JPH0829242B2 - Polysulfone hollow fiber membrane - Google Patents
Polysulfone hollow fiber membraneInfo
- Publication number
- JPH0829242B2 JPH0829242B2 JP17435788A JP17435788A JPH0829242B2 JP H0829242 B2 JPH0829242 B2 JP H0829242B2 JP 17435788 A JP17435788 A JP 17435788A JP 17435788 A JP17435788 A JP 17435788A JP H0829242 B2 JPH0829242 B2 JP H0829242B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- hollow fiber
- finger
- fiber membrane
- thickness
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Artificial Filaments (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、ポリスルホン系中空糸膜に関し、さらに詳
しくは、優れた濾過特性と機械特性を併せもつ中空糸状
ポリスルホン系限外濾過膜に関するものである。TECHNICAL FIELD The present invention relates to a polysulfone-based hollow fiber membrane, and more specifically to a hollow fiber-shaped polysulfone-based ultrafiltration membrane having both excellent filtration characteristics and mechanical characteristics. Is.
（ロ）従来の技術 従来、ポリスルホン系中空糸膜に関する文献は多数存
在するが、膜構造について開示する文献はあまり多くな
い。(B) Conventional Technology Conventionally, there are many documents regarding polysulfone-based hollow fiber membranes, but there are not many documents disclosing membrane structures.
（ハ）発明が解決しようとする課題 内・外表面層、内・外指状構造層、中間層という５つ
の層からなる膜もJournal of Applied Polymer Science
（J.Appl.Polym.Sci.）21巻165ページ〜180ページ（197
9）など、以前より知られていたが、中間層がいずれも
厚いために透水速度に劣る膜しか知られていなかった。(C) Problems to be solved by the invention A film consisting of five layers, an inner / outer surface layer, an inner / outer finger structure layer, and an intermediate layer, is also available in the Journal of Applied Polymer Science.
(J.Appl.Polym.Sci.) Volume 21 Pages 165-180 (197
9), etc., but it has been known for some time, but only the membranes with poor water permeability due to the thick intermediate layers were known.
本発明では、５層構造からなるポリスルホン系中空糸
膜であって、濾過速度が大きく、かつ機械強度の高い膜
について鋭意研究を進め、中間層の大きさを規定するこ
とにより上記問題点を解決できることを見い出し本発明
に至った。In the present invention, a polysulfone-based hollow fiber membrane having a five-layer structure, which has a high filtration rate and a high mechanical strength, is earnestly studied, and the size of the intermediate layer is defined to solve the above problems. The inventors have found what can be done and have reached the present invention.
（ニ）課題を解決するための手段 すなわち、本発明は、断面が内表面層、内指状構造
層、中間層、外指状構造層、外表面層の５つの層からな
り、内指状構造層の厚さに対し、中間層の厚みが0.1〜
0.2倍で、外指状構造層の厚みが0.6〜1.5倍であること
を特徴とするポリスルホン系中空糸膜である。(D) Means for Solving the Problem That is, according to the present invention, the cross section is made up of five layers of an inner surface layer, an inner finger-like structure layer, an intermediate layer, an outer finger-like structure layer and an outer surface layer The thickness of the intermediate layer is 0.1 to the thickness of the structure layer.
The polysulfone-based hollow fiber membrane is characterized in that the outer finger-like structure layer has a thickness of 0.2 to 0.2 and a thickness of 0.6 to 1.5.
本発明のポリスルホン系中空糸膜を形成するポリスル
ホン樹脂は、それ自体公知のものが利用できる。ポリス
ルホン樹脂は、下記の一般式で表される芳香族ポリスル
ホン、又はポリエーテルスルホンであり、およびこれら
の誘導体をも含めるものである。As the polysulfone resin forming the polysulfone-based hollow fiber membrane of the present invention, those known per se can be used. The polysulfone resin is an aromatic polysulfone or a polyether sulfone represented by the following general formula, and also includes derivatives thereof.
なお、これらのポリスルホン、ポリエーテルスルホン
系樹脂は、耐熱性、耐薬品性に優れたエンジニアリング
プラスチックスであり、従って中空糸膜も優れた特性を
与え得る。 Incidentally, these polysulfone and polyether sulfone-based resins are engineering plastics having excellent heat resistance and chemical resistance, and therefore the hollow fiber membrane can also give excellent characteristics.
本発明のポリスルホン系中空糸膜は、たとえば原料の
ポリスルホン系樹脂を適当な添加剤（例：ポリエチレン
グリコール）の存在下で極性有機溶媒（例：ジメチスル
ホキシド）に溶解して紡糸原液を作り、この原液を内部
凝固液（例：ジメチルスルホキシドと水の混液）ととも
に、二重環ノズルを通して押出し、空気中を走行させた
後、外部凝固液（例：水あるいは有機・無機水溶液）中
に導くことによって得ることができる。The polysulfone-based hollow fiber membrane of the present invention is prepared, for example, by dissolving a raw material polysulfone-based resin in a polar organic solvent (eg, dimethysulfoxide) in the presence of a suitable additive (eg, polyethylene glycol) to prepare a spinning dope. By extruding the stock solution with an internal coagulating liquid (eg, a mixture of dimethylsulfoxide and water) through a double-ring nozzle, running in air, and then introducing it into an external coagulating liquid (eg, water or an organic / inorganic aqueous solution) Obtainable.
本発明の中空糸膜は、中空糸の断面構造において、外
表面層、外指状構造層、中間層、内指状構造層、内表面
層からなる５層構造を有する。ここで言う外指状構造層
ならびに内指状構造層とは、それぞれ主に中空糸膜構造
の維持に寄与する層である。一方、外表面層、中間層、
内表面層は比較的緻密な構造を有し、分離特性や透水性
が決定される層である。ここで、内表面層あるいは外表
面層は、どちらか一方に分離のためのふるいの大きさを
規定するより緻密な層部分を有し、中空糸膜全体の分画
特性を決定する層である。この緻密な層部分は、内表面
層における最も内側寄りの表面、あるいは外表面層にお
ける最も外側寄りの表面にある必要はなく、どちらの表
面層でも表面層内ならばどこにあっても良い。The cross-sectional structure of the hollow fiber of the present invention has a five-layer structure including an outer surface layer, an outer finger-shaped structure layer, an intermediate layer, an inner finger-shaped structure layer, and an inner surface layer. The outer finger-like structure layer and the inner finger-like structure layer here are layers mainly contributing to maintenance of the hollow fiber membrane structure. On the other hand, the outer surface layer, the intermediate layer,
The inner surface layer is a layer having a relatively dense structure, and its separation characteristics and water permeability are determined. Here, the inner surface layer or the outer surface layer is a layer that has a denser layer portion that defines the size of the sieve for separation, and determines the fractionation characteristics of the entire hollow fiber membrane. . The dense layer portion does not need to be on the innermost surface of the inner surface layer or the outermost surface of the outer surface layer, and either surface layer may be located anywhere within the surface layer.
この緻密な層部分は、紡糸原液中の溶媒が水と交換す
る際にポリスルホン系ポリマーが凝固して表面層に形成
される。この時ポリマーが凝縮してできるポリマー粒子
が小さい程、より緻密な層部分が形成されることにな
る。また、ポリスルホン系高分子膜の形成においては凝
固液中の水分量が多いほど、またポリマーの相分離速度
を抑え、凝固粒子径が小さくなる様に凝固温度を低くし
たり、紡糸原液組成を変化させるほど緻密な相部分がで
きやすくなる。そして、これら内・外表面層は薄い程透
水速度の大きい膜であると言える。This dense layer portion is formed in the surface layer by solidification of the polysulfone-based polymer when the solvent in the spinning dope is exchanged with water. At this time, the smaller the polymer particles formed by condensation of the polymer, the more dense the layer portion is formed. Further, in forming a polysulfone-based polymer film, the larger the amount of water in the coagulation liquid, the more the phase separation speed of the polymer is suppressed, the coagulation temperature is lowered so that the coagulation particle size becomes smaller, and the spinning dope composition is changed. The denser the phase, the easier it becomes. It can be said that the thinner the inner and outer surface layers, the higher the water permeability.
内指状構造層、外指状構造層は中空糸膜の断面で見
て、中心から半径方向に伸びた指状の形をした空洞が並
んだ層である。この２つの指状構造層に挟まれた層を中
間層と呼ぶが、この層は、膜の強度を維持するのに重要
な役目を果たすだけでなく、透水速度にも大なる影響を
与えている。The inner finger-shaped structure layer and the outer finger-shaped structure layer are layers in which finger-shaped cavities extending in the radial direction from the center are arranged when viewed in the cross section of the hollow fiber membrane. The layer sandwiched between these two finger-like structure layers is called the intermediate layer. This layer not only plays an important role in maintaining the strength of the membrane, but also has a great influence on the water permeation rate. There is.
上記の製膜過程において、中空糸膜の中間層は、紡糸
原液中の溶媒と添加剤が中空糸の中空側へぬけるものと
外表面側にぬけるものがあるためにその境界層として形
成される。中間層の厚みは、両方向への移動速度によっ
て決定され、紡糸溶液組成、内部、外部凝固液の組成、
紡糸原液の組成、凝固液温度及び空中走行距離によって
変化する。中間層の厚みは、厚くなる程透水速度を低下
させるが、内指状構造層の厚みに対して0.1〜0.2倍程度
であれば機械強度を保持したまま透水速度を高めること
ができる。これは、同じ紡糸原液から同サイズの中空糸
を作成した場合に中間層が薄くなっても、指状構造層の
樹脂部分（空隙部分でない所）の密度が高まり、ここで
強度が保持されるためである。中間層の厚みが内指状構
造層の厚みに対して0.1倍以下になると、５層構造が部
分的に保持できず、強度も低下する。又、0.2倍以上で
は透水速度の低下が著しい。In the above film-forming process, the intermediate layer of the hollow fiber membrane is formed as a boundary layer of the solvent and the additive in the spinning dope, because some of them penetrate the hollow fiber to the hollow side and some of them penetrate to the outer surface side. . The thickness of the intermediate layer is determined by the moving speed in both directions, the spinning solution composition, the internal, the composition of the external coagulation liquid,
It varies depending on the composition of the spinning dope, the temperature of the coagulating liquid, and the distance traveled in the air. As the thickness of the intermediate layer increases, the water permeability decreases, but if it is about 0.1 to 0.2 times the thickness of the inner finger structure layer, the water permeability can be increased while maintaining the mechanical strength. This is because even if the intermediate layer becomes thin when hollow fibers of the same size are made from the same spinning dope, the density of the resin portion (not the void portion) of the finger-like structure layer increases and the strength is maintained here. This is because. When the thickness of the intermediate layer is 0.1 times or less the thickness of the inner finger-shaped structure layer, the five-layer structure cannot be partially retained, and the strength is reduced. If it is 0.2 times or more, the permeation rate will decrease significantly.
本発明における内・外指状構造層の厚みは同じ程度が
良い。従って、中間層は膜厚のほぼ中央にある事が望ま
しく、両指状構造層の比、すなわち、外指状構造層／内
指状構造層は0.6〜1.5であることが好ましい。最も好ま
しいのは1.0である。The thickness of the inner and outer finger-shaped structure layers in the present invention is preferably the same. Therefore, it is desirable that the intermediate layer is located in the approximate center of the film thickness, and the ratio of both finger-like structure layers, that is, the outer finger-like structure layer / inner finger-like structure layer is preferably 0.6 to 1.5. Most preferred is 1.0.
（ホ）実施例 以下、本発明を具体例によって示し、さらに詳細に説
明するが本発明はこれに何等限定されない。(E) Example Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.
実施例１ 溶媒としてのジメチルスルホキシド60重量部に、ポリ
エチレングリコール20重量部、ポリエーテルスルホン
（ICI社製5200Pパウダー）20重量部を添加剤のして溶解
し、均一なポリマー溶液とした。このポリマー溶液を、
25℃の一定温度に保ち、同様に25℃に温度調節されたジ
メチルスルホキシド50％水溶液と同時に40℃の水浴中に
吐出させた。この時、空中走行距離を13cmとし、巻き取
り速度を7m/分で行った。Example 1 To 60 parts by weight of dimethyl sulfoxide as a solvent, 20 parts by weight of polyethylene glycol and 20 parts by weight of polyether sulfone (5200P powder manufactured by ICI) were dissolved as an additive to obtain a uniform polymer solution. This polymer solution
The solution was kept at a constant temperature of 25 ° C. and was discharged into a water bath at 40 ° C. simultaneously with a 50% dimethyl sulfoxide aqueous solution whose temperature was similarly adjusted to 25 ° C. At this time, the running distance was 13 cm and the winding speed was 7 m / min.
得られた中空糸膜は、外径1300μｍ、内径800μｍで
断面は５層構造を有しており、その構成は、内表面層は
20μｍ、内指状構造層が100μｍ、中間層15μｍ（内指
状構造層の厚みに対し0.15倍）、外指状構造層が80μ
ｍ、外表面層が35μｍであった。The obtained hollow fiber membrane has an outer diameter of 1300 μm, an inner diameter of 800 μm, and a cross-section having a five-layer structure.
20μm, inner finger structure layer 100μm, intermediate layer 15μm (0.15 times the thickness of inner finger structure layer), outer finger structure layer 80μ
m, and the outer surface layer was 35 μm.
この中空糸膜は内表面層に緻密層が存在し、タンパク
質であるトリプシンインヒビターを60％透過した。中空
糸膜の性能は純水透水性能が400/m2・hr・kg/cm2であ
り、引張り強度が350g/本であった。This hollow fiber membrane had a dense layer on the inner surface layer, and 60% of trypsin inhibitor which was a protein was permeated. Regarding the performance of the hollow fiber membrane, the pure water permeability was 400 / m 2 · hr · kg / cm 2 and the tensile strength was 350 g / piece.
比較例１ 空中走行距離を20cmに変えた他は上記実施例１と同じ
条件下で中空糸を紡糸し、断面５層構造の中空糸膜を得
た。この５層構造の構成は、内表面層が20μｍ、内指状
構造層が90μｍ、中間層が30μｍ、外指状構造層が70μ
ｍ、外表面層が40μｍであった。即ち、内指状構造層の
厚みに対し、中間層の厚みは0.3倍、外指状構造層のそ
れは0.78倍であった。そして、緻密な層部分は内表面層
にあり、分画性能は上記実施例１と実質的に同じであっ
た。Comparative Example 1 A hollow fiber was spun under the same conditions as in Example 1 except that the air travel distance was changed to 20 cm, to obtain a hollow fiber membrane having a five-layer structure in cross section. This five-layer structure has an inner surface layer of 20 μm, an inner finger structure layer of 90 μm, an intermediate layer of 30 μm, and an outer finger structure layer of 70 μm.
and the outer surface layer was 40 μm. That is, the thickness of the intermediate layer was 0.3 times and that of the outer finger-shaped structure layer was 0.78 times the thickness of the inner finger-shaped structure layer. The dense layer portion was on the inner surface layer, and the fractionation performance was substantially the same as in Example 1 above.
この膜の純水透水性能を測定したところ、210/m2・
hr・kg/cm2であり、引張り強度が380g/本であった。When the pure water permeability of this membrane was measured, it was 210 / m 2
It was hr · kg / cm 2 and the tensile strength was 380 g / piece.
実施例２ 上記実施例１で用いたドープを用い、芯液としてジメ
チルスルホキシド50重量部、水50重量部からなる混合溶
液を使用して、60℃の温水から成る外部凝固槽中へ２重
環ノズルから押し出した。Example 2 Using the dope used in Example 1 above, a mixed solution of 50 parts by weight of dimethyl sulfoxide and 50 parts by weight of water was used as a core liquid, and the double ring was introduced into an external coagulation tank consisting of warm water at 60 ° C. Extruded from the nozzle.
得られた中空糸は膜厚140μｍ、内径400μｍの中空糸
膜であり、断面は５層構造であった。その中間層の厚み
は35μｍであり、内指状構造層の厚みは215μｍであ
り、中間層との比は0.16であった。また、外指状構造層
の厚みは200μｍであり、内指状構造層に対する比が0.9
であった。The obtained hollow fiber was a hollow fiber membrane having a thickness of 140 μm and an inner diameter of 400 μm, and the cross section had a five-layer structure. The thickness of the intermediate layer was 35 μm, the thickness of the inner finger-like structure layer was 215 μm, and the ratio with the intermediate layer was 0.16. The thickness of the outer finger-like structure layer is 200 μm, and the ratio to the inner finger-like structure layer is 0.9.
Met.
この膜の純水透水速度は、1120/m2・hr・kg/cm
2（水温25℃）と高く、また、分子量84,000の蛋白質
（コンアルブミン）を90％排除する膜であった。機械強
度も引張り強度で120g/本あり、工業的に充分実用化で
きるものであった。The pure water permeation rate of this membrane is 1120 / m 2 · hr · kg / cm.
It was as high as 2 (water temperature 25 ° C), and it was a membrane that eliminated 90% of proteins (conalbumin) with a molecular weight of 84,000. The mechanical strength was 120 g / strength in terms of tensile strength, which was industrially sufficiently practical.
（ヘ）発明の効果 以上のように、本発明のポリスルホン系中空糸膜は５
つの層から成り、内指状構造層の厚みに対し、中間層の
厚みを0.1〜0.2倍で、外指状構造層の厚みを0.6〜1.5倍
に設定したので、透水性能と機械強度を共に併せ持つ中
空糸膜を得ることができる。すなわち、長期間の使用に
も安定して使用でき、かつ、膜分離における生産性を向
上できるポリスルホン系中空糸膜を提供できる効果があ
る。(F) Effect of the Invention As described above, the polysulfone-based hollow fiber membrane of the present invention has 5
It consists of two layers, the thickness of the middle layer is 0.1-0.2 times and the thickness of the outer finger-like structure layer is 0.6-1.5 times the thickness of the inner finger-like structure layer, so both water permeability and mechanical strength are improved. A hollow fiber membrane having both can be obtained. That is, there is an effect that it is possible to provide a polysulfone-based hollow fiber membrane that can be stably used even for long-term use and that can improve productivity in membrane separation.
Claims (1)
外指状構造層、外表面層の５つの層からなり、内指状構
造層の厚みに対し、中間層の厚みが0.1〜0.2倍で、外指
状構造層の厚みが0.6〜1.5倍であることを特徴とするポ
リスルホン系中空糸膜。1. A cross section having an inner surface layer, an inner finger structure layer, an intermediate layer,
It consists of five layers, the outer finger-like structure layer and the outer surface layer. The thickness of the intermediate layer is 0.1 to 0.2 times and the thickness of the outer finger-like structure layer is 0.6 to 1.5 times the thickness of the inner finger-like structure layer. A polysulfone-based hollow fiber membrane characterized by being present.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17435788A JPH0829242B2 (en) | 1988-07-12 | 1988-07-12 | Polysulfone hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17435788A JPH0829242B2 (en) | 1988-07-12 | 1988-07-12 | Polysulfone hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0226628A JPH0226628A (en) | 1990-01-29 |
| JPH0829242B2 true JPH0829242B2 (en) | 1996-03-27 |
Family
ID=15977212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17435788A Expired - Lifetime JPH0829242B2 (en) | 1988-07-12 | 1988-07-12 | Polysulfone hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0829242B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406033A (en) * | 2013-09-09 | 2013-11-27 | 南京大学 | Preparation method of chitosan-polysulfone hollow fiber membrane |
| CN105013357A (en) * | 2015-06-30 | 2015-11-04 | 浙江工业大学 | Polymer embedded metal organic framework membrane, preparation method, device and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008046779A1 (en) * | 2006-10-18 | 2008-04-24 | Gambro Lundia Ab | Hollow fiber membrane and method for manufacturing thereof |
-
1988
- 1988-07-12 JP JP17435788A patent/JPH0829242B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406033A (en) * | 2013-09-09 | 2013-11-27 | 南京大学 | Preparation method of chitosan-polysulfone hollow fiber membrane |
| CN105013357A (en) * | 2015-06-30 | 2015-11-04 | 浙江工业大学 | Polymer embedded metal organic framework membrane, preparation method, device and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0226628A (en) | 1990-01-29 |
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