Physical Aging, Plasticization and Their Effects on Gas Permeation in “Rigid” Polymers of Intrinsic Microporosity

Handle URI:
http://hdl.handle.net/10754/576174
Title:
Physical Aging, Plasticization and Their Effects on Gas Permeation in “Rigid” Polymers of Intrinsic Microporosity
Authors:
Swaidan, Raja ( 0000-0002-9296-6501 ) ; Ghanem, Bader ( 0000-0002-2044-2434 ) ; Litwiller, Eric ( 0000-0001-5366-0967 ) ; Pinnau, Ingo ( 0000-0003-3040-9088 )
Abstract:
Long-term physical aging and plasticization, two mobility-based phenomena that are counterintuitive in the context of “rigid” polymers of intrinsic microporosity (PIMs), were evaluated using pure- and mixed-gas permeation data for representative ladder and semiladder PIMs. PIMs between 1 and 4 years old retained from 10- to 1000-fold higher H2 and O2 permeabilities than commercial membrane materials with similar or higher selectivities. A triptycene-based ladder polymer (TPIM-1) exhibited very large selectivity gains outweighing permeability losses after 780 days, resulting in unprecedented performance for O2/N2 (P(O2) = 61 Barrer, α(O2/N2) = 8.6) and H2/N2 (P(H2) = 1105 Barrer, α(H2/N2) = 156) separations. Interestingly, TPIM-1 aged more and faster than its more flexible counterpart, PIM-1, which exhibited P(O2) = 317 Barrer and α(O2/N2) = 5.0 at 1380 days. Additionally, the more “rigid” TPIM-1 plasticized more significantly than PIM-1 (i.e., TPIM-1 endured ∼93% increases in mixed-gas CH4 permeability over pure-gas values compared to ∼60% for PIM-1). A flexible 9,10-bridgehead (i.e., TPIM-2) mitigated the enhancements induced by physical aging but reduced plasticization. Importantly, intra-chain rigidity alone, without consideration of chain architecture and ultra-microporosity, is insufficient for designing aging- and plasticization-resistant gas separation membranes with high permeability and high selectivity
KAUST Department:
Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division
Citation:
Physical Aging, Plasticization and Their Effects on Gas Permeation in “Rigid” Polymers of Intrinsic Microporosity 2015:150829080103007 Macromolecules
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
Issue Date:
29-Aug-2015
DOI:
10.1021/acs.macromol.5b01581
Type:
Article
ISSN:
0024-9297; 1520-5835
Additional Links:
http://pubs.acs.org/doi/10.1021/acs.macromol.5b01581
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Physical Sciences and Engineering (PSE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorSwaidan, Rajaen
dc.contributor.authorGhanem, Baderen
dc.contributor.authorLitwiller, Ericen
dc.contributor.authorPinnau, Ingoen
dc.date.accessioned2015-09-01T11:49:00Zen
dc.date.available2015-09-01T11:49:00Zen
dc.date.issued2015-08-29en
dc.identifier.citationPhysical Aging, Plasticization and Their Effects on Gas Permeation in “Rigid” Polymers of Intrinsic Microporosity 2015:150829080103007 Macromoleculesen
dc.identifier.issn0024-9297en
dc.identifier.issn1520-5835en
dc.identifier.doi10.1021/acs.macromol.5b01581en
dc.identifier.urihttp://hdl.handle.net/10754/576174en
dc.description.abstractLong-term physical aging and plasticization, two mobility-based phenomena that are counterintuitive in the context of “rigid” polymers of intrinsic microporosity (PIMs), were evaluated using pure- and mixed-gas permeation data for representative ladder and semiladder PIMs. PIMs between 1 and 4 years old retained from 10- to 1000-fold higher H2 and O2 permeabilities than commercial membrane materials with similar or higher selectivities. A triptycene-based ladder polymer (TPIM-1) exhibited very large selectivity gains outweighing permeability losses after 780 days, resulting in unprecedented performance for O2/N2 (P(O2) = 61 Barrer, α(O2/N2) = 8.6) and H2/N2 (P(H2) = 1105 Barrer, α(H2/N2) = 156) separations. Interestingly, TPIM-1 aged more and faster than its more flexible counterpart, PIM-1, which exhibited P(O2) = 317 Barrer and α(O2/N2) = 5.0 at 1380 days. Additionally, the more “rigid” TPIM-1 plasticized more significantly than PIM-1 (i.e., TPIM-1 endured ∼93% increases in mixed-gas CH4 permeability over pure-gas values compared to ∼60% for PIM-1). A flexible 9,10-bridgehead (i.e., TPIM-2) mitigated the enhancements induced by physical aging but reduced plasticization. Importantly, intra-chain rigidity alone, without consideration of chain architecture and ultra-microporosity, is insufficient for designing aging- and plasticization-resistant gas separation membranes with high permeability and high selectivityen
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/acs.macromol.5b01581en
dc.rightsThis is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. http://pubs.acs.org/page/policy/authorchoice_termsofuse.htmlen
dc.titlePhysical Aging, Plasticization and Their Effects on Gas Permeation in “Rigid” Polymers of Intrinsic Microporosityen
dc.typeArticleen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalMacromoleculesen
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorSwaidan, Rajaen
kaust.authorGhanem, Baderen
kaust.authorLitwiller, Ericen
kaust.authorPinnau, Ingoen
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