JP4013396B2 - Method for producing porous polyamideimide hollow fiber membrane - Google Patents
Method for producing porous polyamideimide hollow fiber membrane Download PDFInfo
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- JP4013396B2 JP4013396B2 JP09769899A JP9769899A JP4013396B2 JP 4013396 B2 JP4013396 B2 JP 4013396B2 JP 09769899 A JP09769899 A JP 09769899A JP 9769899 A JP9769899 A JP 9769899A JP 4013396 B2 JP4013396 B2 JP 4013396B2
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- Prior art keywords
- hollow fiber
- fiber membrane
- polyamideimide
- weight
- porous
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Description
【０００１】
【発明の属する技術分野】
本発明は、多孔質ポリアミドイミド中空糸膜の製造法に関する。更に詳しくは、水蒸気選択透過性にすぐれ、除湿膜などとして好適に使用し得る多孔質ポリアミドイミド中空糸膜の製造法に関する。
【０００２】
【従来の技術】
ポリスルホンによって代表される非水溶性膜形成重合体および水溶性重合体を含有する製膜原液を乾湿式紡糸または湿式紡糸して得られる多孔質中空糸膜は、その多くが水蒸気のみならず空気をも透過させてしまうため、除湿膜として使用することができない。
【０００３】
また、空気を透過せずに水蒸気を選択的に透過する膜においても、除湿性能が低かったり、あるいは膜強度が低いため、圧縮空気によって破損したりするという欠点を有している。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、水蒸気選択透過性および膜強度にすぐれ、従って除湿膜などとして有効に使用し得る多孔質ポリアミドイミド中空糸膜の製造法を提供することにある。
【０００５】
【課題を解決するための手段】
かかる本発明の目的は、ポリアミドイミドおよび水溶性重合体を含有する製膜原液を、芯液および凝固液に炭素数3以下の低級アルコールまたはそれを30重量%以上含有する水溶液を用いて、乾湿式紡糸または湿式紡糸し、多孔質ポリアミドイミド中空糸膜を製造することによって達成される。
【０００６】
【発明の実施の形態】
ポリアミドイミドとしては、次の一般式で表されるくり返し単位を有するアモコ・ジャパン製品トーロン4000Tなどの市販品をそのまま用いることができる。
ポリアミドイミドは、それの良溶媒である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、N-メチルピロリドン、モルホリン、ジオキサン等の有機溶媒、好ましくは非プロトン性極性溶媒中に均一に溶解させた製膜溶液に調製される。その溶液は、ポリアミドイミドが約10〜30重量%、好ましくは約15〜20重量%となるような濃度に調整される。
【０００８】
この製膜溶液中には、ポリビニルピロリドン、ポリエチレングリコール、ポリプロピレングリコール、ポリカプロラクタム等の水溶性重合体が約12重量%以下、好ましくは約1〜10重量%を占めるような割合で添加され、製膜原液を形成させる。
【０００９】
ポリアミドイミドおよび水溶性重合体を含有する製膜原液は、芯液および凝固液に炭素数3以下の低級アルコールまたはそれを30重量%以上含有する水溶液を用いて、乾湿式紡糸または湿式紡糸される。炭素数3以下の低級アルコールとしては、メタノール、エタノール、プロパノールまたはイソプロパノールが用いられ、これらは30重量%以上、好ましくは50重量%以上の水溶液としても用いることができる。これよりも炭素数の多いアルコール、例えばn-ブタノールを用いると、破断強度は高く、除湿性もある程度認められるものの、水蒸気選択透過性に劣るようになる。
【００１０】
かかる紡糸原液を用いての製膜は、乾湿式紡糸法または湿式紡糸法によって行われる。
【００１１】
【発明の効果】
本発明方法によって得られる多孔質ポリアミドイミド中空糸膜は、空気を透過せずに水蒸気のみを透過する選択透過性を示し、除湿性の点でもすぐれている。更に、膜強度の点でも大きく向上している。
【００１２】
【実施例】
次に、実施例について本発明を説明する。
【００１３】
実施例１
ポリアミドイミド(アモコ・ジャパン製品トーロン4000T)20重量部、ポリビニルピロリドン(K-90)4重量部およびジメチルアセトアミド76重量部よりなる製膜原液を、芯液に70重量%エタノール水溶液を、また凝固液にエタノールをそれぞれ用いて、二重環状ノズルから湿式紡糸を行ない、外径約700μm、内径約500μmの多孔質中空糸膜を得た。
【００１４】
得られた多孔質ポリアミドイミド中空糸膜の内側には、相対湿度100%の空気を0.05MPaの圧力状態において100ml/分の一定流量で流し、外側には大気圧の空気を400ml/分の一定流量で流した。この中空糸膜の内管部分を通過した空気を冷却トラップに通し、単位時間当りにトラップされた水重量を単位時間当りに供給した水蒸気重量で除した値を、出口空気の相対湿度と定義すると、その値は40%であった。
【００１５】
また、内圧型のクロスフロー方式により窒素ガス透過係数を求めたところ、3×10-8cm3(STP)/(cm・秒・cmHg)という低い値を示し、水蒸気選択透過性にすぐれていた。更に、多孔質中空糸膜の破断強度を、標点間距離3cm、引張速度1cm/分の条件下において測定された破断時の荷重を膜断面積で除した値として算出すると、270Kgf/cm２と高い値を示した。
【００１６】
比較例１
実施例1において、芯液として70重量% n-ブタノール水溶液を、また凝固液としてn-ブタノールを用い、外径約700μm、内径約500μmの多孔質中空糸膜を得た。得られた湿式紡糸膜の形状は不安定であり、紡糸中は糸切れが生じ易い状態にあった。
【００１７】
この多孔質ポリアミドイミドの破断強度は350Kgf/cm２という高い値を示し、また前記定義の相対湿度も60%であったが、窒素ガス透過係数は2.4×10-4cm3(STP)/(cm・秒・cmHg)と高い値を示し、水蒸気選択透過性に劣っていた。
【００１８】
比較例２
実施例1において、芯液および凝固浴にそれぞれ水を用いて、外径約600μm、内径約400μmの多孔質中空糸膜を得た。この多孔質ポリアミドイミド中空糸膜は、前記定義の相対湿度が30%であり、窒素ガス透過係数も4.8×10-9cm3(STP)/(cm・秒・cmHg)と低く、水蒸気選択透過性にすぐれていたが、破断強度は100Kgf/cm２という低い値しか示さなかった。
【００１９】
比較例３
実施例1において、芯液に70重量％エタノール水溶液を、また凝固浴に水をそれぞれ用いて、外径約600μm、内径約400μmの多孔質中空糸膜を得た。この多孔質ポリアミドイミド中空糸膜は、前記定義の相対湿度が35%であり、窒素ガス透過係数も7.0×10-9cm3(STP)/(cm・秒・cmHg)と低く、水蒸気選択透過性にすぐれていたが、破断強度は130Kgf/cm２という低い値しか示さなかった。
【００２０】
実施例２
実施例1において、二重環状ノズルの吐出部から凝固液の液面迄の距離を5cmに設定し、紡糸された中空糸膜を空走させることにより乾湿式紡糸を行い、外径約700μm、内径約500μmの多孔質中空糸膜を得た。この多孔質ポリアミドイミド中空糸膜は、前記定義の相対湿度が45%であり、窒素ガス透過係数も2.5×10-8cm3(STP)/(cm・秒・cmHg)と低く、水蒸気選択透過性にすぐれており、また破断強度も280Kgf/cm２という高い値を示した。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a porous polyamideimide hollow fiber membrane. More specifically, the present invention relates to a method for producing a porous polyamideimide hollow fiber membrane that has excellent water vapor selective permeability and can be suitably used as a dehumidifying membrane.
[0002]
[Prior art]
A porous hollow fiber membrane obtained by dry-wet spinning or wet spinning of a water-insoluble film-forming polymer represented by polysulfone and a film-forming stock solution containing a water-soluble polymer, most of them not only contain water vapor but also air. Can not be used as a dehumidifying film.
[0003]
In addition, a membrane that selectively permeates water vapor without permeating air also has a drawback that it is damaged by compressed air because of its low dehumidifying performance or low membrane strength.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a porous polyamideimide hollow fiber membrane that is excellent in water vapor selective permeability and membrane strength, and can therefore be used effectively as a dehumidifying membrane.
[0005]
[Means for Solving the Problems]
An object of the present invention is to use a film-forming stock solution containing a polyamideimide and a water-soluble polymer, using a lower alcohol having 3 or less carbon atoms or an aqueous solution containing 30% by weight or more in a core solution and a coagulating solution. This is accomplished by spinning or wet spinning to produce a porous polyamideimide hollow fiber membrane.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
As the polyamideimide, commercially available products such as Amoco Japan product Torlon 4000T having repeating units represented by the following general formula can be used as they are.
Polyamideimide is produced by uniformly dissolving it in an organic solvent such as dimethylformamide, dimethylacetamide, diethylformamide, diethylacetamide, N-methylpyrrolidone, morpholine, dioxane or the like, preferably an aprotic polar solvent. Prepared in membrane solution. The solution is adjusted to a concentration such that the polyamideimide is about 10-30% by weight, preferably about 15-20% by weight.
[0008]
In this film-forming solution, a water-soluble polymer such as polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, and polycaprolactam is added at a ratio of about 12% by weight or less, preferably about 1 to 10% by weight. A membrane stock solution is formed.
[0009]
A film-forming stock solution containing polyamideimide and a water-soluble polymer is dry-wet-spun or wet-spun using a lower alcohol having 3 or less carbon atoms or an aqueous solution containing 30% by weight or more in the core solution and the coagulation solution. . As the lower alcohol having 3 or less carbon atoms, methanol, ethanol, propanol or isopropanol is used, and these can also be used as an aqueous solution of 30% by weight or more, preferably 50% by weight or more. When an alcohol having a higher carbon number than this, for example, n-butanol is used, the breaking strength is high and the dehumidifying property is recognized to some extent, but the water vapor selective permeability is inferior.
[0010]
Film formation using the spinning dope is performed by a dry wet spinning method or a wet spinning method.
[0011]
【The invention's effect】
The porous polyamideimide hollow fiber membrane obtained by the method of the present invention exhibits selective permeability that allows only water vapor to permeate without permeating air, and is excellent in terms of dehumidification. Furthermore, the film strength is greatly improved.
[0012]
【Example】
Next, the present invention will be described with reference to examples.
[0013]
Example 1
A film-forming stock solution consisting of 20 parts by weight of polyamideimide (Amoco Japan product Torlon 4000T), 4 parts by weight of polyvinylpyrrolidone (K-90) and 76 parts by weight of dimethylacetamide, 70% by weight ethanol aqueous solution in the core liquid, and coagulation liquid Wet spinning was performed from a double annular nozzle using ethanol for each, and a porous hollow fiber membrane having an outer diameter of about 700 μm and an inner diameter of about 500 μm was obtained.
[0014]
Inside the obtained porous polyamideimide hollow fiber membrane, 100% relative humidity air was flowed at a constant flow rate of 100 ml / min at a pressure of 0.05 MPa, and atmospheric pressure air was constant at 400 ml / min outside. Flowed at a flow rate. When the air passing through the inner pipe portion of the hollow fiber membrane is passed through a cooling trap, the value obtained by dividing the weight of water trapped per unit time by the weight of water vapor supplied per unit time is defined as the relative humidity of the outlet air. The value was 40%.
[0015]
In addition, when the nitrogen gas permeability coefficient was determined by the internal pressure type cross flow method, it showed a low value of 3 × 10 −8 cm 3 (STP) / (cm · second · cmHg), and was excellent in water vapor selective permeability. . Further, when the breaking strength of the porous hollow fiber membrane is calculated as a value obtained by dividing the load at break measured under the conditions of a distance between the gauge points of 3 cm and a tensile speed of 1 cm / min by the membrane cross-sectional area, 270 kgf / cm 2 And showed a high value.
[0016]
Comparative Example 1
In Example 1, a porous hollow fiber membrane having an outer diameter of about 700 μm and an inner diameter of about 500 μm was obtained using a 70 wt% n-butanol aqueous solution as the core liquid and n-butanol as the coagulation liquid. The shape of the obtained wet-spun membrane was unstable, and yarn breakage was likely to occur during spinning.
[0017]
The breaking strength of this porous polyamideimide showed a high value of 350 kgf / cm 2 , and the relative humidity defined above was 60%, but the nitrogen gas permeability coefficient was 2.4 × 10 −4 cm 3 (STP) / ( cm · sec · cmHg) and a high water vapor selective permeability.
[0018]
Comparative Example 2
In Example 1, a porous hollow fiber membrane having an outer diameter of about 600 μm and an inner diameter of about 400 μm was obtained using water for the core liquid and the coagulation bath, respectively. This porous polyamideimide hollow fiber membrane has a relative humidity of 30% as defined above, a low nitrogen gas permeability coefficient of 4.8 × 10 -9 cm 3 (STP) / (cm · sec · cmHg), and water vapor selective permeation. Although excellent in properties, the breaking strength showed only a low value of 100 kgf / cm 2 .
[0019]
Comparative Example 3
In Example 1, a porous hollow fiber membrane having an outer diameter of about 600 μm and an inner diameter of about 400 μm was obtained using a 70 wt% aqueous ethanol solution as the core liquid and water as the coagulation bath. This porous polyamideimide hollow fiber membrane has a relative humidity of 35% as defined above, and a low nitrogen gas permeability coefficient of 7.0 × 10 -9 cm 3 (STP) / (cm · sec · cmHg), with a selective permeation of water vapor. Although excellent in properties, the breaking strength showed only a low value of 130 kgf / cm 2 .
[0020]
Example 2
In Example 1, the distance from the discharge part of the double annular nozzle to the liquid level of the coagulation liquid is set to 5 cm, and dry and wet spinning is performed by running the spun hollow fiber membrane, the outer diameter is about 700 μm, A porous hollow fiber membrane having an inner diameter of about 500 μm was obtained. This porous polyamideimide hollow fiber membrane has a relative humidity of 45% as defined above, and a low nitrogen gas permeability coefficient of 2.5 × 10 −8 cm 3 (STP) / (cm · second · cmHg), with selective permeation of water vapor. It had excellent properties, and the breaking strength was as high as 280 kgf / cm 2 .
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09769899A JP4013396B2 (en) | 1999-04-05 | 1999-04-05 | Method for producing porous polyamideimide hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09769899A JP4013396B2 (en) | 1999-04-05 | 1999-04-05 | Method for producing porous polyamideimide hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000288370A JP2000288370A (en) | 2000-10-17 |
| JP4013396B2 true JP4013396B2 (en) | 2007-11-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09769899A Expired - Fee Related JP4013396B2 (en) | 1999-04-05 | 1999-04-05 | Method for producing porous polyamideimide hollow fiber membrane |
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| Country | Link |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002289228A (en) * | 2001-03-22 | 2002-10-04 | Nok Corp | Humidifier and its use |
| JP2002289229A (en) * | 2001-03-22 | 2002-10-04 | Nok Corp | Humidifier and its use |
| JP5553699B2 (en) * | 2010-07-14 | 2014-07-16 | ユニチカ株式会社 | Polyamide moisture permeable membrane and method for producing the same |
| RU2510435C1 (en) * | 2012-12-06 | 2014-03-27 | Закрытое акционерное общество "Институт новых углеродных материалов и технологий" (ЗАО "ИНУМиТ") | Method of producing polyamide imide-based hollow fibre based and hollow fibre |
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1999
- 1999-04-05 JP JP09769899A patent/JP4013396B2/en not_active Expired - Fee Related
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| JP2000288370A (en) | 2000-10-17 |
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