Thermally cross-linked diaminophenylindane (DAPI) containing polyimides for membrane based gas separations

Michelle E. Dose; Malgorzata Chwatko; Ivo Hubacek; Nathaniel A. Lynd; Donald R. Paul; Benny D. Freeman

doi:10.1016/j.polymer.2018.11.050

Thermally cross-linked diaminophenylindane (DAPI) containing polyimides for membrane based gas separations

Michelle E. Dose
, Malgorzata Chwatko
, Ivo Hubacek
, Nathaniel A. Lynd
, Donald R. Paul
, Benny D. Freeman

Producción científica: Article › revisión exhaustiva

40 Citas (Scopus)

Resumen

This study aims to expand structure-property relationships of diaminophenylindane (DAPI)-containing polyimides and the influence of thermal cross-linking on gas transport properties of such materials. A polyimide synthesized from hexafluoroisopropylidene diphthalic anhydride (6FDA), DAPI, and diaminobenzoic acid (DABA) in a molar ratio of 0.5/0.33/0.17, 6FDA_0.5-DAPI_0.33/DABA_0.17, was crosslinked by thermal decarboxylation. After cross-linking, pure gas permeability of 6FDA_0.5-DAPI_0.33/DABA_0.17 increased with increased cross-linking time; gas permeability increased by about 30% after cross-linking at 353 °C for 40 min. This increase in permeability correlated with an increase in d-spacing measured by wide angle x-ray scattering, suggesting an increase in inter-chain spacing upon cross-linking. Minimal changes in O₂/N₂ and N₂/CH₄ selectivities occurred with increased thermal cross-linking time for 6FDA_0.5-DAPI_0.33/DABA_0.17. However, CO₂/CH₄ and C₂H₄/C₂H₆ pure gas selectivities increased with thermal treatment, suggesting a potential narrowing of free volume distribution.

Idioma original	English
Páginas (desde-hasta)	16-26
Número de páginas	11
Publicación	Polymer
Volumen	161
DOI	https://doi.org/10.1016/j.polymer.2018.11.050
Estado	Published - ene 14 2019

Nota bibliográfica

Publisher Copyright:
© 2018 Elsevier Ltd

Financiación

This material is based upon work supported in part by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1610403 . The authors gratefully acknowledge partial support from the Division of Chemical Sciences, Geosciences, and Biosciences , Office of Basic Energy Sciences of the U.S. Department of Energy (DOE), USA through Grant DE-FG02-02ER15362 for the synthesis and characterization studies. Additionally, BDF's work in preparing this manuscript was supported in part by the National Science Foundation under Cooperative Agreement No. EEC-1647722 . Any opinions, findings and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. NAL and MC thank the National Science Foundation for partial support of this research (CBET-1706968), specifically for the NMR and molecular weight analysis. Use of the 13 C CP/TOSS solid-state NMR instrumentation is funded in part by NSF grant No. CHE-1623211. The authors acknowledge Steve Swinnea and Steve Sorey from The University of Texas at Austin for their assistance in measuring and interpreting WAXS and SS-NMR results, respectively.

Financiadores	Número del financiador
Office of Basic Energy Sciences
National Science Foundation Arctic Social Science Program
U.S. Department of Energy EPSCoR	CBET-1706968, DE-FG02-02ER15362
Chemical Sciences, Geosciences, and Biosciences Division

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Materials Chemistry

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title = "Thermally cross-linked diaminophenylindane (DAPI) containing polyimides for membrane based gas separations",

abstract = "This study aims to expand structure-property relationships of diaminophenylindane (DAPI)-containing polyimides and the influence of thermal cross-linking on gas transport properties of such materials. A polyimide synthesized from hexafluoroisopropylidene diphthalic anhydride (6FDA), DAPI, and diaminobenzoic acid (DABA) in a molar ratio of 0.5/0.33/0.17, 6FDA0.5-DAPI0.33/DABA0.17, was crosslinked by thermal decarboxylation. After cross-linking, pure gas permeability of 6FDA0.5-DAPI0.33/DABA0.17 increased with increased cross-linking time; gas permeability increased by about 30\% after cross-linking at 353 °C for 40 min. This increase in permeability correlated with an increase in d-spacing measured by wide angle x-ray scattering, suggesting an increase in inter-chain spacing upon cross-linking. Minimal changes in O2/N2 and N2/CH4 selectivities occurred with increased thermal cross-linking time for 6FDA0.5-DAPI0.33/DABA0.17. However, CO2/CH4 and C2H4/C2H6 pure gas selectivities increased with thermal treatment, suggesting a potential narrowing of free volume distribution.",

keywords = "Cross-linking, Diaminophenylindane (DAPI), Polyimides, Pure gas permeability, Thermal decarboxylation",

author = "Dose, \{Michelle E.\} and Malgorzata Chwatko and Ivo Hubacek and Lynd, \{Nathaniel A.\} and Paul, \{Donald R.\} and Freeman, \{Benny D.\}",

note = "Publisher Copyright: {\textcopyright} 2018 Elsevier Ltd",

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doi = "10.1016/j.polymer.2018.11.050",

language = "English",

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T1 - Thermally cross-linked diaminophenylindane (DAPI) containing polyimides for membrane based gas separations

AU - Dose, Michelle E.

AU - Chwatko, Malgorzata

AU - Hubacek, Ivo

AU - Lynd, Nathaniel A.

AU - Paul, Donald R.

AU - Freeman, Benny D.

PY - 2019/1/14

Y1 - 2019/1/14

N2 - This study aims to expand structure-property relationships of diaminophenylindane (DAPI)-containing polyimides and the influence of thermal cross-linking on gas transport properties of such materials. A polyimide synthesized from hexafluoroisopropylidene diphthalic anhydride (6FDA), DAPI, and diaminobenzoic acid (DABA) in a molar ratio of 0.5/0.33/0.17, 6FDA0.5-DAPI0.33/DABA0.17, was crosslinked by thermal decarboxylation. After cross-linking, pure gas permeability of 6FDA0.5-DAPI0.33/DABA0.17 increased with increased cross-linking time; gas permeability increased by about 30% after cross-linking at 353 °C for 40 min. This increase in permeability correlated with an increase in d-spacing measured by wide angle x-ray scattering, suggesting an increase in inter-chain spacing upon cross-linking. Minimal changes in O2/N2 and N2/CH4 selectivities occurred with increased thermal cross-linking time for 6FDA0.5-DAPI0.33/DABA0.17. However, CO2/CH4 and C2H4/C2H6 pure gas selectivities increased with thermal treatment, suggesting a potential narrowing of free volume distribution.

AB - This study aims to expand structure-property relationships of diaminophenylindane (DAPI)-containing polyimides and the influence of thermal cross-linking on gas transport properties of such materials. A polyimide synthesized from hexafluoroisopropylidene diphthalic anhydride (6FDA), DAPI, and diaminobenzoic acid (DABA) in a molar ratio of 0.5/0.33/0.17, 6FDA0.5-DAPI0.33/DABA0.17, was crosslinked by thermal decarboxylation. After cross-linking, pure gas permeability of 6FDA0.5-DAPI0.33/DABA0.17 increased with increased cross-linking time; gas permeability increased by about 30% after cross-linking at 353 °C for 40 min. This increase in permeability correlated with an increase in d-spacing measured by wide angle x-ray scattering, suggesting an increase in inter-chain spacing upon cross-linking. Minimal changes in O2/N2 and N2/CH4 selectivities occurred with increased thermal cross-linking time for 6FDA0.5-DAPI0.33/DABA0.17. However, CO2/CH4 and C2H4/C2H6 pure gas selectivities increased with thermal treatment, suggesting a potential narrowing of free volume distribution.

KW - Cross-linking

KW - Diaminophenylindane (DAPI)

KW - Polyimides

KW - Pure gas permeability

KW - Thermal decarboxylation

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JO - Polymer

JF - Polymer

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Thermally cross-linked diaminophenylindane (DAPI) containing polyimides for membrane based gas separations

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ASJC Scopus subject areas

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