JPS63264121A - Polyimide membrane for separating gas - Google Patents
Polyimide membrane for separating gasInfo
- Publication number
- JPS63264121A JPS63264121A JP62097891A JP9789187A JPS63264121A JP S63264121 A JPS63264121 A JP S63264121A JP 62097891 A JP62097891 A JP 62097891A JP 9789187 A JP9789187 A JP 9789187A JP S63264121 A JPS63264121 A JP S63264121A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- tetracarboxylic acid
- polyimide
- membrane
- skeleton
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 229920001721 polyimide Polymers 0.000 title claims abstract description 58
- 239000004642 Polyimide Substances 0.000 title claims abstract description 56
- 238000000926 separation method Methods 0.000 claims abstract description 41
- -1 aromatic tetracarboxylic acid Chemical class 0.000 claims abstract description 37
- 125000003118 aryl group Chemical group 0.000 claims abstract description 37
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000006157 aromatic diamine group Chemical group 0.000 claims abstract 3
- 239000002253 acid Substances 0.000 claims description 10
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 5
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 3
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 claims 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 55
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 32
- 239000001569 carbon dioxide Substances 0.000 description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- 239000010408 film Substances 0.000 description 13
- 150000004984 aromatic diamines Chemical group 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229920005575 poly(amic acid) Polymers 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 102100021587 Embryonic testis differentiation protein homolog A Human genes 0.000 description 7
- 101000898120 Homo sapiens Embryonic testis differentiation protein homolog A Proteins 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 6
- 125000006159 dianhydride group Chemical group 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 241000315040 Omura Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- MILSYCKGLDDVLM-UHFFFAOYSA-N 2-phenylpropan-2-ylbenzene Chemical class C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 MILSYCKGLDDVLM-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- DVXYMCJCMDTSQA-UHFFFAOYSA-N 3-[2-(3-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=CC(N)=CC=1C(C)(C)C1=CC=CC(N)=C1 DVXYMCJCMDTSQA-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
[発明の分野]
本発明は、ポリイミド気体分J11膜に関するものであ
る。さらに詳しくは1本発明は、二酸化炭素を含有する
気体混合物から二酸化炭素を分離したり、濃縮したりす
るために有用な、芳香族ポリイミドからなる均質層を有
する気体分離膜に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to polyimide gaseous J11 membranes. More specifically, the present invention relates to a gas separation membrane having a homogeneous layer made of aromatic polyimide, which is useful for separating or concentrating carbon dioxide from a gas mixture containing carbon dioxide.
〔発明の背景]
従来、ポリイミドからなる気体分離膜としては1種々の
ものが知られており1例えば、特開昭57−15819
号公報にはビフェニルテトラカルボン酸系のポリイミド
からなる気体分離層を有する気体分離材料が開示されて
いる。しかし、ビフェニルテトラカルボン酸系の芳香族
ポリイミド製気体分gI膜は、二酸化炭素を含有する気
体混合物から二酸化炭素を分離したり、濃縮したりする
用途に使用する場合に、二酸化炭素の透過性能が充分と
はいえない。[Background of the Invention] Conventionally, various types of gas separation membranes made of polyimide have been known.
The publication discloses a gas separation material having a gas separation layer made of biphenyltetracarboxylic acid-based polyimide. However, when biphenyltetracarboxylic acid-based aromatic polyimide gas component gI membranes are used for separating or concentrating carbon dioxide from a gas mixture containing carbon dioxide, the carbon dioxide permeation performance is poor. Not enough.
[発明の目的]
本発明は、二酸化炭素を含む気体混合物から二酸化炭素
を分離、濃縮するために有用であって。[Object of the Invention] The present invention is useful for separating and concentrating carbon dioxide from a gas mixture containing carbon dioxide.
耐熱性を有する、新規な芳香族ポリイミド製気体分!1
39を提供することを目的とする。A new aromatic polyimide gas component with heat resistance! 1
The purpose is to provide 39.
[発明の要旨]
本発明は、芳香族テトラカルボン酸骨格と芳香族ジアミ
ン骨格とからなる芳香族ポリイミドから形成されるポリ
イミド気体分離膜であって1、上記の芳香族テトラカル
ボン酸骨格が、ジフェニルエーテルテトラカルボン酸成
分lO〜100モル%と、オキシ基を持たない芳香族テ
トラカルボン酸成分O〜90モル%とからなることを特
徴とするポリイミド気体分離膜にある。[Summary of the Invention] The present invention provides a polyimide gas separation membrane formed from an aromatic polyimide comprising an aromatic tetracarboxylic acid skeleton and an aromatic diamine skeleton, wherein the aromatic tetracarboxylic acid skeleton is composed of diphenyl ether. A polyimide gas separation membrane is characterized in that it consists of a tetracarboxylic acid component 10 to 100 mol% and an aromatic tetracarboxylic acid component having no oxy group O to 90 mol%.
[発明の詳細な説明]
本発明は、ジフェニルエーテルテトラカルボン酸骨格を
主とする芳香族テトラカルボン酸骨格と、芳香族ジアミ
ン骨格とからなる芳香族ポリイミドから形成され、優れ
た二酸化炭素透過性能を有するポリイミド気体分離膜に
関するものである。[Detailed Description of the Invention] The present invention is made of an aromatic polyimide consisting of an aromatic tetracarboxylic acid skeleton mainly consisting of a diphenyl ether tetracarboxylic acid skeleton and an aromatic diamine skeleton, and has excellent carbon dioxide permeability. This invention relates to polyimide gas separation membranes.
上記のジフェニルエーテルテトラカルボン酸は、一般式
[I] :
[11
で示される。その製法は、特開昭55−136246号
公報に開示されており、主として一般式[I]で示され
るジフェニルエーテルテトラカルボン酸またはその誘導
体からなる芳香族テトラカルボン酸骨格と芳香族ジアミ
ン骨格とから形成される芳香族ポリイミドが知られてい
る。The above diphenyl ether tetracarboxylic acid is represented by the general formula [I]: [11]. The manufacturing method is disclosed in JP-A-55-136246, and is formed mainly from an aromatic tetracarboxylic acid skeleton consisting of diphenyl ether tetracarboxylic acid or a derivative thereof represented by the general formula [I] and an aromatic diamine skeleton. Aromatic polyimides are known.
本発明の芳香族ポリイミドに使用するジフェニルエーテ
ルテトラカルボン酸成分は、3.3’。The diphenyl ether tetracarboxylic acid component used in the aromatic polyimide of the present invention is 3.3'.
4.4°−ジフェニルエーテルテトラカルボン酸、ある
いは2,3.3’、4’−ジフェニルエーテルテトラカ
ルボン酸、またはこれらの酸二無水物、エステル化物、
ハロゲン化塩などのジフェニルエーテルテトラカルボン
酸誘導体であればよいが、酸二無水物である場合に特に
有利に使用できる。4.4°-diphenyl ether tetracarboxylic acid, or 2,3.3',4'-diphenyl ether tetracarboxylic acid, or acid dianhydrides and esters thereof,
Any diphenyl ether tetracarboxylic acid derivative such as a halide salt may be used, but an acid dianhydride can be particularly advantageously used.
未発IJJの芳香族ポリイミドに使用する芳香族テトラ
カルボン酸成分は、上記ジフェニルエーテルテトラカル
ボン酸またはその誘導体を、少なくとも10モル5以上
、さらに30モル%以上、特に45〜100モル%含有
していることが好ましい。The aromatic tetracarboxylic acid component used in the aromatic polyimide of undeveloped IJJ contains at least 10 mol 5 or more, more 30 mol % or more, especially 45 to 100 mol % of the diphenyl ether tetracarboxylic acid or its derivative. It is preferable.
上記の芳香族テトラカルボン酸成分において、ジフェニ
ルエーテルテトラカルボン酸成分が10モル5未満の場
合には、二酸化炭素について実用上充分な透過性能が得
られないので、好ましくなI/)。In the above aromatic tetracarboxylic acid component, if the amount of the diphenyl ether tetracarboxylic acid component is less than 10 mol 5, practically sufficient permeation performance for carbon dioxide cannot be obtained, so I/) is preferred.
また、上記の芳香族テトラカルボン酸成分は、ジフェニ
ルエーテルテトラカルボン酸成分とともに、オキシ基を
持たない芳香族テトラカルボン酸成分を含有するもので
あってもよい。Moreover, the above-mentioned aromatic tetracarboxylic acid component may contain an aromatic tetracarboxylic acid component having no oxy group together with the diphenyl ether tetracarboxylic acid component.
ジフェニルエーテルテトラカルボン酸成分とともに使用
することができる、上記のオキシ基を持たない芳香族テ
トラカルボン酸成分としては、3.3”、4,4“−ビ
フェニルテトラカルボン酸,あるいは2,3,3°,4
°−ビフェニルテトラカルボン酸、またはこれらの酸二
無水物,低級アルコールエステル化物などのビフェニル
テトラカルボン酸類;3,3°,4,4“−ベンゾフェ
ノンテトラカルボン酸、あるいは2,3。The aromatic tetracarboxylic acid component without an oxy group that can be used with the diphenyl ether tetracarboxylic acid component includes 3.3", 4,4"-biphenyltetracarboxylic acid, or 2,3,3° ,4
Biphenyltetracarboxylic acids such as °-biphenyltetracarboxylic acid, acid dianhydrides and lower alcohol esters thereof; 3,3°,4,4"-benzophenonetetracarboxylic acid, or 2,3.
3°,4°−ベンゾフェノンテトラカルボン酸、または
これらの酸二無水物,低級アルコールエステル化物など
のベンゾフェノンテトラカルボン酸類:さらに、ピロメ
リット酸,その酸二無水物、エステル化物などのどロメ
リット酸類などを挙げることができる。Benzophenonetetracarboxylic acids such as 3°, 4°-benzophenonetetracarboxylic acid, or their acid dianhydrides and lower alcohol esters: In addition, pyromellitic acids, such as pyromellitic acid, its acid dianhydrides, and esterified products, etc. can be mentioned.
未発IIにおいては、オキシノ、(を持たない芳香族テ
トラカルボン酸成分として、3.3’,4。In undeveloped II, 3.3',4 as an aromatic tetracarboxylic acid component without oxino, (.
4′−ビフェニルテトラカルボン
2、3,3°,4′−ビフェニルテトラカルボン酸、ま
たはこれらの酸二無水物を使用することが好ましい.上
述のビフェニルテトラカルボンm類を用いることにより
、後述するように有機極性溶媒中で芳香族ポリアミック
酸または芳香族ポリイミドを生成させたのち、安定なド
ープ液が得られ、製1模性が向上するので好適である。It is preferable to use 4'-biphenyltetracarboxylic acid, 2,3,3°,4'-biphenyltetracarboxylic acid, or acid dianhydrides thereof. By using the above-mentioned biphenyltetracarboxes m, after producing aromatic polyamic acid or aromatic polyimide in an organic polar solvent as described later, a stable dope solution can be obtained and the product quality can be improved. Therefore, it is suitable.
−L述のオキシ基を1.シたない芳香族テトラカルボン
酸成分は、全芳香族テトラカルボン酸成分の90モル%
以下、さらに70モル%以下、特に55モル%以下であ
ることが好ましい。-L oxy group as described in 1. The solid aromatic tetracarboxylic acid component is 90 mol% of the total aromatic tetracarboxylic acid component.
Below, it is further preferably 70 mol% or less, particularly 55 mol% or less.
本発明の芳香族ポリイミドを形成する芳香族ジアミン成
分としては、4,4°−ジアミノジフェニルエーテル、
3,3′−ジメチル−4,4°−ジアミノジフェニルエ
ーテル、3,3°−ジメトキシ−4.4”−ジアミノジ
フェニルエーテル、3、3゛−ジアミノジフェニルエー
テルなどのジフェニルエーテル系化合物,4.4’−ジ
アミノジフェニルメタン、3.3′−ジアミノジフェニ
ルメタンなどのジフェニルメタン系化合物、3。The aromatic diamine component forming the aromatic polyimide of the present invention includes 4,4°-diaminodiphenyl ether,
Diphenyl ether compounds such as 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4''-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane , 3. Diphenylmethane compounds such as 3'-diaminodiphenylmethane, 3.
3°−ジアミノジフェこルスルフィド、4.4“−ジア
ミノジフェニルスルフィド、3.3°−ジアミノジフェ
ニルスルホン、4.4°−ジアミノジフェニルスルホン
などのジアミノジフェニルスルフィド系化合物、4.4
′−ジアミノビベンジル、4,4゛−ジアミノ−2,2
°−ジメチルベンチジンどのビベンジル系化合物、4.
4’−ジアミノベンゾフェノン、3.3’−ジアミノベ
ンゾフェノンなどのベンゾフェノン系化合物、2、2−
ビス(3−アミノフェニル)プロパン。Diaminodiphenylsulfide compounds such as 3°-diaminodiphenylsulfide, 4.4″-diaminodiphenylsulfide, 3.3°-diaminodiphenylsulfone, 4.4°-diaminodiphenylsulfone, 4.4
'-Diaminobibenzyl, 4,4'-diamino-2,2
Bibenzyl compounds such as °-dimethylbenzidine, 4.
Benzophenone compounds such as 4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 2,2-
Bis(3-aminophenyl)propane.
2 、 2 − ヒス(4−アミノフェニル)プロパン
、2、2−ビス[4− (4 ’ーアミノフェノキシ)
フェニル]プロパンなどの2,2−ビス(フェニル)プ
ロパン系化合物、3.3′−ジメチルベンチジン、3,
3′−ジメトキシベンチジンなどのベンチジン系化合物
,さらに、O−ジアニシジン、O−、m−、p−フェニ
レンジアミン、3。2,2-his(4-aminophenyl)propane, 2,2-bis[4-(4'-aminophenoxy)
2,2-bis(phenyl)propane compounds such as phenyl]propane, 3,3'-dimethylbenzidine, 3,
Benzidine-based compounds such as 3'-dimethoxybenzidine, O-dianisidine, O-, m-, p-phenylenediamine, 3.
5−ジアミノ安り香酸、2.6−ジンミツビリジンなど
を挙げることができる。Examples include 5-diaminobenzoic acid and 2,6-dinemitubiridine.
本発明に使用する芳香族ジアミン成分としては、」二記
の群から選ばれた芳香族ジアミンを、単独で,あるいは
混合して用いることができるが、4、4′−ジアミノジ
フェニルエーテルまたは0−ジアニシジンを単独で用い
ることが好ましい。As the aromatic diamine component used in the present invention, aromatic diamines selected from the following groups can be used alone or in combination, including 4,4'-diaminodiphenyl ether or 0-dianisidine. It is preferable to use alone.
本発明の気体分離膜の製造に使用される芳香族ポリアミ
ック酸(ポリイミド前駆体)あるいは芳香族ポリイミド
は、上述の芳香族テトラカルボン酸成分と略等モルの上
述の芳香族ジアミン成分とから得られるものであれば公
知のどのような方法で製造されたものであってもよい。The aromatic polyamic acid (polyimide precursor) or aromatic polyimide used in the production of the gas separation membrane of the present invention is obtained from the above-mentioned aromatic tetracarboxylic acid component and the above-mentioned aromatic diamine component in approximately equal moles. It may be manufactured by any known method.
上記の芳香族ポリアミック酸は、その対数粘度(測定温
度:30℃、濃度:0.5g/100mfL溶奴、溶媒
二Nーメチルー2ーピロリドン)が0.1〜7、特に0
.2〜5程度であるような重合体であることが好ましく
、また、芳香族ポリイミドは、その対数粘度(測定温度
=30℃、濃度: 0.5g7100ml溶媒、溶媒:
p−クロルフェノール4容1+o−クロルフェノールl
容量)が0.1〜7、特に0.2〜5程度であるような
重合体であることが好ましい。The above aromatic polyamic acid has a logarithmic viscosity (measurement temperature: 30°C, concentration: 0.5 g/100 mfL melt, solvent 2N-methyl-2-pyrrolidone) of 0.1 to 7, especially 0.
.. It is preferable that the aromatic polyimide is a polymer whose logarithmic viscosity (measurement temperature = 30°C, concentration: 0.5 g 7100 ml solvent, solvent:
p-chlorophenol 4 volumes 1 + o-chlorophenol 1
It is preferable to use a polymer having a capacitance of about 0.1 to 7, particularly about 0.2 to 5.
なお、対数粘度は1重合度または分子量とかなり相関が
あり1次に示す計算式によって算出された値である。Note that the logarithmic viscosity has a considerable correlation with the degree of polymerization or the molecular weight, and is a value calculated using the formula shown in the first order.
対数粘度=(自然対数(溶液の粘度/溶媒の粘度))/
溶液中のポリマーの濃度
本発明のポリイミド気体分離膜は、上述の芳香族テトラ
カルボン酸骨格と芳香族ジアミン骨格とから形成された
芳香族ポリアミック酸、または芳香族ポリイミドの有機
溶媒溶液を製膜用ドープ液として使用して、そのドープ
液から薄膜を形成し、溶媒を除去して固化する乾燥工程
を主体にして製膜する乾式製脱法、またはドープ液から
形成した薄膜を凝固液と接触凝固させて製膜する湿式製
膜法により、平膜状、中空糸状など種々の構造のポリイ
ミド膜を得ることができる。Logarithmic viscosity = (natural logarithm (solution viscosity / solvent viscosity)) /
Concentration of Polymer in Solution The polyimide gas separation membrane of the present invention uses an organic solvent solution of aromatic polyamic acid or aromatic polyimide formed from the above-mentioned aromatic tetracarboxylic acid skeleton and aromatic diamine skeleton for membrane formation. A dry process in which a thin film is formed from the dope by using it as a dope, and the film is formed mainly through a drying process in which the solvent is removed and solidified, or a thin film formed from the dope is coagulated by contact with a coagulation solution. Polyimide membranes with various structures such as flat membranes and hollow fibers can be obtained by the wet membrane-forming method.
例えば1本発明のポリイミド気体分離膜の製造方法とし
ては、下記のような乾式製11)ff法を挙げることが
できる。For example, as a method for manufacturing the polyimide gas separation membrane of the present invention, the following dry method 11) ff method can be mentioned.
(A)ポリアミック酸の溶液からの製膜法上述の芳香族
テトラカルボン酸成分と、芳香族ジアミン成分とを略等
モル、有機極性溶媒中で。(A) Film forming method from a solution of polyamic acid The above-mentioned aromatic tetracarboxylic acid component and aromatic diamine component are mixed in approximately equal moles in an organic polar solvent.
約100℃以下、特に60℃以下の温度で重合して芳香
族ポリアミック酸を製造する。The aromatic polyamic acid is produced by polymerizing at a temperature of about 100°C or less, particularly 60°C or less.
その芳香族ポリアミック酸の有機極性溶媒の溶液(ポリ
マー濃度:約3〜30重量%)を、製膜用ドープ液とし
て使用し、約10−100℃の温度の大村上に塗布また
は流延してドープ液から薄膜を形成して、次いで、その
薄膜から溶媒を徐々に蒸発除去すると共に、次第に加熱
、昇温して、芳香族ポリアミック酸のアミド−酸結合を
イミド環化して芳香族ポリイミドを得る。A solution of the aromatic polyamic acid in an organic polar solvent (polymer concentration: about 3 to 30% by weight) was used as a dope solution for film formation, and was applied or cast onto a Omura surface at a temperature of about 10 to 100°C. A thin film is formed from the dope liquid, and then the solvent is gradually removed by evaporation from the thin film, and the temperature is gradually heated to imide-cyclize the amide-acid bond of the aromatic polyamic acid to obtain an aromatic polyimide. .
最後に約150〜350℃の温度に充分加熱して乾燥、
熱処理して芳香族ポリイミドの均質膜を形成する乾式I
III膜方法。Finally, heat it sufficiently to a temperature of about 150 to 350 degrees Celsius and dry it.
Dry process I to form a homogeneous film of aromatic polyimide by heat treatment
III Membrane Method.
(B)ポリイミドの有機溶媒溶液からの製膜法上述の芳
香族テトラカルボン酸成分と、芳香族ジアミン成分とを
略等モル、フェノール系化合物の有機溶媒中、約140
℃以上の温度で一段階で重合およびイミド化して、芳香
族ポリイミドを形成する。(B) Film forming method from polyimide organic solvent solution The above-mentioned aromatic tetracarboxylic acid component and aromatic diamine component are mixed in approximately equal moles, about 140% in an organic solvent of a phenolic compound.
It is polymerized and imidized in one step at temperatures above 0.degree. C. to form an aromatic polyimide.
この芳香族ポリイミドの有機極性溶媒溶液(濃度:約3
〜30重量%)をドープ液として使用し、約30−15
0℃の温度の大村上に塗布または流延してドープ液から
薄膜を形成し、次いで。A solution of this aromatic polyimide in an organic polar solvent (concentration: about 3
~30% by weight) is used as the dope, and approximately 30-15
A thin film is formed from the dope solution by coating or casting on the Omura at a temperature of 0°C, and then.
その薄膜から溶媒を徐々に蒸発、除去する。The solvent is gradually evaporated and removed from the thin film.
最後に150〜400℃、特に170〜350℃の温度
で充分に乾燥、熱処理して、芳香族ポリイミドの均質膜
を形成する乾式製膜方法。Finally, a dry film forming method in which a homogeneous film of aromatic polyimide is formed by sufficiently drying and heat-treating at a temperature of 150 to 400°C, particularly 170 to 350°C.
上述の均質膜の製造において、最後の高温での乾燥、熱
処理は、使用されている芳香族ポリイミドが溶融しない
温度で行うことは言うまでもないことであり、その高温
での乾燥、熱処理は、約180〜350℃の温度範囲内
において、約0.5〜10時間行うことが最適であり、
この高温の熱処理によって、均質膜の気体分離性ず駈が
著しく向1する。In the production of the above-mentioned homogeneous membrane, it goes without saying that the final high-temperature drying and heat treatment is carried out at a temperature at which the aromatic polyimide used does not melt. It is optimal to carry out for about 0.5 to 10 hours within a temperature range of ~350°C,
This high-temperature heat treatment significantly improves the gas separation properties of the homogeneous membrane.
上述の均質膜の製造において、基材として表面の平滑な
材料(例えば、ガラス板、平面平滑な銅板1表面平滑な
全屈ロールまたはベルトなど)を使用して均質膜を形成
した後に基材から膜を引き剥がせば、極めて趨いフィル
ム状の均質膜が得られる。この極めて薄いフィルム状の
均質膜は、そのまま気体分離材料として使用することも
できるが、他の多孔質膜とtajFしたり貼合わせたり
して使用することもできる。In the production of the above-mentioned homogeneous film, after forming a homogeneous film by using a material with a smooth surface as the base material (for example, a glass plate, a flat smooth copper plate, a fully curved roll or belt with a smooth surface, etc.), from the base material. When the membrane is peeled off, a highly uniform film-like membrane is obtained. This extremely thin film-like homogeneous membrane can be used as it is as a gas separation material, but it can also be used by tajF or bonding with other porous membranes.
さらに、上述の均質膜の製造法において基材として多孔
質膜を使用すれば、上述のようにして均質膜が多孔質膜
の表面に一体に形成された複合気体分離材料が得られる
。Furthermore, if a porous membrane is used as the base material in the above-described homogeneous membrane manufacturing method, a composite gas separation material in which the homogeneous membrane is integrally formed on the surface of the porous membrane as described above can be obtained.
上述の芳香族ポリアミック酸の製造およびそのドープ液
の調製に使用される有機極性溶媒としては、N−メチル
−2−ピロリドン、N、N−ジメチルアセトアミド、N
、N−ジメチルホルムアミド、ジメチルスルホキシド、
テトラメチル尿素などを挙げることができる。The organic polar solvents used in the production of the aromatic polyamic acid and the preparation of its dope solution include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.
, N-dimethylformamide, dimethyl sulfoxide,
Examples include tetramethylurea.
上述の芳香族ポリイミドの製造およびそのポリイミド膜
の製膜用のドープ液の調製に使用される有機極性溶媒と
しては、フェノール、クレゾール、モノハロゲン化フェ
ノール、モノハロゲン化モノアルキルフェノールなどの
フェノール系溶媒または、N−メチル−2−ピロリドン
、N、N−ジメチルアセトアミドなどのアミド系溶媒を
挙げることができる。The organic polar solvent used in the production of the above-mentioned aromatic polyimide and the preparation of the dope solution for forming the polyimide film may include phenolic solvents such as phenol, cresol, monohalogenated phenol, monohalogenated monoalkylphenol, etc. , N-methyl-2-pyrrolidone, and N,N-dimethylacetamide.
本発明のポリイミド気体外!膜は、その膜厚が厚くなる
に従って気体透過速度が低下するので、実用的にはその
膜厚が20uLm以下であることが好ましい。Outside the polyimide gas of the present invention! Since the gas permeation rate of the membrane decreases as the membrane thickness increases, it is practically preferable that the membrane thickness is 20 uLm or less.
[9,明の効果]
本発明のポリイミド気体分離膜は、二酸化炭素について
従来の気体分#膜に比べて特に優れた選択透過性を有し
ている気体分離膜である。[9. Effect of light] The polyimide gas separation membrane of the present invention is a gas separation membrane that has particularly excellent permselectivity for carbon dioxide compared to conventional gas separation membranes.
従って、本発明のポリイミド気体分離膜は、二酸化炭素
を含有する気体混合物から二酸化炭素を分離、精製、濃
縮する用途に好適に用いることができる。Therefore, the polyimide gas separation membrane of the present invention can be suitably used for separating, purifying, and concentrating carbon dioxide from a gas mixture containing carbon dioxide.
さらに、本発明のポリイミド気体分離膜は、公知の芳香
族ポリイミド気体分離膜に対して同等の耐熱性、耐薬品
性、機械的強度を有している。Furthermore, the polyimide gas separation membrane of the present invention has heat resistance, chemical resistance, and mechanical strength equivalent to those of known aromatic polyimide gas separation membranes.
次に実施例および比較例を示す、実施例および比較例に
おいて、気体透過テストは1面積14.65Crn’の
ステンレス製のセルに気体分離膜を設置し、水素、二酸
化炭素およびメタンの混合気体を、50℃、0.5〜2
k g / cゴに加圧して膜の一方の側に接触させ
膜の他方の側を減圧に保つことにより減圧した側に透過
気体の混合物を1!)、該気体混合物の成分および各成
分の容量をガスクロマトグラフ分析で測定し、各気体成
分の透過係数と各気体成分相互の分離係数とを算出した
。Next, Examples and Comparative Examples will be shown. In the Examples and Comparative Examples, a gas permeation test was conducted by installing a gas separation membrane in a stainless steel cell with an area of 14.65 Crn', and passing a mixed gas of hydrogen, carbon dioxide, and methane. , 50℃, 0.5-2
The mixture of permeate gases is applied to the vacuum side by applying pressure to one side of the membrane and keeping the other side of the membrane at vacuum. ), the components of the gas mixture and the volume of each component were measured by gas chromatographic analysis, and the permeability coefficient of each gas component and the mutual separation coefficient of each gas component were calculated.
本発明において、気体透過膜の気体透過速度の程度を示
す気体透過係数(c m” * c m / c tn
’ m秒・cmHg)は、次に示す計算式に従って算出
されたイめである。In the present invention, the gas permeability coefficient (cm" * cm / c tn
' msec·cmHg) is calculated according to the formula shown below.
気体透過係数=(気体の透過量×膜厚)/(膜面積×透
過時間×圧力差)
[実施例1]
攪拌機および窒素導入管の設けられたセパラブルフラス
コに、3.3’、4.4’−ジフェニルエーテルテトラ
カルボン酸二無水物(以下ETDAと略す)20ミリモ
ル、4,4°−ジアミノジフェニルエーテル(以下DA
DEと略す)20ミリモルおよびp−クロルフェノール
85gを入れて、窒素雰囲気下に反応液を攪拌しながら
常温(25℃)から180℃まで約60分間で昇温し、
さらに、その反応液を約20時間180℃に保持して重
合およびイミド化を一段階で行ない、粘稠なポリイミド
溶液を得た。このポリイミド溶液は、ポリマー濃度が約
10重量%であった。Gas permeation coefficient = (gas permeation amount x membrane thickness) / (membrane area x permeation time x pressure difference) [Example 1] In a separable flask equipped with a stirrer and a nitrogen introduction tube, 3.3', 4. 20 mmol of 4'-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as ETDA), 20 mmol of 4,4°-diaminodiphenyl ether (hereinafter abbreviated as DA)
20 mmol (abbreviated as DE) and 85 g of p-chlorophenol were added, and the temperature was raised from room temperature (25°C) to 180°C in about 60 minutes while stirring the reaction solution under a nitrogen atmosphere.
Further, the reaction solution was maintained at 180° C. for about 20 hours to carry out polymerization and imidization in one step to obtain a viscous polyimide solution. This polyimide solution had a polymer concentration of about 10% by weight.
このポリイミド溶液を加圧下に濾過し脱泡して製膜用の
ドープ液を得た。このドープ液をガラス板上に流延し、
ドクターブレードで均一”な厚さく約0.2mm)とし
て、ドープ液のI8I膜を形成し、その薄膜を窒素気流
中で3時間約100℃に維持して、溶媒を徐々に蒸発し
て除去し1次いで室温から300℃まで約1時間で昇温
し、その後300℃で1時間、乾燥・熱処理して、厚さ
7pmの均質膜を形成した。この均質膜を気体分離膜と
して使用し、上述の方法で気体透過テストを行なった。This polyimide solution was filtered and defoamed under pressure to obtain a dope solution for film formation. This dope solution is cast onto a glass plate,
An I8I film of the dope solution was formed using a doctor blade to a uniform thickness of approximately 0.2 mm, and the thin film was maintained at approximately 100°C for 3 hours in a nitrogen stream to gradually evaporate and remove the solvent. 1. Next, the temperature was raised from room temperature to 300°C in about 1 hour, and then dried and heat-treated at 300°C for 1 hour to form a homogeneous membrane with a thickness of 7 pm. This homogeneous membrane was used as a gas separation membrane, and the above-mentioned A gas permeation test was conducted using the method described below.
その結果を第1表に示す。The results are shown in Table 1.
[実施例2]
芳香族テトラカルボン酸成分として、ETDA20ミリ
モルの代わりに、ETDA16ミリモルおよび3,3°
、4,4°−ビフェニルテトラカルボン酸二無水物(以
下BPDAと略す)4ミリモルを使用した外は実施例1
と同様に厚さ71Lmの芳香族ポリイミド均質膜を形成
し、この均質膜を気体分子a膜として気体透過テストを
行なった。[Example 2] As the aromatic tetracarboxylic acid component, instead of 20 mmol of ETDA, 16 mmol of ETDA and 3.3°
, Example 1 except that 4 mmol of 4,4°-biphenyltetracarboxylic dianhydride (hereinafter abbreviated as BPDA) was used.
A homogeneous aromatic polyimide film having a thickness of 71 Lm was formed in the same manner as above, and a gas permeation test was conducted using this homogeneous film as a gas molecule a film.
その結果を第1表に示す。The results are shown in Table 1.
[実施例3]
芳香族テトラカルボン酸成分として、ETDA20ミリ
モルの代わりに、ETDA 10ミリモルおよびBPD
AIOミリモルを使用した外は実施例1と同様にして厚
さ7uLmの芳香族ポリイミド均質膜を形成し、この均
質膜を気体分離膜として気体透過テストを行なった。そ
の結果を第1表に示す。[Example 3] As the aromatic tetracarboxylic acid component, 10 mmol of ETDA and BPD were used instead of 20 mmol of ETDA.
A homogeneous aromatic polyimide membrane having a thickness of 7 μLm was formed in the same manner as in Example 1 except that mmol of AIO was used, and a gas permeation test was conducted using this homogeneous membrane as a gas separation membrane. The results are shown in Table 1.
[比較例1]
芳香族テトラカルボン酸成分としてETDAの代わりに
BPDAを使用した外は、実施例1と同様にして厚さ7
μmの芳香族ポリイミド均質膜を形成し、この均質膜を
気体分離膜として気体透過テストを行なった。その結果
を第1表に示す。[Comparative Example 1] A product with a thickness of 7 was prepared in the same manner as in Example 1, except that BPDA was used instead of ETDA as the aromatic tetracarboxylic acid component.
A micrometer-thick aromatic polyimide homogeneous membrane was formed, and a gas permeation test was conducted using this homogeneous membrane as a gas separation membrane. The results are shown in Table 1.
[実施例4]
芳香族ジアミン成分としてDADEの代わりに0−ジア
ニシジンを使用した外は実施例1と同様にして厚さ7μ
mの芳香族ポリイミド均質膜を形成し、この均質膜を気
体分離膜として気体透過テストを行なった。その結果を
第1表に示す。[Example 4] A product with a thickness of 7 μm was prepared in the same manner as in Example 1 except that 0-dianisidine was used instead of DADE as the aromatic diamine component.
A homogeneous aromatic polyimide membrane of m was formed, and a gas permeation test was conducted using this homogeneous membrane as a gas separation membrane. The results are shown in Table 1.
[比較例2]
芳香族テトラカルボン酸成分としてETDAの代わりに
BPDAを使用した外は、実施例4と同様にして厚さ?
#Lmの芳香族ポリイミド均質膜を形成し、この均質膜
を気体分離膜として気体透過テストを行なった。その結
果を第1表に示す。[Comparative Example 2] The thickness was determined in the same manner as in Example 4, except that BPDA was used instead of ETDA as the aromatic tetracarboxylic acid component.
A homogeneous aromatic polyimide membrane of #Lm was formed, and a gas permeation test was conducted using this homogeneous membrane as a gas separation membrane. The results are shown in Table 1.
第1表
気 体 透 過 係 数 メタンに対す(XIO−”
) る分離係数
H,Co2 CH,co2
実施例1 5.1 1.2 0.0097 12
4実施例2 4.2 1.0 0.0077 1
30実施例3 3.0 G、8 0.0063
128比較例1 1.8 G、22 0.0024
92実施例4 7.2 1.6 0.0145
110比較例2 3.6 (1,600,009
861気体透過係数:cm″m c m / c ni
’ m秒* cmHgメタンに対する分離係数=(CO
,の気体透過係数)/(メタンの気体透過係数)
第1表から1本発明のポリイミド気体分離膜は、芳香族
テトラカルボン酸骨格がBPDAのみから形成された気
体分離膜に比較して、二酸化炭素の透過係数が高く、メ
タンに対する二酸化炭素の分離係数が大であり、優れた
二酸化炭素透過性能を有していることが明らかである。Table 1 Gas permeation coefficient for methane (XIO-”
) Separation coefficient H, Co2 CH, co2 Example 1 5.1 1.2 0.0097 12
4 Example 2 4.2 1.0 0.0077 1
30 Example 3 3.0 G, 8 0.0063
128 Comparative Example 1 1.8 G, 22 0.0024
92 Example 4 7.2 1.6 0.0145
110 Comparative Example 2 3.6 (1,600,009
861 Gas permeability coefficient: cm″m cm/c ni
'm seconds * cmHg Separation factor for methane = (CO
, gas permeability coefficient)/(gas permeability coefficient of methane) From Table 1, the polyimide gas separation membrane of the present invention has a lower carbon dioxide It is clear that the carbon permeability coefficient is high and the separation coefficient of carbon dioxide with respect to methane is large, so that it has excellent carbon dioxide permeation performance.
Claims (1)
とからなる芳香族ポリイミドから形成されるポリイミド
気体分離膜であって、 上記の芳香族テトラカルボン酸骨格が、ジフェニルエー
テルテトラカルボン酸成分10〜100モル%と、オキ
シ基を持たない芳香族テトラカルボン酸成分0〜90モ
ル%とから形成されたものであることを特徴とするポリ
イミド気体分離膜。 2、芳香族テトラカルボン酸骨格が、ジフェニルエーテ
ルテトラカルボン酸成分30〜100モル%と、オキシ
基を持たない芳香族テトラカルボン酸成分0〜70モル
%とから形成されたものであることを特徴とする特許請
求の範囲第1項記載のポリイミド気体分離膜。 3、芳香族テトラカルボン酸骨格が、ジフェニルエーテ
ルテトラカルボン酸成分45〜100モル%と、オキシ
基を持たない芳香族テトラカルボン酸成分0〜55モル
%とから形成されたものであることを特徴とする特許請
求の範囲第1項記載のポリイミド気体分離膜。 4、ジフェニルエーテルテトラカルボン酸成分が、3,
3′,4,4′−ジフェニルエーテルテトラカルボン酸
二無水物であることを特徴とする特許請求の範囲第1項
記載のポリイミド気体分離膜。 5、ジフェニルエーテルテトラカルボン酸成分が、2,
3,3′,4′−ジフェニルエーテルテトラカルボン酸
二無水物であることを特徴とする特許請求の範囲第1項
記載のポリイミド気体分離膜。 6、オキシ基を持たない芳香族テトラカルボン酸成分が
、3,3′,4,4′−ビフェニルテトラカルボン酸二
無水物であることを特徴とする特許請求の範囲第1項記
載のポリイミド気体分離膜。 7、オキシ基を持たない芳香族テトラカルボン酸成分が
、2,3,3′,4′−ビフェニルテトラカルボン酸二
無水物であることを特徴とする特許請求の範囲第1項記
載のポリイミド気体分離膜。 8、膜厚が20μm以下であることを特徴とする特許請
求の範囲第1項記載のポリイミド気体分離膜。[Scope of Claims] 1. A polyimide gas separation membrane formed from an aromatic polyimide consisting of an aromatic tetracarboxylic acid skeleton and an aromatic diamine skeleton, wherein the aromatic tetracarboxylic acid skeleton is a diphenyl ether tetracarboxylic acid skeleton. A polyimide gas separation membrane formed from 10 to 100 mol% of an acid component and 0 to 90 mol% of an aromatic tetracarboxylic acid component having no oxy group. 2. The aromatic tetracarboxylic acid skeleton is formed from 30 to 100 mol% of a diphenyl ether tetracarboxylic acid component and 0 to 70 mol% of an aromatic tetracarboxylic acid component that does not have an oxy group. A polyimide gas separation membrane according to claim 1. 3. The aromatic tetracarboxylic acid skeleton is formed from 45 to 100 mol% of a diphenyl ether tetracarboxylic acid component and 0 to 55 mol% of an aromatic tetracarboxylic acid component that does not have an oxy group. A polyimide gas separation membrane according to claim 1. 4. The diphenyl ether tetracarboxylic acid component is 3.
The polyimide gas separation membrane according to claim 1, characterized in that it is 3',4,4'-diphenyl ether tetracarboxylic dianhydride. 5. The diphenyl ether tetracarboxylic acid component is 2.
The polyimide gas separation membrane according to claim 1, characterized in that it is 3,3',4'-diphenyl ether tetracarboxylic dianhydride. 6. The polyimide gas according to claim 1, wherein the aromatic tetracarboxylic acid component having no oxy group is 3,3',4,4'-biphenyltetracarboxylic dianhydride. Separation membrane. 7. The polyimide gas according to claim 1, wherein the aromatic tetracarboxylic acid component having no oxy group is 2,3,3',4'-biphenyltetracarboxylic dianhydride. Separation membrane. 8. The polyimide gas separation membrane according to claim 1, wherein the membrane thickness is 20 μm or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62097891A JPH0693984B2 (en) | 1987-04-21 | 1987-04-21 | Polyimide gas separation membrane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62097891A JPH0693984B2 (en) | 1987-04-21 | 1987-04-21 | Polyimide gas separation membrane |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63264121A true JPS63264121A (en) | 1988-11-01 |
JPH0693984B2 JPH0693984B2 (en) | 1994-11-24 |
Family
ID=14204378
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62097891A Expired - Fee Related JPH0693984B2 (en) | 1987-04-21 | 1987-04-21 | Polyimide gas separation membrane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0693984B2 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01131245A (en) * | 1987-09-14 | 1989-05-24 | General Electric Co <Ge> | Polyetherimide and precursor thereof |
JPH02268819A (en) * | 1989-04-07 | 1990-11-02 | Ube Ind Ltd | Separation of aqueous solution of organic matter by permeation and vaporization |
US5071452A (en) * | 1989-08-11 | 1991-12-10 | Institut Francais Du Petrole | Gas separation membrane |
US5076816A (en) * | 1989-08-14 | 1991-12-31 | Institut Francais Du Petrole | Gas separation membrane |
US5077382A (en) * | 1989-10-26 | 1991-12-31 | Occidental Chemical Corporation | Copolyimide odpa/bpda/4,4'-oda or p-pda |
US5171828A (en) * | 1989-10-26 | 1992-12-15 | Occidental Chemical Corporation | Copolyimide ODPA/BPDA/4,4'-ODA or P-PDA |
US5178650A (en) * | 1990-11-30 | 1993-01-12 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes and process of using same |
-
1987
- 1987-04-21 JP JP62097891A patent/JPH0693984B2/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01131245A (en) * | 1987-09-14 | 1989-05-24 | General Electric Co <Ge> | Polyetherimide and precursor thereof |
JPH02268819A (en) * | 1989-04-07 | 1990-11-02 | Ube Ind Ltd | Separation of aqueous solution of organic matter by permeation and vaporization |
US5071452A (en) * | 1989-08-11 | 1991-12-10 | Institut Francais Du Petrole | Gas separation membrane |
US5076816A (en) * | 1989-08-14 | 1991-12-31 | Institut Francais Du Petrole | Gas separation membrane |
US5077382A (en) * | 1989-10-26 | 1991-12-31 | Occidental Chemical Corporation | Copolyimide odpa/bpda/4,4'-oda or p-pda |
US5171828A (en) * | 1989-10-26 | 1992-12-15 | Occidental Chemical Corporation | Copolyimide ODPA/BPDA/4,4'-ODA or P-PDA |
US5178650A (en) * | 1990-11-30 | 1993-01-12 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes and process of using same |
Also Published As
Publication number | Publication date |
---|---|
JPH0693984B2 (en) | 1994-11-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5112941A (en) | Aromatic polymide separation membrane | |
US4690873A (en) | Gas separating material | |
US4528004A (en) | Aromatic polyimide composite separating membrane | |
JPS6355974B2 (en) | ||
US4440643A (en) | Process for producing aromatic polyimide composite separating membrane | |
US4485056A (en) | Production of aromatic polyimide separating membranes | |
US4959151A (en) | Pervaporation method of separating liquid organic compound mixture through aromatic imide polymer asymmetric membrane | |
JP3471918B2 (en) | New polyimide gas separation membrane | |
JP2684582B2 (en) | Polyimide separation membrane | |
US5032279A (en) | Separation of fluids using polyimidesiloxane membrane | |
JPS63264121A (en) | Polyimide membrane for separating gas | |
JPS63166415A (en) | Polyimide gas separating membrane | |
JPH038818B2 (en) | ||
WO1991000774A1 (en) | Separative membrane made of aromatic polyimide | |
JPS6261228B2 (en) | ||
JP2745767B2 (en) | Separation method of lower alcohol | |
JPS621615B2 (en) | ||
JPS6223972B2 (en) | ||
JPS621616B2 (en) | ||
JP2649706B2 (en) | Pervaporation separation method of organic mixture | |
JP2827212B2 (en) | Polyamideimide separation membrane | |
JPH0122006B2 (en) | ||
JPH01245830A (en) | Gas separation membrane | |
JP2649707B2 (en) | Pervaporation of organic compound mixture | |
JP2611820B2 (en) | Asymmetric separation membrane and pervaporation separation method using the separation membrane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |