KR100200041B1 - Sponge-like polysulphone hollow fibre membrane having active layer and manufacturing method thereof - Google Patents
Sponge-like polysulphone hollow fibre membrane having active layer and manufacturing method thereof Download PDFInfo
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- KR100200041B1 KR100200041B1 KR1019950050786A KR19950050786A KR100200041B1 KR 100200041 B1 KR100200041 B1 KR 100200041B1 KR 1019950050786 A KR1019950050786 A KR 1019950050786A KR 19950050786 A KR19950050786 A KR 19950050786A KR 100200041 B1 KR100200041 B1 KR 100200041B1
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- 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
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- 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
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- 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
- B01D2325/0233—Asymmetric membranes with clearly distinguishable layers
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- 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
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- 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
- B01D2325/0283—Pore size
- B01D2325/02833—Pore size more than 10 and up to 100 nm
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- 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
- B01D2325/0283—Pore size
- B01D2325/02834—Pore size more than 0.1 and up to 1 µm
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Abstract
본 발명은 내표면에 폭이 0.1 마이크론 이상 2 마이크론 이하의 스폰지 구조 기공이 형성되어 있고, 외표면은 폭이 0.1~0.5 마이크론의 크기를 갖는 스폰지 구조 기공이 형성되어 있으며, 그 내부에 0.01~0.05 마이크론 범위의 미세 기공이 형성된 활성층이 있는 것을 특징으로 하는 스폰지 구조 폴리설폰 중공사막 및 그 제조방법이 제공되는 것으로 습윤강신도 및 투수성이 좋아 가정용 정수기 등에 유용하게 사용된다.In the present invention, sponge structure pores having a width of 0.1 micron or more and 2 microns or less are formed on an inner surface, and sponge structure pores having a size of 0.1 to 0.5 microns in width are formed on an inner surface thereof, and 0.01 to 0.05 inside thereof. Sponge-structured polysulfone hollow fiber membranes and a method for producing the same, which are characterized in that there is an active layer formed with micropores in the micron range is well used in household water purifiers because of good wet strength and water permeability.
Description
본 발명은 활성층을 포함한 스폰지 구조 폴리설폰 중공사막에 관한 것으로, 종래의 중공사막들과는 달리 중공사막의 내표면에는 스폰지 구조의 기공이 형성되어 있고, 외표면에는 활성층을 포함한 스폰지 구조로 되어 단면구조가 외면으로부터 스폰지구조, 활성층, 스폰지구조로 차례로 구비되어 기공율이 높기때문에 투수성이 매우 뛰어난 중공사막에 관한 것이다.The present invention relates to a sponge-structured polysulfone hollow fiber membrane comprising an active layer, unlike conventional hollow fiber membranes, the pores of the sponge structure is formed on the inner surface of the hollow fiber membrane, and the cross-sectional structure of the sponge structure including the active layer on the outer surface The present invention relates to a hollow fiber membrane having excellent water permeability because it is provided with a sponge structure, an active layer, and a sponge structure from the outer surface in order to have high porosity.
중공사막은 동일 부피의 다른 형태의 막들에 비해 표면적이 월등히 크고 모듈화하기 쉽기 때문에 최근 한외여과막을 중심으로 연구개발이 활발히 진행되어 많은 부문에서 실용화 되어있다.Since hollow fiber membranes have a much larger surface area and are easier to modularize than other types of membranes of the same volume, researches and developments have recently been carried out, focusing on ultrafiltration membranes.
지금까지 알려진 중공사막의 소재로는 PVA, CA, PMMA, PP, PE 등이 있으나, 이들은 내열성이 약하기 때문에 내열성이 뛰어난 PS, PES 등이 각광 받는 소재가 되고 있다. 또한 내생물분해성, 내화학성, 내열성, 기계적 성질등이 우수한 폴리설폰수지는 정밀여과용 분리막, 한외여과용 분리막, 역삼투 및 기체분리 복합막의 지지체로서 개발되어 사용되고 있다.As the materials of the hollow fiber membranes known so far, there are PVA, CA, PMMA, PP, PE and the like, but since these materials have poor heat resistance, PS, PES and the like having excellent heat resistance have become the spotlight materials. In addition, polysulfone resins having excellent biodegradability, chemical resistance, heat resistance, mechanical properties, etc., have been developed and used as supports for microfiltration membranes, ultrafiltration membranes, reverse osmosis and gas separation composite membranes.
일반적으로 중공사막은 단면구조에 따라 크게 지상구조(Finger-like structure)와 스폰지구조(Sponge structure), 복합구조(Complex structure)로 나눌 수 있다.In general, the hollow fiber membrane may be classified into a ground-like structure, a sponge structure, and a complex structure according to the cross-sectional structure.
지상구조의 중공사막은 세공이 매우 작은(약 0.001~0.01)중공사막의 경우 투수성을 높이기 위해 고안된 구조인데, 활성층이 내면에 형성되어 있기 때문에 내부로부터 외부로 물이 통과되면서 여과가 이루어진다. 지상구조의 중공사막은 구조의 특성상 높은 압력에서는 압력을 이기지 못하여 활성층이 파기된다는 단점이 있다.The hollow fiber membrane of the ground structure has very small pores (approximately 0.001 ~ 0.01 The hollow fiber membrane is a structure designed to increase permeability. Since the active layer is formed on the inner surface, filtration is performed as water passes from the inside to the outside. Due to the characteristics of the structure, the hollow fiber membrane of the ground structure has a disadvantage in that the active layer is destroyed because the pressure cannot be overcome at high pressure.
스폰지 구조의 중공사막은 세공이 비교적 큰(0.1~1.0)중공사막에 있어서 내압성을 강화하기 위해 고안된 구조이다. 그러나 스폰지구조는 물의 투과저항이 크기 때문에 투수성이 적고, 투수성을 확보하기 위해 세공을 너무 크게 하게 되면 분획성능이 저하되어 보다 작은 크기의 (0.01~0.1)세공을 갖는 중공사막에서는 채택될 수 없다는 단점이 있다.Hollow fiber membrane of sponge structure has relatively large pores (0.1 ~ 1.0 It is a structure designed to strengthen the pressure resistance in the hollow fiber membrane. However, the sponge structure has less water permeability because the water permeation resistance is large, and if the pores are made too large to secure the permeability, the fractionation performance is lowered. ~ 0.1 There is a disadvantage that it cannot be adopted in hollow fiber membranes having pores.
한편 복합구조의 중공사막으로서는, 단면에 공동이 있는 스폰지구조의 중공사막과, 외표면쪽은 스폰지구조이고 내표면쪽은 지상구조의 중공사막이 개발되어 사용되고 있는데 전자의 경우 0.01~0.1정도의 세공을 갖는 중공사막에서는 투수성이 약한 단점이 있고 후자는 투수성은 좋지만 막의 지지도가 약하다는 문제점이 있다.On the other hand, as the hollow fiber membrane of the composite structure, a hollow fiber membrane having a sponge structure with a cavity in the cross section, and a hollow fiber membrane having a ground structure at the outer surface side and a ground structure at the inner surface side have been developed and used. ~ 0.1 In the hollow fiber membrane having a fine pore, the water permeability is weak, and the latter has a good water permeability, but the support of the membrane is weak.
본 발명에서는 상기 서술된 문제점을 개선하기 위해 선택성 및 투수성이 뛰어난 스폰지구조의 중공사막을 제조하기 위한 것으로 막 외표면의 스폰지구조내면에 활성층이 형성되어 있고 내표면에는 스폰지 구조의 기공이 형성되어 있으며, 막의 단면구조는 외표면으로부터 스폰지구조, 활성층, 스폰지구조로 기공율이 매우 높기 때문에 유체역학적 저항에도 불구하고 투수성이 매우 뛰어난 중공사막을 제공하는데 그 목적이 있다.In the present invention is to produce a hollow fiber membrane of the sponge structure excellent in selectivity and water permeability in order to improve the above-described problems, the active layer is formed on the inner surface of the sponge structure of the membrane surface and the pores of the sponge structure is formed on the inner surface In addition, since the membrane has a high porosity from the outer surface to the sponge structure, the active layer, and the sponge structure, an object of the present invention is to provide a hollow fiber membrane having excellent water permeability despite hydrodynamic resistance.
즉, 본 발명의 폴리설폰 중공사막은, 단면구조의 외표면에 0.1~0.5 마이크론의 크기를 갖는 스폰지 구조 기공이 형성되어 있고, 외표면으로부터 5~15 마이크론 거리안에 0.01~0.05 마이크론 크기의 미세 기공이 형성된 활성층이 1~3 마이크론 두께로 구성되어 있으며, 그 내표면에는 폭이 0.1마이크론 이상 2마이크론 이하의 스폰지 구조 기공이 형성되어 있는 것을 특징으로 하는 단위면적당 투수량 600~650/m2 hratm이상으로 매우 높은 투수성을 갖고 있으며 막의 습윤강도, 신도 및 내압성이 우수한 스폰지 구조의 한외여과막임을 특징으로 한다.That is, in the polysulfone hollow fiber membrane of the present invention, sponge structure pores having a size of 0.1 to 0.5 microns are formed on the outer surface of the cross-sectional structure, and micropores having a size of 0.01 to 0.05 microns within a distance of 5 to 15 microns from the outer surface. The formed active layer is composed of 1 to 3 microns thick, the inner surface of the permeate per unit area 600 ~ 650 characterized in that the sponge structure pores having a width of 0.1 micron to 2 microns is formed. / m 2 hr It has a very high water permeability above atm and is a sponge-type ultrafiltration membrane with excellent wet strength, elongation and pressure resistance.
본 발명에 의한 폴리설폰 중공사막의 내표면에는 0.1마이크론 이상의 폭을 갖는 스폰지구조의 세공을 갖고 있는데, 이 세공의 폭이 0.1 마이크론 미만이 되면 막의 분획성능은 좋아지나 투수성이 적어 본래의 목적을 달성할 수 없으며, 반면 폭이 2 마이크론을 초과하면 투수성은 매우 증가하나 막의 분획성능 및 내압성능이 나빠진다. 따라서 막의 기계적 성질 및 투수성, 내압성을 고려할 때 스폰지 구조의 세공의 폭이 0.1~2 마이크론이 적당하다.The inner surface of the polysulfone hollow fiber membrane according to the present invention has pores of sponge structure having a width of 0.1 micron or more. When the width of the pores is less than 0.1 micron, the fractionation performance of the membrane is improved, but the water permeability is small, and thus the original purpose is achieved. On the other hand, if the width exceeds 2 microns, the permeability is greatly increased, but the fractionation performance and the pressure resistance performance of the membrane are deteriorated. Therefore, considering the mechanical properties, permeability, and pressure resistance of the membrane, the width of the pores of the sponge structure is appropriately 0.1 to 2 microns.
또한 막의 외표면에는 0.1~0.5 마이크론의 스폰지 구조 세공이 형성되어 있는데 이때 외부로부터 5~15 마이크론 두께 정도까지는 내부로 들어갈수록 세공의 크기가 작아져 0.01~0.05 마이크론 범위의 미세기공을 가진 활성층이 1~3 마이크론 두께정도로 나타나고 다음에는 내부로 갈수록 스폰지 구조의 세공이 커지게 된다.In addition, 0.1-0.5 micron sponge structure pores are formed on the outer surface of the membrane. At this time, the size of the pores decreases from the outside to the thickness of 5-15 microns, so that the active layer has micropores in the range of 0.01-0.05 microns. It appears to be about 3 microns thick, and then the pores of the sponge structure become larger toward the inside.
여기서 외표면의 세공 크기가 0.1마이크론 미만이 되면 투수량이 급격히 감소하며, 0.5 마이크론을 초과하면 활성층의 세공도 커져 막의 분획성능 및 기계적 성질이 약해지게 된다. 또한 활성층의 두께가 1 마이크론 보다 적게 나타나면 분획성능 및 기계적 특성이 약해지게 되고 3 마이크론보다 두껍게 나타나면 분획성능은 좋아지나 투수량이 급격히 감소한다.If the pore size of the outer surface is less than 0.1 micron, the permeation rate is drastically reduced. If the pore size exceeds 0.5 microns, the pore size of the active layer is increased, and the membrane fractionation performance and mechanical properties are weakened. In addition, when the thickness of the active layer is less than 1 micron, the fractionation performance and mechanical properties are weakened. When the thickness of the active layer is thicker than 3 microns, the fractionation performance is improved, but the permeability decreases rapidly.
그리고 활성층의 위치가 외표면으로부터 5 마이크론 보다 전에 나타나면 외표면의 기공이 0.1 마이크론 이하의 세공이 형성되어 투수성이 떨어지고, 15마이크론 보다 뒤에 나타나면 내표면이 스폰지 구조의 기공이 감소하여 역시 투수량이 떨어지는 단점이 있다.If the position of the active layer is less than 5 microns from the outer surface, the pores of the outer surface are less than 0.1 micron, and the permeability is poor, and if it is later than 15 microns, the inner surface decreases the pores of the sponge structure and the water permeability is also lowered. There are disadvantages.
한편 막이 표면적에 대한 기공의 면적을 백분율로 나타내는 기공율은 지상구조나 공동이 있는 중공사막은 50%이상이 되면 막의 내압성이 떨어지는데 비해 활성층을 포함한 스폰지 구조의 중공사막은 기공율이 50%이상 65%미만일 때에도 기계적 성질이 우수하여 동일한 분획분자량을 가지면서도 기공율은 높기 때문에 투수성이 우수함을 알 수 있다.On the other hand, the porosity of the membrane as a percentage of the pore area relative to the surface area is less than 50% for the hollow fiber membrane with the ground structure or cavity. Even when the mechanical properties are excellent, it has excellent water permeability because it has the same fractional molecular weight and high porosity.
본 발명에 의한 폴리설폰중공사막은 단면구조가 스폰지 구조, 활성층, 스폰지 구조로서 구성되어 있으며 막의 강도는 0.40 g/den이상을 나타내고, 특히 습윤신도는 55% 이상으로 높아 공업적으로 사용하기 위해 모듈을 만들 때 손상을 방지할 수 있으며 취급이 용이하다.Polysulfone hollow fiber membranes according to the present invention has a cross-sectional structure consisting of a sponge structure, an active layer, a sponge structure, the membrane has a strength of 0.40 g / den or more, in particular, the wet elongation is 55% or more high module for industrial use Damage can be prevented when making and easy to handle.
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 응고액 속에 넣어 완전히 응고시킨 후 꺼내어 수세함으로서 제조된다.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 prepared by solidifying it in the inside, taking it out and washing it with water.
폴리설폰 수지의 용매로서는 m-크레졸, 클로로벤젠, N-메틸-2-피롤리돈, 디메틸 설폭사이드, 디메틸아세트아마이드, 디메틸포름아마이드 등이 있고 이들을 단독 또는 2종이상의 혼합 용매를 수용성 고분자와 용해할 수 있도록 적절히 선정하여 사용한다.Examples of the solvent of the polysulfone resin include m-cresol, chlorobenzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, and the like. Select and use appropriately.
변성제로 사용되는 수용성 고분자는 취급이 용이하고 다양한 분자량을 갖고 있으므로 알맞은 종류를 선택함으로써 투과성능을 조절할 수 있고, 또한 사용되는 수용성 고분자의 분자량 및 첨가량에 의해 방사원액의 점도를 조절할 수 있어 많은 이점을 갖고 있다.Since the water-soluble polymer used as the modifier is easy to handle and has various molecular weights, the permeation performance can be controlled by selecting the appropriate type, and the viscosity of the spinning stock solution can be controlled by the molecular weight and the amount of the water-soluble polymer used. Have
이때 수용성 고분자로는 폴리에틸렌 글리콜, 폴리비닐알콜, 폴리비닐피롤리돈 등이 있으며 이들 중 단독 또는 2종이상을 혼합하여 사용한다.At this time, the water-soluble polymers include polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and the like, or a mixture of two or more thereof.
방사원액은 폴리설폰 수지 10~20 중량%, 수용성고분자 20~50중량%를 용매에 용해하여 제조된다. 이때 방사원액의 점도는 막의 구조에 매우 큰 영향을 미치므로 적절히 조절하며 원하는 점도의 원액을 제조해야 하는데, 바람직하기로는 5,000~30,000 센티포아스의 점도를 갖는 방사원액을 제조하는 것이 좋다.The spinning stock solution is prepared by dissolving 10-20 wt% of polysulfone resin and 20-50 wt% of water-soluble polymer in a solvent. At this time, since the viscosity of the spinning stock solution has a very large effect on the structure of the membrane, it is necessary to prepare a stock solution having a desired viscosity by adjusting it appropriately. Preferably, it is preferable to prepare a spinning stock solution having a viscosity of 5,000 to 30,000 centipoas.
내부 응고액의 주입시에 응고가가 너무 높으면 방사 직후에 응고가 일어나지 않게 되고, 반면 응고가가 너무 낮으면 방사직후 강한 응고가 일어나 내부 치밀층이 생성되어 투수성이 떨어지며 방사속도가 느려진다. 그러므로 내표면에 다공성 스폰지 구조의 세공이 생기고 방사속도를 빠르게 할 수 있는 내부응고액의 응고가가 필요하다. 내부응고액의 응고가는 폴리셀폰 15 중량%, 폴리비닐피롤리돈 25 중량%의 혼합물을 디메틸아세트아마이드 용매에 1 중량%로 용해한 용액 500밀리리터를 상전이 시키는데 필요한 응고액의 양을 밀리리터의 수치로 표시한 것이다. 응고가를 조절하기 위해서는 폴리설폰 양 용매와 비용매를 적절히 혼합하면 된다. 응고가 조절용 비용매로서는 물과 비휘발성 유기용제 즉, 에틸렌글리콜, 프로필렌글리콜, 글리세린 등으로서, 이들의 응고가가 20~50, 점도 1~20 센티포아스의 범위내를 갖도록 임의 비율로 혼합한다. 본 발명에서는 내부응고액중 비휘발성 비용매가 5~60 중량% 포함된다.If the coagulation solution is too high at the time of injection of the internal coagulation solution, coagulation does not occur immediately after spinning. On the other hand, if the coagulation cost is too low, strong coagulation occurs immediately after spinning to form an internal dense layer, resulting in poor permeability and slow spinning speed. Therefore, it is necessary to solidify the internal coagulating solution that can form porous sponge structure on the inner surface and accelerate the spinning speed. The coagulation value of the internal coagulation solution indicates the amount of coagulation solution required to phase change 500 milliliters of a solution in which a mixture of 15% by weight of polycellphone and 25% by weight of polyvinylpyrrolidone in 1% by weight of dimethylacetamide solvent is converted into milliliters. It is. In order to control the coagulation value, a polysulfone solvent and a nonsolvent may be mixed as appropriate. 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 a range of 20 to 50 and a viscosity of 1 to 20 centipoas. . In the present invention, the non-volatile non-solvent in the internal coagulating solution is contained 5 to 60% 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 50 내지 100 센티미터가 적당한데, 50센티미터보다 낮으면 외부에 치밀층이 생겨 투수성이 저하되고, 반면 100센티미터보다 높으면 외표면의 상전이가 내부 응고액에 의해 일어나 외표면의 기공크기가 너무 커져 막의 기계적 성질이 좋지 못하게 된다. 외부 응고액으로서는 보통 물을 사용한다. 외부 응고액의 온도는 중공사막의 외표면 세공의 크기와 단면의 기공율을 결정하는 요인 중의 하나로서 중공사막의 투수성과 밀접한 관계가 있다. 본 발명에서는 외부 응고액의 온도를 30~50범위에서 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 suitable to 50 to 100 centimeters, but if it is lower than 50 centimeters, the dense layer is formed on the outside, and the permeability is lowered. Becomes so large that the mechanical properties of the membrane become poor. Normally water is used as the external coagulant. The temperature of the external coagulation liquid is one of the factors that determine the size of the outer surface pores of the hollow fiber membrane and the porosity of the cross section, and is closely related to the permeability of the hollow fiber membrane. In the present invention, the temperature of the external coagulation liquid is 30 to 50 Work in the range.
본 발명에서 폴리설폰 중공사막은 활성층을 갖는 스폰지구조로서 습윤 강신도가 높고, 특히 투수성이 매우 높다. 기존의 중공사막의 강도는 0.2~0.3 g/den인데 비해 본 발명의 중공사막은 0.4~0.5g/den으로 높으며, 투수성 또한 650/m2 hratm이상으로 기존의 중공사막 보다 투수성이 매우 높다.In the present invention, the polysulfone hollow fiber membrane is a sponge structure having an active layer, and has high wet elongation, and particularly has high water permeability. The strength of the conventional hollow fiber membrane is 0.2 ~ 0.3 g / den, while the hollow fiber membrane of the present invention is high 0.4 ~ 0.5 g / den, the water permeability is also 650 / m 2 hr Above atm, the permeability is much higher than that of conventional hollow fiber membranes.
이렇게 습윤 강신도 및 투수성이 높기 때문에 공업적으로 사용할 때 손상을 방지할 수 있어 취급이 용이하고 활성층의 기공에 의해 오염 물질 및 세균의 제거가 가능하며 투수성이 높아 가정용 정수기 등에 유용하게 사용할 수 있다.Because of its high wet strength and permeability, it is possible to prevent damage when used industrially, so it is easy to handle, and it is possible to remove contaminants and bacteria by the pores of the active layer. .
이하, 본 발명을 실시예를 들어 더욱 상세히 설명하고자 한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예 1]Example 1
폴리설폰 수지(Amicon사 P-3500) 200g을 1-메틸-2-피롤리돈 600g과 함께 100에서 6시간 동안 교반하여 용해시킨 후 50로 냉각시켰다. 그리고 이 용액에 폴리에틸렌글리콜(시그마사, 분자량 10,000) 300g을 투입하고 3시간 동안 교반하여 방사원액을 제조 후 20로 냉각하였다. 이 방사원액을 외경 0.65내경 0.35인 2중관형 노즐 외측부에 압출하는 동시에, 내부에는 물 20 중량%, 1-메틸-2-피롤리돈 70 중량%, 에틸렌 글리콜 10 중량%로 이루어진 혼합액을 노즐 내측부에 압출시켜 방사된 중공사막을 40의 공기층을 통과시키고 45의 물로 이루어진 외부 응고액조에 넣어 완전히 상전이를 시킨 후 꺼내어 100물에서 6시간 수세한 후 건조하여 외경 0.63, 내경 0.38로 막 내표면에 는 0.2~1.2 마이크론, 외표면에는 0.1~0.3 마이크론 범위의 기공이 형성되어 있고 막의 단면구조가 외표면 스폰지구조, 8마이크론 안에 0.01~0.05 마이크론 범위의 세공이 형성된 활성층, 내표면 스폰지구조인 중공사막을 얻었다. 막 강도는 0.40g/den, 습윤신도는 65%이고, 투수성은 800/m2 hratm을 나타내었다.200 g of polysulfone resin (Amicon P-3500) with 600 g of 1-methyl-2-pyrrolidone 100 After stirring for 6 hours to dissolve in 50 Cooled to. Then, 300 g of polyethylene glycol (Sigma, molecular weight 10,000) was added to the solution and stirred for 3 hours to prepare a spinning stock solution. Cooled to. This spinning stock solution has an outer diameter of 0.65. Inner diameter 0.35 While extruding the phosphorus double-tubular nozzle to the outside, the inside of the mixture of 20% by weight of water, 70% by weight of 1-methyl-2-pyrrolidone and 10% by weight of ethylene glycol was extruded to the inside of the nozzle to form a spun hollow fiber membrane 40 Through the air layer of 45 Into the external coagulation bath consisting of the water to completely change the phase and take out 100 Washed with water for 6 hours, dried Inside diameter 0.38 The inner surface of the membrane has pores in the range of 0.2 to 1.2 microns, and the outer surface has pores in the range of 0.1 to 0.3 microns, and the cross-sectional structure of the membrane is the outer surface sponge structure, the active layer with pores in the range of 0.01 to 0.05 microns within 8 microns, and the inner surface. A hollow fiber membrane having a sponge structure was obtained. Membrane strength is 0.40g / den, wetting elongation is 65%, water permeability is 800 / m 2 hr atm.
[실시예 2]Example 2
폴리설폰 수지(Amicon사 P-3500) 250g을 N,N-디메틸아마이드 650g과 함께 100에서 6시간 동안 교반하여 용해시킨 후 50로 냉각시켰다.250g of polysulfone resin (Amicon P-3500) with 650g of N, N-dimethylamide 100 After stirring for 6 hours to dissolve in 50 Cooled to.
그리고 이 용액에 폴리에틸렌글리콜(시그마사, 분자량 10,000) 250g을 투입하고 3시간 동안 교반하여 방사원액을 제조 후 20로 냉각하였다. 이 방사원액을 실시예 1 의 2중관형 노즐 외측부에 압출하는 동시에, 내부에는 물 10 중량%, N,N-디메틸아세트아마이드 75 중량%, 글리세린 15 중량%로 이루어진 혼합액을 노즐 내측부에 압출시켜 방사된 중공사막을 15센티미터의 공기층을 통과시키고 40의 물로 이루어진 외부 응고액조에 넣어 완전히 상전이를 시킨 후 꺼내어 100물에서 6시간 수세한 후 건조하여 외경 0.64밀리미터, 내경 0.36밀리미터로 막 내표면에는 0.2~1.0 마이크론, 외표면에는 0.1~0.35마이크론 범위의 기공이 형성되어 있고 막의 단면구조가 외표면 스폰지구조, 6 마이크론 안에 0.01~0.05 마이크론 범위의 세공이 형성된 활성층, 내표면 스폰지구조인 중공사막을 얻었다. 막강도는 0.41g/den, 습윤신도는 65%이고, 투수성은 750/m2 hratm을 나타내었다.250 g of polyethylene glycol (Sigma, molecular weight 10,000) was added to the solution and stirred for 3 hours to prepare a spinning stock solution. 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 10% by weight of water, 75% by weight of N, N-dimethylacetamide, and 15% by weight of glycerin 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 After washing for 6 hours in water and drying, the outer diameter is 0.64mm, the inner diameter is 0.36mm, and the pores are formed in the inner surface of 0.2 ~ 1.0 micron, and the outer surface is 0.1 ~ 0.35 micron. A hollow fiber membrane having an active layer and an inner surface sponge structure in which pores in the range of 0.01 to 0.05 microns were formed in a micron was obtained. Membrane strength is 0.41g / den, wetting elongation is 65%, water permeability is 750 / m 2 hr atm.
[실시예 3]Example 3
폴리설폰 수지(Amicon사 P-3500) 200g을 N,N-디메틸아세트아마이드 650g과 함께 100에서 6시간 동안 교반하여 용해시킨 후 50로 냉각시켰다. 그리고 이 용액에 폴리비닐피롤리돈(시그마사, 분자량 40,000) 400g을 투입하고 3시간 동안 교반하여 방사원액을 제조 후 20로 냉각하였다.200 g of polysulfone resin (Amicon P-3500) with 650 g of N, N-dimethylacetamide 100 After stirring for 6 hours to dissolve in 50 Cooled to. 400 g of polyvinylpyrrolidone (Sigma, molecular weight 40,000) was added to the solution and stirred for 3 hours to prepare a spinning stock solution. Cooled to.
이 방사원액을 실시예 1 의 2중관형 노즐 외측부에 압출하는 동시에, 내부에는 물 20 중량%, N,N-디메틸아세트아마이드 70 중량%, 글리세린 10 중량%로 이루어진 혼합액을 노즐 내측부에 압출시켜 방사된 중공사막을 20의 공기층을 통과시키고 35의 물로 이루어진 외부 응고액조에 넣어 완전히 상전이를 시킨 후 꺼내어 100물에서 6시간 수세한 후 건조하여 외경 0.62, 내경 0.39로 막 내표면에는 0.2~1.0 마이크론, 외표면에는 0.1~0.3 마이크론 범위의 기공이 형성되어있고 막의 단면구조가 외표면 스폰지구조, 10 마이크론 안에 0.01~0.05 마이크론 범위의 세공이 형성된 활성층, 내표면 스폰지구조인 중공사막을 얻었다. 막강도는 0.40g/den, 습윤신도는 65%이고, 투수성은 850/m2 hratm을 나타내었다.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, 70% by weight of N, N-dimethylacetamide, and 10% by weight of glycerin to extrude to the inside of the nozzle. Hollow fiber membranes 20 Passing through the air layer Into the external coagulation bath consisting of the water to completely change the phase and take out 100 Washed with water for 6 hours, dried Inside diameter 0.39 The inner surface of the membrane has pores in the range of 0.2 to 1.0 microns, and the outer surface has pores in the range of 0.1 to 0.3 microns, and the cross-sectional structure of the membrane is an outer surface sponge structure, an active layer with pores in the range of 0.01 to 0.05 microns within 10 microns, and an inner surface sponge. The hollow fiber membrane which is a structure was obtained. Membrane strength is 0.40g / den, wetting elongation is 65%, and water permeability is 850 / m 2 hr atm.
[비교예 1]Comparative Example 1
폴리설폰 수지(Amicon사 P-3500) 200g을 N,N-디메틸아세트아마이드 600g과 함께 100에서 6시간동안 교반하여 용해시킨 후 50로 냉각시켰다.200 g of polysulfone resin (Amicon P-3500) together with 600 g of N, N-dimethylacetamide 100 After stirring for 6 hours to dissolve in 50 Cooled to.
그리고 이 용액에 폴리에틸렌글리콜(시그마사, 분자량 10,000) 300g을 투입하고 3시간 동안 교반하여 방사원액을 제조 후 20로 냉각하였다. 이 방사원액을 실시예 1 의 2중관형 노즐 외측부에 압출하는 동시에, 내부에는 물 20 중량%, N,N-디메틸아세트아마이드 70 중량%, 에틸렌 글리콜 10 중량%로 이루어진 혼합액을 노즐 내측부에 압출시켜 방사된 중공사막을 3의 공기층을 통과시키고 25의 물로 이루어진 외부 응고액조에 넣어 완전히 상전이를 시킨 후 꺼내어 100물에서 6시간 수세한 후 건조하여 외경 0.61, 내경 0.37로 막 내표면에는 0.2~0.5 마이크론, 외표면에는 0.2~0.5 마이크론의 기공이 형성되어 있고 막의 단면구조가 외표면 스폰지구조, 30마이크론내에 0.05~0.2 마이크론 범위의 세공이 형성된 활성층, 내표면 스폰지구조인 중공사막을 얻었다. 막의 강도는 0.30g/den, 습윤신도는 65%이고, 투수성은 100/m2 hratm으로 낮은 값을 나타내었다.Then, 300 g of polyethylene glycol (Sigma, molecular weight 10,000) was added to the solution and stirred for 3 hours to prepare a spinning stock solution. Cooled to. The spinning stock solution was extruded to the outer portion of the double-tubular nozzle of Example 1, and a mixed liquid consisting of 20% by weight of water, 70% by weight of N, N-dimethylacetamide and 10% by weight of ethylene glycol was extruded to the inside of the nozzle. 3 Through the air layer of 25 Into the external coagulation bath consisting of the water to completely change the phase and take out 100 Washed with water for 6 hours, dried Inside diameter 0.37 The inner surface of the membrane is 0.2 to 0.5 microns and the outer surface is formed to have pores of 0.2 to 0.5 microns, and the cross-sectional structure of the membrane is the outer surface sponge structure, the active layer with pores in the range of 0.05 to 0.2 microns within 30 microns, and the inner surface sponge structure. Phosphorus hollow fiber membrane was obtained. Membrane strength is 0.30g / den, wetting elongation is 65%, water permeability is 100 / m 2 hr Atm showed a low value.
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| KR101370475B1 (en) * | 2012-05-31 | 2014-03-06 | (주)유성 | Manufacturing method of polyimid-based hollow fiber membrane with sponge-like structure |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100646312B1 (en) * | 2005-06-10 | 2006-11-23 | (주)에어레인 | Hollow fiber oxygen separation membrane and manufacturing method |
| KR101489746B1 (en) * | 2013-04-30 | 2015-02-04 | 주식회사 퓨어멤 | Preparation method of polysulfone hollow fiber membrane for removing virus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101370475B1 (en) * | 2012-05-31 | 2014-03-06 | (주)유성 | Manufacturing method of polyimid-based hollow fiber membrane with sponge-like structure |
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| KR970033001A (en) | 1997-07-22 |
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