Thermally rearranged (TR) polymer membranes for CO2 separation

Park, Ho Bum; Han, Sang Hoon; Jung, Chang Ho; Lee, Young Moo; Hill, Anita J.

doi:10.1016/j.memsci.2009.09.037

Cited by 348 publications

(156 citation statements)

References 33 publications

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“…The introduction of hydroxyl groups decreased the BET surface area determined with nitrogen from 66 m 2 g -1 for 6FDA-mPDA to 54 m 2 g -1 for 6FDA-DAP and to 45 m 2 g -1 for 6FDA-DAR (in all cases ±3 m 2 /g), which was anticipated based on the effect of interchain hydrogen bonding due to the introduction of hydroxyl groups to the polymer backbone [31]. Similar N 2 -based BET surface areas have previously been reported for other moderate-free-volume glassy polymers, such as poly(phenylene oxides) and polyimides [39][40][41][42]. Interestingly, the gravimetric CO 2 sorption uptake increased in the reverse order of the BET surface areas of the polymers, that is, 6FDA-DAR > 6FDA-DAP > 6FDA-mPDA, indicating that (i) hydroxyl functionalization increases CO 2 sorption and (ii) higher OH concentration per polymer repeat unit also leads to increased CO 2 uptake.…”

Section: Physical Properties Of the Polyimidessupporting

confidence: 82%

Pure- and mixed-gas permeation properties of highly selective and plasticization resistant hydroxyl-diamine-based 6FDA polyimides for CO2/CH4 separation

Alaslai

Ghanem

Alghunaimi

et al. 2016

Journal of Membrane Science

115

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The effect of hydroxyl functionalization on the m-phenylene diamine moiety of 6FDA dianhydride-based polyimides was investigated for gas separation applications. Pure-gas permeability coefficients of He, H 2 , N 2 , O 2 , CH 4 , and CO 2 were measured at 35 °C and 2 atm.The introduction of hydroxyl groups in the diamine moiety of 6FDA-diaminophenol (DAP) and 6FDA-diamino resorcinol (DAR) polyimides tightened the overall polymer structure due to increased charge transfer complex formation compared to unfunctionalized 6FDA-m-phenylene diamine (mPDA). The BET surface areas based on nitrogen adsorption of 6FDA-DAP (54 m 2 g -1 )and of 6FDA-DAR (45 m 2 g -1 ) were ~18% and 32% lower than that of 6FDA-mPDA (66 m 2 g -1 ).6FDA-mPDA had a pure-gas CO 2 permeability of 14 Barrer and CO 2 /CH 4 selectivity of 70. The hydroxyl-functionalized polyimides 6FDA-DAP and 6FDA-DAR exhibited very high pure-gas CO 2 /CH 4 selectivities of 92 and 94 with moderate CO 2 permeability of 11 and 8 Barrer, respectively. It was demonstrated that hydroxyl-containing polyimide membranes maintained very high CO 2 /CH 4 selectivity (~ 75 at CO 2 partial pressure of 10 atm) due to CO 2 plasticization resistance when tested under high-pressure mixed-gas conditions. Functionalization with hydroxyl groups may thus be a promising strategy towards attaining highly selective polyimides for economical membrane-based natural gas sweetening.

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Section: Physical Properties Of the Polyimidessupporting

confidence: 82%

Pure- and mixed-gas permeation properties of highly selective and plasticization resistant hydroxyl-diamine-based 6FDA polyimides for CO2/CH4 separation

Alaslai

Ghanem

Alghunaimi

et al. 2016

Journal of Membrane Science

115

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“…The significantly enhanced gas selectivity along with high permeability push the overall gas transport properties to surpass the upper bound that has been limiting the polymer membranes for decades. To the best of our knowledge, the overall separation performance of TOX-PIM-1 membranes is higher than all existing soluble polymers including commercial polymers 40 , soluble PIMs 41 and compares very well against TR polymers 18,31,34,[42][43][44] .…”

Section: Characterization Of Membranesmentioning

confidence: 78%

“…One approach is improving the solubility selectivity (S A /S B ), such as PIMs substituted with CO 2 -philic tetrazole groups (TZPIMs) 20 . An alternative approach is increasing the rigidity of polymer chains while maintaining large interchain spacing, such as thermal rearranged (TR) polymers 18,31 , and PIMs with more rigid backbone 21,[32][33][34] , for example, PIMs containing rigid Troger's Base (TB) units 21 , and triptycene-based PIMs 33,34 . In particular, for separations of industrially and environmentally important gases, such as condensable CO 2 and hydrocarbons in natural gas, all of the existing PIMs polymers have only shown modest selectivity (for example, selectivity of CO 2 /CH 4 B10).…”

mentioning

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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“…PIMs are now recognized as one member of the third generation of polymer materials for membranes (along with thermally rearranged polymers) [127][128][129][130] following on from the commercially useful but low performance cellulose-based polymers and better performing polymers such as polyimides, which are now becoming commercially exploited. The intense activity on PIMs for gas separations should result in better materials and optimized membrane fabrication.…”

Section: Gas Separation Membranesmentioning

confidence: 99%

Polymers of Intrinsic Microporosity

McKeown

2012

ISRN Materials Science

183

136

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This paper focuses on polymers that demonstrate microporosity without possessing a network of covalent bonds-the so-called polymers of intrinsic microporosity (PIM). PIMs combine solution processability and microporosity with structural diversity and have proven utility for making membranes and sensors. After a historical account of the development of PIMs, their synthesis is described along with a comprehensive review of the PIMs that have been prepared to date. The important methods of characterising intrinsic microporosity, such as gas absorption, are outlined and structure-property relationships explained. Finally, the applications of PIMs as sensors and membranes for gas and vapour separations, organic nanofiltration, and pervaporation are described.

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Thermally rearranged (TR) polymer membranes for CO2 separation

Cited by 348 publications

References 33 publications

Pure- and mixed-gas permeation properties of highly selective and plasticization resistant hydroxyl-diamine-based 6FDA polyimides for CO2/CH4 separation

Pure- and mixed-gas permeation properties of highly selective and plasticization resistant hydroxyl-diamine-based 6FDA polyimides for CO2/CH4 separation

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

Polymers of Intrinsic Microporosity

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