High‐Performance Membranes from Polyimides with Intrinsic Microporosity

Ghanem, Bader S.; McKeown, Neil B.; Budd, Peter M.; Selbie, James D.; Fritsch, Detlev

doi:10.1002/adma.200702400

Cited by 311 publications

(253 citation statements)

References 40 publications

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“…The integration of all protons was found to be in good agreement. 13 C NMR spectrum of THADM was consistent with the proposed structure (Supporting Information Fig. S4).…”

Section: Resultssupporting

confidence: 60%

“…PIM-1 is a widely studied candidate in the class of PIMs due to its rigid and contorted structure. 9 Since then, several examples of PIMs containing units such as triptycene, 10,11 spirobisindane, 12,13 Tr€ oger's base, [14][15][16][17] spirobischromane, 18 spirobifluorene, 19 hexaphenylbenzene, 20 naphthalene, 21 tetraphenylethylene, 22 phthalimide, 23 tribenzotriquinacene, 24 cardo PIMs, and so on 25 have been synthesized and evaluated as membrane materials for gas separation.…”

mentioning

confidence: 99%

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Synthesis, characterization, and gas permeation properties of adamantane‐containing polymers of intrinsic microporosity

Shrimant

Shaligram

Kharul

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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A new bis(catechol) monomer, namely, 4,4 0 -((1r,3r)-adamantane-2,2-diyl)bis(benzene-1,2diol) (THADM) was synthesized by condensation of 2-adamantanone with veratrole followed by demethylation of the formed (1r,3r)-2,2-bis(3,4 dimethoxyphenyl)adamantane. Polycondensation of THADM and various compositions of THADM and 5,5,6 0 ,6 0 -tetrahydroxy-3,3,3 0 ,3 0 -tetramethylspirobisindane was performed with 2,3,5,6-tetrafluoroterephthalonitrile (TFTPN) to obtain the homopolymer and copolymers. These polymers demonstrated good solubility in common organic solvents such as dichloromethane, chloroform, and tetrahydrofuran and could be cast into tough films from their chloroform solutions. GPC analysis revealed that number average molecular weights of polymers were in the range 48,100-61,700 g mol 21 , suggesting the formation of reasonably high molecular weight polymers. They possessed intrinsic microporosity with Brunauer-Emmett-Teller (BET) surface area in the range 703-741 m 2 g 21 . Thermogravimetric analysis of polymers indicated that 10% weight loss temperature was in the range 513-518 8C demonstrating their excellent thermal stability. THADM-based polymer of intrinsic microporosity (PIM) showed P(CO 2 ) 5 1080, P(O 2 ) 5 232 and appreciable selectivity [a(CO 2 /CH 4 ) 5 22.6, a(CO 2 /N 2 ) 5 26.7, and a(O 2 /N 2 )5 5.7]. The gas permeability measurements revealed that with increase in the content of adamantane units in PIMs, selectivity increased and permeability decreased, following the trade-off relationship. The gas separation properties of PIMs containing adamantane units were located close to 2008 Robeson upper bound for gas pairs such as CO

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“…The integration of all protons was found to be in good agreement. 13 C NMR spectrum of THADM was consistent with the proposed structure (Supporting Information Fig. S4).…”

Section: Resultssupporting

confidence: 60%

mentioning

confidence: 99%

Synthesis, characterization, and gas permeation properties of adamantane‐containing polymers of intrinsic microporosity

Shrimant

Shaligram

Kharul

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…One class of PIMs is based on high-free-volume aromatic polyimides (PIM-PIs) that contain rigid contortion sites either in their dianhydride and/or diamine moiety. Examples of such molecular building blocks are: (i) spirobisindane dianhydrides [7,12,13] and diamines [14,15], ethanoanthracene dianhydride [6,16], spirobifluororene dianhydride [17] and diamines [18,19], Tröger's base diamines [20][21][22], and triptycene dianhydrides [10,23] and diamines [15,24,25].…”

Section: Introductionmentioning

confidence: 99%

“…Recently developed polymers of intrinsic microporosity (PIM) have demonstrated excellent gas separation performance, often exceeding the latest 2008 upper bounds [5][6][7][8][9][10][11]. These amorphous glassy polymers are characterized by: (i) very high thermal stability; (ii) solubility in organic solvents; (iii) high BET surface area (up to ~ 1000 m 2 /g); (iv) microporosity (pore size < 20 Å) as well as ultra-microporosity (< 7 Å).…”

Section: Introductionmentioning

confidence: 99%

Gas permeation and physical aging properties of iptycene diamine-based microporous polyimides

Alghunaimi

Ghanem

Alaslai

et al. 2015

Journal of Membrane Science

100

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The synthesis and gas permeation properties of two 6FDA-dianhydride-based polyimides prepared from 2,6-diaminotriptycene (6FDA-DAT1) and its extended iptycene analog (6FDA-DAT2) are reported. The additional benzene ring on the extended triptycene moiety in 6FDA-DAT2 increases the free volume over 6FDA-DAT1 and reduces the chain packing efficiency. The BET surface area based on nitrogen adsorption in 6FDA-DAT2 (450 m 2 g -1 ) is ~40% greater than that of 6FDA-DAT1 (320 m 2 g -1 ). 6FDA-DAT1shows a CO 2 permeability of 120 Barrer and CO 2 /CH 4 selectivity of 38, whereas 6FDA-2 DAT2 exhibits a 75% increase in CO 2 permeability to 210 Barrer coupled with a moderate decrease in selectivity (CO 2 /CH 4 = 30). Interestingly, minimal physical aging was observed over 150 days for both polymers and attributed to the high internal free volume of the shape-persistent iptycene geometries. The aged polyimides maintained CO 2 /CH 4 selectivities of 25-35 along with high CO 2 permeabilities of 90-120 Barrer up to partial CO 2 pressures of 10 bar of an aggressive 50:50 CO 2 :CH 4 mixed-gas feed, suggesting potential application in membranes for natural gas sweetening.

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“…Polymers of intrinsic microporosity (PIMs) [20][21][22][23][24][25][26][27] , invented by Budd and McKeown and coworkers, are a novel subclass of microporous polymers with unique rigid and contorted macromolecular backbone structure (for example, PIM-1 in Fig. 1a, chemical structure is given in the Supplementary Fig.…”

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confidence: 99%

Controlled thermal oxidative crosslinking of polymers of intrinsic microporosity towards tunable molecular sieve membranes

et al. 2014

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Organic open frameworks with well-defined micropore (pore dimensions below 2 nm) structure are attractive next-generation materials for gas sorption, storage, catalysis and molecular level separations. Polymers of intrinsic microporosity (PIMs) represent a paradigm shift in conceptualizing molecular sieves from conventional ordered frameworks to disordered frameworks with heterogeneous distributions of microporosity. PIMs contain interconnected regions of micropores with high gas permeability but with a level of heterogeneity that compromises their molecular selectivity. Here we report controllable thermal oxidative crosslinking of PIMs by heat treatment in the presence of trace amounts of oxygen. The resulting covalently crosslinked networks are thermally and chemically stable, mechanically flexible and have remarkable selectivity at permeability that is three orders of magnitude higher than commercial polymeric membranes. This study demonstrates that controlled thermochemical reactions can delicately tune the topological structure of channels and pores within microporous polymers and their molecular sieving properties.

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High‐Performance Membranes from Polyimides with Intrinsic Microporosity

Abstract: Membranes with high permeability to gases are formed from polyimides with rigid backbones that incorporate a spiro-centre. A route to this new range of high-free-volume polyimides is demonstrated, and exceptional performance is obtained for a polymer containing a dimethyl binaphthyl unit.

Cited by 311 publications

References 40 publications

Synthesis, characterization, and gas permeation properties of adamantane‐containing polymers of intrinsic microporosity

Synthesis, characterization, and gas permeation properties of adamantane‐containing polymers of intrinsic microporosity

Gas permeation and physical aging properties of iptycene diamine-based microporous polyimides

Controlled thermal oxidative crosslinking of polymers of intrinsic microporosity towards tunable molecular sieve membranes

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