JPH0634910B2 - Method for producing polysulfone-based membrane - Google Patents
Method for producing polysulfone-based membraneInfo
- Publication number
- JPH0634910B2 JPH0634910B2 JP15965385A JP15965385A JPH0634910B2 JP H0634910 B2 JPH0634910 B2 JP H0634910B2 JP 15965385 A JP15965385 A JP 15965385A JP 15965385 A JP15965385 A JP 15965385A JP H0634910 B2 JPH0634910 B2 JP H0634910B2
- Authority
- JP
- Japan
- Prior art keywords
- polysulfone
- polymer
- gas
- membrane
- 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.)
- Expired - Lifetime
Links
Landscapes
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- External Artificial Organs (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ガス分離膜、限外濾過膜、逆浸透膜として有
用な、透過量が大きく、選択透過性の大きな、ポリスル
ホン膜の製造方法に関するものである。The present invention relates to a method for producing a polysulfone membrane, which is useful as a gas separation membrane, an ultrafiltration membrane, and a reverse osmosis membrane and has a large permeation amount and a large selective permeability. It is about.
気体混合物から特定の成分気体を分離することは、工業
上重要な操作である。例えば、石油精製業界での水添プ
ラントで発生する水素ガス回収、石炭ガスからの発生す
る水素と一酸化炭素の混合気体のモル比調節、リフォー
マーから発生する水素の濃縮、アンモニア合成プラント
等のパージガスからの水素回収、アンモニア、水素のモ
ル比調節、メタノール合成プラント等のパージガスから
の水素回収、オキソ合成ガス中の水素と一酸化炭素のモ
ル比調節、空気中からの酸素濃縮、空気中からの窒素の
濃縮、地下に埋められた廃棄ゴミ中からのメタンの濃縮
等である。Separation of certain constituent gases from a gas mixture is an industrially important operation. For example, recovery of hydrogen gas generated in hydrogenation plants in the oil refining industry, adjustment of the molar ratio of the mixed gas of hydrogen and carbon monoxide generated from coal gas, concentration of hydrogen generated from reformers, purge gas for ammonia synthesis plants, etc. Recovery of hydrogen from ammonia, adjustment of the molar ratio of ammonia and hydrogen, recovery of hydrogen from purge gas in methanol synthesis plants, etc., adjustment of the molar ratio of hydrogen and carbon monoxide in oxo synthesis gas, oxygen concentration from the air, from the air Concentration of nitrogen, concentration of methane from wastes buried underground, etc.
最近、これらの気体分離に高分子膜が用いられるように
なって来た。高性能な高分子膜の出現と共に、従来プロ
セスに比べ省エネルギー可能で、コンパクトで、取扱い
が簡単である等の利点を追及して、更に高性能の膜が要
求されているのは良く知られている。Recently, polymer membranes have been used for separating these gases. With the advent of high-performance polymer membranes, it is well known that higher performance membranes are required in pursuit of advantages such as energy saving, compact size, and easy handling compared with conventional processes. There is.
高分子膜の気体分離への応用については、均質膜、多孔
膜、複合膜等種々の膜についての研究が行われるように
なった。Regarding the application of polymer membranes to gas separation, various membranes such as homogeneous membranes, porous membranes and composite membranes have been studied.
気体分離膜として従来から知られているものに三つのタ
イプがある。その一つは、特開昭50-99971号公報に見ら
れるような芳香族イミド、エステル、アミド等を主鎖に
持つ高分子よりなる均一なフイルム、特公昭39-30141号
公報に見られるようなポリエチレンテレフタレート、ポ
リスチレン等の均質膜中空糸フイラメントよりなるもの
である。There are three types of conventionally known gas separation membranes. One of them is a uniform film composed of a polymer having an aromatic imide, ester, amide or the like in the main chain as disclosed in Japanese Patent Laid-Open No. 50-99971 and Japanese Patent Publication No. 39-30141. It is made of a homogeneous membrane hollow fiber filament such as polyethylene terephthalate and polystyrene.
もう一つは、所望の分離係数を有する高分子を適当な多
孔性支持体膜上に極薄膜として形成させるものであり、
実用上有益な程度に気体の透過速度を大きくするために
は、極薄膜の厚さを１μｍ以下、望ましくは0.1μｍ以
下の膜厚にしなければならない。シリコーン膜を利用し
た例は、特開昭51-89564号公報に開示されている。しか
し、このような極薄膜をピンホールなく工業的に生産す
るためには、空気中のゴミ等の影響を受けるためにコー
ティングポリマー溶液と空気を極限まで清浄化する必要
があり、クリーンベンチを用いた高度な清浄化システム
の導入、振動防止等を採用したとしても潜在的欠陥を埋
めることはできず、支持体上にすくい上げ、更に２〜３
層積層する必要があり製造工程も複雑で収率も悪くコス
ト高となり、工業的実施に不向きである。The other is to form a polymer having a desired separation coefficient as an ultrathin film on a suitable porous support membrane,
In order to increase the gas permeation rate to a practically useful level, the thickness of the ultrathin film must be 1 μm or less, preferably 0.1 μm or less. An example using a silicone film is disclosed in Japanese Patent Application Laid-Open No. 51-89564. However, in order to industrially produce such an ultra-thin film without pinholes, it is necessary to clean the coating polymer solution and air to the utmost limit because it is affected by dust in the air. Even if the advanced cleaning system was introduced and vibration prevention was adopted, the potential defects could not be filled, and the scooping was done on the support, and further 2-3
Since it is necessary to stack layers, the manufacturing process is complicated, the yield is poor, and the cost is high, which is unsuitable for industrial implementation.
もう一つの方法は、特開昭52-55719号公報や特開昭53-8
6684号公報に開示されているように、高い気体選択性を
有する高分子多孔膜上に、シリコーンゴムや液体のよう
な低い気体選択性を有し、浸透性のあるゴムを多孔膜に
浸透させ、多孔膜表面にあるピンホールをゴムで閉塞さ
せる方法である。この方法では、コーティングする材質
が浸透して、多孔膜表面にあるピンホールをすべて閉塞
させないと、膜の選択透過性が上がらない。又このため
には多孔膜の孔径も小さくせねばならず、このため多孔
膜の気体透過度も低いものを使用せざるを得ない。これ
らの結果コーティング材が中空糸奥深くまで侵入し、余
分なコーティング材が中空糸多孔膜の埋めなくても良い
孔まで閉塞して抵抗が増すし、多孔膜も小さい気体透過
度のものを用いなければならない。Another method is disclosed in JP-A-52-55719 and JP-A-53-8.
As disclosed in Japanese Patent No. 6684, on a polymer porous membrane having high gas selectivity, a rubber having low gas selectivity such as silicone rubber or a liquid and having permeability is permeated into the porous membrane. In this method, a pinhole on the surface of the porous film is closed with rubber. In this method, the selective permeability of the membrane cannot be improved unless the material to be coated permeates to block all the pinholes on the surface of the porous membrane. For this purpose, the pore diameter of the porous membrane must be made small, so that the porous membrane having a low gas permeability must be used. As a result of these, the coating material penetrates deep into the hollow fiber, excess coating material closes the holes that do not need to be filled in the hollow fiber porous membrane, increasing resistance, and the porous membrane must also have a small gas permeability. I have to.
限外濾過膜、逆浸透膜の有用性は、最近医薬、食品、超
ＬＳＩ用純水等の分野で知られている。The usefulness of ultrafiltration membranes and reverse osmosis membranes has recently been known in the fields of medicines, foods, pure water for VLSI and the like.
ポリスルホン膜は、膜素材として、耐熱性、耐薬品性、
安全性の面から優れており、研究が盛んである。Polysulfone membrane is used as membrane material for heat resistance, chemical resistance,
It is excellent in terms of safety and is actively researched.
ポリスルホン限外濾過膜の製造方法については、例えば
特開昭58-156018 号公報に見られるように、幾つかの従
来技術がある。しかし、小孔径（カット率が小さい）に
おいて透過性が大きな膜を得ることはできなかった。即
ち、逆浸透膜より孔径が大きく、従来の限外濾過膜より
孔径の小さい分野の膜は未開拓であった。Regarding the method for producing a polysulfone ultrafiltration membrane, there are some conventional techniques as disclosed in, for example, Japanese Patent Laid-Open No. 58-156018. However, it was not possible to obtain a membrane having high permeability with a small pore size (small cut rate). That is, a membrane in a field having a pore size larger than that of a reverse osmosis membrane and smaller than that of a conventional ultrafiltration membrane has not been developed.
本発明の目的は、製作上の困難が少なく、かつ、分離性
能の良い気体分離用膜の製造方法を提供することであ
る。It is an object of the present invention to provide a method for producing a gas separation membrane that has less difficulty in production and has good separation performance.
本発明は、ポリスルホン系重合体をイミダゾリジノンを
含む溶媒に溶解した溶液を、該溶媒とは混和するが、ポ
リスルホン系重合体を溶解しない液体と接触させて脱溶
媒を行うことを特徴とするポリスルホン系膜の製造方法
に関するものである。The present invention is characterized in that a solution prepared by dissolving a polysulfone-based polymer in a solvent containing imidazolidinone is contacted with a liquid that is miscible with the solvent but does not dissolve the polysulfone-based polymer to perform desolvation. The present invention relates to a method for producing a polysulfone-based membrane.
以下に本発明を詳細に説明する。The present invention will be described in detail below.
本発明で用いられるポリスルホン系重合体は、耐熱性、
耐溶剤性、気体透過性、選択透過性にすぐれた重合体で
あり、次の繰り返し構造単位を有する脂肪族または芳香
族ポリスルホンである。The polysulfone-based polymer used in the present invention has heat resistance,
It is a polymer having excellent solvent resistance, gas permeability and selective permeability, and is an aliphatic or aromatic polysulfone having the following repeating structural unit.
但し、Ｒ1、Ｒ2は、同一又は異なった約１〜40の炭素原
子を含む脂肪族又は芳香族炭素原子よりなる化合物であ
る。更に好ましい重合体は下記の式(2)、(3)及び(4)で
示される芳香族ポリスルホンである。 However, R 1 and R 2 are the same or different compounds consisting of aliphatic or aromatic carbon atoms containing about 1 to 40 carbon atoms. More preferred polymers are aromatic polysulfones represented by the following formulas (2), (3) and (4).
但し、Ｘ、Ｘ1、Ｘ2、Ｘ3、Ｘ4、Ｘ5、Ｘ6、Ｘ7、Ｘ8は
メチル、エチル、ピロピル、ブチル等のアルキル基、フ
ッ素、塩素、臭素、沃素のハロゲン等の非解離性置換
基、又は−ＣＯＯＨ、−Ｓ3ＯＨ、−ＮＨ3、−ＮＨ▲+ 4
▼等の置換基である。ｉ、ｍ、ｎ、ｏ、ｐ、ｑ、ｒ、
ｓ、ｔは１又は４以下の整数である。 However, X, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 are alkyl groups such as methyl, ethyl, propyl, butyl, halogens such as fluorine, chlorine, bromine and iodine. non-dissociable substituent, or -COOH, -S 3 OH, -NH 3 , -NH ▲ + 4
A substituent such as ▼. i, m, n, o, p, q, r,
s and t are integers of 1 or 4 or less.
ポリスルホン重合体の平均分子量は、5000〜100000であ
り、好ましくは10000〜100000である。分子量が小さい
と製膜された膜の機械的強度が上がらず、又、糸に欠陥
が生じ易い。The average molecular weight of the polysulfone polymer is 5,000 to 100,000, preferably 10,000 to 100,000. When the molecular weight is small, the mechanical strength of the formed film does not increase, and the yarn tends to have defects.
本発明の特徴は、重合体を溶解する溶媒に、イミダゾリ
ジノを用いる点にある。本発明で言うイミダゾリジノン
とは、以下の一般式(5)に示されるものを言う。The feature of the present invention is that imidazolidino is used as a solvent for dissolving the polymer. The imidazolidinone referred to in the present invention is represented by the following general formula (5).
Ｒ1,2は、炭素数１〜４のアルキル基、又は水素Ｒ
3,4は、炭素数１〜４のアルキル基、水素、ベンゼン
環、シクロヘキサン環、及びその誘導体、弗素、塩素、
臭素、沃素のハロゲン等の非解離性置換基、又は−ＣＯ
ＯＲ、−ＳＯ3Ｈ、ＮＲＲ′等（Ｒ、Ｒ′は水素及び炭
素数１〜４のアルキル基）の解離性置換基である。アル
キル基はn-アルキルであるのが好ましい。Ｒ1、Ｒ2がメ
チル基、Ｒ3、Ｒ4が水素であるジメチルイミダゾリジノ
ンが入手の容易性から好ましい。 R 1,2 is an alkyl group having 1 to 4 carbon atoms, or hydrogen R
3,4 is an alkyl group having 1 to 4 carbon atoms, hydrogen, a benzene ring, a cyclohexane ring and its derivatives, fluorine, chlorine,
Non-dissociative substituent such as halogen of bromine and iodine, or --CO
OR, —SO 3 H, NRR ′ and the like (R and R ′ are hydrogen and an alkyl group having 1 to 4 carbon atoms) are dissociative substituents. The alkyl group is preferably n-alkyl. Dimethylimidazolidinone in which R 1 and R 2 are methyl groups and R 3 and R 4 are hydrogen is preferable from the viewpoint of easy availability.
又、イミダゾリジノンは他の溶媒との混合溶媒として使
用しても構わない。好ましい他の溶媒としては、ヘキサ
メチルホスホルアミド（ＨＭＰＡ）、ジメチルホルムア
ミド、ジメチルアセトアミド、ジエチルホルムアミド、
ジエチルアセトアミド等、及びこれらのジプロピル、ジ
ブチル化物、N-メチルピロリドン、ジメチルスルホキシ
ド、アセチルピペリジン、ホルミルピペリジン、ホルム
ミルモルホリン、アセチルモルホリン、テトラメチルウ
レア等の任意に水と相溶性のなる極性有機溶媒が良い。In addition, imidazolidinone may be used as a mixed solvent with another solvent. Other preferred solvents include hexamethylphosphoramide (HMPA), dimethylformamide, dimethylacetamide, diethylformamide,
Diethylacetamide and the like, and dipropyl, dibutyl compound, N-methylpyrrolidone, dimethylsulfoxide, acetylpiperidine, formylpiperidine, formylmorpholine, acetylmorpholine, tetramethylurea and the like are optionally compatible with water and polar organic solvents. good.
紡糸用の重合体溶液には、重合体の非溶媒を少量含有さ
せることもできる。非溶媒とは、重合体を溶解する能力
の殆どない溶媒を云う。この非溶媒の添加によって、得
られる中空糸膜の気体透過性能の向上が期待できる。可
能な非溶媒の添加量は個々の非溶媒により異なるが、多
くの場合、重合体溶液に対して50重量％以下であり、好
ましくは35重量％以下、更には１〜30重量％の範囲であ
る。50重量％を超える量の添加では、重合体溶液の安定
性を損ない白濁や失透を生じさせるおそれがある。用い
得る非溶媒としては、エチレングリコール、ジエチレン
グリコール、トリエチレングリコール、ポリエチレング
リコール（平均分子量200〜6000）、テトラエチレング
リコール等のグリコール類、ホルムアミド、アセトアミ
ド、水、トリメチルアミン、イソプロピルアミン、メタ
ノール、エタノール、プロパノール、ニトロメタン、２
-ピロリドン、酢酸、蟻酸、グリセリン、グリセロール
等の多価アルコール類、アセトン、メチルエチルケトン
が挙げられる。又、塩化リチウム、臭化リチウム、塩化
ナトリウム、硝酸リチウム、硝酸ナトリウム、亜硝酸ナ
トリウム、塩化亜鉛、過塩素酸マグネシウム等の低分子
無機塩の添加も有用である。無機塩を添加することによ
り、溶媒のポリマーに対する溶解度が増大すると共に重
合体溶液の安定性が増大する。The polymer solution for spinning may contain a small amount of a non-solvent for the polymer. The non-solvent means a solvent having almost no ability to dissolve the polymer. The addition of this non-solvent can be expected to improve the gas permeability of the resulting hollow fiber membrane. The amount of non-solvent that can be added varies depending on the individual non-solvent, but in many cases it is 50% by weight or less, preferably 35% by weight or less, and more preferably 1 to 30% by weight with respect to the polymer solution. is there. Addition of more than 50% by weight may impair the stability of the polymer solution and cause clouding or devitrification. Non-solvents that can be used include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (average molecular weight 200 to 6000), glycols such as tetraethylene glycol, formamide, acetamide, water, trimethylamine, isopropylamine, methanol, ethanol, propanol. , Nitromethane, 2
-Pyrrolidone, acetic acid, formic acid, polyhydric alcohols such as glycerin, glycerol, acetone, and methyl ethyl ketone. It is also useful to add a low molecular weight inorganic salt such as lithium chloride, lithium bromide, sodium chloride, lithium nitrate, sodium nitrate, sodium nitrite, zinc chloride or magnesium perchlorate. The addition of the inorganic salt increases the solubility of the solvent in the polymer and the stability of the polymer solution.
重合体溶液の重合体濃度は17〜50重量％、好ましくは20
〜35重量％である。17重量％未満の濃度では低すぎて、
中空糸を紡糸し、凝固させる際に、気体を選択的に分離
する表面活性層を形成することが出来ず、選択透過係数
の著しい低下を引き起こす。又、重合体濃度が50重量％
を超えると、濃すぎて形成される膜表面の活性層が厚く
なるので、透過性が著しく低下する。The polymer concentration of the polymer solution is 17 to 50% by weight, preferably 20
~ 35% by weight. Concentrations below 17% by weight are too low,
When the hollow fiber is spun and solidified, a surface active layer that selectively separates gas cannot be formed, causing a significant decrease in the selective permeation coefficient. Also, the polymer concentration is 50% by weight.
If it exceeds, the active layer on the surface of the film which is formed too thick becomes thick, so that the permeability remarkably decreases.
重合体溶液の粘度は、30℃において10センチポイズ以上
106センチポイズ(cps )以下であることが望ましい。粘
度が10cps未満では低すぎて、高分子重合体が溶液中で
充分に広がっていない状態か、又は、低濃度重合体溶液
であるために、良い中空糸は得られ難い。一方、重合体
溶液の粘度が106センチポイズを超えた場合、このよう
な粘稠な溶液をノズルから押し出すのに要する圧力が高
くなりすぎるばかりでなく、このような原液を濾過して
ゴミを除く際にも、高圧力下で濾過せねばならず、容易
にきれいな原液を得ることが困難である。Viscosity of polymer solution is 10 centipoise or more at 30 ℃
It is desirable to be 10 6 centipoise (cps) or less. If the viscosity is less than 10 cps, it is too low and the high-molecular polymer is not sufficiently spread in the solution, or because it is a low-concentration polymer solution, it is difficult to obtain a good hollow fiber. On the other hand, when the viscosity of the polymer solution exceeds 10 6 centipoise, not only the pressure required to extrude such a viscous solution from the nozzle becomes too high, but also such a stock solution is filtered to remove dust. Also in this case, it is necessary to filter under high pressure, and it is difficult to easily obtain a clean stock solution.
膜は中空糸、平膜、支持体入平膜の何れでも良い。The membrane may be a hollow fiber, a flat membrane, or a flat membrane containing a support.
紡糸用原液の温度は、普通−50〜200℃、好ましくは−3
0〜150℃である。原液温度が−50℃より低いと、原液の
粘度が挙がり、濾過し難いだけでなく、中空糸用紡口か
ら原液を押し出す際に吐出圧力が高くなり、製膜が難し
くなる。The temperature of the spinning dope is usually -50 to 200 ° C, preferably -3.
It is 0 to 150 ° C. When the temperature of the stock solution is lower than -50 ° C, the viscosity of the stock solution is increased and it is difficult to filter the stock solution, and the discharge pressure becomes high when the stock solution is extruded from the spinneret for hollow fiber, which makes film formation difficult.
一方、200℃を超えると、多くの溶媒が沸点以上の温度
となり、蒸発し易くなるので好ましくない。しかし、20
0℃以上であっても、沸点が200℃以上の溶媒を用いる場
合は、好ましい原液温度として採用することも出来る。On the other hand, if the temperature exceeds 200 ° C., many of the solvents have a temperature higher than the boiling point and are easily evaporated, which is not preferable. But 20
Even when the temperature is 0 ° C or higher, when a solvent having a boiling point of 200 ° C or higher is used, it can be adopted as a preferable stock solution temperature.
紡糸原液は紡糸前に濾過される。濾材としては、金属粉
末を焼結した焼結多孔体、ステンレス等のメッシュフイ
ルター、高分子材料のテフロン、ポリエチレンなどによ
って作られた高分子多孔膜、繊維を集合させた濾紙等が
挙げられる。濾材の孔の大きさは小さい程良く、10μｍ
以下、好ましくは２μｍ以下の孔径のものが良い。孔径
が10μｍを超えると、中空糸表面の気体分離を行うスキ
ン層中に大きなゴミ、不純物等が混入し易く、気体の選
択透過性を上げることはできない。The spinning dope is filtered before spinning. Examples of the filter material include a sintered porous body obtained by sintering metal powder, a mesh filter such as stainless steel, a polymer material Teflon, a polymer porous membrane made of polyethylene or the like, a filter paper in which fibers are assembled, and the like. The smaller the pore size of the filter material, the better, 10 μm
Hereafter, it is preferable that the pore diameter is 2 μm or less. If the pore diameter exceeds 10 μm, large dust, impurities, etc. are likely to be mixed in the skin layer for gas separation on the surface of the hollow fiber, and the gas selective permeability cannot be increased.
凝固液としては、水、メタノール、エタノール、プロパ
ノール、ブタノール等のアルコール類、エチレングリコ
ール、ジエチレングリコール等のグリコール等、エーテ
ル、n-ヘキサン、n-ヘプタン、n-ペンタン等の脂肪族炭
化水素類、グリセリン等のグリセロール類などポリマー
を溶解しないものなら何でも用いることが出来る。好ま
しいのは、水、アルコール類又はこれらの液体との２種
以上の混合液体である。又、これらの液体中に溶媒を加
えて凝固速度を遅くすることも可能である。例えば、水
にヘキサメチルホルアミドを50重量％混入させても良
い。これらの凝固液は中空糸の外部凝固液として用いら
れ、内部凝固液としても用いられる。As the coagulating liquid, water, alcohols such as methanol, ethanol, propanol and butanol, glycols such as ethylene glycol and diethylene glycol, ethers, aliphatic hydrocarbons such as n-hexane, n-heptane and n-pentane, glycerin Any glycerol that does not dissolve the polymer can be used. Preferred is water, alcohols, or a mixed liquid of two or more of these liquids. It is also possible to slow the coagulation rate by adding a solvent to these liquids. For example, 50% by weight of hexamethylformamide may be mixed in water. These coagulation liquids are used as the external coagulation liquid of the hollow fiber and also as the internal coagulation liquid.
中空糸の内部凝固液は、前述の凝固液と同じものも用い
得るが、更に窒素、空気、不活性気体のヘリウム、アル
ゴン、ネオン、クリプトン、キセノン、ハロゲン系気体
を注入しても良い。As the internal coagulating liquid of the hollow fiber, the same coagulating liquid as described above can be used, but nitrogen, air, inert gas helium, argon, neon, krypton, xenon, or halogen-based gas may be further injected.
凝固液温度は−50〜100℃が良い。好ましくは80℃以下
である。80℃を超えると、得られる中空糸膜の選択分離
性が悪くなり、好ましくない。又あまり低すぎると、凝
固液として用いている液体が固化するので、液体の凝固
点以上が良い。The coagulating liquid temperature is preferably -50 to 100 ° C. It is preferably 80 ° C or lower. If it exceeds 80 ° C, the selective separation of the resulting hollow fiber membrane becomes poor, which is not preferable. On the other hand, if it is too low, the liquid used as the coagulating liquid is solidified, so that it is better than the freezing point of the liquid.
紡糸速度は１〜50m／minが良く、１m／min未満の速度で
は、中空糸が紡口を離れて凝固液に達するまで空気中を
通過する時間が長くなり過ぎ、中空糸の形状を保たせる
ために内部凝固液注入速度をバランスさせるのが難しく
なり好ましくない。又、50m／minを超える速度では、糸
を高速で引っ張るために糸の伸延が生じ易く好ましくな
い。The spinning speed is preferably 1 to 50 m / min. At a speed of less than 1 m / min, the hollow fiber takes too long time to pass through the air until it leaves the spinneret and reaches the coagulation liquid, and the shape of the hollow fiber can be maintained. Therefore, it is difficult to balance the injection speed of the internal coagulation liquid, which is not preferable. On the other hand, if the speed exceeds 50 m / min, the yarn is stretched at a high speed, so that the yarn is easily stretched, which is not preferable.
空中走行距離、即ち、ノズルから凝固液までの距離は、
0.1〜50cm、さらには１〜15cmが良く、あまり長すぎて
も、中空形状が崩れるので好ましくない。又、０cmにす
るとノズルの原液吐出口付近にノズルと凝固液の温度差
により気泡が発生し、中空糸膜の透過性能にばらつきが
生じ易く好ましくない。The air travel distance, that is, the distance from the nozzle to the coagulating liquid is
The length is preferably 0.1 to 50 cm, more preferably 1 to 15 cm. Even if the length is too long, the hollow shape will collapse, which is not preferable. On the other hand, when it is set to 0 cm, bubbles are generated in the vicinity of the stock solution discharge port of the nozzle due to the temperature difference between the nozzle and the coagulating liquid, and the permeation performance of the hollow fiber membrane tends to vary, which is not preferable.
原液は、ノズルより吐出後空気中に出ると、原液中に空
気中の水分が混入して、中空糸表面スキン層の孔径が大
きくなるので、ノズルより凝固液までの間は、窒素ガ
ス、ヘリウムガスなどの水分を含まない一定温度の気体
を満たしたフードで囲って一定流量で流してやるのが良
い。気体を流動させないと、原液中の溶媒蒸気が蒸発し
て濃度が上がって来るために一定品質の中空糸を得るこ
とが難しい。あまり流量を上げすぎても気体によって中
空糸が振動を始めるので好ましくない。又、気体は１μ
ｍ以下のフイルターでゴミを完全に除去しなければなら
ない。When the stock solution is discharged into the air after being discharged from the nozzle, the water content in the air is mixed into the stock solution and the pore diameter of the hollow fiber surface skin layer increases, so nitrogen gas and helium are introduced between the nozzle and the coagulating solution. It is better to let it flow at a constant flow rate by surrounding it with a hood filled with a gas at a constant temperature that does not contain water such as gas. If the gas is not made to flow, it is difficult to obtain hollow fibers of constant quality because the solvent vapor in the stock solution evaporates and the concentration increases. If the flow rate is increased too much, the hollow fiber starts to vibrate due to the gas, which is not preferable. Also, the gas is 1μ
Dust must be completely removed with a filter of m or less.
このような製法によって得られたポリスルホン系重合体
中空糸膜は、中空糸の少なくとも片面に存在するスキン
層とこれを支持する支持層よりなる。スキン層は高分子
物質の密に詰まった集合体からなり、走査顕微鏡写真に
より２００Å以上の空孔の存在は認められないものであ
る。スキン層の厚みは10μｍ以下である。支持層は均一
な細胞よりなる場合もあるが、ボイドが存在する場合も
ある。ボイドの存在は、透過性を向上させるので好まし
い。中空糸膜のとり得る構造は、ボイドの存在しない均
一構造、ボイドが一層と表裏面二層のスキン層よりなる
三層構造、二層にボイド層が存在し、外側からスキン
層、ボイド層、均一な細胞のみよりなる中間層、ボイド
層、スキン層よりなる五層構造等があり、これらの構造
に必ずしも縛られることはない。スキン層は、内表面、
外表面に同一のものが二つあっても、内表面のスキン層
は密であるが、外表面のスキン層に比べると孔径が大き
いような異なるスキン層構造を持たせたもの、或いは内
外スキン層構造が入れ換わったもの等が可能である。こ
れらの構造は、内外凝固液の種類を変えて選ぶことによ
り形成することができる。The polysulfone-based polymer hollow fiber membrane obtained by such a production method comprises a skin layer present on at least one side of the hollow fiber and a support layer supporting the skin layer. The skin layer is composed of densely packed aggregates of polymer substances, and the presence of pores of 200 Å or more is not recognized by scanning micrograph. The thickness of the skin layer is 10 μm or less. The support layer may consist of uniform cells, but voids may also be present. The presence of voids is preferable because it improves the permeability. The structure that the hollow fiber membrane can take is a uniform structure without voids, a three-layer structure in which voids are a single layer and a skin layer of two front and back surfaces, a void layer exists in two layers, and a skin layer, a void layer from the outside, There is a five-layer structure including an intermediate layer composed of only uniform cells, a void layer, and a skin layer, and is not necessarily restricted to these structures. The skin layer is the inner surface,
Even if there are two identical outer surfaces, the skin layer on the inner surface is dense, but with a different skin layer structure such that the pore size is larger than the skin layer on the outer surface, or the inner and outer skins It is possible that the layer structures are interchanged. These structures can be formed by changing the type of the inner and outer coagulation liquids and selecting them.
イミダゾリジノンを溶媒を用いた場合、特にスキン層構
造中に100 Å程度の均一な粒子が非常に密に詰まったフ
イルム状の10μｍ以下の厚みの比較的厚い層を形成し、
この層により気体は完全に選択的に分離されるようにな
る。例えば、ポリスルホン（ＵＣＣ製、コーデルポリサ
ルホンP-3500)を用いた場合、気体の選択透過係数は、
コーテング等をしなくても、水素と窒素の分離では、40
以上の値を得ることが出来る。ただし、糸が外部から傷
を受けないように保護することはあり得る。この場合、
コーテング無しの状態で中空糸膜の選択透過性は充分に
高くなっているので、コーテングより選択透過係数を更
に上げる必要はない。When imidazolidinone is used as a solvent, a relatively thick layer with a thickness of 10 μm or less, which is a film in which uniform particles of about 100 Å are very densely packed in the skin layer structure, is formed.
This layer allows the gas to be completely selectively separated. For example, in the case of using polysulfone (UCC, Cordel polysulfone P-3500), the selective permeation coefficient of gas is
Even if you do not use coating, etc., 40
The above values can be obtained. However, it is possible to protect the thread from external damage. in this case,
Since the selective permeability of the hollow fiber membrane is sufficiently high without coating, it is not necessary to further increase the selective permeability coefficient over that of coating.
以下に実施例を示す。 Examples will be shown below.
実施例１ ポリスルホン（ＵＣＣ製、コーデルポリサルホンP-350
0）を溶媒のジメチルイミダゾリジノンに溶解して、25
重量％の均一な紡糸用原液を調製した。この原液を孔径
１μｍの多孔体フイルターを通して濾過しゴミ、不純物
を除去して、−５℃に保ち、中空糸紡糸用ノズルより押
し出して紡糸した。内部凝固液として０℃の水溶液を用
い、外部凝固液に５℃の水を用い、空中走行距離を１cm
として、ノズルから凝固液までフードで囲み、窒素ガス
を流しながら紡糸を行った。紡速は10m／minであった。Example 1 Polysulfone (UCC, Cordel Polysulfone P-350)
0) is dissolved in dimethyl imidazolidinone as a solvent to give 25
A uniform spinning dope was prepared at a weight percentage of 1. This stock solution was filtered through a porous filter having a pore size of 1 μm to remove dust and impurities, kept at −5 ° C., and extruded from a hollow fiber spinning nozzle for spinning. An aqueous solution of 0 ° C is used as the internal coagulating liquid, water of 5 ° C is used as the external coagulating liquid, and the air travel distance is 1 cm.
As the above, the nozzle to the coagulating liquid were surrounded by a hood, and spinning was performed while flowing nitrogen gas. The spinning speed was 10 m / min.
得られた中空糸は、常温の水中に一昼夜保存した後３日
間常温で水洗し、溶媒を完全に脱溶媒し、本中空糸に１
kg／cm2の圧力をかけて精製水の透過性を測定した所3.5
ml／m.min.kg／cm2であった。又、ポリエチレングリコ
ール（平均分子量10000）水溶液に対してカット率を求
めた所45％カットした。常温で一昼夜風乾後、真空乾燥
した後、気体の透過測定を行ったところ、水素及び窒素
の０℃１気圧における透過係数は、それぞれ1.2×10-4c
m3(STP)／cm2.sec.cmHg（以後PUと略す）及び４．６×1
0-6(PU)で、気体の選択性は、 であった。中空糸の内径は0.2mm、外径は0.4mm、膜厚は
100mμであった。The obtained hollow fiber was stored in water at room temperature for one day and then washed with water at room temperature for 3 days to completely remove the solvent, and
The permeability of purified water was measured by applying a pressure of kg / cm 2 3.5.
It was ml / m.min.kg / cm 2 . Further, when the cut rate was determined for a polyethylene glycol (average molecular weight 10,000) aqueous solution, 45% was cut. After air-drying at room temperature for 24 hours and then vacuum-drying, gas permeation measurements were performed. The permeation coefficients of hydrogen and nitrogen at 0 ° C and 1 atm were 1.2 x 10 -4 c each.
m 3 (STP) / cm 2 .sec.cmHg (hereinafter abbreviated as PU) and 4.6 × 1
At 0 -6 (PU), the gas selectivity is Met. The inner diameter of the hollow fiber is 0.2 mm, the outer diameter is 0.4 mm, and the film thickness is
It was 100 mμ.
比較例１ 実施例１と同じポリスルホンを溶媒としてN-メチルピロ
リドンを用いて、25重量％の均一な紡糸用原液を調製し
た。この紡糸原液を用いて実施例１と同様な条件で紡糸
を行った。得られた中空糸の内径は0.2mm、外径は0.4m
m、膜厚は100 μｍであり、実施例１の中空糸と同一で
あった。Comparative Example 1 Using N-methylpyrrolidone as the solvent of the same polysulfone as in Example 1, a uniform spinning dope of 25% by weight was prepared. Using this spinning dope, spinning was performed under the same conditions as in Example 1. The hollow fiber obtained has an inner diameter of 0.2 mm and an outer diameter of 0.4 m.
m, the film thickness was 100 μm, which was the same as that of the hollow fiber of Example 1.
気体の透過測定を行ったところ、水素及び窒素の０℃１
気圧における透過係数は、それぞれ0.50×10-4(PU)、0.
13×10-4(PU)、 であった。Gas permeation measurement showed that hydrogen and nitrogen were 0 ° C 1
Permeability coefficient at atmospheric pressure is 0.50 × 10 -4 (PU) and 0.
13 × 10 -4 (PU), Met.
実施例２〜８ ポリスルホン(P-3500)をジメチルイミダゾリジノンに溶
解して15〜35重量％の各種均一溶液を調製した。Examples 2 to 8 Polysulfone (P-3500) was dissolved in dimethylimidazolidinone to prepare various homogeneous solutions of 15 to 35% by weight.
該溶液を製膜用原液として実施例１と同様な方法におい
て、中空糸紡糸を行った。Hollow fiber spinning was performed in the same manner as in Example 1 using the solution as a stock solution for film formation.
製膜された中空糸の内外径は、それぞれ200、400μｍ、
膜厚100μｍであった。The inner and outer diameters of the film-formed hollow fiber are 200 and 400 μm,
The film thickness was 100 μm.
気体透過係数その他の測定結果を第１表に示す。The gas permeability coefficient and other measurement results are shown in Table 1.
実施例９〜17 実施例２と同様に、ポリスルホン(P-3500)、ジメチルイ
ミダゾリジノン、及び各種添加剤を加えて、均一な溶液
を調製し、中空糸紡糸を行った。Examples 9 to 17 In the same manner as in Example 2, polysulfone (P-3500), dimethylimidazolidinone, and various additives were added to prepare a uniform solution, and hollow fiber spinning was performed.
中空糸の内／外径は何れも200 ／400 μｍであった。The inner and outer diameters of the hollow fibers were both 200/400 μm.
気体透過係数その他の測定結果を第２表に示す。The gas permeability coefficient and other measurement results are shown in Table 2.
実施例18、19（平膜） ポリスルホン(UCC 社製コーデルポリサルホンP-3500)、
ポリエーテルスルホン(ICI 社製ビクトレックス)を、溶
媒としてジメチルイミダゾリジノンに溶解して25重量％
の均一な製膜用原液を調製した。Examples 18 and 19 (flat membrane) Polysulfone (UCC Cordel Polysulfone P-3500),
25% by weight of polyether sulfone (ICI Victrex) dissolved in dimethylimidazolidinone as a solvent
A uniform stock solution for film formation was prepared.
この原液を孔径１μｍの多孔体フイルターにて濾過後、
100 μｍ厚みのドクターブレードを用いてガラス板上に
キャストし、５秒後に30℃の水中に浸漬した。この時原
液温度は−３℃であった。After filtering this stock solution with a porous filter having a pore size of 1 μm,
It was cast on a glass plate using a doctor blade having a thickness of 100 μm, and after 5 seconds, it was immersed in water at 30 ° C. At this time, the stock solution temperature was -3 ° C.
得られた平膜を完全に脱溶媒した後乾燥し、気体透過性
を測定した所、水素及び窒素の０℃１気圧に於ける気体
透過係数、及び選択透過係数は第３表の数値となった。The obtained flat membrane was completely desolvated and then dried, and the gas permeability was measured. The gas permeation coefficient and selective permeation coefficient of hydrogen and nitrogen at 0 ° C. and 1 atmospheric pressure were as shown in Table 3. It was
本発明の方法によって得られるポリスルホン系重合体の
中空糸膜は、気体の選択透過性に優れたものである。The polysulfone-based polymer hollow fiber membrane obtained by the method of the present invention has excellent gas permselectivity.
Claims (3)
を含む溶媒に溶解した溶液を、該溶媒とは混和するが、
ポリスルホン系重合体を溶解しない液体と接触させて脱
溶媒を行うことを特徴とするポリスルホン系膜の製造方
法。1. A solution of a polysulfone polymer dissolved in a solvent containing imidazolidinone is mixed with the solvent,
A method for producing a polysulfone-based membrane, which comprises removing the solvent by bringing the polysulfone-based polymer into contact with a liquid that does not dissolve the polysulfone-based polymer.
許請求の範囲第１項記載のポリスルホン系膜の製造方
法。2. The method for producing a polysulfone-based membrane according to claim 1, wherein the polymer solution is discharged from an annular nozzle.
液を使用する特許請求の範囲第１項又は第２項記載のポ
リスルホン系膜の製造方法。3. The method for producing a polysulfone-based membrane according to claim 1 or 2, which uses a stock solution for membrane formation in which a nonsolvent is added to a polymer solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15965385A JPH0634910B2 (en) | 1985-07-19 | 1985-07-19 | Method for producing polysulfone-based membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15965385A JPH0634910B2 (en) | 1985-07-19 | 1985-07-19 | Method for producing polysulfone-based membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6219209A JPS6219209A (en) | 1987-01-28 |
| JPH0634910B2 true JPH0634910B2 (en) | 1994-05-11 |
Family
ID=15698408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15965385A Expired - Lifetime JPH0634910B2 (en) | 1985-07-19 | 1985-07-19 | Method for producing polysulfone-based membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0634910B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH089801B2 (en) * | 1988-01-22 | 1996-01-31 | エヌオーケー株式会社 | Method for producing porous hollow fiber |
| DE3814715A1 (en) * | 1988-04-30 | 1989-11-09 | Basf Ag | THREAD MOLDED THREADS FROM AT LEAST ONE AROMATIC POLYMER |
| US5013767A (en) * | 1989-09-27 | 1991-05-07 | Permea, Inc. | Asymmetric gas separation membranes having improved strength |
-
1985
- 1985-07-19 JP JP15965385A patent/JPH0634910B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6219209A (en) | 1987-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4127625A (en) | Process for preparing hollow fiber having selective gas permeability | |
| US4051300A (en) | Hollow synthetic fibers | |
| US5013339A (en) | Compositions useful for making microporous polyvinylidene fluoride membranes, and process | |
| US5820659A (en) | Multicomponent or asymmetric gas separation membranes | |
| JPS61209027A (en) | Gas permselective membrane | |
| US5443728A (en) | Method of preparing membranes from blends of polyetherimide and polyimide polymers | |
| CA2154070C (en) | Process of making microporous pps membranes | |
| JPH05212255A (en) | Hollow fiber membrane | |
| JPH08257381A (en) | Fluid separation membrane prepared of blend of polyimide polymer | |
| JPS6214916A (en) | Manufacture of composite asymmetric membrane for mutually separating gas | |
| EP0012630B1 (en) | Process for producing a cellulose acetate-type permselective membrane, permselective membrane thus produced, and use of such membrane in artificial kidney | |
| US6017474A (en) | Highly permeable polyethersulfone hollow fiber membranes for gas separation | |
| KR101161711B1 (en) | Method of producing forward osmosis membranes based on acetylated alkyl cellulose | |
| JP3386904B2 (en) | Cellulose acetate hollow fiber separation membrane and method for producing the same | |
| JPH0478729B2 (en) | ||
| JPH0634910B2 (en) | Method for producing polysulfone-based membrane | |
| JP2688882B2 (en) | Method for producing composite membrane for gas separation | |
| JPS6190709A (en) | Production of polysulfone hollow membrane | |
| WO1994004253A2 (en) | Polyazole polymer-based membranes for fluid separation | |
| JPS59228016A (en) | Hollow yarn membrane of aromatic polysulfone | |
| JPS62152508A (en) | Preparation of polysulfone membrane | |
| Koops | Dehydration of acetic acid by pervaporation: Material science aspects | |
| JP2904324B2 (en) | Polysulfone-based hollow fiber membrane and production method | |
| JP2000042342A (en) | External pressure type composite hollow fiber membrane for gas separation and its production | |
| JPH03174233A (en) | Production of aromatic polysulfone hollow-fiber membrane |