Synthesis and gas permeation properties of poly(4-methyl-2-pentyne) |
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| Institution: | 1. Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, Kyoto 606-8501, Japan;2. Graduate School of Energy Science, Kyoto University, Kyoto 606-8501, Japan;1. A.V.Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky Prospect, 29, Moscow, Russia;2. N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect, 47, Moscow, Russia;3. N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina Street, 4, Moscow, Russia;1. Schuit Institute of Catalysis, Laboratory of Inorganic Materials Chemistry, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands;2. Catalysis Engineering, ChemE, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands;1. Department of Physical Chemistry, University of Chemistry and Technology Prague, Technická 5, Prague 6, 166 28, Czech Republic;2. Institute on Membrane Technology (ITM-CNR), Via P. Bucci, 17/C, 87036 Rende, CS, Italy;3. School of Chemistry, University of Manchester, Manchester M13 9PL, United Kingdom;4. School of Chemistry, University of Edinburgh, Joseph Black Building, West Mains Road, Edinburgh EH9 3JJ, United Kingdom |
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| Abstract: | Poly(4-methyl-2-pentyne) PMP] is an amorphous, glassy, di-substituted acetylene-based polymer. PMP has a low density of 0.78 g/cm3 and a high fractional free volume of 0.28. The permeabilities for helium, hydrogen, nitrogen, oxygen, carbon dioxide, methane, ethane, propane, and n-butane were determined at temperatures from 20 to 65°C and pressures from 10 to 150 psig. PMP is the most permeable purely hydrocarbon-based polymer known; its permeabilities are only exceeded by poly(1-trimethylsilyl-1-propyne) PTMSP] and poly(1-trimethylgermyl-1-propyne) PTMGeP]. The oxygen permeability of PMP at 25°C is 2700 × 10?10 cm3(STP) cm/cm2 s cmHg and the nitrogen permeability is 1330 × 10?10 cm3(STP) cm/cm2 s cmHg. The high gas permeabilities in PMP result from its very high free volume, and probably, interconnectivity of the free-volume-elements. For a glassy polymer, PMP exhibits unusual organic vapor permeation properties. Permeabilities in PMP are higher for large, condensable gases, such as n-butane, than for small, permanent gases such as helium. The permeabilities of condensable gases and permanent gases decrease as the temperature is increased. This behavior is completely unexpected for a glassy polymer and has been observed previously in only high-free-volume glassy PTMSP. |
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