WO2012128470A9 - Film en fibres creuses à base de polysulfone présentant une très grande résistance et une très bonne perméabilité à l'eau, et son procédé de fabrication - Google Patents

Film en fibres creuses à base de polysulfone présentant une très grande résistance et une très bonne perméabilité à l'eau, et son procédé de fabrication Download PDF

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WO2012128470A9
WO2012128470A9 PCT/KR2012/000789 KR2012000789W WO2012128470A9 WO 2012128470 A9 WO2012128470 A9 WO 2012128470A9 KR 2012000789 W KR2012000789 W KR 2012000789W WO 2012128470 A9 WO2012128470 A9 WO 2012128470A9
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Prior art keywords
polysulfone
hollow fiber
spinning
organic solvent
fiber membrane
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PCT/KR2012/000789
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English (en)
Korean (ko)
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WO2012128470A2 (fr
WO2012128470A4 (fr
WO2012128470A3 (fr
Inventor
박진신
정종호
허미
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주식회사 휴비스
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Publication of WO2012128470A3 publication Critical patent/WO2012128470A3/fr
Publication of WO2012128470A4 publication Critical patent/WO2012128470A4/fr
Publication of WO2012128470A9 publication Critical patent/WO2012128470A9/fr

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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
    • B01D69/087—Details relating to the spinning process
    • B01D69/0871—Fibre guidance after spinning through the manufacturing apparatus
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01D69/087—Details relating to the spinning process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/02—Hydrophilization
    • 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
    • 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

Definitions

  • the present invention relates to a polysulfone-based hollow fiber membrane improved in water permeability and strength and a method for producing the hollow fiber membrane.
  • Membranes are materials with selective permeability that separate undissolved particles from a fluid.
  • the shape of the membrane is divided into two types: flat membrane and hollow fiber membrane.
  • the hollow fiber membrane has the largest surface area of the membrane within the same volume and is most widely used for water treatment because of its high filtration efficiency.
  • the hollow fiber membrane can be roughly classified into two types according to the manufacturing method.
  • the hollow fiber membrane can be roughly divided into a nonsolvent induced phase preparation process (NIPS) and a thermally induced phase preparation process (TIPS) have.
  • NIPS nonsolvent induced phase preparation process
  • TIPS thermally induced phase preparation process
  • the separation membrane prepared by the NIPS method can change various conditions of the spinning conditions to form various structures of the separation membrane, especially asymmetric structure, and it is easy to adjust the pore size by adding various additives, But it has a disadvantage that the strength is generally weak.
  • the separation membrane produced by the TIPS method generally has the same structure as the outer surface and the inner surface of the separation membrane, and has a high separation membrane strength, and thus can be widely used for industrial purposes.
  • fluorine-based polymers have been introduced and used in fluorine-based hollow fiber membranes having excellent strength.
  • the TIPS method has the advantage of obtaining high strength properties, it is difficult to easily control the pore size, and it is difficult to solve the hydrophobic and hydrophilic additives of the fluorine-based polymer, so that the water permeability is generally higher than that of the sulfone-based polymer Have a falling problem.
  • the general characteristics required for water treatment hollow fiber membranes are as follows. First, the characteristics affecting the separation function include proper porosity (number of pores) for the purpose of separation efficiency, uniform pore distribution for improving the fractionation accuracy, and optimal pore size for effectively separating the separation object . Next, chemical resistance, chemical resistance, heat resistance, and the like are required for chemical treatment as material characteristics. In addition, properties that affect the operating capability are required to have good mechanical strength to extend service life, and water permeability associated with operating costs.
  • US Pat. No. 4,871,494 has attempted to increase the concentration of polymer in the preparation of polysulfone type membranes by the NIPS method, and to improve the strength by inhibiting the formation of macropores. However, And the separation membrane performance is deteriorated.
  • Korean Patent No. 129816 discloses a separation membrane manufacturing process in which a spinning nozzle is modified to use a triple nozzle and the macropore is suppressed by controlling the composition and coagulation speed of the polymer solution to increase the strength.
  • the triple nozzle has a complicated manufacturing method as compared with a single nozzle, and has a disadvantage that the manufacturing cost is high due to the supplement of the additional equipment.
  • a membrane made of dense micropores without macropores was prepared by controlling the spinning conditions without changing the composition of the spinning solution, changing the ratio, or introducing additional processes.
  • the permeability does not exhibit remarkably excellent performance as compared with the conventional separator.
  • the inventors of the present invention invented an industrial hollow fiber membrane that retains excellent permeability by using a polysulfone-based polymer having good hydrophilicity and improves the weak mechanical strength of a conventional polysulfone-based polymer.
  • An object of the present invention is to provide a polysulfone-based hollow fiber membrane having excellent strength and water permeability.
  • Another object of the present invention is to provide a process for producing a polysulfone-based hollow fiber membrane having excellent strength and water permeability.
  • a process for producing a polyurethane resin composition comprising 20 to 25% by weight of a polysulfone resin (A), 40 to 50% by weight of an organic solvent (B) To 35% by weight, wherein the hollow fiber membrane has an asymmetric sponge structure in which the pore size continuously increases from the outer surface layer to the inner surface layer, and the ratio of the pore sizes of the outer surface layer and the inner surface layer is 1: 10 to 1: 10,000.
  • the polysulfone-based hollow fiber membrane has a strength of at least 800 gf / L and a water permeability of 2,000 L / m 2 * kgf * h.
  • the polysulfone resin (A) is polysulfone or polyisocyanate
  • the organic solvent (B) is dimethylacetamide (DMAc), dimethylformamide (DMF)
  • the hydrophilic additive (C) is selected from the group consisting of chloroform, N-methyl-2-pyrrolidone, dimethylsulfoxide, (Weight average molecular weight Mw: 15,000 to 90,000), polyethylene glycol (Mw: 200 to 1,000), ethylene glycol, methyl alcohol, glycerin, cellulose acetate, polyvinyl alcohol, sodium chloride, lithium chloride, polypropylene Glycol, castor oil, zinc chloride, and mixtures thereof.
  • a spinning solution comprising a polysulfone resin (A), an organic solvent (B), and a hydrophilic additive (C) ; Preparing an internal coagulating solution; Radiating the spinning solution and the internal coagulating solution through a double nozzle; The organic solvent (B) and the hydrophilic additive (C) are converted into non-solvent and phase in a coagulation tank and a washing tank to form pores; Wherein the step of forming the pores includes spinning the polysulfone-based hollow fiber membrane in a total retention time of more than 90 seconds in the coagulation bath and the washing bath.
  • the residence time in the coagulation bath of the spinning step is characterized by exceeding 15 seconds.
  • the coagulation bath temperature of the spinning step is 50 to 70 ° C.
  • the present invention provides an asymmetric sponge structure in which a pinhole or finger structure is not formed, and a polysulfone-based hollow fiber membrane having a larger pore of an inner surface layer than an outer surface layer is provided, and the hollow fiber membrane of the present invention has an excellent water permeability and strength.
  • FIG. 1 is a schematic diagram of a manufacturing process of a hollow fiber membrane.
  • Fig. 2 shows the principle of structure formation according to the phase change speed.
  • Example 3 is an electrophotograph obtained by enlarging a cross section of the hollow fiber membrane according to Example 2 by a scanning electron microscope 50 times.
  • Fig. 4 is an electrophotograph obtained by enlarging the internal surface of the hollow fiber membrane according to Example 2 by 90 times using a scanning electron microscope.
  • Example 5 is an electrophotograph obtained by enlarging the outer surface of the hollow fiber membrane according to Example 2 by a scanning electron microscope 30,000 times.
  • Example 6 is an electrophotograph obtained by enlarging the cross section of the hollow fiber membrane according to Example 3 by a scanning electron microscope 400 times.
  • FIG. 7 is an electrophotograph obtained by enlarging the inner surface of the hollow fiber membrane according to the third embodiment by a scanning electron microscope 90 times.
  • Example 8 is an electrophotograph obtained by enlarging the outer surface of the hollow fiber membrane according to Example 3 by a scanning electron microscope 30,000 times.
  • 11 is an electrophotograph obtained by enlarging the outer surface of the hollow fiber membrane according to Comparative Example 7 by a scanning electron microscope 30,000 times.
  • the polysulfone-based hollow fiber membrane of the present invention comprises a spinning stock solution containing 20 to 25% by weight of a polysulfone resin (A), 40 to 50% by weight of an organic solvent (B) and 30 to 35% by weight of a hydrophilic additive (C)
  • the present invention is characterized in that it is manufactured by spinning an internal coagulating solution.
  • the polysulfone resin (A) is the polysulfone resin (A)
  • polysulfone resin of the present invention polysulfones, polyethersulfones, and mixtures thereof can be used as a base resin.
  • Polysulfone resins are excellent in chemical resistance and heat resistance, have a wide pH range to be applied, and are excellent in solubility in an organic solvent, thereby facilitating the liquid preparation of a spinning dope.
  • the polysulfone resin (A) is preferably contained in an amount of 20 to 25% by weight based on the total weight of the spinning solution.
  • the polysulfone resin is less than 20% by weight, the hollow fiber is not formed, the hollow fiber is not formed, the air gap is difficult to control, and the radioactivity is poor.
  • the polysulfone resin is more than 25% by weight, the solubility in the spinning solution decreases, It may happen or its appearance may become uneven.
  • Examples of the organic solvent (B) of the present invention used for dissolving the polysulfone resin (A) include dimethylacetamide (DMAc), dimethylformamide (DMF), chloroform, N-methyl-2-pyrrolidone, dimethylsulfoxide, and the like.
  • the organic solvent is contained in an amount of 30 to 60% by weight, preferably 40 to 50% by weight, based on the total weight of the spinning solution.
  • the hydrophilic additive (C) is the hydrophilic additive (C)
  • the present invention includes a hydrophilic additive for imparting hydrophilization to the hollow fiber or controlling pore size.
  • the hydrophilic additive include polyvinyl pyrrolidone (weight average molecular weight Mw: 15,000 to 90,000), polyethylene glycol (Mw: 200 to 1,000), ethylene glycol, methyl alcohol, glycerin, cellulose acetate, polyvinyl alcohol, Lithium, polypropylene glycol, castor oil, zinc chloride, and the like.
  • the hydrophilic additive affects pore formation and hydrophilicity impartation of the hollow fiber, and is closely related to the water permeability. More specifically, the hydrophilic additive existing in the spinning stock solution during absorption of the spinning stock solution from the double tubular nozzle and staying in the coagulation tank absorbs the non-spinning solution of the coagulation tank, so that the spinning stock solution can be easily converted into the solvent. In addition, the hydrophilic additive acts as a swelling agent to increase the pore size or cross-linkage of the hydrophilic group inside the polysulfone resin, thereby increasing the hydrophilicity of the hollow fiber.
  • the hydrophilic additive (C) is contained in an amount of 10 to 40% by weight, preferably 20 to 35% by weight based on the total weight of the spinning solution. If the content of the hydrophilic additive (C) is 10% by weight or less, pores in the hollow fiber are not formed and the water permeability is significantly reduced. In particular, as shown in FIG. 9, a finger-like structure is formed . On the other hand, when it is contained in an amount of 40 wt% or more, large pores (pinholes) are formed as shown in FIG. 6, and durability and pressure resistance may be lowered.
  • the method for producing a polysulfone-based hollow fiber membrane of the present invention comprises the steps of: preparing a spinning stock solution containing a polysulfone resin (A), an organic solvent (B), and a hydrophilic additive (C); Preparing an internal coagulating solution; Radiating the spinning solution and the internal coagulating solution through a double nozzle; The organic solvent (B) and the hydrophilic additive (C) are converted into non-solvent and phase in a coagulation tank and a washing tank to form pores; And a winding step.
  • the internal coagulating solution is used to form the pores in the hollow fiber membrane.
  • a solvent such as dimethylacetamide (DMAc), dimethylformamide (DMF), chloroform, tetrahydrofuran, N N-Methyl-2-Pyrrolidone, Dimethylsulfoxide, or a mixture thereof.
  • the mixing ratio is 0 to 30% by weight, preferably 5 to 25% by weight, and the organic solvent is 70 to 100% by weight, preferably 75 to 95% by weight.
  • the internal coagulating liquid is mixed at a mixing temperature of 50 to 70 ° C and a stirring speed of 80 to 120 rpm for 12 to 24 hours and then defoaming is carried out for 6 to 12 hours under a vacuum of -5 to -1 kgf, .
  • the spinning apparatus used in the spinning step of the spinning stock solution and the inner coagulating solution includes a spinning dope and an inner coagulating liquid tank, a nozzle holder, a primary coagulating bath, a washing tank, a winding drum, and a water bath for removing the residual organic solvent of the sample. More specifically, the spinning process schematic diagram of the present invention related thereto is shown in FIG. 1 as an example.
  • a fruiting system in the processing line of the spinning dope and inner coagulating liquid manufacturing tank and the nozzle holder, can be constructed to maintain the temperature in the range of 25 to 200 ° C.
  • the nozzle holder can be moved up and down and left and right to control the air gap between the nozzle and the coagulation bath.
  • the air gap is a section in which the primary phase change occurs, and the water in the air and the organic solvent in the spinning liquid are exchanged to effect the phase change.
  • the coagulation tank is provided with a multi-stage godet roller in the coagulation tank to prolong the residence time of the separation membrane.
  • the retention time can be adjusted by installing a multi-stage godet roller in the cleaning tank.
  • the residence time of the coagulation bath exceeds 10 seconds, preferably 15 seconds or more.
  • the retention time of the coagulation tank is 10 seconds or less, the secondary phase conversion is not sufficiently performed, and the pore formation is reduced, and the water permeability is decreased.
  • the residence time of the cleaning bath is 80 seconds or more, preferably 90 seconds or more.
  • the retention stage of the washing tank is a stage where the phase of the spinning stock solution, in which the phase change in the clotting tank has not been completed, is converted into the tertiary phase and washing of the inner coagulant is performed. If the residence time of the washing tub is less than 80 seconds, the washing of the additive and the internal coagulant may not be complete and residual organic solvent may remain.
  • the total residence time of the coagulation bath and the washing bath is 90 seconds or more, preferably 105 seconds or more.
  • the longer the total residence time the more advantageous for phase change and cleaning, but the longer the production process time and the lower the productivity, so it is desirable to select the optimum condition at an appropriate level.
  • the hollow fiber yarn is discharged by spinning the prepared spinning stock solution and inner coagulating solution using a double-tubular nozzle, and the first phase is changed in the air gap.
  • the second phase is switched through the coagulation bath.
  • the additive and the residual organic solvent are removed from the washing tank, and then the water is transferred to the winding drum and wound, thereby completing the spinning process.
  • the length of the air gap should be 10 cm or less, preferably 1 to 5 cm. If the air gap is more than 10 cm, the primary phase of the organic solvent in the DOPE and the water vapor in the atmosphere is sufficiently converted to increase the water permeability to increase the water permeability, but the hollow yarn twist phenomenon occurs, The radioactivity may be lowered. On the other hand, if there is no air gap, the radioactivity is excellent, but since the first phase is not converted, the second phase is immediately converted, so that the porosity is lowered and the water permeability may decrease.
  • the phase conversion is a principle in which the organic solvent and the hydrophilic additive in the spinning liquid (DOPE) escape and the vacancy is filled with the non-solvent of the external coagulation bath to form pores.
  • DOPE spinning liquid
  • the temperature of the external coagulation bath is excessively high exceeding 70 ⁇ , the radioactivity may be deteriorated or the working environment may become poor due to supersaturation of the atmospheric humidity and single yarn.
  • the temperature of the external coagulation bath is lower than 30 ° C., only the outer surface where the spinning solution comes into contact with the non-solvent is converted into phase, and the organic solvent and the additive therein can not escape, Pores are formed to form a finger-like structure.
  • the permeation rate of the non-solvent means the rate at which ultra pure water in the coagulation bath permeates into the spinning solution
  • the permeation rate of the solvent means the rate at which the solvent in the spinning solution exits into the coagulation bath. That is, the ultrapure water of the coagulation tank must rapidly penetrate into the spinning solution to form a sponge structure.
  • the infiltration rate increases and the conversion speed also increases.
  • the coagulation bath and the washing bath are filled with water or a mixture of water and organic solvent, and then the temperature is 30 to 80 ⁇ , To 70 < 0 > C.
  • the cross section of the water treatment hollow fiber can be divided into a finger structure and a sponge structure.
  • FIG. 6 illustrates a finger structure. Referring to FIG. 6, the outermost skin layer is formed in a dense structure, and the water permeability is remarkably decreased. This is because the solvent remaining in the cross- And the pressure resistance is weakened due to the formation of macropores on the cross section, and the contaminants are permeated as they are when the outer surface is leaked, failing to function as a separation membrane.
  • the sponge structure can be divided into a symmetric membrane structure and an asymmetric membrane structure.
  • the symmetric membrane structure has the same pore size on the outer surface and the inner surface, and the asymmetric membrane structure has a structure in which the pore size of the outer surface and the inner surface are different .
  • ≪ / RTI > 3 shows a symmetrical membrane structure as an example of a sponge structure.
  • the asymmetric membrane has an advantage in that it has less channel resistance than that of the symmetric membrane and has a high permeation efficiency.
  • the cross-sectional structure is formed in a more compact structure than the finger structure, so that pressure resistance and durability are excellent.
  • the inventors of the present invention produced hollow fiber membranes having the following structural features by the above-mentioned manufacturing method in order to improve the disadvantages of the conventional sponge structure having a symmetric structure. More specifically, referring to FIG. 3 to FIG. 5, the drawing is a scanning electron microscope (SEM) image of a hollow fiber membrane of the present invention, wherein the hollow fiber membrane of the present invention has a finger structure (FIG. 9) And the pore size increases from the outer surface to the inner surface. Particularly, among the inner surface layer, the pore size of the outermost thin layer is 2 to 200 ⁇ m, which is a very large structural feature.
  • SEM scanning electron microscope
  • the temperature of the spinning liquid was maintained at 35 ° C and the temperature of the internal coagulating solution was maintained at 60 ° C.
  • a double tube type nozzle having an outer diameter of 1300 ⁇ m, an inner diameter of 800 ⁇ m and an injection hole diameter of 600 ⁇ m .
  • the spun hollow fiber was continuously passed through an air gap of 2 cm, passed through a coagulation tank and a washing tank containing 70 ° C ultrapure water in order, and then wound on a winder. At this time, the retention time of the coagulation bath was 20 seconds and the retention time of the washing bath was 90 seconds.
  • the hollow fiber wound on the winder was cut into a length of 1 m, dipped in a washing bath containing ultrapure water at 60 ° C for 24 hours, and dried in a hot air drier at 80 ° C for 24 hours.
  • a hollow fiber specimen was prepared in the same manner as in Example 2, except that the temperature of the coagulation bath was 50 ° C.
  • a hollow fiber specimen was prepared in the same manner as in Example 2.
  • a hollow fiber specimen was prepared in the same manner as in Example 2, except that the temperature of the coagulation bath was 25 ° C.
  • a hollow fiber specimen was prepared in the same manner as in Example 2, except that the coagulation tank retention time was 10 seconds.
  • a hollow fiber specimen was prepared in the same manner as in Example 2, except that the coagulation tank retention time was 5 seconds.
  • the amount of ultrapure water passed through the unit area is measured by applying a constant pressure. At this time, the ultrapure water was kept at 25 ⁇ and measured under an atmosphere of an environmental temperature of 25 ⁇ and a relative humidity of 50%.
  • Average pore size Average pore size was measured by a half-dry method according to ASTM F316-03 using a non-mercury capillary pressure measuring device CF-1000 Porometer (AEL, USA) manufactured by PMI. Perfluoropolyester (trade name: Galwick) was used as a test solution.
  • Fractional Performance (0.1 ⁇ m Bead Removal Rate): A latex bead with a diameter of 0.1 ⁇ m was diluted to 100 ppm in ultrapure water, permeated at a pressure of 1 kgf for a certain time, and the concentration of latex beads was measured to evaluate the fractionation performance .
  • Examples 1 to 3 of the present invention had a strength of 800 gf / L or more and a water permeability of 2,000 L / m 2 * kgf * h or more. Generally, as the content of polyisocyanate is increased, the strength is increased, but the space for forming pores is reduced and water permeability is lowered. In Example 2 of the present invention, the strength of 850 gf / 2,000 LMH. This is a result obtained by lengthening the residence time in comparison with Comparative Examples 8 and 9 and increasing the coagulation bath temperature from Comparative Example 7.
  • Comparative Examples 1 to 5 it was found that the composition of the spinning solution was out of the preferable content range of the present invention and the water permeability was lowered or the strength was remarkably lowered.
  • Comparative Example 6 PVDF: polyvinylidene fluoride, Mw: 300,000 to 500,000 used for producing a hollow fiber of the present invention was applied, and the water permeability was remarkably lowered.
  • Comparative Examples 1 and 2 it was found that the content of the polysulfone resin was less than the preferred content range of the present invention, the content of the organic solvent was more than the preferable content range of the present invention, and the strength and the 0.1 ⁇ m bead removal rate were lowered have. This is because the polysulfone-based resin content decreased, the organic solvent content increased, the strength of the pores in the hollow fiber increased, the strength decreased, and the average pore size increased to 0.1 ⁇ m or more.
  • Comparative Example 7 the water permeability and the strength were simultaneously lowered because the coagulation bath temperature was low.
  • Comparative Examples 8 to 9 since the retention time of the coagulation tank was short and the phase conversion was not properly performed, It can be seen that the transmittance is decreased.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne un film en fibres creuses à base de polysulfone comportant 20 à 25 % en poids d'une résine de polysulfone (A), 45 à 55 % en poids d'un solvant organique (B) et 30 à 35 % en poids d'un additif hydrophile (C), ledit film en fibres creuses présentant une structure spongieuse asymétrique, dans laquelle la taille des pores augmente sans interruption en allant d'une couche superficielle extérieure vers une couche superficielle intérieure, le rapport entre la taille des pores de la couche superficielle extérieure et celle de la couche superficielle intérieure variant de 1/10 à 1/10 000. L'invention concerne également un procédé de fabrication dudit film en fibres creuses à base de polysulfone comprenant les étapes consistant à préparer une solution non diluée de filage contenant une résine à base de polysulfone (A), un solvant organique (B) et un additif hydrophile (C) ; à préparer un coagulant interne ; à filer la solution non diluée de filage et le coagulant interne ; à former des pores ; et à procéder à un bobinage, l'étape de formation des pores étant achevée lorsque le temps de séjour total dans le bain de coagulation et le bain de lavage dépasse 90 secondes.
PCT/KR2012/000789 2011-03-18 2012-02-01 Film en fibres creuses à base de polysulfone présentant une très grande résistance et une très bonne perméabilité à l'eau, et son procédé de fabrication WO2012128470A2 (fr)

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KR1020110024302A KR101077954B1 (ko) 2011-03-18 2011-03-18 강도 및 수투과도가 우수한 폴리설폰계 중공사막 및 그 제조방법
KR10-2011-0024302 2011-03-18

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KR101483740B1 (ko) * 2013-06-04 2015-01-16 주식회사 에코니티 비대칭성 폴리비닐리덴플루오라이드 중공사막의 제조방법 및 이로부터 제조된 중공사막
KR102160309B1 (ko) * 2013-12-30 2020-09-25 도레이첨단소재 주식회사 이온 제거능이 우수한 중공사형 나노분리막 및 이의 제조방법
KR101763991B1 (ko) * 2014-09-22 2017-08-02 주식회사 휴비스워터 강도 및 수투과도가 향상된 중공사막 방사용 조성물 및 이를 이용한 중공사막의 제조방법
KR101665189B1 (ko) * 2014-10-02 2016-10-24 주식회사 휴비스워터 내화학성이 우수한 폴리설폰계 중공사막 및 이의 제조방법
KR101689440B1 (ko) * 2014-10-31 2016-12-23 주식회사 휴비스워터 건식 중공사막, 이의 제조방법 및 이를 포함하는 수처리 모듈
KR101723904B1 (ko) * 2014-11-05 2017-04-06 주식회사 휴비스워터 공정효율이 향상된 중공사막의 제조방법 및 방사설비
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