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    • 1. 发明申请
    • SOLVENT-RESISTANT ASYMMETRIC HOLLOW FIBER GAS SEPARATION MEMBRANE, AND METHOD FOR PRODUCTION THEREOF
    • 耐溶剂不对称中空纤维气体分离膜及其生产方法
    • US20110048229A1
    • 2011-03-03
    • US12863125
    • 2009-01-19
    • Harutoshi HoshinoTomonori KanougiToshimune YoshinagaYoji KaseKenji Fukunaga
    • Harutoshi HoshinoTomonori KanougiToshimune YoshinagaYoji KaseKenji Fukunaga
    • B01D53/22C08J9/00
    • B01D69/08B01D53/228B01D71/40B01D71/80B01D2323/08B01D2325/24B01D2325/30C08G73/1039C08G73/1042C08G73/1064C08G73/1067D01F6/74
    • An asymmetric hollow fiber gas separation membrane obtained by subjecting an asymmetric hollow fiber polyimide membrane to a heat treatment having a maximum temperature of from 350 to 450° C., wherein the asymmetric hollow fiber polyimide membrane is formed with a polyimide essentially having a repeating unit represented by a general formula (1); is excellent in a solvent resistance and a thermal stability, and as well has such a mechanical strength that a tensile elongation at break is not less than 10% as a hollow fiber membrane. In the general formula (1), 20 to 80 mol % of A is a tetravalent unit based on a biphenyl structure represented by formula (2), 20 to 80 mol % of A is a tetravalent unit based on a diphenylhexafluoropropane structure represented by formula (3), and 0 to 30 mol % of A is a tetravalent unit based on a phenyl structure represented by formula (4); and in the general formula (1), 30 to 70 mol % of R is a divalent unit represented by formula (5) and/or formula (6), and 30 to 70 mol % of R is a divalent unit having one or two other aromatic rings than formula (5) or (6), wherein, R1 and R2 are a hydrogen atom or an organic group, and n is 0, 1 or 2, wherein, R1 and R2 are a hydrogen atom or an organic group, X is —CH2— or —CO—, and n is 0, 1 or 2.
    • 通过使不对称中空纤维聚酰亚胺膜进行350〜450℃的最高温度的热处理而得到的不对称中空纤维气体分离膜,其中,所述不对称中空纤维聚酰亚胺膜形成有基本上具有重复单元的聚酰亚胺 由通式(1)表示; 耐溶剂性和热稳定性优异,作为中空纤维膜,具有拉伸断裂伸长率为10%以上的机械强度。 在通式(1)中,A为20〜80摩尔%,为基于式(2)所示的联苯结构的四价单元,A为20〜80摩尔%,基于式(2)表示的二苯基六氟丙烷结构的四价单元 (3)表示,0〜30摩尔%的A为基于式(4)表示的苯基结构的四价单元。 在通式(1)中,R为作为式(5)和/或式(6)所示的二价单元的30〜70摩尔%,R为30〜70摩尔%,为1或2个 (5)或(6)中的其它芳环,其中R1和R2是氢原子或有机基团,n是0,1或2,其中R1和R2是氢原子或有机基团, X是-CH 2 - 或-CO-,n是0,1或2。
    • 4. 发明授权
    • Solvent-resistant asymmetric hollow fiber gas separation membrane, and method for production thereof
    • 耐溶剂型不对称中空纤维气体分离膜及其制造方法
    • US08580012B2
    • 2013-11-12
    • US12863125
    • 2009-01-19
    • Harutoshi HoshinoTomonori KanougiToshimune YoshinagaYoji KaseKenji Fukunaga
    • Harutoshi HoshinoTomonori KanougiToshimune YoshinagaYoji KaseKenji Fukunaga
    • B01D53/22B01D71/64
    • B01D69/08B01D53/228B01D71/40B01D71/80B01D2323/08B01D2325/24B01D2325/30C08G73/1039C08G73/1042C08G73/1064C08G73/1067D01F6/74
    • An asymmetric hollow fiber gas separation membrane obtained by subjecting an asymmetric hollow fiber polyimide membrane to a heat treatment having a maximum temperature of from 350 to 450° C., wherein the asymmetric hollow fiber polyimide membrane is formed with a polyimide essentially having a repeating unit represented by a general formula (1); is excellent in a solvent resistance and a thermal stability, and as well has such a mechanical strength that a tensile elongation at break is not less than 10% as a hollow fiber membrane. In the general formula (1), 20 to 80 mol % of A is a tetravalent unit based on a biphenyl structure represented by formula (2), 20 to 80 mol % of A is a tetravalent unit based on a diphenylhexafluoropropane structure represented by formula (3), and 0 to 30 mol % of A is a tetravalent unit based on a phenyl structure represented by formula (4); and in the general formula (1), 30 to 70 mol % of R is a divalent unit represented by formula (5) and/or formula (6), and 30 to 70 mol % of R is a divalent unit having one or two other aromatic rings than formula (5) or (6), wherein, R1 and R2 are a hydrogen atom or an organic group, and n is 0, 1 or 2, wherein, R1 and R2 are a hydrogen atom or an organic group, X is —CH2— or —CO—, and n is 0, 1 or 2.
    • 通过使不对称中空纤维聚酰亚胺膜进行350〜450℃的最高温度的热处理而得到的不对称中空纤维气体分离膜,其中,所述不对称中空纤维聚酰亚胺膜形成有基本上具有重复单元的聚酰亚胺 由通式(1)表示; 耐溶剂性和热稳定性优异,作为中空纤维膜,具有拉伸断裂伸长率为10%以上的机械强度。 在通式(1)中,A为20〜80摩尔%,为基于式(2)所示的联苯结构的四价单元,A为20〜80摩尔%,基于式(2)表示的二苯基六氟丙烷结构的四价单元 (3)表示,0〜30摩尔%的A为基于式(4)表示的苯基结构的四价单元。 在通式(1)中,R为作为式(5)和/或式(6)所示的二价单元的30〜70摩尔%,R为30〜70摩尔%,为1或2个 (5)或(6)中的其它芳环,其中R1和R2是氢原子或有机基团,n是0,1或2,其中R1和R2是氢原子或有机基团, X是-CH 2 - 或-CO-,n是0,1或2。
    • 5. 发明授权
    • Asymmetric hollow-fiber gas separation membrane, gas separation method and gas separation membrane module
    • 不对称中空纤维气体分离膜,气体分离法和气体分离膜组件
    • US07803214B2
    • 2010-09-28
    • US11878206
    • 2007-07-23
    • Yoji KaseToshimune YoshinagaKenji FukunagaHarutoshi Hoshino
    • Yoji KaseToshimune YoshinagaKenji FukunagaHarutoshi Hoshino
    • B01D53/22
    • B01D63/02B01D53/22B01D53/228B01D71/64B01D2325/20B01D2325/34
    • The present invention relates to an asymmetric hollow-fiber gas separation membrane made of a polyimide having a specific repeating unit, an improved tensile elongation at break of 15% or more as a hollow-fiber membrane itself, an oxygen gas permeation rate (P′O2) of 4.0×10−5 cm3(STP)/cm2·sec·cmHg or more and a gas ratio of permeation rate of oxygen to nitrogen (P′O2/P′N2) of 4 or more that are measured at 50° C., a gas separation method and a gas separation membrane module using the asymmetric hollow-fiber gas separation membrane.In addition, the present invention relates to an asymmetric hollow-fiber gas separation membrane obtained by heat-treating the asymmetric hollow-fiber gas separation membrane at a maximum temperature of from 350 to 450° C. The asymmetric hollow-fiber gas separation membrane has sufficient mechanical strength even after the heat-treatment at a maximum temperature of from 350 to 450° C.
    • 本发明涉及一种由具有特定重复单元的聚酰亚胺,中空纤维膜本身的拉伸断裂伸长率提高15%以上的不对称中空纤维气体分离膜,氧气渗透速率(P' O2)为4.0×10-5cm 3(STP)/ cm 2·sec·cmHg以上,氧在氮气的渗透速率(P'O2 / P'N2)为50以上时测定的4以上 C.,气体分离方法和使用不对称中空纤维气体分离膜的气体分离膜组件。 另外,本发明涉及通过在350〜450℃的最高温度下热处理不对称中空纤维气体分离膜得到的不对称中空纤维气体分离膜。不对称中空纤维气体分离膜具有 即使在350至450℃的最高温度下的热处理之后也具有足够的机械强度。
    • 6. 发明申请
    • Asymmetric hollow-fiber gas separation membrane, gas separation method and gas separation membrane module
    • 不对称中空纤维气体分离膜,气体分离法和气体分离膜组件
    • US20080017029A1
    • 2008-01-24
    • US11878206
    • 2007-07-23
    • Yoji KaseToshimune YoshinagaKenji FukunagaHarutoshi Hoshino
    • Yoji KaseToshimune YoshinagaKenji FukunagaHarutoshi Hoshino
    • B01D53/22
    • B01D63/02B01D53/22B01D53/228B01D71/64B01D2325/20B01D2325/34
    • The present invention relates to an asymmetric hollow-fiber gas separation membrane made of a polyimide having a specific repeating unit, an improved tensile elongation at break of 15% or more as a hollow-fiber membrane itself, an oxygen gas permeation rate (P′O2) of 4.0×10−5 cm3 (STP)/cm2·sec·cmHg or more and a gas ratio of permeation rate of oxygen to nitrogen (P′O2/P′N2) of 4 or more that are measured at 50° C., a gas separation method and a gas separation membrane module using the asymmetric hollow-fiber gas separation membrane. In addition, the present invention relates to an asymmetric hollow-fiber gas separation membrane obtained by heat-treating the asymmetric hollow-fiber gas separation membrane at a maximum temperature of from 350 to 450° C. The asymmetric hollow-fiber gas separation membrane has sufficient mechanical strength even after the heat-treatment at a maximum temperature of from 350 to 450° C.
    • 本发明涉及一种由具有特定重复单元的聚酰亚胺,中空纤维膜本身的拉伸断裂伸长率提高15%以上的不对称中空纤维气体分离膜,氧气渗透速率(P' (STP)/ cm 2·sec·sec·cmHg以上,和/或 在50℃下测得的4或更多的氧气与氮气的渗透速率(P'/ O 2 / P'N 2 N 2)的气体比,气体分离方法 以及使用该不对称中空纤维气体分离膜的气体分离膜组件。 另外,本发明涉及通过在350〜450℃的最高温度下热处理不对称中空纤维气体分离膜得到的不对称中空纤维气体分离膜。不对称中空纤维气体分离膜具有 即使在350至450℃的最高温度下的热处理之后也具有足够的机械强度。