAandtriptycene-containingdianhydrides. J. Membr. Sci. 2015 , 475 ,571−581..
Jung,C.H.;Lee,Y.M.Gaspermeationpropertiesofhydroxyl-groupcontainingpolyimidemembranes. Macromol. Res. 2008 , 16 ,555−560..
Coleman,M.R.;Koros,W.J.Isomericpolyimidesbasedonfluorinateddianhydridesanddiaminesforgasseparationapplications. J. Membr. Sci. 1990 , 50 ,285−297..
Alaslai,N.;Ma,X.;Ghanem,B.;Wang,Y.;Alghunaimi,F.;Pinnau,I.Synthesisandcharacterizationofanovelmicroporousdihydroxyl-functionalizedtriptycene-diamine-basedpolyimidefornaturalgasmembraneseparation. Macromol. Rapid Commun. 2017 , 38 ,1700303..
Low,Z.X.;Budd,P.M.;McKeown,N.B.;Patterson,D.A.Gaspermeationproperties,physicalaging,anditsmitigationinhighfreevolumeglassypolymers. Chem. Rev. 2018 , 118 ,5871−5911..
Lau,C.H.;Mulet,X.;Konstas,K.;Doherty,C.M.;Sani,M.A.;Separovic,F.;Hill,M.R.;Wood,C.D.Hypercrosslinkedadditivesforagelessgas-separationmembranes. Angew. Chem. Int. Ed. 2016 , 55 ,1998−2001..
Swaidan,R.;Ghanem,B.;Litwiller,E.;Pinnau,I.Physicalaging,plasticizationandtheireffectsongaspermeationin"rigid"polymersofintrinsicmicroporosity. Macromolecules 2015 , 48 ,6553−6561..
Costello,L.M.;Koros,W.J.Effectofstructureonthetemperaturedependenceofgastransportandsorptioninaseriesofpolycarbonates. J. Polym. Sci., Part B: Polym. Phys. 1994 , 32 ,701−713..
Muruganandam,N.;Koros,W.J.;Paul,D.R.Gassorptionandtransportinsubstitutedpolycarbonates. J. Polym. Sci., Part B: Polym. Phys. 1987 , 25 ,1999−2026..
Li,P.;Chung,T.S.;Paul,D.R.TemperaturedependenceofgassorptionandpermeationinPIM-1. J. Membr. Sci. 2014 , 450 ,380−388..
Wang,Y.;Ma,X.;Ghanem,B.S.;Alghunaimi,F.;Pinnau,I.;Han,Y.Polymersofintrinsicmicroporosityforenergy-intensivemembrane-basedgasseparations. Mater. Today Nano 2018 , 3 ,69−95..
0
Views
208
Downloads
1
CSCD
Publicity Resources
Related Articles
Related Author
Related Institution
京公网安备11010802046900号