PIM-CO19基热致刚性膜材料的制备和气体分离性能

doi:10.11901/1005.3093.2017.295

材料研究学报

2018, Vol. 32

Issue (4): 271-277 DOI: 10.11901/1005.3093.2017.295

研究论文

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PIM-CO19基热致刚性膜材料的制备和气体分离性能

鲁云华¹(

), 郝继璨¹, 李琳², 宋晶², 肖国勇¹, 王同华²(

)

1 辽宁科技大学化学工程学院鞍山 114051
2 大连理工大学化工学院精细化工国家重点实验室大连 116024

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

引用本文:

鲁云华, 郝继璨, 李琳, 宋晶, 肖国勇, 王同华. PIM-CO19基热致刚性膜材料的制备和气体分离性能[J]. 材料研究学报, 2018, 32(4): 271-277.
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[J]. Chinese Journal of Materials Research, 2018, 32(4): 271-277.

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摘要:

以邻苯二酚和2-丁酮为原料合成四羟基化合物3,3’-二乙基-5,5’,6,6’-四羟基-3,3’,2-三甲基-1,1’-螺旋双茚满,然后与四氟对苯二腈发生聚合反应制备出自具微孔聚合物PIM-CO19。将PIM-CO19分别在300℃、350℃和400℃进行热处理,得到热致刚性膜材料。使用红外光谱仪(FTIR)、质谱(MS)、X-射线光电子能谱(XPS)、热重分析仪(TGA)、差示扫描量热仪(DSC)、X-射线衍射仪(XRD)以及气体渗透性能测试仪表征了PIM-CO19和热致刚性膜材料的结构和性能。结果表明：在氮气氛围下PIM-CO19中的-CN间发生了热诱导的交联反应。调控热处理温度可提高PIM-CO19基热致刚性膜材料的气体渗透性能,使PIM-CO19-350对H₂、O₂、N₂、CO₂和CH₄的渗透通量分别达到了1758 Barrer、586 Barrer、180 Barrer、4075 Barrer和277 Barrer。当热处理温度提高到400℃时膜材料的气体渗透性逐渐降低,但其选择性明显提高,O₂/N₂和CO₂/CH₄的气体分离系数分别达到4.76和38.78。

关键词 ：有机高分子材料, 自具微孔聚合物, 气体分离, 热致刚性膜, 渗透性, 选择性

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 CH₄are 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

收稿日期: 2017-05-03

基金资助:资助项目国家自然科学基金(21406102, 21436009, 21506020, 21676044),辽宁省教育厅优秀人才项目(LJQ2015053)

作者简介:

作者简介鲁云华,1977年生,博士

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https://www.cjmr.org/CN/10.11901/1005.3093.2017.295 或 https://www.cjmr.org/CN/Y2018/V32/I4/271

图1 自具微孔聚合物PIM-CO19的合成

图2 3,3’-二乙基-5,5’,6,6’-四羟基-3,3’,2-三甲基-1,1’-螺旋双茚满的质谱图

图3 3,3’-二乙基-5,5’,6,6’-四羟基-3,3’,2-三甲基-1,1’-螺旋双茚满的红外光谱图

图4 PIM-CO19及其热致刚性膜材料的红外光谱

图5 PIM-CO19形成的热交联结构

图6 PIM-CO19及其热致刚性膜材料的XPS谱图

图7 PIM-CO19聚合物的DSC曲线

图8 PIM-CO19聚合物的热重分析曲线

图9 PIM-CO19及其热致刚性膜材料的XRD曲线

表1 PIM-CO19及其热致刚性膜材料的气体分离性能

图10 PIM-CO19及其热致刚性膜材料的气体渗透性与选择性间的平衡关系

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