JPS63175115A - Hollow yarn having void of finger-shaped structure and production thereof - Google Patents
Hollow yarn having void of finger-shaped structure and production thereofInfo
- Publication number
- JPS63175115A JPS63175115A JP120687A JP120687A JPS63175115A JP S63175115 A JPS63175115 A JP S63175115A JP 120687 A JP120687 A JP 120687A JP 120687 A JP120687 A JP 120687A JP S63175115 A JPS63175115 A JP S63175115A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- repeating unit
- formulas
- mol
- hollow fiber
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000011800 void material Substances 0.000 title abstract 3
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 18
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000012510 hollow fiber Substances 0.000 claims description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 38
- 239000011148 porous material Substances 0.000 abstract description 25
- 125000003118 aryl group Chemical group 0.000 abstract description 12
- 238000009987 spinning Methods 0.000 abstract description 8
- 239000004962 Polyamide-imide Substances 0.000 abstract description 3
- 229920002312 polyamide-imide Polymers 0.000 abstract description 3
- 238000005345 coagulation Methods 0.000 description 33
- 230000015271 coagulation Effects 0.000 description 33
- 239000002904 solvent Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 239000012528 membrane Substances 0.000 description 10
- -1 phenol compound Chemical class 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- 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 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000011012 sanitization Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、３．≠、 Ｊ’、 ｐ’−ベンゾフェノンテ
トラカルボン酸二無水物をトリレンジインシアネートお
よびメチレンビスフェニルイソシアネートの混合物と反
応させて得られた芳香族コポリイミド及び／又は、４４
．ｌＡ’−メチレンビスフェニルインクアナートをトリ
メリット酸無水物およびイソフタル酸の混合物と反応さ
せて得られた芳香族コポリアミドイミドの中空糸および
その製造方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention comprises 3. ≠, J', p'-Aromatic copolyimide obtained by reacting p'-benzophenone tetracarboxylic dianhydride with a mixture of tolylene diin cyanate and methylene bisphenyl isocyanate and/or 44
．． The present invention relates to hollow fibers of aromatic copolyamideimide obtained by reacting lA'-methylenebisphenyl inquanate with a mixture of trimellitic anhydride and isophthalic acid, and a method for producing the same.
すなわち、本発明はベンゾフェノンテトラカルボン酸系
の芳香族ポリイミド及び／又は、メチレンビスフェニル
イソシアネート系の芳香族ポリアミドイミドが極性有機
溶媒を主成分とする溶媒に溶解している１容液を中空糸
の紡−多用ドープ液として使用し、そのドープ液の中空
糸状体を形成し、凝固させる指型構造の空孔を有する中
空糸郊及びその製造方法に関するものである。That is, in the present invention, one volume of a solution in which a benzophenone tetracarboxylic acid-based aromatic polyimide and/or a methylene bisphenyl isocyanate-based aromatic polyamideimide is dissolved in a solvent whose main component is a polar organic solvent is poured into a hollow fiber. The present invention relates to a hollow fiber having finger-shaped pores that is used as a dope for various spinning applications, to form and solidify the dope into a hollow fiber, and to a method for producing the same.
従来、ポリイミド中空糸の製造方法としては。 Conventionally, the method for manufacturing polyimide hollow fibers is as follows.
種々の方法が提案されており、たとえば、特開昭５７−
２０！ｆ／７号公報に記載されているように、ベンゾフ
ェノンテトラカルボン酸系の芳香族ポリイミドをフェノ
ール系化合物を主成分とする溶媒に溶解させた溶液をド
ープ液として使用して中空糸を製造する方法がある。ま
た、特開昭ｙ７−／／；７弘／≠号公報に記載されてい
るように、ビフェニルテトラカルボン酸系の芳香族ポリ
イミドを７工ノール系化合物を主成分とする溶媒に溶解
させた溶液をドープ液として使用して中空糸を製造する
方法等が知られているが、この方法によるとフェノール
系化合物として、たとえば、ｐ−クロルフェノールであ
れば、（１）高融点（４Ｌ３℃）であるため室温での取
扱いが困ね、
（ｉｉ） 高沸点（２／り、７５℃）であるため中空
糸製造の最終段階で溶媒除去が困雌、
０１Ｄ 有害、腐食性があるため作業性が悪い、等の
欠点を有しており、有利な方法とは宵えない。Various methods have been proposed, for example, JP-A-57-
20! As described in Publication F/7, a method for producing hollow fibers using a solution in which benzophenone tetracarboxylic acid-based aromatic polyimide is dissolved in a solvent containing a phenol compound as a main component is used as a dope liquid. There is. In addition, as described in Japanese Patent Application Laid-open No. 1977-17-7; 7-Hiroshi/≠, a solution in which biphenyltetracarboxylic acid-based aromatic polyimide is dissolved in a solvent containing a 7-ethanol-based compound as a main component. There is a known method for manufacturing hollow fibers using p-chlorophenol as a dope, but according to this method, if the phenolic compound is, for example, p-chlorophenol, (1) it has a high melting point (4L3℃); (ii) It has a high boiling point (2/2, 75°C), so it is difficult to remove the solvent at the final stage of hollow fiber manufacturing; 01D It is harmful and corrosive, so it is difficult to handle It has disadvantages such as poor performance, and cannot be considered an advantageous method.
本発明者らは先にペンゾフエノンテトラ力ルポ７ｅ系の
芳香族コポリイミドが極性有機溶媒に溶解しているコポ
リイミドｍＱをドープ液として使用して、中空糸を紡糸
することによって、耐熱性が高く、耐薬品性、機械的強
度に優れた芳香族コポリイミド中空糸を有利に製造でき
ることを見い出した。（特願昭６７−乙り４４７／号）
今回、本発明者等は、ベンゾフェノンテトラカルボン酸
系の芳香族コポリイミド、及び／又はメチレンビスフェ
ニルインシアネート系の芳香族ポリアミドイミドを極性
有機溶媒に溶解させて固形分濃度２〜２５重量％に調整
した溶液をドープ液として使用し、中空糸を紡糸するこ
七によって、耐熱性が高く、耐薬品性、機械的強度に優
れ、しかも液体の透過速度の高い指型攬造の空孔を有す
る中空糸を有利に製造できることを見い出し、本発明に
到達し虎。The present inventors have previously developed a heat-resistant material by spinning hollow fibers using copolyimide mQ, in which a penzophenone tetrafluoro7e-based aromatic copolyimide is dissolved in a polar organic solvent, as a dope solution. It has been found that it is possible to advantageously produce aromatic copolyimide hollow fibers with high chemical resistance and mechanical strength. (Special application 1986-Otori 447/No.)
This time, the present inventors dissolved benzophenonetetracarboxylic acid-based aromatic copolyimide and/or methylene bisphenyl incyanate-based aromatic polyamideimide in a polar organic solvent to a solid content concentration of 2 to 25% by weight. By using the prepared solution as a dope and spinning hollow fibers, it has high heat resistance, excellent chemical resistance, and mechanical strength, and has finger-shaped holes with high liquid permeation rate. He discovered that hollow fibers could be manufactured advantageously and arrived at the present invention.
すなわち本発明の要旨は、一般式（Ｉ）壬はＲが＋ｃｈ
２−Ｑ−’１ ：７４％わすものであり、上記繰返し単
位の９０〜７０モル％はＲが、コポリイミド、及び／又
は、繰返し単位の９０〜７０モルチが式（ＩＩ）
で表わされる構造を有し、かつ！￥！返し単位の７０〜
３０モルチが式（ｍ）
で表わされる構造を有するコポリアミドイミドを主たる
構成材料とする中空糸であって、核中空糸の外側表面と
内＠Ｉ衣表面はさまれた内部に、指型構造の空孔を有す
る中９糸及びその與遣方法に存する。That is, the gist of the present invention is that in the general formula (I), R is +ch
2-Q-'1: 74%, R is copolyimide, and 90 to 70 mol% of the repeating units are copolyimide, and/or 90 to 70 mol% of the repeating units are a structure represented by formula (II) and! ¥! Return unit 70~
30 molti is a hollow fiber mainly composed of copolyamideimide having a structure represented by the formula (m), and a finger-shaped structure is sandwiched between the outer surface and the inner surface of the core hollow fiber. The invention consists in a medium 9 yarn having pores and a method of arranging it.
本発明の中空糸は気体混合物、液体混合物の分離に好適
に用いることができる。特に本発明の中９糸は水系、非
水系の液体混合物の分離に好適に用いることができる。The hollow fibers of the present invention can be suitably used for separating gas mixtures and liquid mixtures. In particular, the middle 9 threads of the present invention can be suitably used for separating aqueous and non-aqueous liquid mixtures.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明においては、上記の式（Ｄ、（ＩＩ）および（Ｉ
ＩＩ）で表わされるコポリイミド及び／又はコボ液体透
過性に優れた中空糸を再現性よく安定的に製造すること
ができる。In the present invention, the above formulas (D, (II) and (I)
The copolyimide and/or cobo hollow fiber represented by II) having excellent liquid permeability can be stably produced with good reproducibility.
分離膜の形状としては、シート状、スパイラル状、管状
、中空糸状等種々あるが、本発明のような中空糸状とす
ることにより単位容積当りの有効膜面積を大きくするこ
とができ、また中空糸の外周側から加圧する娑合には、
管壁の厚さが小さい割に高圧に対する機械的強度が高い
等の利点が得られる。There are various shapes of separation membranes, such as sheet, spiral, tubular, and hollow fiber shapes, but by using the hollow fiber shape as in the present invention, the effective membrane area per unit volume can be increased. When applying pressure from the outer periphery of the
Advantages such as high mechanical strength against high pressure can be obtained despite the small thickness of the tube wall.
本発明の中空糸において、指型構造の空孔とは中空糸の
内側表面と外側表面にはさまれ念内部に形成されており
、円周方向に７列あるいは複数列形成されている。空孔
の大きさは、たとえば空孔が円周方向に７列に形成され
る場合、空孔の長径が中空糸の肉厚未満であればよく、
好ましくは肉厚のタタ〜／％、より好ましくはデタ〜Ｓ
Ｏチであればよい。また、たとえば空孔が円周方向に２
列以上に形成される場合、同−直径上の各空孔の長径の
和が肉厚未満であればよく、好〜ましくは肉厚のり９〜
１％、より好ましくはデタル５０チであればよい。空孔
の短径の大きさは、上記長径と同等か短かければよい。In the hollow fiber of the present invention, the finger-shaped holes are formed inside the hollow fiber between the inner and outer surfaces of the hollow fiber, and are formed in seven or more rows in the circumferential direction. The size of the pores may be such that, for example, when the pores are formed in seven rows in the circumferential direction, the long diameter of the pores is less than the wall thickness of the hollow fiber;
Preferably wall thickness tat~/%, more preferably tat~S
It is fine as long as it is Ochi. Also, for example, if the holes are 2 in the circumferential direction,
When the holes are formed in rows or more, the sum of the long diameters of the holes on the same diameter should be less than the wall thickness, and preferably the wall thickness is 9 to 9.
1%, more preferably a total of 50 inches. The size of the short axis of the hole may be equal to or shorter than the long axis.
本発明の中空糸の内表面と外表面にはさまり。Sandwiched between the inner and outer surfaces of the hollow fiber of the present invention.
た内部において、上記指型構造の空孔以外の部分は両表
面に連通し、かつその平均孔径が厚み方向において変化
している傾斜型多孔質構造をとっており、空孔の表面に
も連通した細孔が存在するため、空孔部分の透過抵抗は
実質的に無視することが可能であり、十分な誘過速度及
び機械的強度を得ることができる。比較的孔径の小さい
多孔質層のみが存在していると、多孔質層における透過
抵抗が大きくなり、十分な透過速度を得ることができな
い。また、比較的孔径の大きい多孔質層のみが存在して
いると、多孔質、ｅにおける透過抵抗は減少する恵め好
ましいが、多孔質層全体の機械的強度が低下し、内表面
及び／又は外表面に緻密層が存在する場合には緻密層を
支持することが困難となり好壕しくない。Inside the finger-shaped structure, the part other than the pores has an inclined porous structure in which the finger-shaped structure communicates with both surfaces and the average pore diameter changes in the thickness direction, and also communicates with the surface of the pores. Because of the presence of such pores, the permeation resistance of the pores can be substantially ignored, and sufficient induced velocity and mechanical strength can be obtained. If only a porous layer with a relatively small pore size is present, the permeation resistance in the porous layer increases, making it impossible to obtain a sufficient permeation rate. Furthermore, if only a porous layer with a relatively large pore size is present, it is preferable because the permeation resistance in the porous layer is reduced, but the mechanical strength of the entire porous layer is reduced, and the inner surface and/or When a dense layer exists on the outer surface, it becomes difficult to support the dense layer, which is not favorable.
多孔質層の平均孔径は、厚み方向の各位置で７８ｍ以下
であることが好ましい。これより孔径が大きいと機械的
強度が低下し好ましくない。The average pore diameter of the porous layer is preferably 78 m or less at each position in the thickness direction. If the pore diameter is larger than this, the mechanical strength will decrease, which is not preferable.
また本発明の中空糸は、平均孔径が５００Ａ以下であり
、厚みが７８ｍ以下である緻密層を両表面のいずれか一
方又は両方に有していてもよい。平均孔径がｒｏｏ’ｐ
ｈより大きいと分離性能が低下し、！た厚みがこＦ＋−
より厚いと透ボ速度が低くなって好ましくない。Further, the hollow fiber of the present invention may have a dense layer having an average pore diameter of 500 A or less and a thickness of 78 m or less on either or both of its surfaces. Average pore size is roo'p
If it is larger than h, the separation performance will decrease. The thickness is F+-
If it is thicker, the throughput speed will be lower, which is not preferable.
微密層を両表面のいずれか一方又は両方に有している場
合には、緻密層に近い方の多孔質層の平均孔径が１００
〜１０ｏｏ′ｋ、緻密層から十分はなれた多孔質層の平
均孔径が／ ０００− ｊθθ０Ｘであることが好まし
い。これらの範囲より孔径の小さいものは透過速度が小
さくなシ、これらの範囲より孔径の大きいものは緻密層
を支持することが困難となり、機械的強度も小さくなる
ため、いずれも好ましくない。また、多孔質層の孔径は
緻密層の孔径よりも大きくなければならない。When the micro-dense layer is present on either or both surfaces, the average pore diameter of the porous layer closer to the dense layer is 100
It is preferable that the average pore diameter of the porous layer which is sufficiently separated from the dense layer is /000-jθθ0X. If the pore diameter is smaller than these ranges, the permeation rate will be low, and if the pore diameter is larger than these ranges, it will be difficult to support the dense layer and the mechanical strength will be low, so both are not preferred. Also, the pore size of the porous layer must be larger than the pore size of the dense layer.
次に、上記本発明中空糸の製造方法について説明する。Next, a method for manufacturing the hollow fiber of the present invention will be explained.
本発明において使用される芳香族コポリイミドは一般式
（１）
の繰返し単位の存在を特徴とするコポリイミドであり、
ここで上記繰返し単位の７０〜３０モル％はＲが−ｃ）
−ＣＨ２−ｃ＞ を表わすものであり、上記等φ返し
単位の９０〜７０モルチはＲがこのコポリイミドは例え
ばＴＪＢＦ ３，７０１．弘ｊ／号にも記載されている
ようにｊ 、 ｊ’、 ４４ 、参′−ベンゾフェノン
テトラカルボン酸二無水物を適当々モル比ノψ、弘′−
メチレンピスフェニルイソンアネート（≠、４４′−ジ
フェニルメタンジインシアネート）およびトリレンジイ
ソシアネート（２，Ｉｆ −異性体、あるいは２．を−
異性体、あるいはそれらの混合物）とともに極性溶媒の
存在下で反応させることにより容易に得ることができる
。The aromatic copolyimide used in the present invention is a copolyimide characterized by the presence of a repeating unit of general formula (1),
Here, in 70 to 30 mol% of the above repeating units, R is -c)
-CH2-c>, and R represents 90 to 70 moles of the above-mentioned φ return units.This copolyimide is, for example, TJBF 3,701. As described in the Hiroj/issue, j, j', 44, 3'-benzophenone tetracarboxylic dianhydride were mixed in appropriate molar ratios ψ, Hiro'-
Methylenepisphenylisonanate (≠, 44'-diphenylmethane diincyanate) and tolylene diisocyanate (2,If-isomer, or 2.-
isomers or mixtures thereof) in the presence of a polar solvent.
また、本発明において使用される芳香族コポリアミドイ
ミドは繰返し単位の２０〜９０モル係が式（ｎ）
で表わされる構造を有し、かつ繰返し単位の３０〜７０
モルチが式（ＩＩＩ）
で表わされる構造ｆｃＭするコポリアミドイミドである
。このコポリアミドイミドは米国特許第Ｊ、１２９，４
９／−＠に教示の方法により容易に製造される。このよ
うなコポリアミドイミドは、前記特許に記載の操作を用
いて約÷θモルチから約２θモルチ対約３Ｑモルチから
約１０モルチの割合のトリメリット酸蕪水物とイソフタ
ル酸の混合物とほぼ等稲の１００モルチ割合の弘沙′−
メテレンビスフェニルイソシアナートの反応から容易に
得ることができる。Further, the aromatic copolyamideimide used in the present invention has a structure in which 20 to 90 molar units of repeating units are represented by formula (n), and 30 to 70 molar units of repeating units are
Molch is a copolyamideimide having a structure fcM represented by formula (III). This copolyamideimide is described in U.S. Patent No. J, 129,4.
It is easily produced by the method taught in 9/-@. Such copolyamideimides can be prepared using the procedures described in the aforementioned patents to approximately equal proportions of trimellitic acid dihydrate and isophthalic acid in a ratio of about ÷θ molti to about 2θ molti to about 3Q molti to about 10 molti. 100 molti ratio of Hirosha'-
It can be easily obtained from the reaction of methylene bisphenyl isocyanate.
コポリイミド又はコポリアミドイミドの重合、および溶
解させるのに用いられる溶媒は、極性有機溶媒でありジ
メチルホルムアミド、ジメチルアセトアミド、Ｎ−メチ
ルピロリドン、ジメチルスルホキシド、ジメチルスルホ
ン、ヘキサメチルホスホルアミド、テトラメチル尿素、
ピリジン々どが例示されるが、待に限定されるものでは
ない。また、これらを混合して使用してもかまわない。The solvents used for polymerizing and dissolving the copolyimide or copolyamideimide are polar organic solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dimethylsulfone, hexamethylphosphoramide, tetramethylurea. ,
Examples include pyridine, but are not limited to pyridine. Moreover, these may be used in combination.
本発明においてコポリイミドに対しては、好ましくはジ
メチルホルムアミド及びＮ−メチルピロリドンが用いら
れ、より好ましくはジメチルホルムアミドが用いられる
。コポリアミドイミドに対しては好ましくはジメチルホ
ルムアミド、ジメチルアセトアミド、Ｎ −メチルピロ
リドンが用いられ、より好ましくはジメチルホルムアミ
ドが用いられる。For the copolyimide in the present invention, preferably dimethylformamide and N-methylpyrrolidone are used, more preferably dimethylformamide is used. For the copolyamideimide, preferably dimethylformamide, dimethylacetamide, N-methylpyrrolidone is used, more preferably dimethylformamide is used.
上述の重合に使用する極性有機溶媒の分量は、すべての
反応体が最初に溶解するのに少なくとも十分なものであ
ることが好ましい。溶媒の使用量は求めるコポリイミド
、又はコポリアミドイミドの粘度によって言１１節され
るものであり、コポリイミド、又はコポリアミドイミド
の重量％は、通常的ｊｉｔ％から約３！重量％まで存在
しうる。Preferably, the amount of polar organic solvent used in the above polymerization is at least sufficient to initially dissolve all reactants. The amount of solvent to be used depends on the desired viscosity of the copolyimide or copolyamide-imide, and the weight percent of the copolyimide or copolyamide-imide ranges from the usual jit% to about 3! It may be present up to % by weight.
本発明で用いられるコポリイミド又はコポリアミドイミ
ドの対数粘度（ηｉｎｈ ） ＃′ｉｏ、／ｃｔｔ／
を以上、よシ好ましくは０．Ｊ〜４ｃｄｔ／ｆ （Ｎ−
メチルピロリドン中、０，６％、３０℃で測定）の範囲
から選ばれる。Logarithmic viscosity (ηinh) of copolyimide or copolyamideimide used in the present invention #'io, /ctt/
or more, preferably 0. J~4cdt/f (N-
0.6% in methylpyrrolidone, measured at 30°C).
本発明においては上記コポリイミド及び／又はコポリア
ミドイミドの溶液を固形分＃度ｒ〜−２５ｊｌ（ｔパー
セント、好ましくは１０−コθ重量パーセントに一周整
してドープ液として使用する。In the present invention, the above copolyimide and/or copolyamide-imide solution is adjusted to a solid content of r to -25jl (t percent, preferably 10-coθ weight percent) and used as a dope.
固形分ｍ度が２５重量パーセント以上であると指型構造
が形成されにくくなり、また、♂重量 バーセント以下
であると粘度が低いため中空糸状体自体の安定な形成が
困難になる恵め、いずれも好ましくない。If the solid content is more than 25% by weight, it will be difficult to form a finger-shaped structure, and if the solid content is less than 25% by weight, the viscosity will be low, making it difficult to form the hollow fibers themselves stably. I also don't like it.
上記のドープ液を用いて中空糸を形成する方法としては
、基本的には、中空糸の内側表面を芯液あるいは芯ガス
等の流体と接触させ、かつ核中空糸の外側表面を凝固浴
と接触させることＫよって行う。本発明による中空糸は
このような芯液あるいは芯ガスと凝固浴による凝固条件
によって透過性能がコントロールされ、さらに熱処理条
件によっても透過性能と９械的強度がコントロールされ
る。The method for forming hollow fibers using the above dope solution basically involves bringing the inner surface of the hollow fiber into contact with a fluid such as a core liquid or core gas, and bringing the outer surface of the core hollow fiber into a coagulation bath. This is done by making contact. The permeation performance of the hollow fiber according to the present invention is controlled by the coagulation conditions of the core liquid or core gas and coagulation bath, and the permeation performance and mechanical strength are also controlled by the heat treatment conditions.
また、中空糸用ノズル出口と凝固浴間の距離（エアギャ
ップ）の設定の仕方によっても凝固条件をコントロール
することが可能である。Furthermore, the coagulation conditions can also be controlled by setting the distance (air gap) between the hollow fiber nozzle outlet and the coagulation bath.
芯液あるいは芯ガスと凝固浴による凝固条件のコントロ
ールとは、具体的には凝固速度の制御であり、凝固速度
の速い側の表面はど緻密層が形成されやすい。Controlling the coagulation conditions using the core liquid or core gas and coagulation bath specifically means controlling the coagulation rate, and a dense layer is more likely to be formed on the surface where the coagulation rate is faster.
本発明では上記のコントロールを行うことにより広範囲
の透過性能を有する中空糸を容易に製造することができ
る。たとえば、中空糸の内側の表面に、透過性能をコン
トロールする緻密層を形成させ、外側の表面に傾斜型多
孔質層を形成させるならば、芯液としては良溶媒である
極性有機溶媒、すなわちジメチルホルムアミド、ジメチ
ルアセトアミド、Ｎ−メチルピロリドン、ジメチルスル
ホキシド、ジメチルスルホン、ヘキサメチルホスホルア
ミド、テトラメチル尿素、ピリジン等が挙げられ、また
貧溶媒である水、プロパツール等の低級アルコール類、
アセトン等のケトン類、エチレングリコール等のニーチ
ル類、トルエン等の芳香族類、あるいはこれらの混合物
等が挙げられる。これらの中で良溶媒と貧溶媒の特定の
涜金物が好ましい。なかでもジメチルホルムアミドと水
を特定の割合で混合した混合物が特に好適に用いられる
。貧溶媒とは溶液中の溶媒と相溶性を有し、かつ溶質と
の溶解性の低い溶媒であり、ここではドープ液との相溶
性が良好であってコポリイミドとの溶解性が低いもので
ある。In the present invention, by performing the above control, hollow fibers having a wide range of permeation performance can be easily manufactured. For example, if a dense layer is formed on the inner surface of the hollow fiber to control permeation performance, and a graded porous layer is formed on the outer surface, a polar organic solvent that is a good solvent for the core liquid, namely dimethyl Examples include formamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dimethylsulfone, hexamethylphosphoramide, tetramethylurea, pyridine, and water as a poor solvent, lower alcohols such as propatool,
Examples include ketones such as acetone, nityls such as ethylene glycol, aromatics such as toluene, and mixtures thereof. Among these, certain types of good solvents and poor solvents are preferred. Among these, a mixture of dimethylformamide and water in a specific ratio is particularly preferably used. A poor solvent is a solvent that is compatible with the solvent in the solution and has low solubility with the solute. Here, it is a solvent that has good compatibility with the dope solution and low solubility with the copolyimide. be.
水とジメチルホルムアミドのような良溶媒と貧溶媒の混
合割合は特に制限されるものではなく、混合割合によっ
て異った透過性節を有する中空糸が得られる。The mixing ratio of a good solvent such as water and dimethylformamide and a poor solvent is not particularly limited, and hollow fibers having different permeability nodes can be obtained depending on the mixing ratio.
芯液の代りに芯ガスとして空気、♀素等の不活性気体を
用いてもよい。Instead of the core liquid, an inert gas such as air or ♀ element may be used as the core gas.
凝固させるのは液体中でも気体中でもよく、例えば液体
の凝固浴としては、水、プロパツール等の低級アルコー
ル類、アセトン等のケトン類、エチレンクリコール等の
エーテル類、トルエン等の芳香族類あるいはこれらの混
合物等が用いられる。なかでも水が好適に用いられる。Coagulation may be carried out in liquid or gas. For example, as a liquid coagulation bath, water, lower alcohols such as propatool, ketones such as acetone, ethers such as ethylene glycol, aromatics such as toluene, or any of these may be used. A mixture of these is used. Among them, water is preferably used.
中空糸用ノズルは凝固浴上に適当な間隔（エアギャップ
）をおいて設置されることが好ましい。It is preferable that the hollow fiber nozzles are installed on the coagulation bath at appropriate intervals (air gaps).
また、中空糸の外側表面に緻密層を形成させる場合には
、芯ガスとして空気等を用い、液体の凝固浴として水あ
るいは水と極性有機溶媒との混合物等を用いればよい。Further, when forming a dense layer on the outer surface of the hollow fiber, air or the like may be used as the core gas, and water or a mixture of water and a polar organic solvent may be used as the liquid coagulation bath.
また、気体の凝固−浴としては空気、窒素等の不活性気
体が好ましい。Further, as the gas coagulation bath, an inert gas such as air or nitrogen is preferable.
この発明の方法において、ポリイミド組成物（ドープ液
）の中空糸状体を形成する中空糸用ノズルとしては、ポ
リマー溶液組成物のドープ液から中空糸状体を押出して
形成することができれば、どのような形式の中空糸用ノ
ズルであってもよく、例えば、チューブ・イン・オリフ
ィス型ノズル（ｔｕｂｅ ｉｎ ｏｒｉｆｉｃｅ ｔｙ
ｐｅ ） 、セグメンテイツド・アーク型ノズル（Ｓｅ
ｇｍｅｎｔｅｄａｒｃ ｔｙｐｅ）などを挙げることが
できる。この発明では、チューブ−イン・オリフィス型
ノズルが、中空糸用ノズルとして好適である。このチュ
ーブ・イン・オリフィス型ノズルとしては、ノズルヘッ
ドの底面の中央に開口しているオリフィス（内径０．２
〜２団）の中央に、チューブ（外径０．７ｊ〜／、ご鱈
、内径０．θ！〜／、弘洞）が位置しているものであり
、オリフィスの開口内周面とチューブの外周面との間の
空隙部（現状部）からドープ液を背圧で押し比し、同時
にチューブの内孔から気体、または液体（芯液ともいう
）を供給して、中空糸状体を形成するのである。In the method of this invention, the hollow fiber nozzle for forming the hollow fibers of the polyimide composition (dope solution) can be any type of hollow fiber nozzle that can be formed by extruding the hollow fibers from the dope solution of the polymer solution composition. For example, a tube-in-orifice nozzle may be used.
pe ), segmented arc nozzle (Se
gmentedarc type). In this invention, a tube-in-orifice type nozzle is suitable as the hollow fiber nozzle. This tube-in-orifice type nozzle has an orifice (inner diameter 0.2
A tube (outer diameter 0.7j~/, cod, inner diameter 0.θ!~/, Hirodo) is located in the center of the orifice opening inner circumferential surface and the tube. The dope liquid is pushed through the gap (current area) between the tube and the outer circumferential surface using back pressure, and at the same time, gas or liquid (also called core liquid) is supplied from the inner hole of the tube to form a hollow filament. It is.
この発明では、前述の中空糸状体の押し出しの際に、前
記中空糸用ノズルの内部のチューブから押し出されつつ
ある中空糸状体の内部へ、気体または液体（芯液）を供
給しながら行うのである。In this invention, the extrusion of the hollow fiber is carried out while supplying gas or liquid (core liquid) from the tube inside the hollow fiber nozzle to the inside of the hollow fiber that is being extruded. .
つぎに、中空糸形成時の操作φ件について説明する。中
空糸の製造条件、例えば、ドープ液の押出し速度、芯液
あるいは芯ガスの吐出量、ノズル出口と凝固浴間の距離
（エアギャップ）、凝固時間、中空糸の引取り速度等は
、中空糸の外径１０θ〜１０００μｍ、管壁の厚さ５０
〜２００μｍとなるようにそれぞれの優性を調節するこ
とによυ決められるのであって、目的とする寸法に形成
されるならば、特に制限されない。Next, the operations φ during hollow fiber formation will be explained. The manufacturing conditions of the hollow fiber, such as the extrusion speed of the dope liquid, the discharge amount of the core liquid or core gas, the distance between the nozzle outlet and the coagulation bath (air gap), the coagulation time, the take-up speed of the hollow fiber, etc. outer diameter 10θ~1000μm, tube wall thickness 50μm
It is determined by adjusting the respective predominance so that it becomes ~200 μm, and is not particularly limited as long as it is formed to the desired size.
例えば、中空糸外径６７０μｍ１内径３！０μの中空糸
を製造する場合には、ドープ液濃度を！〜２５重ｔ％と
すると、ドープ液の押出し速度として０，７〜１０ｏｔ
／分、芯液として水とジメチルホルム、アミドを重量比
弘θ〜７Ｑ／にθ〜３０の割合で十分混合した液、該芯
液の吐出量として０．０３〜３０？／分、エアギャップ
としてＱ〜３ｒＩｔ、凝固時間／ 〜（００秒、引取り
速度０．７〜２００ ｍ／分で製造することができる。For example, when manufacturing hollow fibers with a hollow fiber outer diameter of 670 μm and an inner diameter of 3!0 μm, the concentration of the dope solution is ! If it is ~25% by weight, the extrusion speed of the dope liquid is 0.7~10ot.
/min, as a core liquid, a solution in which water, dimethylform, and amide are sufficiently mixed at a weight ratio θ~7Q/ in a ratio of θ~30, and the discharge rate of the core liquid is 0.03~30? /min, air gap Q~3rIt, solidification time/~(00 seconds, take-up speed 0.7~200 m/min).
中空糸用ノズルから垂直真下に押出されたドープ液およ
び芯液または芯ガスは凝固液中に導かれるが、このとき
ノズル出口と凝固浴の間に間隔があると、この部分でド
ープ液中の溶媒の一部が大気中に蒸発し、一方で、芯液
での凝固速度が速い場合は中空糸内側表面よりゲル化が
進行し、あるいは芯ガスが空気であって凝固浴中より凝
固速度が遅い場合は中空糸外側表面よりゲル化が進行す
る。The dope liquid and core liquid or core gas extruded vertically downward from the hollow fiber nozzle are introduced into the coagulation liquid. At this time, if there is a gap between the nozzle outlet and the coagulation bath, the concentration of the dope liquid in this part If some of the solvent evaporates into the atmosphere, but on the other hand, the coagulation rate in the core liquid is fast, gelation may progress from the inner surface of the hollow fiber, or if the core gas is air and the coagulation rate is slower than in the coagulation bath. If it is slow, gelation will progress from the outer surface of the hollow fiber.
中空糸用ノズルの出口を凝固浴中に浸漬して、直接凝固
浴中に押出してもよい。The outlet of the hollow fiber nozzle may be immersed in a coagulation bath and extruded directly into the coagulation bath.
こうして形成された中空糸状体を十分に水洗して本発明
の中空糸は製造される。The hollow fibers thus formed are thoroughly washed with water to produce the hollow fibers of the present invention.
また、本発明の中空糸は、このちとさらに常温で風乾さ
せて、中空糸中に残留している溶媒、芯液、凝固液等を
完全に除去して乾燥させてもよい。乾燥させることによ
って中空糸はわずかに収縮し、構造が緻密化し、分離性
能を向上させることができる。Further, the hollow fibers of the present invention may be further air-dried at room temperature to completely remove the solvent, core liquid, coagulation liquid, etc. remaining in the hollow fibers. By drying, the hollow fibers shrink slightly, making the structure denser and improving the separation performance.
また、本発明の中空糸は、凝固・水洗工程のあと、湿潤
状態のまま、さらにｍ度！０〜１００℃、好ましくは２
０〜１０θ℃の水で処理してもよい。処理時間は中空糸
の用途に応じて適宜選択すればよく、通常数秒〜数時間
、好ましくは７〜３０分である。加圧下であれば上記水
の温度は１００℃以上のφ件でもよい。大気圧下濃度５
０〜１００℃の水によって処理することにより、本発明
の中空糸における気体および液体の透過速度を向上させ
ることができる。In addition, the hollow fiber of the present invention remains wet after the coagulation and water washing process, and can be maintained at an additional temperature of m degrees! 0-100℃, preferably 2
It may be treated with water at 0 to 10[theta]C. The treatment time may be appropriately selected depending on the use of the hollow fiber, and is usually from several seconds to several hours, preferably from 7 to 30 minutes. As long as the water is under pressure, the temperature of the water may be φ of 100° C. or more. Concentration under atmospheric pressure 5
By treating with water at 0 to 100°C, the permeation rate of gas and liquid in the hollow fibers of the present invention can be improved.
本発明の中空糸は、凝固・水洗工程のあと風乾させ、さ
らにｆｌ、 度ｊＯ〜１００℃の水で処理した場合には
透過速度の向上の程度は小さく、好ましいとは言えない
。When the hollow fibers of the present invention are air-dried after the coagulation and water-washing steps and further treated with water at a temperature of 100°C to 100°C, the degree of improvement in permeation rate is small and cannot be said to be preferable.
また、本発明の中空糸は、凝固・水洗工程のあと、ある
いは風乾のあと、あるいは温度！θ〜１００Ｃ：、の水
で処理したあと、さらに乾燥炉で熱処理を行うこともで
きる。熱処理を行うことによって膜の機械的強度や耐薬
品性、耐溶剤性を増大させることができる。また熱処理
の温度に応じて膜の分離性能を制御することが可能であ
るので、目的とするガス透過速度が得られるよう熱処理
温度、時間等を決めればよい。たとえば、熱処理の温度
としては、常温〜３！θ℃、好ましくは／Ｑ〜ＪＯＯ℃
、熱処理の時間としては、７〜６０分、好オしくに３〜
３０分程度が好適である。In addition, the hollow fibers of the present invention can be used after the coagulation/washing process, after air drying, or at a certain temperature! After treatment with water at θ~100C, it is also possible to further perform heat treatment in a drying oven. Heat treatment can increase the mechanical strength, chemical resistance, and solvent resistance of the film. Furthermore, since it is possible to control the separation performance of the membrane depending on the heat treatment temperature, the heat treatment temperature, time, etc. may be determined so as to obtain the desired gas permeation rate. For example, the heat treatment temperature ranges from room temperature to 3! θ℃, preferably /Q~JOO℃
The heat treatment time is 7 to 60 minutes, preferably 3 to 60 minutes.
Approximately 30 minutes is suitable.
熱処理の仕方としては徐々に昇温させてもよいし、急激
に昇温させてもよい。The heat treatment may be performed by gradually increasing the temperature or by rapidly increasing the temperature.
このようにして本発明の中空糸は製造される。In this way, the hollow fiber of the present invention is manufactured.
なお、上記の中空糸の製造工程において、熱水処理、熱
処理以外の部分は室温、大気雰囲気下で行うことができ
る。また、中空糸は適当な諸条件をコントロールするこ
とにより広範囲の性能を付与することができる。In addition, in the manufacturing process of the hollow fiber described above, the portions other than the hot water treatment and heat treatment can be performed at room temperature and in an atmospheric atmosphere. Furthermore, hollow fibers can be given a wide range of performance by controlling appropriate conditions.
つぎに本発明の中空糸′５Ｉ：製造する装置婬について
説明する。本発明の方法は、第３図に示すような紡糸装
置によって行うことができる。Next, the apparatus for producing the hollow fiber '5I of the present invention will be explained. The method of the present invention can be carried out using a spinning apparatus as shown in FIG.
すなわち、コポリイミド及び／又はコポリアミドイミド
溶液（ドープ液）ｌを適当な孔径を有する濾過フィルタ
ー−を通過させながら連続的にチューブ・イン・オリフ
ィス型ノズル金有する紡糸用ノズルヘッドに供給し、同
時に該ノズルのチューブに芯液（あるいは芯ガス）４’
ｅ供給しつつ、該ノズルのオリフィス内周面とチューブ
外周面との間の環状空隙からドープ液を中空糸状に押出
し、ドープ液の中空糸状体を形成し、その中空糸状体に
引張り力を加えて伸張させながら凝固浴！の中で凝固さ
せ、次いで、その中空糸状体を適当な張力下乾燥、熱処
理炉乙を通過させ、巻取機７によシ適当な張力、曲率で
巻き取る。That is, a copolyimide and/or copolyamide-imide solution (dope solution) is continuously supplied to a spinning nozzle head having a tube-in-orifice type nozzle while passing through a filtration filter having an appropriate pore size, and at the same time. Add core liquid (or core gas) 4' to the nozzle tube.
While supplying the dope, the dope is extruded into a hollow fiber shape from the annular gap between the inner peripheral surface of the orifice of the nozzle and the outer peripheral surface of the tube to form a hollow fiber-like body of the dope, and a tensile force is applied to the hollow fiber-like body. Coagulation bath while stretching! The hollow filament is then dried under an appropriate tension, passed through a heat treatment furnace (B), and wound up by a winder 7 with an appropriate tension and curvature.
以下に実施例を挙げて本発明をさらに詳しく説明する。 The present invention will be explained in more detail with reference to Examples below.
製造参考例／
米国特許第３７０７４Ｌｊｒ号の実施例弘に述べられて
いる手順を使用しｊ 、３１．≠、弘′−ベンゾフェノ
ンテトラカルボン酸無水物と？θモルチのトリレンジイ
ソシアネー１− （２，ｕ−異性体約２θモルチと２，
６−異性体約２θモルチの混合物）および２０モルチの
弘、弘′−ジフェニルメタンジイソシアネートを含む混
合物より共重合ポリイミドを重合した。Manufacture Reference Example/Using the procedure described in Example No. 37074Ljr, 31. ≠, Hiro'-benzophenonetetracarboxylic acid anhydride? Tolylene diisocyanate 1- (2, u-isomer of θmolti and 2,
A copolymerized polyimide was polymerized from a mixture containing about 20 mol of Hiro, Hiro'-diphenylmethane diisocyanate) and 20 mol of Hiro, Hiro'-diphenylmethane diisocyanate.
重合溶媒はＮ、Ｎ−ジメチルホルムアミド（以下、ＤＭ
Ｆと略称）を使用し衛脂物ｅ度は２／を量チであった。The polymerization solvent was N,N-dimethylformamide (hereinafter referred to as DM
(abbreviated as F) was used, and the degree of sanitizing agent was 2/2.
このものを濃縮器にかけて２ｆ１ＩＣ−ｆｋチのコポリ
イミド樹脂を得た。This product was passed through a concentrator to obtain a 2f1IC-fk copolyimide resin.
このコポリイミドは３０℃において固有粘度（ＤＭＦ中
、０．５％） ０．６ ｄｉｌｆを有していた。This copolyimide had an intrinsic viscosity (0.5% in DMF) of 0.6 dilf at 30°C.
製造参考例２
予備乾燥した１０ｔの反応器に≦／弘、！−ｔ（Ｊ、、
２０モル）のトリメリット酸無水物および／３２．りｏ
ｙ（ｏ、ｒｏモル）のイソフタル酸全装入した。この反
応器はｍ度計、凝縮器、攪拌機及び９素人口を備えてい
次。Production reference example 2 In a pre-dried 10 t reactor ≦/Hiro,! −t(J,,
20 mol) of trimellitic anhydride and /32. Rio
A total of y (o, ro moles) of isophthalic acid was charged. The reactor is equipped with a temperature meter, a condenser, a stirrer and a 9-meter unit.
！ｔの乾燥したびん中に１０θθ、９≦？（≠、θモル
）の弘、弘′−メチレンビスフェニルインシアナート（
以下ＭＤＩと略称）をはかり取り、次いで≠３μｄのＮ
−メチルピロリドン（以下ＮＭＰと略称）をはかシ取っ
てＭＩ）工を溶解した。このＭＤＩ溶液を反応器に加え
、次いでＭＤＩをはかり取つ念びんをすすぐために３６
６０＠ｌのＮＭＰを加えた。! 10θθ, 9≦? (≠, θ mole) of Hiro, Hiro'-methylene bisphenyl incyanate (
(hereinafter abbreviated as MDI), and then N of ≠ 3 μd.
-Methylpyrrolidone (hereinafter abbreviated as NMP) was removed and MI) was dissolved. This MDI solution was added to the reactor and then 36 minutes
60@l NMP was added.
４ ｊ ｒｐｍの攪拌速度および！累算囲気の下でこの
溶液を３時間≠θ分にわたって５３℃から７７０℃まで
加熱しさらに／時間！！分／≦？℃〜／７／’ＣＫ加熱
した。このようにして繰返し単位の約ｒθモルチが
の構造を有し繰返し単位の約２０モル％かの構造を有す
るランダムコポリアミドイミドのＮＭＰの２５重トチ溶
液が得られた。Stirring speed of 4 j rpm and! This solution was heated from 53°C to 770°C over 3 hours ≠ θ minutes under a cumulative atmosphere and further / hour! ! Minutes/≦? Heated at ~/7/'CK. In this way, a 25-fold solution of NMP of random copolyamideimide having a structure of about rθ moles of repeating units and about 20 mole % of repeating units was obtained.
このコポリアミドイミドの３θ℃における対数粘度（η
１ｎｈ） （Ｎ Ｍ Ｐ中、Ｑ、ｊ％）は０．ｔ＜ Ｏ
Ｊｄｉ／ｌであった。The logarithmic viscosity (η
1nh) (N M P, Q, j%) is 0. t<O
It was Jdi/l.
この溶液をメタノール中に加え、ポリマーを析出させた
後、１５０℃で３時間乾燥し、コポリアミドイミド粉末
を得た。This solution was added to methanol to precipitate a polymer, which was then dried at 150° C. for 3 hours to obtain a copolyamide-imide powder.
コポリアミドイミド粉末をＤＭＩＩ′にて溶解し７７重
量％の溶液とし分離膜のドープ液とした。Copolyamide-imide powder was dissolved in DMII' to form a 77% by weight solution, which was used as a dope solution for a separation membrane.
実施例／
中空糸製造用ノズルから型造参考例／で得られ之コポリ
イミド溶液を／！重重量の固形分濃度となるようにＤＭ
ＩＦで希釈したドープ液を一定流量で押出し、同時に芯
ガスとして空気を一定流量で押出して形成された中空糸
状体を直接水からなる凝固浴液中へ導き７０秒間浸漬し
たのち≠、５１ｒＬ／分で引き取った。この後水中に７
０分間浸漬し一昼夜風乾後、コθ０℃よシ１０分かけて
３００℃とし、７５分間熱処理を行った。この中空糸を
液体Ｎ２中で破断し、断面を走査型電子顕微帰（×３０
０）で観察した結果、次の様であった。また、第１図は
得られた中空糸の形状を示す図面代用写真である。Example/Reference example of mold making from a nozzle for manufacturing hollow fibers/The copolyimide solution obtained in/! DM so that the solid content concentration is
The dope solution diluted with IF was extruded at a constant flow rate, and at the same time, air was extruded at a constant flow rate as a core gas.The hollow filament formed was directly introduced into a coagulation bath consisting of water and immersed for 70 seconds, then ≠ 51 rL/min. I picked it up. 7 in the water after this
After being immersed for 0 minutes and air-dried overnight, the temperature was raised to 300°C over 10 minutes from θ0°C, and heat treatment was performed for 75 minutes. This hollow fiber was broken in liquid N2, and the cross section was examined using a scanning electron microscope (×30
0), the results were as follows. Moreover, FIG. 1 is a photograph substituted for a drawing showing the shape of the obtained hollow fiber.
中空糸の形状
内径 デθＯμ
外径 ｊ？θμ
厚さ ｉｔｏμ
指型構造を有する空孔の形状
長径 ／３θ〜／！θμ
短径 ７〜／弘μ
実施例コ
襄造参考例コで得られたコポリアミドイミド溶液を中空
糸製造用ノズルから一定流量で押し出し、同時に芯液と
して水とジメチルホルムアミドをｊＯ／ｓＯ（重量比）
の割合で混合した液を一定？Ｒ４で押出して形成された
中空糸状体を／２ＣｒｌＩのエアギャップをとって水か
らなる凝固浴中へ導き７秒間浸漬したのち一定速度で引
き取った。この後水中に７０分間浸漬し一昼夜風乾後、
２５０℃で３０分間熱処理を行った。実施例／と同様に
簾察した結果、次の様であった。Hollow fiber shape Inner diameter DeθOμ Outer diameter j? θμ Thickness itoμ Long diameter of hole with finger-shaped structure /3θ~/! θμ Minor diameter 7~/Hiroμ The copolyamide-imide solution obtained in Example 1 and Reference Example ratio)
Is the liquid mixed at a constant ratio? The hollow filament formed by extrusion with R4 was introduced into a coagulation bath consisting of water with an air gap of /2CrlI, immersed for 7 seconds, and then withdrawn at a constant speed. After that, it was immersed in water for 70 minutes and air-dried for a day and night.
Heat treatment was performed at 250°C for 30 minutes. The results of blind inspection in the same manner as in Example 1 were as follows.
また、第２図は得られた中空糸の形状を示す図面代用写
真である。Moreover, FIG. 2 is a photograph substituted for a drawing showing the shape of the obtained hollow fiber.
中空糸の形状
外径 ？５０μ
内径 に、２０μ
厚さ ／６！μ
指状構造を有する空孔の形状
長径 約４ｔ４〜／３μ
短径 約２０−．２３μ
実施例３
芯液として水とジメチルホルムアミドを７ｊ／２ｊ（重
量比）の割合で混合した液を使用したこと以外は実施例
コと同様にして中空糸を製造し／昼夜風乾した。この中
空糸の断面観察した結果、実施例コと類似の指状構造を
示した。又、この中空糸の透過性能は、透水量＝にθｔ
／−１ｈｒ、ａｔｍ、 ＱＮＩ ＝コＸ ／ Ｏｃｃ／
ｌｙｄ、 ｓｅｃ 、ｃｍＨｙ 。Hollow fiber shape outer diameter? 50μ inner diameter, 20μ thickness /6! μ Shape of pore with finger-like structure Major axis: Approximately 4t4~/3μ Short axis: Approximately 20-. 23μ Example 3 Hollow fibers were produced in the same manner as in Example 3 except that a mixture of water and dimethylformamide at a ratio of 7j/2j (weight ratio) was used as the core liquid and air-dried day and night. Observation of the cross section of this hollow fiber showed a finger-like structure similar to that of Example A. In addition, the permeation performance of this hollow fiber is determined by water permeation amount = θt
/-1hr, atm, QNI=koX/Occ/
lyd, sec, cmHy.
ｃｔＨｔｏ（水蒸気）＝ｘ、ｒｘ／θ ｃｃ／ ｃｉｌ
、 ８９Ｃ、２Ｈｙであった。ctHto (water vapor) = x, rx/θ cc/cil
, 89C, 2Hy.
集施例弘〜／／
製造参考例／で得られたコポリイミド溶液を、固型分濃
度７７重ｔ％となるようにジメチルホルムアミドで希釈
したドープ液を中空糸製造ノズルからコ、り２／分の派
幸で押出し、同時に芯液として水とジメチルホルムアミ
ドをｊθ／ ｓ Ｏ（重量比）の割合で混合した液を一
定流量で押出し、形成された中空糸状体を直接水からな
る凝固浴中へ導きｔ秒間浸漬した後一定速度弘、／ｍ／
分で引き取った。この後水中１ｉ１０分間浸した。その
後光／に示すφ件下で処理した。この中空糸の透水量の
測定結果を表／に示す。A dope solution obtained by diluting the copolyimide solution obtained in Example 2 with dimethylformamide to a solid content concentration of 77% by weight is pumped through a hollow fiber manufacturing nozzle 2/ At the same time, a liquid mixture of water and dimethylformamide at a ratio of jθ/sO (weight ratio) was extruded as a core liquid at a constant flow rate, and the formed hollow fibers were directly placed in a coagulation bath consisting of water. After being immersed for t seconds at a constant speed, /m/
I picked it up in minutes. After this, it was immersed in water for 10 minutes. Thereafter, it was treated under the conditions shown in . The measurement results of the water permeability of this hollow fiber are shown in Table/.
実施例１２
製造参考例コで得らｈｐコポリアミドイミド溶液を一定
流量で中空糸製造用ノズルから押出し、同時に芯液とし
て水を一定流量で押出して形成さｆｉた中空糸状体を／
２ＣＭのエアギャップをとって水からなる凝固浴中へ導
き、を秒間浸漬し之のち一定速度で引き取った。この後
水中に１０分間浸漬し、−昼夜風乾した後λθθ℃で３
０分間熱処理を行った。Example 12 A hollow fiber body was formed by extruding the HP copolyamideimide solution obtained in Production Reference Example 1 at a constant flow rate through a nozzle for manufacturing hollow fibers, and at the same time extruding water as a core liquid at a constant flow rate.
An air gap of 2 CM was removed and the sample was introduced into a coagulation bath consisting of water, immersed for seconds, and then withdrawn at a constant speed. After that, it was immersed in water for 10 minutes, air-dried day and night, and then heated to λθθ℃ for 3
Heat treatment was performed for 0 minutes.
この中空糸を用いて、水蒸気、Ｎ２の透過速度、純水の
透水量及びポリエチレングリコール（ｐｚｏ）の分両分
子霊を測定した。Using this hollow fiber, the permeation rate of water vapor and N2, the amount of water permeation of pure water, and the molecular weight of polyethylene glycol (pzo) were measured.
Ｑ Ｎ！ ＝ Ｊ 、ｊ Ｘ ／ Ｏ
ｃｃ／Ｃｊイ、 θＦ３Ｃｌ（７ｍ ＨｙＱ、Ｆｉｔ
ＯＣ水蒸気）＝ Ｊ、Ｊ ｘ １０−’透水量＝ｃｆ’
Ｌ／ｍ’−ｈｒ−ａｔｍＰＥＧの分画分子量 弘０
０００
なお、この膜の分画分子！ｉはその膜が排除率りｏ％を
示すポリエチレングリコール（ＰＥＧ）の平均分子量で
評価した。QN! = J, j X / O
cc/Cj I, θF3Cl (7m HyQ, Fit
OC water vapor) = J, J x 10 - 'Water permeability = cf'
L/m'-hr-atmPEG molecular weight cut off 0
000 Furthermore, the fractionated molecules of this membrane! i was evaluated based on the average molecular weight of polyethylene glycol (PEG) for which the membrane exhibits an exclusion rate of 0%.
本発明の方法で製造される中空糸は耐熱性、耐薬品性、
機械的強度が優れていると共に芯液の組成のコントロー
ルや、熱処理灸件のコントロールによって透過性能の調
節が可能であり、液体分離膜としてきわめて好適である
。また、ガス分離膜、透析膜、各種膜材料を支持する多
孔質体等としても使用することができる。The hollow fibers produced by the method of the present invention have heat resistance, chemical resistance,
It has excellent mechanical strength, and its permeability can be adjusted by controlling the composition of the core liquid and the conditions of heat treatment, making it extremely suitable as a liquid separation membrane. It can also be used as a gas separation membrane, a dialysis membrane, a porous body supporting various membrane materials, and the like.
第３図は本発明の中空糸を製造する紡糸装置の一例の概
略説明図である。ｌはドーグ液、コは濾過フィルター、
３は紡糸用ノズル、≠は芯液又は芯ガス、ｊは凝固浴、
には乾燥・熱処理炉、７は巻取機をそれぞれ示す。
出 願 人 三菱化成工業株式会社
代 理 人 弁理士 長谷用 −（ほか７名）
第１ 圓
°晃２国FIG. 3 is a schematic explanatory diagram of an example of a spinning apparatus for manufacturing hollow fibers of the present invention. l is dogu liquid, ko is filtration filter,
3 is the spinning nozzle, ≠ is the core liquid or core gas, j is the coagulation bath,
7 shows a drying/heat treatment furnace, and 7 shows a winding machine. Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney: Yo Hase - (and 7 others) 1st En: Akira 2nd country
Claims (5)
） の繰返し単位で表わされる構造を有するコポリイミドで
あつて、上記繰返し単位の１０〜３０モル％はＲが▲数
式、化学式、表等があります▼を表わす ものであり、上記繰返し単位の９０〜７０モル％はＲが
、 ▲数式、化学式、表等があります▼及び／又は▲数式、
化学式、表等があります▼を表わすものであるコポリイ
ミド、及び／又は、繰返し単位の９０〜７０モル％が式
（II） ▲数式、化学式、表等があります▼・・・・・・（II） で表わされる構造を有し、かつ繰返し単位の１０〜３０
モル％が式（III） ▲数式、化学式、表等があります▼・・・・・・（III
） で表わされる構造を有するコポリアミドイミド を主たる構成材料とする中空糸であつて、該中空糸の外
側表面と内側表面にはさまれた内部に、指型構造の空孔
を有する中空糸。(1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) is a copolyimide having a structure represented by a repeating unit, in which 10 to 30 mol% of the above repeating unit has R representing ▲Numerical formula, chemical formula, table, etc.▼, and 90 to 30 mol% of the above repeating unit 70 mol% is R, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and/or ▲Mathematical formulas,
There are chemical formulas, tables, etc.▼ Copolyimide that represents ▼ and/or 90 to 70 mol% of the repeating unit is formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼・・・・・・(II ), and has a repeating unit of 10 to 30
Mol% is formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) A hollow fiber whose main constituent material is copolyamideimide having a structure represented by:
） の繰返し単位で表わされる構造を有するコポリイミドで
あつて、上記繰返し単位の１０〜３０モル％はＲが▲数
式、化学式、表等があります▼を表わす ものであり、上記繰返し単位の９０〜７０モル％はＲが
、 ▲数式、化学式、表等があります▼及び／又は▲数式、
化学式、表等があります▼を表わすものであるコポリイ
ミド、及び／又は、繰返し単位の９０〜７０モル％が式
（II） ▲数式、化学式、表等があります▼・・・・・・（II） で表わされる構造を有し、かつ繰返し単位の１０〜３０
モル％が式（III） ▲数式、化学式、表等があります▼・・・・・・（III
） で表わされる構造を有するコポリアミドイミドを極性有
機溶媒に溶解させて、固形分濃度８〜２５重量％に調整
した溶液をドープ液として使用し、前記ドープ液を中空
糸用ノズルから押出すと同時に芯液あるいは芯ガスを該
ノズルの中心部より押出して中空糸状体を形成し、該中
空糸状体を凝固させることを特徴とする指型構造の空孔
を有する中空糸の製造方法。(2) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) is a copolyimide having a structure represented by a repeating unit, in which 10 to 30 mol% of the above repeating unit has R representing ▲Numerical formula, chemical formula, table, etc.▼, and 90 to 30 mol% of the above repeating unit 70 mol% is R, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and/or ▲Mathematical formulas,
There are chemical formulas, tables, etc.▼ Copolyimide that represents ▼ and/or 90 to 70 mol% of the repeating unit is formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼・・・・・・(II ), and has a repeating unit of 10 to 30
Mol% is formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) A copolyamideimide having the structure represented by is dissolved in a polar organic solvent, a solution adjusted to a solid content concentration of 8 to 25% by weight is used as a dope liquid, and the dope liquid is extruded from a hollow fiber nozzle. A method for producing hollow fibers having finger-shaped holes, characterized in that a core liquid or core gas is simultaneously extruded from the center of the nozzle to form a hollow fiber body, and the hollow fiber body is solidified.
させることを特徴とする特許請求の範囲第２項記載の製
造方法。(3) The manufacturing method according to claim 2, characterized in that after solidifying the hollow fibers, the hollow fibers are further air-dried at room temperature.
００℃の水で処理することを特徴とする特許請求の範囲
第２項に記載の製造方法。(4) After solidifying the hollow filament, the temperature is further increased to 50 to 1
The manufacturing method according to claim 2, characterized in that the treatment is performed with water at 00°C.
後、あるいは濃度５０〜１００℃の水で処理した後、さ
らに温度１００〜３５０℃の条件下で熱処理することを
特徴とする特許請求の範囲第２項ないし第４項のいずれ
か１項に記載の製造方法。(5) A patent claim characterized in that after the hollow filament is solidified, air-dried, or treated with water at a concentration of 50 to 100°C, it is further heat-treated at a temperature of 100 to 350°C. The manufacturing method according to any one of items 2 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62001206A JPH0788601B2 (en) | 1987-01-07 | 1987-01-07 | Method for producing hollow fiber having finger-shaped pores |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62001206A JPH0788601B2 (en) | 1987-01-07 | 1987-01-07 | Method for producing hollow fiber having finger-shaped pores |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63175115A true JPS63175115A (en) | 1988-07-19 |
| JPH0788601B2 JPH0788601B2 (en) | 1995-09-27 |
Family
ID=11494988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62001206A Expired - Fee Related JPH0788601B2 (en) | 1987-01-07 | 1987-01-07 | Method for producing hollow fiber having finger-shaped pores |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788601B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009226397A (en) * | 2008-02-27 | 2009-10-08 | Toray Ind Inc | Hollow fiber membrane for humidification and membrane module for humidification |
| WO2012077810A1 (en) * | 2010-12-09 | 2012-06-14 | 宇部興産株式会社 | Asymmetric gas separating membrane and method for separating methanol from mixed organic vapor using same |
| JP2015193852A (en) * | 2009-07-23 | 2015-11-05 | エボニック ファイバース ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｆｉｂｒｅｓ ＧｍｂＨ | Polyimide membranes made of polymerization solutions |
| CN107022802A (en) * | 2017-04-10 | 2017-08-08 | 北京化工大学 | A kind of porous polyimide fiber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5217133A (en) * | 1975-08-01 | 1977-02-08 | Hitachi Ltd | Carbreator |
| JPS60150806A (en) * | 1984-01-20 | 1985-08-08 | Agency Of Ind Science & Technol | Preparation of polyimide hollow yarn membrane |
| JPS60246812A (en) * | 1984-05-18 | 1985-12-06 | Daicel Chem Ind Ltd | Hollow polysulfone based resin fiber |
| JPS61164602A (en) * | 1985-01-17 | 1986-07-25 | Daicel Chem Ind Ltd | Hllow yarn membrane made of polysulfone resin and its preparation |
| JPS61257202A (en) * | 1985-05-09 | 1986-11-14 | Agency Of Ind Science & Technol | Separation membrane |
-
1987
- 1987-01-07 JP JP62001206A patent/JPH0788601B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5217133A (en) * | 1975-08-01 | 1977-02-08 | Hitachi Ltd | Carbreator |
| JPS60150806A (en) * | 1984-01-20 | 1985-08-08 | Agency Of Ind Science & Technol | Preparation of polyimide hollow yarn membrane |
| JPS60246812A (en) * | 1984-05-18 | 1985-12-06 | Daicel Chem Ind Ltd | Hollow polysulfone based resin fiber |
| JPS61164602A (en) * | 1985-01-17 | 1986-07-25 | Daicel Chem Ind Ltd | Hllow yarn membrane made of polysulfone resin and its preparation |
| JPS61257202A (en) * | 1985-05-09 | 1986-11-14 | Agency Of Ind Science & Technol | Separation membrane |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009226397A (en) * | 2008-02-27 | 2009-10-08 | Toray Ind Inc | Hollow fiber membrane for humidification and membrane module for humidification |
| JP2014012273A (en) * | 2008-02-27 | 2014-01-23 | Toray Ind Inc | Hollow fiber membrane for humidification, and membrane module for humidification |
| JP2015193852A (en) * | 2009-07-23 | 2015-11-05 | エボニック ファイバース ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｆｉｂｒｅｓ ＧｍｂＨ | Polyimide membranes made of polymerization solutions |
| US10118136B2 (en) | 2009-07-23 | 2018-11-06 | Evonik Fibres Gmbh | Polyimide membranes made of polymerization solutions |
| WO2012077810A1 (en) * | 2010-12-09 | 2012-06-14 | 宇部興産株式会社 | Asymmetric gas separating membrane and method for separating methanol from mixed organic vapor using same |
| JPWO2012077810A1 (en) * | 2010-12-09 | 2014-05-22 | 宇部興産株式会社 | Asymmetric gas separation membrane and method for separating methanol using the same |
| US9211497B2 (en) | 2010-12-09 | 2015-12-15 | Ube Industries, Ltd. | Asymmetric gas separation membrane and method for separating methanol from mixed organic vapor using the same |
| CN107022802A (en) * | 2017-04-10 | 2017-08-08 | 北京化工大学 | A kind of porous polyimide fiber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0788601B2 (en) | 1995-09-27 |
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