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.
Bibliographical noteKAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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.
ASJC Scopus subject areas
- Materials Chemistry
- Organic Chemistry
- Polymers and Plastics
- Inorganic Chemistry