PIM-CO19基热致刚性膜材料的制备和气体分离性能

Preparation and Gas Separation Properties of PIM-CO19 Based Thermally Induced Rigid Membranes

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PIMCO19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H_2、O_2、N_2、CO_2和CH_4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,O_2/N_2和CO_2/CH_4的气体分离系数分别达到4.76和38.78。

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-tet- rafluorotere phthalonitrile. The structures and properties of the PIM-CO19 po/ymer were characterized by Fourier transform infrared （FTIR）, mass spectrometry （MS）, X-ray photoelectron spectrometer （XPS）, dif- ferential 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, re-spectively. 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 tem- perature. 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 im- proved. The selectivity of O2/N2 and CO2/CH4 were 4.76 and 38.78, respectively.