KR100200040B1 - Sponge-like polysulphone hollow fibre membrane and manufacturing method thereof - Google Patents
Sponge-like polysulphone hollow fibre membrane and manufacturing method thereof Download PDFInfo
- Publication number
- KR100200040B1 KR100200040B1 KR1019950058499A KR19950058499A KR100200040B1 KR 100200040 B1 KR100200040 B1 KR 100200040B1 KR 1019950058499 A KR1019950058499 A KR 1019950058499A KR 19950058499 A KR19950058499 A KR 19950058499A KR 100200040 B1 KR100200040 B1 KR 100200040B1
- Authority
- KR
- South Korea
- Prior art keywords
- hollow fiber
- fiber membrane
- membrane
- water
- sponge
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000000835 fiber Substances 0.000 title description 2
- 239000012510 hollow fiber Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- 230000035699 permeability Effects 0.000 abstract description 23
- 238000005194 fractionation Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 description 18
- 230000015271 coagulation Effects 0.000 description 18
- 238000009987 spinning Methods 0.000 description 14
- 239000011148 porous material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 230000001112 coagulating effect Effects 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- B01D69/082—Hollow fibre membranes characterised by the cross-sectional shape of the fibre
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
- B01D2325/0232—Dense layer on both outer sides of the membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/026—Sponge structure
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
본 발명은 중공사막의 단면구조에 있어서 내, 외표면에 0.1~0.25의 미세 활성층을갖고 막의 중심부는 0.3~3.0정도의 망상구조를 이루는 것을 특징으로하는 스폰지구조의 폴리설폰 중공사막 및 그의 제조방법에 관한 것으로, 본 발명에 의해 제조된 중공사막은 기계적 성질 및 분획성능이 우수하고, 투수성이 높기 때문에 산업용 및 정수기 등에 다양하게 사용될 수 있다.The present invention in the cross-sectional structure of the hollow fiber membrane 0.1 to 0.25 on the inner and outer surface Membrane has a fine active layer of 0.3 ~ 3.0 The present invention relates to a polysulfone hollow fiber membrane having a sponge structure, and a method for manufacturing the same, wherein the hollow fiber membrane produced by the present invention has excellent mechanical properties and fractionation performance, and has high water permeability. It can be used in various ways.
Description
본 발명은 내,외표면에 미세 활성층을 가지는 망상(網狀)구조의 폴리설폰 중공사막에 관한 것으로, 더욱 상세하게는 종공사막의 중심부에는 망상 구조의 기공이 형성되어 있고 내,외표면에는 미세 활성층으로 되어 있어, 분획 성능 및 기계적 성질인 강,신도가 뛰어나 내압성이 좋을 뿐 아니라 기공율이 높아 투수성이 우수한 중공사막에 관한 것이다.The present invention relates to a polysulfone hollow fiber membrane having a network structure having a fine active layer on the inner and outer surfaces, and more particularly, the pores of the network structure are formed in the center of the longitudinal fiber membrane, and the inner and outer surfaces are fine. It is made of an active layer, and has excellent strength and elongation, which is excellent in fractional performance and mechanical properties, and has good pressure resistance as well as high porosity, and thus relates to a hollow fiber membrane having excellent water permeability.
일반적으로 중공사막은 동일 부피의 다른 형태 막들에 비해 표면적이 월등히 크고 모듈화가 쉽기 때문에 최근 한외여과막을 중심으로 연구개발이 활발히 진행되어, 의료분야, 정밀 산업분야, 정수분야등 많은 부문에서 실용화되어 있다.In general, since hollow fiber membranes have a much larger surface area and are easier to modularize than other membranes having the same volume, research and development has been actively conducted around ultrafiltration membranes. .
선택 투과성을 갖는 분리막 재질에 관해서는 많은 연구가 이루어져 셀룰로오스계, 폴리아미드계, 폴리비닐등이 알려져 있으나, 이들은 내생물 분해성, 내화학성, 내열성등이 약하기 때문에 이러한 단점들을 보완하기 위해 엔프라로 사용되는 수지에 대한 분리막 재질로의 응용이 진행되어 내열성, 내화학성이 우수하고 기계적 성질이 뛰어난 폴리설폰 등의 엔프라 수지가 개발되어 정밀여과용 분리막, 한외과용 분리막, 역삼투 및 기체분리 복합막의 지지체로서 사용되고 있다.Many studies have been conducted on membrane materials having selective permeability, and cellulose, polyamide, and polyvinyl are known. However, they are used as an enpra to compensate for these disadvantages because they have poor biodegradability, chemical resistance, and heat resistance. Enpra resins such as polysulfone, which are excellent in heat resistance, chemical resistance, and mechanical properties, have been developed by application to membrane materials for the resins used to support microfiltration membranes, ultrafiltration membranes, reverse osmosis and gas separation composite membranes. It is used as.
중공사막은 단면구조에 따라 크게 지상구조(Finger-like structure)와 스폰지구조(Sponge structure), 복합구조(Complex structure)로 나눌 수 있다.Hollow fiber membranes can be divided into a ground-like structure, a sponge structure, a complex structure according to the cross-sectional structure.
지상구조의 중공사막은 세공이 매우 작은(약 0.001~0.01)중공사막에 있어서, 투수성을 높이기 위해 고안된 구조로써 투수성 및 분획성은 좋으나 내압성이 약해 의료용 이외에 공업용과 같은 장시간 사용에는 문제가 있다.The hollow fiber membrane of the ground structure has very small pores (approximately 0.001 ~ 0.01 In the hollow fiber membrane, it is a structure designed to improve the permeability and has good water permeability and fractionality, but has a low pressure resistance and thus has problems in long-term use such as industrial use in addition to medical use.
스폰지 구조의 중공사막은 세공이 비교적 큰(0.1~1.0) 중공사막에 있어서 내압성을 강화하기 위해 고안된 구조이나, 물의 투과저항이 크기 때문에 투수성이 작고, 투수성을 확보하기 위해 세공을 너무 크게 하게 되면 분획성능이 저하되는 등의 단점이 있다. 한편, 복합구조의 중공사막은 크게 단면에 공동이 있는 스폰지구조의 중공사막과, 외표면쪽은 스폰지구조이고 내표면쪽은 지상구조인 중공사막으로 나눌 수 있는데, 전자와 같이 0.01~0.1정도의 세공을 갖는 스폰지구조의 중공사막에서는 투수성이 약한 단점이 있고, 후자의 중공사막은 투수성은 좋지만 막의 지지도가 약한 문제점이 있다.Hollow fiber membrane of sponge structure has relatively large pores (0.1 ~ 1.0 In the hollow fiber membrane, the structure designed to enhance the pressure resistance, but the water permeability is large because the water permeation resistance is large, there are disadvantages such as the fractionation performance is lowered if the pores are too large to secure the permeability. On the other hand, the hollow fiber membrane of the composite structure can be divided into a hollow fiber membrane of a sponge structure having a cavity in the cross-section, and a hollow fiber membrane of a sponge structure on the outer surface side and a ground structure on the inner surface side. ~ 0.1 In the hollow fiber membrane of the sponge structure having a degree of pores, the water permeability has a weak disadvantage, the latter hollow fiber membrane has a good water permeability but has a weak support of the membrane.
따라서, 본 발명의 목적은 상술한 종래 중공사막의 문제점을 개선하여 선택성 및 투수성이 뛰어난 스폰지구조의 폴리설폰 중공사막을 제공하기 위한 것으로, 구체적으로 막의 중심부에는 망상구조로서 0.3~3의 기공이, 내, 외표면에는 0.1~0.25정도의 미세활성층이 형성되어 있어 선택성이 우수하며, 또한 막의 구조가 외표면으로부터 미세활성층, 스폰지구조, 미세활성층으로 되어 있어 기공률이 매우 높기 때문에 유체역학적 저항에도 불구하고 투수성이 매우 뛰어난 스폰지 구조의 폴리설폰 중공사막을 제공하는 것이다.Accordingly, an object of the present invention is to provide a polysulfone hollow fiber membrane having a sponge structure excellent in selectivity and water permeability by improving the problems of the conventional hollow fiber membrane described above, and specifically 0.3 to 3 as a network structure at the center of the membrane. The pore of the inside and the outer surface is 0.1 ~ 0.25 The fine active layer is formed to a high degree of selectivity, and the membrane structure is composed of the micro active layer, the sponge structure and the micro active layer from the outer surface, so that the porosity is very high. It is to provide a polysulfone hollow fiber membrane.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
본 발명의 폴리설폰 중공사막은 지상구조와 스폰지구조의 장단점들을 절충 보완한 것으로 투수성 및 분획성이 우수하며, 수용성 고분자의 종류, 분자량 및 방사원액의 점도, 방사조건(방사높이, 방사온도, 습도, 토출량, 외부 응고제 온도 등)들을 조절하여 제조됨을 특징으로 한다.Polysulfone hollow fiber membrane of the present invention is a complementary complement of the advantages and disadvantages of the ground structure and sponge structure, excellent water permeability and fractionality, type of water-soluble polymer, molecular weight and viscosity of spinning stock solution, spinning conditions (spinning height, spinning temperature, Humidity, amount of discharge, external coagulant temperature).
본 발명에 의한 폴리설폰 중공사막은 내,외표면에는 0.1~0.25정도의 수많은 미세활성층을 갖고 있는데, 이 미세활성층을 이루는 세공의 폭이 0.1미만에서는 막의 분획성능은 좋아지나 투수성이 적어 본래의 목적을 달성할 수 없으며, 반면 폭이 0.25을 초과하는 경우에는 투수성은 증가하나 막의 분획성능 및 내압성능이 나빠지게 된다. 또한 중공사막 내부의 스폰지구조는 분획성능 측면보다는 지지체로서 목적을 갖고 있기 때문에 통수되기에 충분한 크기의 발포성 구조를 띄는 것이 바람직하다.Polysulfone hollow fiber membrane according to the present invention is 0.1 on the inner, outer surface ~ 0.25 It has a large number of microactive layers of about 0.1, and the pore width of the microactive layer is 0.1 Below, the membrane's fractionation performance is good but its water permeability is insufficient to achieve its original purpose, while its width is 0.25 In the case of exceeding the water permeability, the membrane's fractionation performance and pressure resistance performance deteriorate. In addition, since the sponge structure inside the hollow fiber membrane has a purpose as a support rather than a fractionation performance side, it is preferable to have a foamable structure of sufficient size to pass water.
한편 막의 표면적에 대한 기공의 면적을 백분율로 나타낸 기공율은 지상구조나 공동이 있는 중공사막의 경우 50% 이상이 되면 막의 내압성이 떨어지는데 비해 스폰지 구조의 중공사막은 기공율이 50%이상 60%미만일 때에도 기계적 성질이 우수하여 동일한 분획분자량을 가지면서도 기공율이 높기 때문에 투수성이 우수함을 알 수 있다.On the other hand, the porosity, expressed as a percentage of the pore area relative to the surface area of the membrane, is less than 50% for the ground structure or the hollow fiber membrane with cavities, whereas the membrane's pressure resistance is inferior. It can be seen that it has excellent water permeability because of its excellent properties and high porosity while having the same fractional molecular weight.
본 발명의 중공사막은 폴리설폰 수지, 수용성 고분자 및 이들의 공통용매로 이루어진 폴리머 원액을 2중관형 노즐의 외부에 압출하고 동시에 내부에는 응고성 액체를 주입하면서 계속적으로 공기중에 방사하고 이를 외부 응고액속에 통과시킴으로서 응고되고, 잔류 솔벤트를 추출하여 수득된다.The hollow fiber membrane of the present invention extrudes a polymer stock solution consisting of polysulfone resin, water-soluble polymer and their common solvent to the outside of the double-tubular nozzle and at the same time continuously spins into the air while injecting a coagulating liquid into the external coagulating solution. It is solidified by passing through and obtained by extracting residual solvent.
이때, 폴리설폰 수지의 용매로서는 m-크레졸, 클로로벤젠, N-메틸-2-피롤리돈, 디메틸 설폭사이드, 디메틸아세트아마이드, 디메틸포름아마이드등이 있고, 이들을 단독 또는 2종이상의 혼합 용매를 수용성 고분자와 용해할 수 있도록 적절히 선정 사용한다.At this time, as a solvent of the polysulfone resin, m-cresol, chlorobenzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, and the like are used. Use properly selected to dissolve with polymer.
수용성 고분자는 폴리에틸렌 글리콜, 폴리비닐알콜, 폴리비닐피롤리돈 등이 있으며 이들을 단독 또는 2종이상을 혼합하여 사용한다.The water-soluble polymers include polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and the like, and these are used alone or in combination of two or more thereof.
방사원액은 폴리설폰 수지 10-20중량%, 수용성고분자 10-30중량%를 용매 50-80중량%에 용해한다. 또한 방사 원액의 점도는 막의 구조에 매우 큰 영향을 미치므로 적절한 조절이 필요한데 점도가 너무 낮으면 망상 구조를 얻을 수 없을 뿐 아니라 방사성도 매우 나쁘게 되고, 점도가 너무 높으면 치밀한 망상 구조가 되어투수성이 떨어지게 된다.The spinning stock solution dissolves 10-20% by weight of polysulfone resin and 10-30% by weight of water-soluble polymer in 50-80% by weight of a solvent. In addition, the viscosity of the spinning stock solution has a great effect on the structure of the membrane, so proper adjustment is required. If the viscosity is too low, the network structure cannot be obtained and the radioactivity is very bad. If the viscosity is too high, the viscosity becomes a dense network structure. Will fall.
내부 응고액으로서는 응고가가 너무 높으면 방사 직후에 응고가 일어나지 않게되는 반면 응고가가 너무 낮으면 방사직후 강한 응고가 일어나 내부 치밀층이 두터워져 투수성이 떨어지며 방사속도가 느려진다. 그러므로 내표면에 다공성 망상구조의 세공이 생기고 방사속도를 빠르게 할 수 있는 내부응고액의 응고가가 필요하다. 여기서 내부응고액의 응고가는 폴리설폰 15중량%, 폴리비닐피롤리돈 25중량%의 혼합물을 디메틸아세트아마이드 용매에 1중량%로 용해한 용액 500밀리리터를 상전이 시키는데 필요한 응고액의 양을 밀리리터의 수치로 표시한 것이다. 응고가를 조절하기 위해서는 폴리설폰 양용매와 비용매를 적절히 혼합하면 된다. 응고가 조절용 비용매로서는 물과 비휘발성 유기용제 즉, 에틸렌글리콜, 프로필렌글리콜, 글리세린등으로서, 이들의 응고가가 20-50, 점도 1-20 센티포아스의 범위내를 갖도록 임의 비율로 혼합한다. 본 발명에서는 내부응고액 중 비휘발성 비용매가 5-50중량% 포함되도록 하였다.As the internal coagulating solution, if the coagulation cost is too high, coagulation does not occur immediately after spinning, while if the coagulation cost is too low, strong coagulation occurs immediately after spinning, resulting in a thick inner dense layer, resulting in poor permeability and slow spinning speed. Therefore, it is necessary to coagulate the internal coagulating solution that can form porous pores on the inner surface and accelerate the spinning speed. Here, the coagulation value of the internal coagulation solution is the amount of coagulation solution required to phase-transfer 500 milliliters of a solution of 15 wt% polysulfone and 25 wt% polyvinylpyrrolidone in 1% by weight of dimethylacetamide solvent in milliliters. It is displayed. In order to adjust the coagulation cost, a good polysulfone good solvent and a non-solvent may be appropriately mixed. As the nonsolvent for controlling the coagulation value, water and a nonvolatile organic solvent, ie, ethylene glycol, propylene glycol, glycerin, etc., are mixed at an arbitrary ratio such that the coagulation value is within the range of 20-50 and viscosity 1-20 centipoas. . In the present invention, the non-volatile non-solvent in the internal coagulating solution was included 5-50% by weight.
중공사막을 방사할 때는 공기중에 방사한 후 외부 응고액에 넣는데 이렇게 공기층을 통과시키는 것은 중공사막의 외표면의 상전이를 지연시킴으로써 세공의 크기조절이 가능하게 하기 위해서이다. 이때 공기층의 거리는 15내지 40센티미터가 적당한데, 10센티미터 미만이면 외부에 치밀층이 생겨 투수성이 낮고, 반면 40센티미터를 초과하면 외표면의 상전이가 내부 응고액에 의해 일어나 외표면의 기공크기가 너무 커져 막의 기계적 성질이 좋지 못하게 된다. 외부 응고액으로서는 보통 물을 사용하는데, 외부 응고액의 온도는 중공사막의 외표면 세공의 크기와 단면의 기공율을 결정하는 요인 중의 하나로서 중공사막의 투수성과 밀접한 관계가 있다. 본 발명에서는 이 외부 응고액의 온도를 35-45범위에서 작업을 하였다.When the hollow fiber membrane is spun, it is spun into the air and then put into an external coagulation liquid. The air layer is passed through to delay the phase transition of the outer surface of the hollow fiber membrane so that the size of the pores can be controlled. At this time, the distance of the air layer is 15 to 40 centimeters, but if it is less than 10 centimeters, a dense layer is formed on the outside, so that the permeability is low. On the other hand, if the thickness exceeds 40 centimeters, the phase transition of the outer surface is caused by the internal coagulation solution. It becomes so large that the mechanical properties of the membrane are poor. Normally water is used as the external coagulation solution. The temperature of the external coagulation solution is closely related to the permeability of the hollow fiber membrane as one of the factors that determine the size of the external surface pores of the hollow fiber membrane and the porosity of the cross section. In the present invention, the temperature of this external coagulation liquid is 35-45 Work in the range.
본 발명으로 제조된 스폰지구조의 폴리설폰 중공사막은 기존의 중공사막의 강도가 0.2-0.25 g/den인데 비해 0.30g/den 이상으로 높으며, 특히 신도는 45% 이상으로 기존의 중공사막에 비해 10%이상 높아 공업적으로 사용할 때 손상을 방지할 수 있어 취급이 용이하고, 투수성 또한 600 1/m2.hr.atm이상으로 매우 높다. 또한 기계적 성질 및 분획성능이 우수하고, 투수성이 높기 때문에 산업용 및 정수기 등에 다양하게 사용될 수 있다.Sponge-structured polysulfone hollow fiber membrane prepared by the present invention has a strength of 0.30 g / den or more, compared with 0.2-0.25 g / den of the existing hollow fiber membrane, and in particular, the elongation is 45% or more compared to the conventional hollow fiber membrane 10 It is easy to handle because it can prevent damage when used industrially because it is higher than%, and the water permeability is also very high, more than 600 1 / m 2 .hr.atm. In addition, because of excellent mechanical properties and fractionation performance, high water permeability can be used in a variety of industrial and water purifiers.
이하 실시예를 들어 본 발명을 설명한다.The present invention will be described with reference to the following Examples.
[실시예 1]Example 1
폴리설폰 수지(Amicon사 P-3500) 100g과 폴리비닐피롤리돈(시그마사, 분자량 40,000) 150g을 N,N-디메틸아세트아마이드 400g과 함께 95에서 6시간동안 교반하여 용해시켜 방사원액을 제조한 후 20로 냉각하였다. 이 방사원액을 외경 0.7, 내경 0.30인 2중관형 노즐 외측부에 압출하는 동시에 내부에는 물 20중량%, N,N-디메틸아세트아마이드 60중량%, 글리세린 20중량%로 이루어진 혼합액을 노즐 내축부에 압출시켜 방사된 중공사막을 25센티미터의 공기층을 통과시키고 40의 물로 이루어진 외부응고액조에 넣어 완전히 상전이를 시킨 후 꺼내어 100물에서 2시간씩 3회 수세한 후 건조하여 외경 0.55, 내경 0.39로 막의 내, 외표면에는 0.1~0.25의 미세 세공이 형성되어 있고, 막의 내부에는 0.3~3.0정도의 스폰지구조인 중공사막을 수득하였다. 막의 강도는 0.31g/den, 신도는 45%이고, 투수성은 650 1/m2.hr.atm을 나타내었다.100 g of polysulfone resin (Amicon P-3500) and 150 g of polyvinylpyrrolidone (Sigma, molecular weight 40,000) together with 400 g of N, N-dimethylacetamide 95 Was stirred for 6 hours at Cooled to. This spinning stock solution has an outer diameter of 0.7 Inside diameter 0.30 While extruded to the outer portion of the phosphorus double-tubular nozzle at the same time, a mixture of 20% by weight of water, 60% by weight of N, N-dimethylacetamide and 20% by weight of glycerin was extruded to the nozzle inner shaft to spin the hollow fiber membrane 25 cm Through the air layer and 40 Put in an external coagulation solution consisting of water and make a phase change completely. Washed with water 3 times for 2 hours and dried Inside diameter 0.39 0.1 to 0.25 on the inner and outer surfaces of the membrane Fine pores are formed, and the inside of the membrane 0.3 ~ 3.0 A hollow fiber membrane having a degree of sponge structure was obtained. The membrane had a strength of 0.31 g / den, an elongation of 45%, and a permeability of 650 1 / m 2 .hr.atm.
[비교예 1]Comparative Example 1
폴리설폰 수지(Amicon사 P-3500) 100g과 폴리비닐피롤리돈(시그마사, 분자량 40,000) 170g을 N,N-디메틸아세트아마이드 450g과 함께 95에서 6시간동안 교반하여 용해시켜 방사원액을 제조한 후 20로 냉각하였다. 이 방사원액을 실시예 1 의 2중관형 노즐 외측부에 압출하는 동시에 내부에는 물 15중량%, 글리세린 20중량%, N,N-디메틸아세트아마이드 60중량%으로 이루어진 혼합액을 노즐 내축부에 압출시켜 방사된 중공사막을 30센티미터의 공기층을 통과시키고 45의 물로 이루어진 외부 응고액조에 넣어 완전히 상전이를 시킨 후 꺼내어 100물에서 2시간씩 3회 수세한 후 건조하여 외경 0.53, 내경 0.38로 막의 내,외표면에는 0.4~0.7의 세공이 형성되어 있고, 막의 내부에는 0.5~5.0정도의 스폰지 구조인 중공사막을 수득하였다. 막의 강도는 0.25g/den, 신도는 38%이고, 투수성은 680 1/m2.hr.atm을 나타내었다.100 g of polysulfone resin (A-3, P-3500) and 170 g of polyvinylpyrrolidone (Sigma, molecular weight 40,000) together with 450 g of N, N-dimethylacetamide 95 Was stirred for 6 hours at Cooled to. The spinning stock solution was extruded to the outside portion of the double-tubular nozzle of Example 1, and the inside was mixed with 15% by weight of water, 20% by weight of glycerin, and 60% by weight of N, N-dimethylacetamide to the nozzle inner shaft. The hollow fiber membrane through a 30 cm air layer Into the external coagulation bath consisting of the water to completely change the phase and take out 100 Washed with water 3 times for 2 hours and dried Inside diameter 0.38 0.4 to 0.7 on the inner and outer surfaces of the membrane Pores are formed, 0.5 to 5.0 inside the membrane A hollow fiber membrane having a sponge structure of degree was obtained. The membrane had a strength of 0.25 g / den, an elongation of 38%, and a water permeability of 680 1 / m 2 .hr.atm.
[비교예 2]Comparative Example 2
폴리설폰 수지(Amicon사 P-3500) 100g과 폴리비닐피롤리돈(시그마사, 분자량 40,000) 140g을 N,N-디메틸아세트아마이드 450g과 함께 95에서 6시간동안 교반하여 용해시켜 방사원액을 제조한 후 20로 냉각하였다. 이 방사원액을 실시예 1 의 2중관형 노즐 외측부에 압출하는 동시에, 내부에는 물 20중량%, 글리세린 15중량%, N,N-디메틸아세트아마이드 65중량%로 이루어진 혼합액을 노즐 내측부에 압출시켜 방사된 중공사막을 15센티미터의 공기층을 통과시키고 38의 물로 이루어진 외부 응고액조에 넣어 완전히 상전이를 시킨 후 꺼내어 100물에서 2시간씩 3회 수세한 후 건조하여 외경 0.57, 내경 0.40로 막의 내,외표면에는 0.05~0.1의 미세세공이 형성되어 있고, 막의 내부에는 0.2~1.5정도의 스폰지구조인 중공사막을 수득하였다. 막의 강도는 0.35g/den, 신도는 47%이고, 투수성은 450 1/m2.hr.atm을 나타내었다.100 g of polysulfone resin (Amicon P-3500) and 140 g of polyvinylpyrrolidone (Sigma, molecular weight 40,000) together with 450 g of N, N-dimethylacetamide 95 Was stirred for 6 hours at Cooled to. The spinning stock solution was extruded to the outside of the double-tubular nozzle of Example 1, and the inside was mixed with 20% by weight of water, 15% by weight of glycerin and 65% by weight of N, N-dimethylacetamide to the inside of the nozzle for spinning. The hollow fiber membrane through a 15-cm air layer, Into the external coagulation bath consisting of the water to completely change the phase and take out 100 Washed with water 3 times for 2 hours and dried Inner diameter 0.40 0.05 ~ 0.1 on inner and outer surface of membrane Micropores are formed, and 0.2-1.5 in the membrane A hollow fiber membrane having a degree of sponge structure was obtained. The strength of the membrane was 0.35 g / den, the elongation was 47%, and the permeability was 450 1 / m 2 .hr.atm.
- 실시예 1)에서와 같이 분획성능이 우수하고, 기계적 성질 및 투수성이 우수한 스폰지구조의 폴리설폰 중공사막을 제조하였다.-As in Example 1), a polysulfone hollow fiber membrane having a sponge structure having excellent fractionation performance and excellent mechanical properties and water permeability was prepared.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950058499A KR100200040B1 (en) | 1995-12-27 | 1995-12-27 | Sponge-like polysulphone hollow fibre membrane and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950058499A KR100200040B1 (en) | 1995-12-27 | 1995-12-27 | Sponge-like polysulphone hollow fibre membrane and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR970033003A KR970033003A (en) | 1997-07-22 |
| KR100200040B1 true KR100200040B1 (en) | 1999-06-15 |
Family
ID=19444972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019950058499A KR100200040B1 (en) | 1995-12-27 | 1995-12-27 | Sponge-like polysulphone hollow fibre membrane and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100200040B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101939328B1 (en) * | 2012-12-21 | 2019-01-16 | 주식회사 엘지화학 | Hollow Fiber Membrane Having Novel Structure and Method of Preparing the Same |
-
1995
- 1995-12-27 KR KR1019950058499A patent/KR100200040B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR970033003A (en) | 1997-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5232597A (en) | Polysulfone porous hollow fiber | |
| KR101597829B1 (en) | Porous Membrane and Method for Manufacturing The Same | |
| KR101462939B1 (en) | Hydrophilic Polyvinylidene Fluoride Based Hollow Fiber Membrane and Preparing Method Thereof | |
| EP0880399A1 (en) | Self supporting hollow fiber membrane and method of construction | |
| CN103501878B (en) | Performance enhancing additives for fiber formation and polysulfone fibers | |
| US5833896A (en) | Method of making a hollow fibre membrane | |
| EP2557111A1 (en) | Process for production of porous membrane | |
| CA2202969C (en) | Selectively permeable hollow fiber membrane and process for producing same | |
| KR20080057637A (en) | Method for manufacturing polyvinylidene fluoride hollow fiber membrane and hollow fiber membrane | |
| JP2736992B2 (en) | Polysulfone hollow fiber membrane and method for producing the same | |
| KR20130040620A (en) | Preparation method of hollow fiber membrane with high mechanical properties made of hydrophilic modified polyvinylidenefluoride for water treatment | |
| JPS61164602A (en) | Hllow yarn membrane made of polysulfone resin and its preparation | |
| KR20180015797A (en) | Inner coagulant for producing polysulfone-based hollow fiber membrange and method of producing polysulfone-based hollow fiber membrane by using the same | |
| KR950006517B1 (en) | The manufacturing method of porosing membrane | |
| KR100200040B1 (en) | Sponge-like polysulphone hollow fibre membrane and manufacturing method thereof | |
| KR101331066B1 (en) | Polyethersulfone hollow fiber membrane and method of manufacturing the same | |
| JPH08108053A (en) | Cellulose acetate hollow-fiber separation membrane and its production | |
| KR0136978B1 (en) | Polysulfone hollow fiber membrane having sponge structure and good permeability and preparation method thereof | |
| KR100200041B1 (en) | Sponge-like polysulphone hollow fibre membrane having active layer and manufacturing method thereof | |
| KR20070102011A (en) | Porous poly(vinylidene fluoride) hollow fiber membranes for high water permeance and methods to make membranes | |
| KR0177273B1 (en) | Sponge-like polysulfone hollow fiber membrane with active layer and manufacturing method thereof | |
| KR20070103187A (en) | Porous poly(vinylidene fluoride) hollow fiber membranes composed of both fibril and nodular structures | |
| KR100602429B1 (en) | A polysulfone typed hollow fiber membrane, and a process of preparing for the same | |
| JPS59228016A (en) | Hollow yarn membrane of aromatic polysulfone | |
| KR20130040625A (en) | Polyvinylidenefluoride hollow fiber membrane with secondary barrier for water treatment and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20111216 Year of fee payment: 14 |
|
| FPAY | Annual fee payment |
Payment date: 20121220 Year of fee payment: 15 |
|
| LAPS | Lapse due to unpaid annual fee |