JPH0226628A - Polysulfone hollow fiber membrane - Google Patents
Polysulfone hollow fiber membraneInfo
- Publication number
- JPH0226628A JPH0226628A JP17435788A JP17435788A JPH0226628A JP H0226628 A JPH0226628 A JP H0226628A JP 17435788 A JP17435788 A JP 17435788A JP 17435788 A JP17435788 A JP 17435788A JP H0226628 A JPH0226628 A JP H0226628A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- fingerlike
- hollow fiber
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title abstract description 31
- 239000012510 hollow fiber Substances 0.000 title abstract description 29
- 229920002492 poly(sulfone) Polymers 0.000 title abstract description 19
- 239000010410 layer Substances 0.000 claims description 80
- 239000002344 surface layer Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000009987 spinning Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000035699 permeability Effects 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 230000001112 coagulating effect Effects 0.000 abstract description 4
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000003495 polar organic solvent Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 description 7
- 230000015271 coagulation Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 208000014674 injury Diseases 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108010026206 Conalbumin Proteins 0.000 description 1
- 101710162629 Trypsin inhibitor Proteins 0.000 description 1
- 229940122618 Trypsin inhibitor Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000472 traumatic effect Effects 0.000 description 1
- 239000002753 trypsin inhibitor Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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)
Abstract
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仕もつ中空糸状ポ
リスルホン系限外濾過膜に関するものである。Detailed Description of the Invention (a) Industrial Application Field The present invention relates to a polysulfone hollow fiber membrane, and more particularly to a hollow fiber polysulfone ultrafiltration membrane that has both excellent filtration properties and mechanical properties. It is something.
（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) Prior Art Conventionally, there are many documents regarding polysulfone-based hollow fiber membranes, but there are not so many documents disclosing the membrane structure.
（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 ５ｃｉｅｎｃｅ （Ｊ、 Ａｐｐｌ、
Ｐｏｌｙｍ、 Ｓｃｉ、） ２１巻１６５ページ〜１
８０ページ（１９７９）など、以前より知られていたが
、中間層がいずれら厚いために透水速度に劣る膜し力ぐ
知られていなかった。(c) Problems to be solved by the invention A film consisting of five layers: inner and outer surface layers, inner and outer finger-like structure layers, and an intermediate layer is also Journal of Applied
Polymer 5science (J, Appl,
Polym, Sci,) Volume 21, Pages 165-1
80 pages (1979), but it was not known that the intermediate layer was thick and had poor water permeability.
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, we have carried out intensive research on a polysulfone-based hollow fiber membrane with a five-layer structure that has a high filtration rate and high mechanical strength, and solved the above problems by specifying the size of the intermediate layer. We have discovered what we can do and have come up with the present invention.
（ニ）課題を解決するための手段
すなうち、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 problems, namely, the present invention has a cross section of an inner surface layer, an inner finger-like structure layer,
Consists of five layers: intermediate layer, outer finger-like structure layer, and outer surface layer.
The thickness of the intermediate layer is 0.1 to 0 relative to the thickness of the inner finger-like structure layer.
．． This is a polysulfone-based hollow fiber membrane characterized in that the outer finger-like structure layer has a thickness of 0.6 to 1.5 times.
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 hollow fiber membrane of the present invention, any known polysulfone resin can be used. The polysulfone resin is aromatic polysulfone or 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、従って中空糸膜ら優れた特性を与
え得る。These polysulfone and polyether sulfone resins are engineering plastics with excellent heat resistance and chemical resistance, and therefore can provide excellent properties to hollow fiber membranes.
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（例ニジメチルスル
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（例ニ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ろ。The polysulfone-based hollow fiber membrane of the present invention can be produced by, for example, preparing a spinning stock solution by dissolving the raw material polysulfone-based resin in a polar organic solvent (e.g., dimethyl sulfoxide) in the presence of an appropriate additive (e.g., polyethylene glycol). By extruding the stock solution together with an internal coagulating liquid (e.g. a mixture of dimethyl sulfoxide and water) through a double ring nozzle, running it through air, and introducing it into an external coagulating liquid (e.g. water or an organic/inorganic aqueous solution). You can get it.
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 hollow fiber membrane of the present invention has a five-layer structure in the cross-sectional structure of the hollow fiber, consisting of an outer surface layer, an outer finger-like structure layer, an intermediate layer, an inner finger-like structure layer, and an inner surface layer. The outer finger-like structure layer and the inner finger-like structure layer referred to herein are layers that each mainly contribute to maintaining the hollow fiber membrane structure. On the other hand, the outer surface layer, intermediate layer, and inner surface layer have relatively dense structures, and are layers that determine separation characteristics and water permeability. Here, either the inner surface layer or the outer surface layer has a denser layer part that defines the size of the sieve for separation, and is a layer that determines the fractionation characteristics of the entire hollow fiber membrane. . This dense layer portion does not need to be located on the innermost surface of the inner surface layer or the outermost surface of the outer surface layer, and may be located anywhere within either 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
際にボー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層部分ができ
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 on the surface layer by coagulation of the Bolisulfone 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 will be formed. In addition, when forming a polysulfone-based polymer film, the higher the water content in the coagulation solution, the lower the coagulation temperature and the composition of the spinning stock solution so that the phase separation rate of the polymer is suppressed and the coagulation particle size becomes smaller. The more you do it, the easier it is to form a dense layer. It can be said that the thinner the inner and outer surface layers are, the higher the water permeation rate.
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-like structure layer and the outer finger-like structure layer are seen in the cross section of the hollow fiber membrane.
This layer is lined with finger-shaped cavities extending radially from the center. The layer sandwiched between these two finger-like structural layers is called the intermediate layer, and this layer not only plays an important role in maintaining the strength of the membrane, but also has a large effect 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。In the above membrane-forming process, the intermediate layer of the hollow fiber membrane is formed as a boundary layer between the solvent and additives in the spinning dope, because some of the solvent and additives in the spinning dope pass through to the hollow side of the hollow fiber and others to the outer surface side. . The thickness of the intermediate layer is determined by the speed of movement in both directions and varies depending on the spinning solution composition, the composition of the internal and external coagulation liquids, the composition of the spinning dope, the coagulation liquid temperature and the air travel distance.
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、５ＦＪ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。The thicker the intermediate layer, the lower the water permeation rate.
If the thickness is approximately 0.1 to 0.2 times the thickness of the inner finger structure layer, the water permeation rate can be increased while maintaining mechanical strength. This is because when hollow fibers of the same size are created from the same spinning solution, even if the intermediate layer becomes thinner, the density of the resin part of the finger-like structure layer (where there are no voids) increases, and the strength is maintained here. It's for a reason. When the thickness of the intermediate layer is less than 0.1 times the thickness of the inner finger-like structure layer, the 5FJ structure cannot be partially maintained and the strength also decreases. Moreover, if it is 0.2 times or more, the water permeation rate decreases 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。In the present invention, the thicknesses of the inner and outer finger-like structure layers are preferably about the same. Therefore, it is desirable that the intermediate layer be located approximately at the 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同等限定されない。(E) Examples Hereinafter, the present invention will be illustrated by specific examples and explained in more detail, but the present invention is not limited to these examples.
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
（ＩＣ１社製 ５２００Ｐパウダー）２０重量部を添加
剤として溶解し、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 In 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 IC1) were dissolved as additives to prepare a uniform polymer solution. This polymer solution was maintained at a constant temperature of 25°C and discharged into a 40°C water bath at the same time as a 50% dimethyl sulfoxide aqueous solution whose temperature was also controlled at 25°C. At this time, the air travel distance was 13 cm, and the winding speed was 7 m/min.
得られた中空糸膜は、外径１３００μｍ１内径８００μ
ｍで断面は５層構造を有しており、その構成は、内表面
層は２０μｍ１内指状構造層が１００μｍ１中間層１５
μｍ（内指状構造層の厚みに対し；〕１１５倍、外傷状
構造層か８０μｍ１外表面層が３５μｍであった。The obtained hollow fiber membrane has an outer diameter of 1300 μm and an inner diameter of 800 μm.
The cross section has a five-layer structure with an inner surface layer of 20 μm, an inner finger-like structure layer of 100 μm, and an intermediate layer of 15
μm (relative to the thickness of the inner finger-like structure layer;) 115 times, the trauma-like structure layer was 80 μm, 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４ｏＯＱ、／ｍ”−ｈｒ
−ｋｇ／ｃｍ”であり、引張り強度が３５０９／本であ
った。This hollow fiber membrane had a dense layer on its inner surface layer and allowed 60% of trypsin inhibitor, a protein, to permeate through it. The hollow fiber membrane has a pure water permeability of 4oOQ,/m”-hr.
-kg/cm'', and the tensile strength was 3509/piece.
比較例１
空中走行距離を２０ｃｍに変えた他は上ヌ己実施例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、外傷状構
造層が７０μｍ、外表面層が４０μｍであった。Comparative Example 1 Hollow fibers were spun under the same conditions as in Example 1 except that the aerial travel distance was changed to 20 cm to obtain a hollow fiber membrane with a five-layer structure in cross section. This five-layer structure has an inner surface layer of 20 μm,
The inner finger-like structure layer was 90 μm, the middle layer was 30 μm, the trauma-like structure layer was 70 μm, and the outer surface layer was 40 μm.
即ち、内指状構造層の厚みに対し、中間層の厚みは０．
３倍、外傷状構造層のそれは０．７８倍であった。That is, the thickness of the intermediate layer is 0.0 mm compared to the thickness of the inner finger-like structure layer.
3 times, and that of the trauma-like structure layer was 0.78 times.
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。The dense layer portion was located in 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、２１０Ｑ／ｍ
” ・ｈｒ−に９／ａｍ”であり、引張り強度は３８０
９／本であった。When we measured the pure water permeability of this membrane, it was found to be 210Q/m.
"・hr-9/am", and the tensile strength is 380
It was 9/books.
害１ｔトＬ
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２１５０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。Using the dope used in Example 1 above, and using a mixed solution of 2150 parts by weight of dimethyl sulfoxide and 50 parts by weight of water as the core solution, the mixture was poured into an external coagulation tank consisting of warm water at 60°C. It was extruded from a heavy ring nozzle.
得られた中空糸は膜厚１４０μｍ１内径４００Ｉｉｍ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２１５
μｍであり、中間層との比は０，１６であった。また、
外傷状構造層の厚みは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 membrane thickness of 140 μm and an inner diameter of 400 Im, and had a five-layer structure in cross section. The thickness of the intermediate layer is 35μm, and the thickness of the inner finger-like structure layer is 215μm.
μm, and the ratio to the intermediate layer was 0.16. Also,
The thickness of the traumatic structure layer was 200 μm and the ratio to the internal finger structure layer was 0.9.
この膜の純水透水速度は、１１２０Ｑ／ｍ”−ｈｒ−に
９７ａｍ’ （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１２０９／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 as high as 1120 Q/m"-hr-97 am' (water temperature 25°C), and the molecular weight is 84
,000 protein (conalbumin) by 90%. The mechanical strength was 1209/piece in terms of tensile strength, which was sufficient for industrial practical use.
（へ）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Ｑ、１〜０．２倍で、外傷状構造層の厚みを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) Effects of the invention As described above, the polysulfone hollow fiber membrane of the present invention consists of five layers, and the thickness of the intermediate layer is Q, 1 to 0.2 times the thickness of the inner finger-like structure layer. , the thickness of the trauma-like structure layer is 0.6
Since it is set to ~1.5 times, a hollow fiber membrane having both water permeability and mechanical strength can be obtained. That is, it is possible to provide a polysulfone-based hollow fiber membrane that can be stably used over a long period of time and improve productivity in membrane separation.
Claims (1)
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. The cross section consists of five layers: an inner surface layer, an inner finger-like structure layer, an intermediate layer, an outer finger-like structure layer, and an outer surface layer, and the thickness of the middle 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.
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 true JPH0226628A (en) | 1990-01-29 |
| JPH0829242B2 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010506709A (en) * | 2006-10-18 | 2010-03-04 | ガンブロ・ルンディア・エービー | Hollow fiber membrane and method for producing hollow fiber membrane |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406033B (en) * | 2013-09-09 | 2015-10-21 | 南京大学 | The preparation method of chitosan-polysulfonehollow hollow fiber membrane |
| CN105013357B (en) * | 2015-06-30 | 2017-02-22 | 浙江工业大学 | Polymer-embedded metal organic framework film, and preparation method, device and application thereof |
-
1988
- 1988-07-12 JP JP17435788A patent/JPH0829242B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010506709A (en) * | 2006-10-18 | 2010-03-04 | ガンブロ・ルンディア・エービー | Hollow fiber membrane and method for producing hollow fiber membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0829242B2 (en) | 1996-03-27 |
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