Polymers of intrinsic microporosity with dinaphthyl and thianthrene segments

Handle URI:
http://hdl.handle.net/10754/561552
Title:
Polymers of intrinsic microporosity with dinaphthyl and thianthrene segments
Authors:
Du, Naiying; Robertson, Gilles P.; Pinnau, Ingo ( 0000-0003-3040-9088 ) ; Guiver, Michael D.
Abstract:
Novel intrinsically microporous homopolymers and copolymers derived from PIM-1 monomers (5,5,6,6-tetrahydroxy-3,3,3,3-tetramethylspirobisindane and 2,3,5,6-tetrafluoroterephthalonitrile) with two additional monomers- tetrahydroxydinaphthyl and tetrafluorotetraoxide thianthrene-are reported as potential materials for membrane-based gas separations. The resulting copolymers prevent efficient space packing of the stiff polymer chains and consequently exhibit analogous behavior to that of PIM-1, the most widely reported polymer in this class of materials. In addition, the copolymerization provides high molecular weight copolymers and low polydispersity if the polymerization reactions were conducted at elevated temperature for an extended period of time. Detailed structural characterization of the new monomers and polymers was determined by 1H and 19F nuclear magnetic resonance spectroscopy (NMR). The thermal properties were detected by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Polymer free volume was calculated from the polymer density and specific van der Waals volume. Under the same testing conditions, the homopolymer containing thianthrene units and most of the analogous copolymers have an excellent combination of properties with good film-forming characteristics. The gas transport properties show higher selectivity for gas pairs such as O 2/N2, CO2/N2, and H 2/N2 with a corresponding decrease in permeability compared to PIM-1. This work also demonstrates that significant improvements in properties may be obtained through copolymers of intrinsic microporosity (CoPIM)s. Furthermore, this work extends the spectrum of high molecular weight soluble PIMs beyond those reported previously. © 2010 American Chemical Society.
KAUST Department:
Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Chemical and Biological Engineering Program
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
Issue Date:
26-Oct-2010
DOI:
10.1021/ma101930x
Type:
Article
ISSN:
00249297
Sponsors:
This work was partly supported by the Climate Change Technology and Innovation Initiative, Greenhouse Gas project (CCT11, GHG), Natural Resources Canada (NRCan). M.D.G. acknowledges partial support from the WCU program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (No. R31-2008-000-10092-0). The authors are grateful to Mr. Floyd Toll for the elemental analysis, BET, and mechanical properties testing. The authors are also grateful to Dr. Li Jian Jun and Mr. Jacek Stupak, National Research Council, Institute for Biological Sciences, for the MALDI-TOF MS measurements.
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Chemical and Biological Engineering Program

Full metadata record

DC FieldValue Language
dc.contributor.authorDu, Naiyingen
dc.contributor.authorRobertson, Gilles P.en
dc.contributor.authorPinnau, Ingoen
dc.contributor.authorGuiver, Michael D.en
dc.date.accessioned2015-08-02T09:14:02Zen
dc.date.available2015-08-02T09:14:02Zen
dc.date.issued2010-10-26en
dc.identifier.issn00249297en
dc.identifier.doi10.1021/ma101930xen
dc.identifier.urihttp://hdl.handle.net/10754/561552en
dc.description.abstractNovel intrinsically microporous homopolymers and copolymers derived from PIM-1 monomers (5,5,6,6-tetrahydroxy-3,3,3,3-tetramethylspirobisindane and 2,3,5,6-tetrafluoroterephthalonitrile) with two additional monomers- tetrahydroxydinaphthyl and tetrafluorotetraoxide thianthrene-are reported as potential materials for membrane-based gas separations. The resulting copolymers prevent efficient space packing of the stiff polymer chains and consequently exhibit analogous behavior to that of PIM-1, the most widely reported polymer in this class of materials. In addition, the copolymerization provides high molecular weight copolymers and low polydispersity if the polymerization reactions were conducted at elevated temperature for an extended period of time. Detailed structural characterization of the new monomers and polymers was determined by 1H and 19F nuclear magnetic resonance spectroscopy (NMR). The thermal properties were detected by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Polymer free volume was calculated from the polymer density and specific van der Waals volume. Under the same testing conditions, the homopolymer containing thianthrene units and most of the analogous copolymers have an excellent combination of properties with good film-forming characteristics. The gas transport properties show higher selectivity for gas pairs such as O 2/N2, CO2/N2, and H 2/N2 with a corresponding decrease in permeability compared to PIM-1. This work also demonstrates that significant improvements in properties may be obtained through copolymers of intrinsic microporosity (CoPIM)s. Furthermore, this work extends the spectrum of high molecular weight soluble PIMs beyond those reported previously. © 2010 American Chemical Society.en
dc.description.sponsorshipThis work was partly supported by the Climate Change Technology and Innovation Initiative, Greenhouse Gas project (CCT11, GHG), Natural Resources Canada (NRCan). M.D.G. acknowledges partial support from the WCU program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (No. R31-2008-000-10092-0). The authors are grateful to Mr. Floyd Toll for the elemental analysis, BET, and mechanical properties testing. The authors are also grateful to Dr. Li Jian Jun and Mr. Jacek Stupak, National Research Council, Institute for Biological Sciences, for the MALDI-TOF MS measurements.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titlePolymers of intrinsic microporosity with dinaphthyl and thianthrene segmentsen
dc.typeArticleen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical and Biological Engineering Programen
dc.identifier.journalMacromoleculesen
dc.contributor.institutionInstitute for Chemical Process and Environmental Technology, National Research Council of Canada, Ottawa, ON K1A 0R6, Canadaen
dc.contributor.institutionWCU Department of Energy Engineering, Hanyang University, Seoul 133-791, South Koreaen
kaust.authorPinnau, Ingoen
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