镧系金属有机骨架/聚酰亚胺复合材料的制备及其性能
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摘要
采用水热法合成两种含镧系稀土金属的金属有机骨架:1,3,5-均苯三甲酸铽(Tb(BTC))和1,3,5-均苯三甲酸铕(Eu(BTC)),采用原位法以1,4-双(2-三氟甲基-4-氨基苯氧基)苯(6FAPB)和1,2,3,4-环丁烷四酸二酐(CBDA)为单体,将Tb(BTC)和Eu(BTC)分别引入到聚酰亚胺(PI)中,制备出Tb(BTC)和Eu(BTC)质量分数分别为7wt%的Tb(BTC)/PI和Eu(BTC)/PI两种复合材料膜。利用FTIR、紫外-可见光谱仪(UV-vis)、TGA、XRD、SEM、万能拉伸试验机和气体渗透性测试等对Tb(BTC)/PI和Eu(BTC)/PI复合材料的结构和性能进行表征。研究结果表明,Tb(BTC)和Eu(BTC)含有较少的孔结构,且孔径在介孔范围,但热稳定性较高。Tb(BTC)和Eu(BTC)的加入提高了Tb(BTC)/PI和Eu(BTC)/PI复合材料的热性能和力学性能,玻璃化转变温度由纯PI(6FAPB-CBDA)的351.9℃分别提高到358.0℃和354.8℃,失重5%热分解温度由431.6℃分别提高到447.8℃和441.1℃,拉伸强度由60.8MPa分别提高到77.7 MPa和70.4 MPa,杨氏模量由1.54GPa分别提高到2.80GPa和2.17GPa。但Tb(BTC)/PI和Eu(BTC)/PI复合材料膜的光透明性有所降低,500nm处的光透过率由82.3%分别下降到23.0%和24.2%。气体渗透测试结果表明,Tb(BTC)和Eu(BTC)的加入均可提高PI(6FAPB-CBDA)膜的气体渗透性,Eu(TBC)/PI对H2、O2、N2和CO2的渗透性较高,分别为119.23、15.02、3.21和90.35Barrer,O2/N2为4.68,CO2/N2为28.15。
Two kinds of lanthanide metal-organic frameworks such as terbium benzene-1,3,5-tricarboxylate(Tb(BTC))and europium benzene-1,3,5-tricarboxylate(Eu(BTC))were synthesized by hydrothermal method.1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene(6 FAPB)and 1,2,3,4-cyclobutane dianhydride(CBDA)as the monomers of polyimide(PI),the Tb(BTC)/PI and Eu(BTC)/PI composites containing 7 wt% Tb(BTC)or Eu(BTC)(mass fraction)were prepared by the in-situ polymerization.The structure and properties of the Tb(BTC)/PI and Eu(BTC)/PI composites were characterized by FTIR,UV-visible spectrometer(UV-vis),TGA,XRD,SEM,universal tensile testing machine and gas permeabilities testing.These experimental results show that Tb(BTC)and Eu(BTC)contain very few pore structures,belonging to the mesoporous range,and exhibit high thermal stabilities.The introduction of Tb(BTC)and Eu(BTC)improves the thermal and mechanical properties of PI(6 FAPB-CBDA).The glass transition temperatures increase from 351.9℃ of pure PI(6 FAPB-CBDA)to 358.0℃ and 354.8℃,and the 5%thermal decomposition temperatures increase from 431.6℃to 447.8℃ and 441.1℃.The tensile strengthsof Tb(BTC)/PI and Eu(BTC)/PI composites increase from 60.8 MPa to 77.7 MPa and 70.4 MPa,and the Young's modulus increase from 1.54 GPa to 2.80 GPa and 2.17 GPa,respectively.However,the optical transmittances at 500 nm of Tb(BTC)/PI and Eu(BTC)/PI composites reduce from 82.3%to 23.0%and 24.2%.The results of gas permeability testing show that both of Tb(BTC)and Eu(BTC)can improve the gas permeabilities of the PI-(6 FAPB-CBDA)membrane.The effect of Eu(BTC)is better than Tb(BTC).The permeabilities of H_2,O_2,N_2 and CO_2 of Eu(TBC)/PI composite are 119.23,15.02,3.21 and 90.35 Barrer,respectively,and O_2/N_2 is 4.68,CO_2/N_2 is 28.15.
Two kinds of lanthanide metal-organic frameworks such as terbium benzene-1,3,5-tricarboxylate(Tb(BTC))and europium benzene-1,3,5-tricarboxylate(Eu(BTC))were synthesized by hydrothermal method.1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene(6 FAPB)and 1,2,3,4-cyclobutane dianhydride(CBDA)as the monomers of polyimide(PI),the Tb(BTC)/PI and Eu(BTC)/PI composites containing 7 wt% Tb(BTC)or Eu(BTC)(mass fraction)were prepared by the in-situ polymerization.The structure and properties of the Tb(BTC)/PI and Eu(BTC)/PI composites were characterized by FTIR,UV-visible spectrometer(UV-vis),TGA,XRD,SEM,universal tensile testing machine and gas permeabilities testing.These experimental results show that Tb(BTC)and Eu(BTC)contain very few pore structures,belonging to the mesoporous range,and exhibit high thermal stabilities.The introduction of Tb(BTC)and Eu(BTC)improves the thermal and mechanical properties of PI(6 FAPB-CBDA).The glass transition temperatures increase from 351.9℃ of pure PI(6 FAPB-CBDA)to 358.0℃ and 354.8℃,and the 5%thermal decomposition temperatures increase from 431.6℃to 447.8℃ and 441.1℃.The tensile strengthsof Tb(BTC)/PI and Eu(BTC)/PI composites increase from 60.8 MPa to 77.7 MPa and 70.4 MPa,and the Young's modulus increase from 1.54 GPa to 2.80 GPa and 2.17 GPa,respectively.However,the optical transmittances at 500 nm of Tb(BTC)/PI and Eu(BTC)/PI composites reduce from 82.3%to 23.0%and 24.2%.The results of gas permeability testing show that both of Tb(BTC)and Eu(BTC)can improve the gas permeabilities of the PI-(6 FAPB-CBDA)membrane.The effect of Eu(BTC)is better than Tb(BTC).The permeabilities of H_2,O_2,N_2 and CO_2 of Eu(TBC)/PI composite are 119.23,15.02,3.21 and 90.35 Barrer,respectively,and O_2/N_2 is 4.68,CO_2/N_2 is 28.15.
引文
[1]BAKER R W.Future directions of membrane gas separation technology[J].Industrial and Engineering Chemistry Research,2002,41(6):1393-1411.
[2]HASHIM S S,MOHAMED A R,BHATIA S.Oxygen separation from air using ceramic-based membrane technology for sustainable fuel production and power generation[J].Renewable and Sustainable Energy Reviews,2011,15(2):1284-1293.
[3]陈曦,王耀,江雷.CO2选择性透过膜材料的制备[J].高等学校化学学报,2013,34(2):249-268.CHEN X,WANG Y,JIANG L.Research progress of preparation methods of CO2-favored permeation membranes[J].Chemical Journal of Chinese Universities,2013,34(2):249-268(in Chinese).
[4]鲁云华,郝继璨,李琳,等.热致刚性膜材料的合成与气体分离性能研究[J].高分子学报,2016(8):1145-1150.LU Y H,HAO J C,LI L,et al.Synthesis of thermally induced rigid membranes and their gas separation properties[J].Acta Polymerica Sinica,2016(8):1145-1150(in Chinese).
[5]CHUNG T S,JIANG L Y,LI Y,et al.Mixed matrix membranes(MMMs)comprising organic polymers with dispersed inorganic fillers for gas separation[J].Progress in Polymer Science,2007,32(4):483-507.
[6]NASIR R,MUKHTAR H,MAN Z,et al.Material advancements in fabrication of mixed-matrix membranes[J].Chemical Engineering&Technology,2013,36(5):717-727.
[7]JUSOH N,YEONG F Y,LAU K K,et al.Enhanced gas separation performance using mixed matrix membranes containing zeolite T and 6FDA-durene polyimide[J].Journal of Membrane Science,2017,525:175-186.
[8]CHEN B,YANG Y,ZAPATA F,et al.Luminescent open metal sites within a metal-organic framework for sensing small molecules[J].Advanced Materials,2007,19(13):1693-1696.
[9]段翠佳,曹义鸣,介兴明,等.金属有机骨架材料/聚酰亚胺混合基质膜的制备及气体分离性能[J].高等学校化学学报,2014,35(7):1584-1589.DUAN C J,CAO Y M,JIE X M,et al.Preparation and gas separation properties of metal-organic frameworks/polyimide mixed matrix membranes[J].Chemical Journal of Chinese Universities,2014,35(7):1584-1589(in Chinese).
[10]WANG Z G,WANG D,ZHANG S X,et al.Interfacial design of mixed matrix membranes for improved gas separation performance[J].Advanced Materials,2016,28(17):3399-3405.
[11]VINOBA M,BHAGIYALAKSHMI M,ALQAHEEM Y,et al.Recent progress of fillers in mixed matrix membranes for CO2separation:A review[J].Separation and Purification Technology,2017,188(29):431-450.
[12]龚金华,王臣辉,卞子君,等.多孔材料表面修饰聚酰亚胺非对称混合基质膜对CO2/N2和CO2/CH4的气体分离[J].物理化学学报,2015,31(10):1963-1970.GONG J H,WANG C H,BIAN Z J,et al.Asymmetric polyimide mixed matrix membranes with porous materialsmodified surfaces for CO2/N2and CO2/CH4separations[J].Acta Physico-Chimica Sinica,2015,31(10):1963-1970(in Chinese).
[13]CHEN X Y,VINH-THANG H,RODRIGUE D,et al.Amine-functionalized MIL-53 metal-organic framework in polyimide mixed matrix membranes for CO2/CH4separation[J].Industrial&Engineering Chemistry Research,2012,51(19):6895-6906.
[14]NIK O G,CHEN X Y,KALIAGUINE S.Functionalized metal organic framework-polyimide mixed matrix membranes for CO2/CH4separation[J].Journal of Membrane Science,2012,413-414:48-61.
[15]CASTARLENAS S,TELLEZ C,CORONAS J.Gas separation with mixed matrix membranes obtained from MOF UiO-66-graphene oxide hybrids[J].Journal of Membrane Science,2017,526(15):205-211.
[16]MEDINA-VELAZQUEZ D Y,ALEJANDRE-ZUNIGA B Y,LOERA-SERNA S,et al.An alkaline one-pot reaction to synthesize luminescent Eu-BTC MOF nanorods,highly pure and water-insoluble,under room conditions[J].Journal of Nanoparticle Research,2016,18(12):352.
[17]TANAKA K,KITA H,OKANO M,et al.Permeability and permselectivity of gases in fluorinated and non-fluorinated polyimides[J].Polymer,1992,33(3):585-592.
[18]HAN K,JANG W,RHEE T H.Synthesis of fluorinated polyimides and their application to passive optical waveguides[J].Journal of Applied Polymer Science,2015,77(10):2172-2177.
[19]TONG H,HU C,YANG S.Preparation of fluorinated polyimides with bulky structure and their gas separation performance correlated with microstructure[J].Polymer,2015,69:138-147.
[20]DONG W,GUAN Y,SHANG D.Novel soluble polyimides containing pyridine and fluorinated units:Preparation,characterization,and optical and dielectric properties[J].RSCAdvances,2016,6(26):21662-21671.
[21]NIWA M,NAGAOKA S,KAWAKAMI H.Preparation of novel fluorinated block copolyimide membranes for gas separation[J].Journal of Applied Polymer Science,2010,100(3):2436-2442.
[22]DAMACEANU M D,CONSTANTIN C,NICOLESCU A.Highly transparent and hydrophobic fluorinated polyimide films with ortho-kink structure[J].European Polymer Journal,2014,50(1):200-213.
[23]LU Y H,HU Z Z,WANG Y F,et al.Organosoluble and light-colored fluorinated semialicyclic polyimide derived from1,2,3,4-cyclobutanetetracarboxylic dianhydride[J].Journal of Applied Polymer Science,2012,125(2):1371-1376.
[24]崔晓萍,朱光,刘文元.纳米Al2O3/聚酰亚胺复合薄膜的介电与力学性能[J].复合材料学报,2016,33(11):2419-2425.CUI X P,ZHU G,LIU W Y.Dielectric and mechanical properties of nano Al2O3/polyimide composite films[J].Acta Materiae Compositae Sinica,2016,33(11):2419-2425(in Chinese).
[25]吕静,党智敏.低热膨胀系数纳米碳化硅/聚酰亚胺复合薄膜的制备与性能[J].复合材料学报,2011,28(5):41-45.LV J,DANG Z M.Preparation and properties of nano-SiC/polyimide composite films with low thermal expansion characteristic[J].Acta Materiae Compositae Sinica,2011,28(5):41-45(in Chinese).
[26]GUO H L,ZHU S J,CAI D N,et al.Fabrication of ITOglass supported Tb-MOF film for sensing organic solvent[J].Inorganic Chemistry Communications,2014,41:29-32.
[27]CAI D N,GUO H L,WEN L,et al.Fabrication of hierarchical architectures of Tb-MOF by a“green coordination modulation method”for the sensing of heavy metal ions[J].Crystal Engineering Communications,2013,15(34):6702-6708.
[2]HASHIM S S,MOHAMED A R,BHATIA S.Oxygen separation from air using ceramic-based membrane technology for sustainable fuel production and power generation[J].Renewable and Sustainable Energy Reviews,2011,15(2):1284-1293.
[3]陈曦,王耀,江雷.CO2选择性透过膜材料的制备[J].高等学校化学学报,2013,34(2):249-268.CHEN X,WANG Y,JIANG L.Research progress of preparation methods of CO2-favored permeation membranes[J].Chemical Journal of Chinese Universities,2013,34(2):249-268(in Chinese).
[4]鲁云华,郝继璨,李琳,等.热致刚性膜材料的合成与气体分离性能研究[J].高分子学报,2016(8):1145-1150.LU Y H,HAO J C,LI L,et al.Synthesis of thermally induced rigid membranes and their gas separation properties[J].Acta Polymerica Sinica,2016(8):1145-1150(in Chinese).
[5]CHUNG T S,JIANG L Y,LI Y,et al.Mixed matrix membranes(MMMs)comprising organic polymers with dispersed inorganic fillers for gas separation[J].Progress in Polymer Science,2007,32(4):483-507.
[6]NASIR R,MUKHTAR H,MAN Z,et al.Material advancements in fabrication of mixed-matrix membranes[J].Chemical Engineering&Technology,2013,36(5):717-727.
[7]JUSOH N,YEONG F Y,LAU K K,et al.Enhanced gas separation performance using mixed matrix membranes containing zeolite T and 6FDA-durene polyimide[J].Journal of Membrane Science,2017,525:175-186.
[8]CHEN B,YANG Y,ZAPATA F,et al.Luminescent open metal sites within a metal-organic framework for sensing small molecules[J].Advanced Materials,2007,19(13):1693-1696.
[9]段翠佳,曹义鸣,介兴明,等.金属有机骨架材料/聚酰亚胺混合基质膜的制备及气体分离性能[J].高等学校化学学报,2014,35(7):1584-1589.DUAN C J,CAO Y M,JIE X M,et al.Preparation and gas separation properties of metal-organic frameworks/polyimide mixed matrix membranes[J].Chemical Journal of Chinese Universities,2014,35(7):1584-1589(in Chinese).
[10]WANG Z G,WANG D,ZHANG S X,et al.Interfacial design of mixed matrix membranes for improved gas separation performance[J].Advanced Materials,2016,28(17):3399-3405.
[11]VINOBA M,BHAGIYALAKSHMI M,ALQAHEEM Y,et al.Recent progress of fillers in mixed matrix membranes for CO2separation:A review[J].Separation and Purification Technology,2017,188(29):431-450.
[12]龚金华,王臣辉,卞子君,等.多孔材料表面修饰聚酰亚胺非对称混合基质膜对CO2/N2和CO2/CH4的气体分离[J].物理化学学报,2015,31(10):1963-1970.GONG J H,WANG C H,BIAN Z J,et al.Asymmetric polyimide mixed matrix membranes with porous materialsmodified surfaces for CO2/N2and CO2/CH4separations[J].Acta Physico-Chimica Sinica,2015,31(10):1963-1970(in Chinese).
[13]CHEN X Y,VINH-THANG H,RODRIGUE D,et al.Amine-functionalized MIL-53 metal-organic framework in polyimide mixed matrix membranes for CO2/CH4separation[J].Industrial&Engineering Chemistry Research,2012,51(19):6895-6906.
[14]NIK O G,CHEN X Y,KALIAGUINE S.Functionalized metal organic framework-polyimide mixed matrix membranes for CO2/CH4separation[J].Journal of Membrane Science,2012,413-414:48-61.
[15]CASTARLENAS S,TELLEZ C,CORONAS J.Gas separation with mixed matrix membranes obtained from MOF UiO-66-graphene oxide hybrids[J].Journal of Membrane Science,2017,526(15):205-211.
[16]MEDINA-VELAZQUEZ D Y,ALEJANDRE-ZUNIGA B Y,LOERA-SERNA S,et al.An alkaline one-pot reaction to synthesize luminescent Eu-BTC MOF nanorods,highly pure and water-insoluble,under room conditions[J].Journal of Nanoparticle Research,2016,18(12):352.
[17]TANAKA K,KITA H,OKANO M,et al.Permeability and permselectivity of gases in fluorinated and non-fluorinated polyimides[J].Polymer,1992,33(3):585-592.
[18]HAN K,JANG W,RHEE T H.Synthesis of fluorinated polyimides and their application to passive optical waveguides[J].Journal of Applied Polymer Science,2015,77(10):2172-2177.
[19]TONG H,HU C,YANG S.Preparation of fluorinated polyimides with bulky structure and their gas separation performance correlated with microstructure[J].Polymer,2015,69:138-147.
[20]DONG W,GUAN Y,SHANG D.Novel soluble polyimides containing pyridine and fluorinated units:Preparation,characterization,and optical and dielectric properties[J].RSCAdvances,2016,6(26):21662-21671.
[21]NIWA M,NAGAOKA S,KAWAKAMI H.Preparation of novel fluorinated block copolyimide membranes for gas separation[J].Journal of Applied Polymer Science,2010,100(3):2436-2442.
[22]DAMACEANU M D,CONSTANTIN C,NICOLESCU A.Highly transparent and hydrophobic fluorinated polyimide films with ortho-kink structure[J].European Polymer Journal,2014,50(1):200-213.
[23]LU Y H,HU Z Z,WANG Y F,et al.Organosoluble and light-colored fluorinated semialicyclic polyimide derived from1,2,3,4-cyclobutanetetracarboxylic dianhydride[J].Journal of Applied Polymer Science,2012,125(2):1371-1376.
[24]崔晓萍,朱光,刘文元.纳米Al2O3/聚酰亚胺复合薄膜的介电与力学性能[J].复合材料学报,2016,33(11):2419-2425.CUI X P,ZHU G,LIU W Y.Dielectric and mechanical properties of nano Al2O3/polyimide composite films[J].Acta Materiae Compositae Sinica,2016,33(11):2419-2425(in Chinese).
[25]吕静,党智敏.低热膨胀系数纳米碳化硅/聚酰亚胺复合薄膜的制备与性能[J].复合材料学报,2011,28(5):41-45.LV J,DANG Z M.Preparation and properties of nano-SiC/polyimide composite films with low thermal expansion characteristic[J].Acta Materiae Compositae Sinica,2011,28(5):41-45(in Chinese).
[26]GUO H L,ZHU S J,CAI D N,et al.Fabrication of ITOglass supported Tb-MOF film for sensing organic solvent[J].Inorganic Chemistry Communications,2014,41:29-32.
[27]CAI D N,GUO H L,WEN L,et al.Fabrication of hierarchical architectures of Tb-MOF by a“green coordination modulation method”for the sensing of heavy metal ions[J].Crystal Engineering Communications,2013,15(34):6702-6708.