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Chinese Journal of Materials Research  2018, Vol. 32 Issue (4): 271-277    DOI: 10.11901/1005.3093.2017.295
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Preparation and Gas Separation Properties of PIM-CO19 Based Thermally Induced Rigid Membranes
Yunhua LU1(), Jican HAO1, Lin LI2, Jing SONG2, Guoyong XIAO1, Tonghua WANG2()
1 School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, China
2 State Key Lab of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
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Yunhua LU, Jican HAO, Lin LI, Jing SONG, Guoyong XIAO, Tonghua WANG. Preparation and Gas Separation Properties of PIM-CO19 Based Thermally Induced Rigid Membranes. Chinese Journal of Materials Research, 2018, 32(4): 271-277.

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Abstract  

3,3’-diethyl-5,5’,6,6’-tetrahydroxy-3,3’,2-trimethyl-1,1’-spirobisindane was synthesized from pyrocatechol and 2-butanone, then the yellow polymers of intrinsic microporosity (PIM-CO19) were prepared from the 3,3’-diethyl-5,5’,6,6’-tetrahydroxy-3,3’,2-trimethyl-1,1’-spirobisindane and 2,3,5,6-tetrafluorotere phthalonitrile. The structures and properties of the PIM-CO19 polymer were characterized by Fourier transform infrared (FTIR), mass spectrometry (MS), X-ray photoelectron spectrometer (XPS), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA) and gas permeability test. The PIM-CO19 polymer membranes were thermally treated at 300℃, 350℃ and 400℃ in N2 atmosphere, respectively. The structures and properties of the PIM-CO19 based thermally induced rigid membranes were characterized by FTIR, X-ray diffraction (XRD) and the gas permeability testing. The results show that the crosslinking reaction of PIM-CO19 was thermally induced, and the gas permeabilities of the PIM-CO19 based thermally induced rigid membranes were further improved by controlling the processing temperature. Especially for the PIM-CO19-350, the permeabilities of H2, O2, N2, CO2 and CH4 are 1758 Barrer, 586 Barrer, 180 Barrer, 4075 Barrer and 277 Barrer separately. When the treatment temperature reached 400℃, the permeabilities of the gas separation membranes were decreased, but the selectivity was improved. The selectivity of O2/N2 and CO2/CH4 were 4.76 and 38.78, respectively.
Key words:  organic polymer materials      polymers of intrinsic microporosity      gas separation      thermally induced rigid membrane      permeability      selectivity     
Received:  03 May 2017     
Fund: Supported by National Natural Science Foundation of China (Nos. 21406102, 21436009, 21506020 ＆ 21676044) and the Talent Project of Educational Commission of Liaoning Province (No. LJQ2015053)
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Yunhua LU
Jican HAO
Lin LI
Jing SONG
Guoyong XIAO
Tonghua WANG

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https://www.cjmr.org/EN/10.11901/1005.3093.2017.295     OR     https://www.cjmr.org/EN/Y2018/V32/I4/271

Fig.1  Synthesis of polymers of intrinsic microporosity PIM-CO19
Fig.2  Mass spectrum of 3,3’-diethyl-5,5’,6,6’-tetrahydroxy-3,3’,2-trimethyl-1,1’-spirobisindane
Fig.3  FTIR spectra of 3,3’-diethyl-5,5’,6,6’-tetrahydroxy-3,3’,2-trimethyl-1,1’-spirobisindane
Fig.4  FTIR spectra of PIM-CO19 and corresponding thermally reduced rigid membranes
Fig.5  Thermal cross linking structure of PIM-CO19
Fig.6  XPS of PIM-CO19 and corresponding thermally reduced rigid membranes (a) C 1s; (b) N 1s
Fig.7  DSC curves of PIM-CO19 polymer
Fig.8  TGA analysis of PIM-CO19 polymer
Fig.9  XRD curves of PIM-CO19 and corresponding thermally reduced rigid membranes
Sample Permeabilities/Barrera Ideal selectivity
H2 O2 N2 CO2 CH4 O2/N2 CO2/CH4
PIM-CO19 1562 483 140 3044 195 3.45 15.61
PIM-CO19-300 1606 508 159 3569 225 3.19 15.85
PIM-CO19-350 1758 586 180 4075 277 3.26 14.70
PIM-CO19-400 1437 369 78 2150 55 4.76 38.78
Table 1  Gas separation properties of PIM-CO19 and corresponding thermally reduced rigid membranes
Fig.10  Permeability/selectivity tradeoff of PIM-CO19 and corresponding thermally reduced rigid membranes (a)O2/N2 vs O2; (b) CO2/CH4 vs CO2
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