JPH0243930A - Preparation of polyether sulfone hollow yarn membrane - Google Patents
Preparation of polyether sulfone hollow yarn membraneInfo
- Publication number
- JPH0243930A JPH0243930A JP19423388A JP19423388A JPH0243930A JP H0243930 A JPH0243930 A JP H0243930A JP 19423388 A JP19423388 A JP 19423388A JP 19423388 A JP19423388 A JP 19423388A JP H0243930 A JPH0243930 A JP H0243930A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- spinning
- membrane
- polyether sulfone
- raw
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 39
- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 20
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 20
- 238000009987 spinning Methods 0.000 claims abstract description 43
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005345 coagulation Methods 0.000 claims abstract description 12
- 230000015271 coagulation Effects 0.000 claims abstract description 12
- 239000012510 hollow fiber Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000011550 stock solution Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000035699 permeability Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はポリエーテルスルホン中空糸膜の製造方法に関
し、詳しくは膜分離技術法により水溶液中の物質の分離
濃縮を行う際に用いるポリエーテルスルホン中空糸膜の
製造方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing polyethersulfone hollow fiber membranes, and more specifically, polyethersulfone used when separating and concentrating substances in an aqueous solution by membrane separation technology. The present invention relates to a method for manufacturing a hollow fiber membrane.
〔従来の技術及び発明が解決しようとする課題〕近年、
膜分離技術はその省エネルギー性、コンパクト性といっ
た面で注目され、浄水分野においては、海水の淡水化、
電子工業用超純水の製造、原子力発電設備の原子炉冷却
水中に含まれる腐食底生物の除去など、また、食品工業
分野においては、果汁の清澄化、？′Ｉ！１類の濃縮や
発酵菌の除去等に、医療分野においては、人工肺、人工
腎臓、血液濾過等、さまざまな分野に利用されつつある
。[Problems to be solved by conventional techniques and inventions] In recent years,
Membrane separation technology is attracting attention for its energy saving and compactness, and in the water purification field, it is used for seawater desalination,
The production of ultra-pure water for the electronics industry, the removal of corrosive bottom organisms contained in the reactor cooling water of nuclear power generation facilities, etc. Also, in the food industry, it is used for the clarification of fruit juice, etc. 'I! In the medical field, it is being used in various fields such as type 1 concentration and removal of fermentation bacteria, artificial lungs, artificial kidneys, and blood filtration.
分離膜の膜素材には、セルロース系、ポリアミド系、ポ
リアクリロニトリル系、ポリスルホン系樹脂などが使用
されているが、なかでもポリエーテルスルホン樹脂は元
来エンジニアリングプラスチックスとして開発されてお
り、その機械的強度、耐薬品性、耐熱性に優れているた
め、分離膜の膜素材としても多く利用されている。Separation membrane materials include cellulose, polyamide, polyacrylonitrile, and polysulfone resins, among which polyethersulfone resin was originally developed as an engineering plastic. Because it has excellent strength, chemical resistance, and heat resistance, it is often used as a membrane material for separation membranes.
また、分＃膜の形態としては、中空糸膜がコンパクト性
から利用されることが多い。ポリエーテルスルホン類の
中空糸膜は既に特開昭５９−２２８０１７号公報や特開
昭６１−２００８０５号公報などで製造方法が公知とな
っているが、これらの膜はいずれも限外濾過膜としての
十分な透水性能を満たすものではなかった。Furthermore, as a form of membrane, hollow fiber membranes are often used due to their compactness. Manufacturing methods for polyether sulfone hollow fiber membranes are already known in Japanese Patent Application Laid-Open No. 59-228017 and Japanese Patent Application Laid-open No. 61-200805, but none of these membranes can be used as an ultrafiltration membrane. It did not meet sufficient water permeability.
中空糸膜の透水性能だけを高めるためには、紡糸原液濃
度を下げれば良いことが従来より知られている。しかし
ながら、この方法では中空糸膜の機械的強度が下がるな
ど、実用性の面から問題があった。It has been known that in order to improve only the water permeability of hollow fiber membranes, it is sufficient to lower the concentration of the spinning solution. However, this method has problems from a practical standpoint, such as a decrease in the mechanical strength of the hollow fiber membrane.
〔課題を解決するための手段］
本発明者らは、機械強度、分画性能を維持したまま透水
性能が高い中空糸分離膜を製造すべく鋭意研究の結果、
本発明を完成するに到った。[Means for Solving the Problems] As a result of intensive research by the present inventors in order to manufacture a hollow fiber separation membrane with high water permeability while maintaining mechanical strength and fractionation performance,
The present invention has now been completed.
即ち、本発明は、ポリエーテルスルホンのジメチルスル
ホキシド溶液を紡糸原液に用いたポリエーテルスルホン
中空糸膜の製造方法において、紡糸原液及び紡糸芯液を
４０℃以上にして二重背型紡糸ロ金より紡糸原液温度以
上の凝固浴に吐出することを特徴とするポリエーテルス
ルホン中空糸膜の製造方法を提供するものである。That is, the present invention provides a method for producing a polyethersulfone hollow fiber membrane using a dimethyl sulfoxide solution of polyethersulfone as a spinning stock solution, in which the spinning stock solution and the spinning core solution are heated to 40° C. or higher from a double-back spinning rod. The present invention provides a method for producing a polyethersulfone hollow fiber membrane, which is characterized by discharging the membrane into a coagulation bath at a temperature higher than that of the spinning dope.
以下、さらに詳細に本発明を説明する。The present invention will be explained in more detail below.
本発明に用いられるポリエーテルスルホン（ＰＥＳ）と
は、下記の式（１）で表される構造を存する化合物及び
その誘導体をさして言う。The polyether sulfone (PES) used in the present invention refers to a compound having a structure represented by the following formula (1) and derivatives thereof.
中空糸の製造は、湿式あるいは乾湿式法として一般的に
知られている方法に従い、二重背型紡糸ロ金より凝固浴
に紡糸原液と紡糸芯液を同時に吐出することにより行わ
れる。この際、紡糸原液としてＰＥＳを溶解する溶媒に
ジメチルスルホキシド（ＤＭＳＯ）を用いることが本発
明で満たすべき第１の要件である。ＤＭＳＯはＰＥＳを
溶解し、高温でＰＥＳの安定な溶液として存在すること
ができる。また沸点が高く、毒性が小さいことも、多量
に使用するのに優れた性質の一つである。特に、ポリエ
チレングリコール（ＰＥＧ）やポリプロピレングリコー
ル（ＰＰＧ）などのグリコール類を添加剤に用いた時に
は、常温から温度を上げていくと紡糸原液の溶液構造が
成長し、そのために高い温度の紡糸原液から紡糸した中
空糸は大きな粒子からなる多孔質構造を形成し、従って
透水時に抵抗が小さ（、高透水性能の膜が得られる。The production of hollow fibers is carried out by simultaneously discharging a spinning stock solution and a spinning core solution into a coagulation bath from a double-back type spinning die according to a method generally known as a wet method or a wet-dry method. At this time, the first requirement of the present invention is to use dimethyl sulfoxide (DMSO) as a solvent for dissolving PES as a spinning stock solution. DMSO dissolves PES and can exist as a stable solution of PES at elevated temperatures. Furthermore, it has a high boiling point and low toxicity, which are also excellent properties for use in large quantities. In particular, when glycols such as polyethylene glycol (PEG) and polypropylene glycol (PPG) are used as additives, the solution structure of the spinning dope grows as the temperature is raised from room temperature. The spun hollow fibers form a porous structure consisting of large particles, and therefore have low resistance during water permeation (a membrane with high water permeability can be obtained).
紡糸原液及び紡糸芯液を４０℃以上に加温することが本
発明の第２の要件である。即ち、紡糸原液及び芯液の温
度は４０℃以上で著しく高い透水性能の膜を与える。操
作性の問題と膜性能を鑑みると、紡糸原液の温度は４０
℃から８０℃が望ましく、さらに望ましいのは４５℃か
ら７０゛ｃである。この温度範囲に紡糸原液を保ち、芯
液組成を適当に選択することにより膜全体にわたる多孔
質構造と表面構造を変えることができるため、
任意の分画分子量を有する高透水性中空糸膜を得ること
ができる。The second requirement of the present invention is to heat the spinning stock solution and the spinning core solution to 40° C. or higher. That is, when the temperature of the spinning dope and core solution is 40° C. or higher, a membrane with extremely high water permeability can be obtained. Considering operability issues and membrane performance, the temperature of the spinning dope was set at 40°C.
The temperature is preferably from 0.degree. C. to 80.degree. C., and more preferably from 45.degree. C. to 70.degree. By keeping the spinning dope in this temperature range and appropriately selecting the core liquid composition, it is possible to change the porous structure and surface structure throughout the membrane, thereby obtaining a highly water permeable hollow fiber membrane with an arbitrary molecular weight cutoff. be able to.
また、ＤＭＳＯ溶液を紡糸原液とした場合、溶液の曳糸
性が向上するため高速で紡糸することも可能となる長所
も付随していることがわかった。Furthermore, it has been found that when a DMSO solution is used as a spinning stock solution, the spinnability of the solution is improved, so that high-speed spinning becomes possible.
この様に４０℃以上に加温したＤＭＳＯ溶液からなる紡
糸原液、及び紡糸芯液を、紡糸原液温度以上の凝固浴に
吐出することが本発明の第３の要件である。紡糸原液よ
り高い温度の凝固浴に吐出すると、紡糸原液中で形成さ
れた溶液構造のまま凝固するため、高透水性能を有する
膜が形成される。凝固浴は作業性の問題もあるため、紡
糸原液より０〜１０℃高い温度であればその目的を達す
る。The third requirement of the present invention is to discharge the spinning dope made of the DMSO solution heated to 40° C. or higher and the spinning core solution into a coagulation bath at a temperature equal to or higher than the temperature of the spinning dope. When discharged into a coagulation bath at a temperature higher than that of the spinning dope, the solution structure formed in the spinning dope is coagulated, forming a membrane with high water permeability. Since the coagulation bath has problems with workability, its purpose can be achieved if the temperature is 0 to 10° C. higher than the spinning dope.
〔実 施 例］
以下、本発明を実施例により更に詳細に説明するが、本
発明はこれらの実施例に限定されるものではない。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例ｌ
ＰＥ５（ＩＣ１社製５２００Ｐ） 、ＰＥＧ２００（三
洋化成■製”） 、ＤＭＳＯ（昭和工業■製）をそれぞ
れ２０／２０／６０の重量比で混合し、均一な溶液とし
、紡糸原液とした。紡糸芯液としての５０％のＤＭＳＯ
水溶液と共に、このＰ Ｅ Ｓ 溶液を二重管紡糸ロ金
からの吐出時に４６℃になる様に加温した。凝固浴は５
０℃の湯浴とし、空中走行時間０．３秒で凝固浴中に浸
漬するように吐出及び巻き取りを行った。Example 1 PE5 (5200P manufactured by IC1), PEG200 (manufactured by Sanyo Kasei), and DMSO (manufactured by Showa Kogyo) were mixed at a weight ratio of 20/20/60, respectively, to form a uniform solution, which was used as a spinning dope. .50% DMSO as spinning core liquid
Together with the aqueous solution, this P E S solution was heated to 46° C. at the time of discharge from the double tube spinning rod. The coagulation bath is 5
A hot water bath was set at 0° C., and the product was discharged and wound up so as to be immersed in the coagulation bath for an air travel time of 0.3 seconds.
得られた中空糸膜は内径５００μｍ、外径８００μｍで
、純水透水性能が内圧測定で６４０４１！／ｍ”・ｈｒ
−ｋｇ／ｃｒｍｚであった。また、分子ｆｆ１２８．０
００の蛋白質の透過率は５０％、引張り破断強度が１２
０ｇ／本、破断伸度３５％であった。The obtained hollow fiber membrane has an inner diameter of 500 μm and an outer diameter of 800 μm, and has a pure water permeability of 64,041 as measured by internal pressure! /m”・hr
-kg/crmz. Also, the molecule ff128.0
The transmittance of 00 protein is 50%, and the tensile strength at break is 12.
It was 0 g/piece and the elongation at break was 35%.
実施例２
紡糸原液及び芯液の吐出温度を６２℃とし、凝固浴の温
度を７０℃とした他は実施例Ｉと同様な操作を行ってＰ
ＥＳ中空糸膜を得た。Example 2 The same operation as in Example I was carried out except that the discharge temperature of the spinning dope and core solution was 62°C and the temperature of the coagulation bath was 70°C.
An ES hollow fiber membrane was obtained.
得られた中空糸膜は純水透水性能が内圧測定で８７０１
／ ｍ”−ｈｒ−ｋｇ／ｃｍ２であり、分子ｆ１２Ｂ
、 ０００の蛋白質の透過率が８４％であった。機械強
度は実施例１と同等で、引張り破断強度が２１０ｇ／本
、破断伸度３５％であった。The obtained hollow fiber membrane has a pure water permeability of 8701 as measured by internal pressure.
/ m”-hr-kg/cm2, and the molecule f12B
, 000 protein transmittance was 84%. The mechanical strength was the same as in Example 1, with a tensile strength at break of 210 g/piece and elongation at break of 35%.
比較例１
紡糸原液及び芯液の吐出温度を２２℃，凝固浴温度を４
０℃とした他は全て実施例１と同様な操作によりＰＥＳ
中空糸膜を得た。Comparative Example 1 The discharge temperature of the spinning dope and core solution was 22°C, and the coagulation bath temperature was 4°C.
PES was prepared in the same manner as in Example 1 except that the temperature was 0°C.
A hollow fiber membrane was obtained.
得られた中空糸膜の純水透水性能は３ＢＯｆ ／ｒｔｒ
” −ｈｒ −ｋｇ／ｃｔａ２と低いものであった。The pure water permeability of the obtained hollow fiber membrane was 3BOf/rtr.
”-hr-kg/cta2.
本発明の方法により製造したＰＥＳ中空糸膜は透水性が
高く、膜を用いた分離や濃縮において生産性が向上する
。The PES hollow fiber membrane produced by the method of the present invention has high water permeability and improves productivity in separation and concentration using the membrane.
Claims (1)
糸原液に用いたポリエーテルスルホン中空糸膜の製造方
法において、紡糸原液及び紡糸芯液を４０℃以上にして
二重管型紡糸口金より紡糸原液温度以上の凝固浴に吐出
することを特徴とするポリエーテルスルホン中空糸膜の
製造方法。In a method for producing a polyethersulfone hollow fiber membrane using a dimethyl sulfoxide solution of polyethersulfone as a spinning stock solution, the spinning stock solution and the spinning core solution are heated to 40°C or higher, and the coagulation bath is heated to a temperature higher than the spinning stock solution temperature using a double tube spinneret. A method for producing a polyethersulfone hollow fiber membrane, characterized by discharging the polyethersulfone hollow fiber membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19423388A JPH0829243B2 (en) | 1988-08-03 | 1988-08-03 | Method for producing polyethersulfone hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19423388A JPH0829243B2 (en) | 1988-08-03 | 1988-08-03 | Method for producing polyethersulfone hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0243930A true JPH0243930A (en) | 1990-02-14 |
| JPH0829243B2 JPH0829243B2 (en) | 1996-03-27 |
Family
ID=16321184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19423388A Expired - Lifetime JPH0829243B2 (en) | 1988-08-03 | 1988-08-03 | Method for producing polyethersulfone hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0829243B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5355747A (en) * | 1991-09-04 | 1994-10-18 | Kabushiki Kaisha Daikin Seisakusho | Flywheel assembly |
-
1988
- 1988-08-03 JP JP19423388A patent/JPH0829243B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5355747A (en) * | 1991-09-04 | 1994-10-18 | Kabushiki Kaisha Daikin Seisakusho | Flywheel assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0829243B2 (en) | 1996-03-27 |
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