Sub- T g Cross-Linking of a Polyimide Membrane for Enhanced CO 2 Plasticization Resistance for Natural Gas Separation

Handle URI:
http://hdl.handle.net/10754/599793
Title:
Sub- T g Cross-Linking of a Polyimide Membrane for Enhanced CO 2 Plasticization Resistance for Natural Gas Separation
Authors:
Qiu, Wulin; Chen, Chien-Chiang; Xu, Liren; Cui, Lili; Paul, Donald R.; Koros, William J.
Abstract:
Decarboxylation-induced thermal cross-linking occurs at elevated temperatures (∼15 °C above glass transition temperature) for 6FDA-DAM:DABA polyimides, which can stabilize membranes against swelling and plasticization in aggressive feed streams. Despite this advantage, such a high temperature might result in collapse of substructure and transition layers in the asymmetric structure of a hollow fibers based on such a material. In this work, the thermal cross-linking of the 6FDA-DAM:DABA at temperatures much below the glass transition temperature (∼387 °C by DSC) was demonstrated. This sub-Tg cross-linking capability enables extension to asymmetric structures useful for large scale membranes. The resulting polymer membranes were characterized by swelling in known solvents for the un-cross-linked materials, TGA analysis, and permeation tests of aggressive gas feed stream at higher pressure. The annealing temperature and time clearly influence the degree of cross-linking of the membranes, and results in a slight difference in selectivity for membranes under various cross-linking conditions. Results indicate that the sub-Tg thermal cross-linking of 6FDA-DAM:DABA dense film membrane can be carried out completely even at a temperature as low as 330 °C. Permeabilities were tested for the polyimide membranes using both pure gases (He, O2, N2, CH4, CO2) and mixed gases (CO2/CH4). The selectivity of the cross-linked membrane can be maintained even under very aggressive CO2 operating conditions that are not possible without cross-linking. Moreover, the plasticization resistance was demonstrated up to 700 psia for pure CO 2 gas or 1000 psia for 50% CO2 mixed gas feeds. © 2011 American Chemical Society.
Citation:
Qiu W, Chen C-C, Xu L, Cui L, Paul DR, et al. (2011) Sub- T g Cross-Linking of a Polyimide Membrane for Enhanced CO 2 Plasticization Resistance for Natural Gas Separation . Macromolecules 44: 6046–6056. Available: http://dx.doi.org/10.1021/ma201033j.
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
KAUST Grant Number:
KUS-I1-011-21
Issue Date:
9-Aug-2011
DOI:
10.1021/ma201033j
Type:
Article
ISSN:
0024-9297; 1520-5835
Sponsors:
This research was supported by the U.S. Department of Energy Grant DE-FG02-04ER15510, and was supported in part by, Award No. KUS-I1-011-21, made by King Abdullah University of Science and Technology (KAUST).
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Full metadata record

DC FieldValue Language
dc.contributor.authorQiu, Wulinen
dc.contributor.authorChen, Chien-Chiangen
dc.contributor.authorXu, Lirenen
dc.contributor.authorCui, Lilien
dc.contributor.authorPaul, Donald R.en
dc.contributor.authorKoros, William J.en
dc.date.accessioned2016-02-28T06:09:57Zen
dc.date.available2016-02-28T06:09:57Zen
dc.date.issued2011-08-09en
dc.identifier.citationQiu W, Chen C-C, Xu L, Cui L, Paul DR, et al. (2011) Sub- T g Cross-Linking of a Polyimide Membrane for Enhanced CO 2 Plasticization Resistance for Natural Gas Separation . Macromolecules 44: 6046–6056. Available: http://dx.doi.org/10.1021/ma201033j.en
dc.identifier.issn0024-9297en
dc.identifier.issn1520-5835en
dc.identifier.doi10.1021/ma201033jen
dc.identifier.urihttp://hdl.handle.net/10754/599793en
dc.description.abstractDecarboxylation-induced thermal cross-linking occurs at elevated temperatures (∼15 °C above glass transition temperature) for 6FDA-DAM:DABA polyimides, which can stabilize membranes against swelling and plasticization in aggressive feed streams. Despite this advantage, such a high temperature might result in collapse of substructure and transition layers in the asymmetric structure of a hollow fibers based on such a material. In this work, the thermal cross-linking of the 6FDA-DAM:DABA at temperatures much below the glass transition temperature (∼387 °C by DSC) was demonstrated. This sub-Tg cross-linking capability enables extension to asymmetric structures useful for large scale membranes. The resulting polymer membranes were characterized by swelling in known solvents for the un-cross-linked materials, TGA analysis, and permeation tests of aggressive gas feed stream at higher pressure. The annealing temperature and time clearly influence the degree of cross-linking of the membranes, and results in a slight difference in selectivity for membranes under various cross-linking conditions. Results indicate that the sub-Tg thermal cross-linking of 6FDA-DAM:DABA dense film membrane can be carried out completely even at a temperature as low as 330 °C. Permeabilities were tested for the polyimide membranes using both pure gases (He, O2, N2, CH4, CO2) and mixed gases (CO2/CH4). The selectivity of the cross-linked membrane can be maintained even under very aggressive CO2 operating conditions that are not possible without cross-linking. Moreover, the plasticization resistance was demonstrated up to 700 psia for pure CO 2 gas or 1000 psia for 50% CO2 mixed gas feeds. © 2011 American Chemical Society.en
dc.description.sponsorshipThis research was supported by the U.S. Department of Energy Grant DE-FG02-04ER15510, and was supported in part by, Award No. KUS-I1-011-21, made by King Abdullah University of Science and Technology (KAUST).en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleSub- T g Cross-Linking of a Polyimide Membrane for Enhanced CO 2 Plasticization Resistance for Natural Gas Separationen
dc.typeArticleen
dc.identifier.journalMacromoleculesen
dc.contributor.institutionGeorgia Institute of Technology, Atlanta, United Statesen
dc.contributor.institutionUniversity of Texas at Austin, Austin, United Statesen
kaust.grant.numberKUS-I1-011-21en
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