WO2012128470A2 - 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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WO2012128470A2
WO2012128470A2 PCT/KR2012/000789 KR2012000789W WO2012128470A2 WO 2012128470 A2 WO2012128470 A2 WO 2012128470A2 KR 2012000789 W KR2012000789 W KR 2012000789W WO 2012128470 A2 WO2012128470 A2 WO 2012128470A2
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Prior art keywords
polysulfone
hollow fiber
spinning
fiber membrane
industrial
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PCT/KR2012/000789
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English (en)
Korean (ko)
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WO2012128470A3 (fr
WO2012128470A4 (fr
WO2012128470A9 (fr
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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 hollow fiber membrane and a method for manufacturing the same, and more particularly, to a polysulfone-based hollow fiber membrane and a method of manufacturing the improved water permeability and strength.
  • Separation membrane refers to a material having a selective permeability to separate the undissolved particles from the fluid.
  • the membrane is divided into two types: flat membrane and hollow fiber membrane. Hollow fiber membranes are most used for water treatment because they have high filtration efficiency within the same volume.
  • Hollow fiber membranes can be classified into two types according to the manufacturing method, which can be broadly classified into nonsolvent induced phase preparation process (NIPS) method using non-solvent and thermally induced phase preparation process (TIPS) method manufactured using heat.
  • NIPS nonsolvent induced phase preparation process
  • TIPS thermally induced phase preparation process
  • the membrane prepared by the NIPS method can give a variety of changes to the spinning conditions to form a variety of structures, particularly asymmetrical structure of the membrane, it is easy to adjust the pore size by adding various additives, hydrophilization to the membrane There is an advantage to obtain a high water permeability by imparting, but generally has a disadvantage of weak strength.
  • the separator prepared by the TIPS method is generally the same structure on the outside and inside the surface of the separator, the high strength of the separator can be widely used mainly in the industry.
  • fluorine-based polymers have been introduced and applied to fluorine-based hollow fiber membranes having excellent strength.
  • the TIPS method has the advantage of obtaining high strength properties, but it is difficult to control pore size easily and difficult to solution hydrophobic and hydrophilic additives of fluorine-based polymers. Has a problem of falling.
  • the general characteristics required for hollow fiber membranes for water treatment are as follows. First of all, the characteristics affecting the separation function are appropriate porosity (number of empty holes) for the purpose of separation efficiency, uniform pore distribution for the purpose of improving the fractional accuracy, and optimum pore size to effectively separate the separation object. To be required. Next, as material properties, chemical resistance, chemical resistance, heat resistance, etc. to chemical treatment are required. In addition, there is a need for excellent mechanical strength and water permeability associated with operating costs to extend the service life due to characteristics affecting the driving ability.
  • Polysulfone hollow fiber membranes developed in the prior art have a high water permeability due to relatively hydrophilic material characteristics than fluorinated resins, but due to the low mechanical strength, periodic backwashing is required, which is problematic for industrial use. Is being used by.
  • vinylidene fluoride-based hollow fiber membranes which are fluorine-based resins having mechanical strength superior to those of polysulfone-based resins.
  • the moldability is not good, and because of the hydrophobicity, the water permeability is significantly low.
  • Korean Patent No. 129816 discloses a membrane manufacturing process in which a spinning nozzle is modified to use a triple nozzle, and a polymer solution composition and solidification rate are controlled to suppress macropores to enhance strength.
  • the triple nozzle has a disadvantage in that the manufacturing method is more complicated than a single nozzle, and the manufacturing cost is high due to supplementation of additional equipment.
  • the separator was made of only fine micropores without macropores by controlling the spinning conditions without changing the composition and ratio of the spinning solution or introducing additional processes. It can be seen that the permeability is not significantly superior to the conventional membrane.
  • the research group of the present inventors invented an industrial hollow fiber membrane which maintains excellent permeability by using a polysulfone polymer having good hydrophilicity and enhanced the weak mechanical strength of the conventional polysulfone 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 method for producing a polysulfone hollow fiber membrane having excellent strength and water permeability.
  • the present invention is 20 to 25% by weight of a polysulfone resin (A), 40 to 50% by weight of an organic solvent (B) and a hydrophilic additive (C) 30
  • a polysulfone hollow fiber membrane comprising 35% by weight, wherein the hollow fiber membrane is an asymmetric sponge structure in which the pore size is continuously increased 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: It provides a polysulfone hollow fiber membrane, characterized in that 10 to 1: 10000.
  • the polysulfone hollow fiber membrane has a strength of 800 gf / ⁇ or more and a water permeability of 2,000 L / m 2 * kgf * h.
  • the polysulfone resin (A) is polysulfone or polyisulfone
  • the organic solvent (B) is dimethyl acetamide (dimethylacetamide, DMAc), dimethyl formamide (DMF), Chloroform, N-methyl-2-pyrrolidone (NMP / N-Methyl-2-Pyrrolidone), dimethyl sulfoxide (Dimethylsulfoxide), and mixtures thereof
  • the hydrophilic additive C
  • Polyvinylpyrrolidone weight average molecular weight Mw: 15,000 to 90,000
  • polyethylene glycol Mw: 200 to 1,000
  • ethylene glycol ethylene glycol
  • methyl alcohol, glycerin polyvinyl alcohol
  • cellulose acetate polyvinyl alcohol
  • polyvinyl alcohol sodium chloride
  • lithium chloride lithium chloride
  • polypropylene And glycol castor oil
  • zinc chloride and mixtures thereof.
  • the present invention is prepared a spinning solution containing a polysulfone resin (A), an organic solvent (B), and a hydrophilic additive (C) Doing; Preparing an internal coagulating solution; Spinning the spinning stock solution and the internal coagulating solution through a double nozzle; Forming organic pores by phase-conversion with the nonsolvent in the coagulation bath and the cleaning bath by the organic solvent (B) and the hydrophilic additive (C); And a winding step, wherein the forming of the pores provides a method for producing a polysulfone-based hollow fiber membrane, wherein the total residence time in the coagulation bath and the cleaning bath is radiated in excess of 90 seconds.
  • a spinning solution containing a polysulfone resin (A), an organic solvent (B), and a hydrophilic additive (C) Doing; Preparing an internal coagulating solution; Spinning the spinning stock solution and the internal coagulating solution through a double nozzle; Forming organic pores by phase-conversion with the nonsolvent in
  • the residence time in the coagulation bath of the spinning step is characterized in that more than 15 seconds.
  • the coagulation bath temperature of the spinning step is characterized in that 50 to 70 °C.
  • the present invention provides a polysulfone hollow fiber membrane having an asymmetric sponge structure in which no pinholes or finger structures are formed and the pores of the inner surface layer are larger than the outer surface layer, and the hollow fiber membrane of the present invention has excellent water permeability and strength.
  • FIG. 3 is an electrophotograph obtained by magnifying a cross section of the hollow fiber membrane according to Example 2 with a scanning electron microscope 50 times.
  • FIG. 3 is an electrophotograph obtained by magnifying a cross section of the hollow fiber membrane according to Example 2 with a scanning electron microscope 50 times.
  • Figure 4 is an electrophotographic measurement of the inner surface of the hollow fiber membrane according to Example 2 magnified 90 times with a scanning electron microscope.
  • Example 5 is an electrophotographic image of an outer surface of a hollow fiber membrane according to Example 2, at 30,000 times magnification, measured by a scanning electron microscope.
  • FIG. 6 is an electrophotograph obtained by magnifying a cross section of a hollow fiber membrane according to Example 3 with a scanning electron microscope 400 times.
  • FIG. 6 is an electrophotograph obtained by magnifying a cross section of a hollow fiber membrane according to Example 3 with a scanning electron microscope 400 times.
  • FIG. 7 is an electrophotographic image of the inner surface of a hollow fiber membrane according to Example 3 at 90 times magnification with a scanning electron microscope.
  • Example 8 is an electrophotographic image of an outer surface of a hollow fiber membrane according to Example 3, at 30,000 times magnification, measured by a scanning electron microscope.
  • FIG. 9 is an electrophotograph obtained by magnifying a cross section of a hollow fiber membrane according to Comparative Example 7 with a scanning electron microscope.
  • 11 is an electrophotographic measurement of an outer surface of a hollow fiber membrane according to Comparative Example 7 magnified 30,000 times with a scanning electron microscope.
  • Polysulfone hollow fiber membrane of the present invention is a spinning solution containing 20 to 25% by weight of polysulfone resin (A), 40 to 50% by weight of an organic solvent (B), and 30 to 35% by weight of a hydrophilic additive (C) and It is a feature of the invention to be produced by spinning the internal coagulating solution.
  • polysulfone resin of the present invention polysulfone, polyethersulfon, and mixtures thereof may be used as the base resin.
  • Polysulfone resins have the advantages of excellent chemical resistance and heat resistance, wide pH range applied, and excellent solubility in organic solvents, making it easy to prepare a spinning solution (dope).
  • the polysulfone resin (A) is preferably included in 20 to 25% by weight relative to the total weight of the spinning solution.
  • the polysulfone resin is 20 wt% or less, the hollow fiber is not formed due to the low viscosity, and it is difficult to control the air gap, resulting in poor radioactivity.
  • the polysulfone resin is 25 wt% or more, the solubility in the spinning stock solution is decreased. May occur or the appearance may be uneven.
  • the organic solvent (B) of the present invention used to dissolve the polysulfone resin (A) is dimethyl acetamide (dimethylacetamide, DMAc), dimethyl formamide (DMF), chloroform, N-methyl-2- It is preferable to use one or more selected from the group consisting of pyrrolidone (N-Methyl-2-Pyrrolidone) and dimethyl sulfoxide (Dimethylsulfoxide).
  • the organic solvent is contained in 30 to 60% by weight, preferably 40 to 50% by weight relative to the total weight of the spinning solution.
  • the present invention includes a hydrophilic additive to impart hydrophilization or control the pore size to the hollow fiber to be produced.
  • the hydrophilic additive include polyvinylpyrrolidone (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, chloride Hydrophilic additives such as lithium, polypropylene glycol, castor oil, and zinc chloride.
  • the hydrophilic additives affect the pore formation and hydrophilicity of the hollow fiber and are closely related to the water permeability. More specifically, the hydrophilic additive present in the spinning solution during the stay in the coagulation bath after the spinning solution is discharged from the double-tubular nozzle may absorb the non-solvent of the coagulation bath, thereby facilitating phase inversion with the solvent of the spinning solution. In addition, the hydrophilic additive acts as a swelling agent to increase the pore size, or cross-linkage of the hydrophilic group in the polysulfone resin to increase the hydrophilicity of the hollow fiber.
  • the hydrophilic additive (C) is contained in 10 to 40% by weight, preferably 20 to 35% by weight relative to the total weight of the spinning solution.
  • the content of the hydrophilic additive (C) is less than 10% by weight, pores are not formed inside the hollow fiber, so that the water permeability is remarkably lowered. In particular, as illustrated in FIG. 9, a finger-like structure may be formed. Can be.
  • the large pores (Pin-Hole) is formed may be reduced durability and pressure resistance.
  • Method for producing a polysulfone 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; Spinning the spinning stock solution and the internal coagulating solution through a double nozzle; Forming organic pores by phase-conversion with the nonsolvent in the coagulation bath and the cleaning bath by the organic solvent (B) and the hydrophilic additive (C); And a winding step.
  • the polysulfone resin (A), the organic solvent (B), and the hydrophilic additive (C) are dissolved at a compounding temperature of 30 to 40 ° C. and a stirring speed of 80 to 120 rpm for 12 to 24 hours, and then -5 to Degassing under a vacuum of -1 kgf for 12 to 24 hours to remove bubbles in the spinning stock solution (DOPE).
  • DOPE spinning stock solution
  • the internal coagulation solution is used to form pores inside the hollow fiber membrane, and the solvent is dimethyl acetamide (DMAc), dimethyl formamide (DMF), chloroform, tetrahydrofuran, N in non-solvent water.
  • DMAc dimethyl acetamide
  • DMF dimethyl formamide
  • chloroform chloroform
  • tetrahydrofuran N in non-solvent water.
  • the blending ratio is formulated in an amount of 0 to 30% by weight, preferably 5 to 25% by weight, and 70 to 100% by weight, preferably 75 to 95% by weight, of an organic solvent.
  • the mixing temperature of the internal coagulation solution is 50 to 70 °C, the stirring speed is mixed for 12 to 24 hours at 80 to 120 rpm, and then degassed for 6 to 12 hours under a vacuum of -5 to -1 kgf bubbles in the core (Core) Remove it.
  • the spinning equipment used in the spinning step of the spinning stock solution and the internal coagulating solution is a spinning stock solution (Dope) and internal coagulating solution (Core) manufacturing tank, nozzle holder, primary coagulation tank, washing tank, winding tank, and the specimen after the spinning finish (Sample) is composed of a washing tank for removing the residual organic solvent, more specifically the spinning process schematic diagram of the present invention related to this is shown as an example in FIG.
  • the radiation source solution (Dope) and the internal coagulation solution (Core) production tank, nozzle holder process line to build a fruit system can be controlled and maintained in the temperature range of 25 to 200 °C.
  • the nozzle holder is manufactured to be movable up, down, left, and right to adjust an air gap between the nozzle and the coagulation bath.
  • the air gap is a section in which the primary phase change occurs, and the phase change is performed by exchanging the organic solvent in the atmospheric moisture and the radiation source solution.
  • the coagulation bath is installed with a multi-stage Gorod Roller in the coagulation bath to extend the phase change time to the place where the secondary phase conversion occurs to extend the residence time of the membrane.
  • the residence time can be adjusted by providing a multi-stage high roller in the cleaning tank.
  • the residence time of the coagulation bath is more than 10 seconds, preferably 15 seconds or more. If the residence time of the coagulation bath is less than 10 seconds, the secondary phase inversion is not sufficiently achieved, the pore formation is lowered and the water permeability falls.
  • the residence time of the washing tank is 80 seconds or more, preferably 90 seconds or more.
  • Retention step of the washing tank is a third phase conversion process and the washing of the internal coagulant is carried out in which the phase change of the spinning stock solution is not completed in the coagulation tank. If the residence time of the cleaning tank is less than 80 seconds, there is a problem that residual organic solvent remains because the washing of the additive and the internal coagulant is not complete.
  • 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 better the phase conversion and cleaning, but the longer the production process, the lower the productivity.
  • the hollow yarn is discharged by spinning the prepared spinning stock solution and the internal coagulating solution using a double-tubular nozzle, and a primary phase conversion is performed in an air gap. Secondary phase transitions are then made through the coagulation bath. After removing the additives and the residual organic solvent in the washing tank is transported to the take-up tank, the spinning process is completed.
  • the length of the air gap is 10 cm or less, preferably 1 to 5 cm. If the air gap exceeds 10 cm, the primary phase of the organic solvent in the atmospheric water vapor and DOPE is sufficient to increase the porosity and increase the water permeability, but the hollow fiber twist or single yarn Such as radioactivity may be lowered. On the other hand, if there is no air gap, the radioactivity is excellent, but since the second phase inversion is performed immediately without the first phase inversion, the porosity is lowered, which may cause a problem of decreasing the water permeability.
  • Phase conversion is the principle that the organic solvent and hydrophilization additive in the radiation source solution (DOPE) are taken out, and the voids are filled with the non-solvent in the external coagulation bath to form pores.
  • DOPE radiation source solution
  • the temperature of the external coagulation bath is excessively high, exceeding 70 °C, the atmospheric humidity is oversaturated, so that single yarns occur, the radioactivity may be lowered, or the working environment may be poor.
  • the permeation rate of the non-solvent refers to the rate at which the ultrapure water of the coagulation bath penetrates into the spinning solution
  • the permeation rate of the solvent refers to the speed at which the solvent inside the spinning solution flows out into the coagulation bath. That is, the sponge structure can be formed only if the ultrapure water of the coagulation bath rapidly penetrates into the spinning solution.
  • the higher the temperature of the coagulation bath the higher the permeation rate and the phase change rate is also increased.
  • the coagulation bath and the washing tank water is filled with water or a mixture of water and an organic solvent, the temperature is 30 to 80 °C, more preferably 50 Maintaining at from 70 to 70 °C is characterized by the invention.
  • the cross section of the hollow fiber for water treatment can be largely divided into a finger structure and a sponge structure.
  • FIG. 6 illustrates a finger structure.
  • the outermost layer skin layer
  • the water permeability is remarkably inferior. This is because it melts and forms large pores in the cross section, and thus the pressure resistance is weakened, and when the external surface leaks, contaminants pass through as they are and thus do not function as a separation membrane.
  • the sponge structure may be divided into a symmetric membrane structure and an asymmetric membrane structure
  • the symmetric membrane structure is a structure with the same pore size of the outer surface and the inner surface
  • the asymmetric membrane structure is a structure having a different pore size of the outer surface and the inner surface
  • It can be defined as. 3 illustrates a symmetric membrane structure as an example of a sponge structure.
  • the asymmetric membrane has the advantage of having a high channel resistance compared to the symmetric membrane with less flow resistance.
  • the cross-sectional structure is formed in a compact structure than the finger structure is excellent in pressure resistance and durability.
  • the inventor of the present invention produced a hollow fiber membrane having the following structural features by the above-mentioned manufacturing method.
  • the figure is a scanning electron micrograph showing the hollow fiber membrane of the present invention
  • the hollow fiber membrane of the present invention has a finger structure (Fig. 9) or macropores (Fig. 6) of the prior art ) Is not formed, and the pore size increases from the outer surface to the inner surface, and in particular, the pore size of the outermost thin layer among the inner surface layers is 2 to 200 ⁇ m, and has a very large structural feature.
  • a spinning solution was prepared by dissolving 20% by weight of polyisulfone (Mw: 30,000 to 70,000), 6.2% by weight of polyvinylpyrrolidone, 23.4% by weight of polyethylene glycol, 47.9% by weight of dimethyl acetamide, and 2.6% by weight of lithium chloride. . 90 wt% of dimethyl acetamide and 10 wt% of ultrapure water were stirred and dissolved to prepare an internal coagulation solution. The spinning stock solution and the internal coagulating solution were stirred at 100 rpm at 35 ° C. for 24 hours, and then degassed under vacuum of ⁇ 1 kgf for 24 hours to remove bubbles.
  • the temperature of the spinning stock solution was maintained at 35 ° C and the internal coagulating solution at 60 ° C. Spinning.
  • the spun hollow fiber was continuously passed through a 2 cm air gap, and then passed through a coagulation bath and a washing bath containing 70 ° C. ultrapure water, and then wound up in a winder.
  • the residence time of the coagulation bath was 20 seconds
  • the residence time of the cleaning bath was 90 seconds.
  • the hollow fiber wound on the winder was cut to a length of 1 m and immersed in a water bath containing 60 ° C. ultrapure water for 24 hours, and then dried in an 80 ° C. hot air dryer 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 spinning solution was prepared by dissolving 16% by weight of polyisulfone (Mw: 30,000 to 70,000), 7.5% by weight of polyvinylpyrrolidone, 13.5% by weight of polyethylene glycol, 61.8% by weight of dimethyl acetamide, and 1.2% by weight of lithium chloride. Except that was prepared in the hollow fiber specimens in the same manner as in Example 2.
  • a spinning stock solution was prepared by dissolving 13.7 wt% of polyisulfone (Mw: 30,000-70,000), 7.5 wt% of polyvinylpyrrolidone, 16.1 wt% of polyethylene glycol, 62.1 wt% of dimethyl acetamide, and 0.6 wt% of lithium chloride. Except that was prepared in the hollow fiber specimens in the same manner as in Example 2.
  • Hollow fiber specimens were prepared in the same manner as in Example 2 except that the temperature of the coagulation bath was 25 ° C.
  • Hollow fiber specimens were prepared in the same manner as in Example 2 except that the coagulation bath residence time was 10 seconds.
  • Hollow fiber specimens were prepared in the same manner as in Example 2 except that the coagulation bath residence time was 5 seconds.
  • Tensile tester Instron 5564 was used under the conditions of the initial sample length of 100 mm and the crosshead speed of 200 mm / min in an atmosphere of temperature 25 °C, 50% relative humidity. Curved grips are used to minimize damage to the bite points.
  • Water permeability Measure the amount of super pure water passed by applying a constant pressure to the unit area. At this time, ultrapure water was maintained at 25 ° C., and measured under an atmosphere of 25 ° C. and 50% relative humidity.
  • Average pore The average pore was measured by PMI's non-mercury capillary pressure gauge CF-1000 Porometer (AEL, USA) by the half-dry method according to ASTM F316-03. Perfluoropolyester (brand name: Galwick) was used for the test solution.
  • Fractional performance (0.1 ⁇ m Bead removal rate): 0.1 ⁇ m diameter latex beads (Latex Beads) are diluted in 100 ppm of ultrapure water, permeated at a pressure of 1 kgf for a certain time, and the concentration of latex beads is measured to evaluate the fractional performance. .
  • Examples 1 to 3 of the present invention have a strength of 800 gf / gf or more, and at the same time, a water permeability of 2,000 L / m 2 * kgf * h or more.
  • the strength increases, but the water permeability decreases due to a decrease in the space for forming pores.
  • Example 2 of the present invention the same strength as in Example 1 is maintained while maintaining the strength of 850 gf / ⁇ . It has a high water permeability of 2,000 LMH. This is a result obtained by lengthening the residence time in comparison with Comparative Examples 8 and 9 and making the coagulation bath temperature higher than Comparative Example 7.
  • Comparative Examples 1 to 5 the composition of the spinning solution is out of the preferred content range of the present invention can be seen that the water permeability is lowered or the strength is significantly reduced
  • Comparative Example 6 is a polysulfone resin dash conventional as a base resin Polyvinylidene fluoride (PVDF: 300,000 to 500,000) used for the production of hollow fiber was applied, and the water permeability was remarkably reduced.
  • the content of the polysulfone-based resin was less than the preferred content range of the present invention, and the content of the organic solvent was more than the preferred content range of the present invention, indicating that the strength and the removal rate of 0.1 ⁇ m were lowered. have.
  • Comparative Example 7 can be seen that the water permeability and strength at the same time due to the low coagulation bath temperature, Comparative Examples 8 to 9 are poor pore formation due to poor pore formation because the residence time of the coagulation bath is short It can be seen that the transmittance is reduced.

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

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WO2012128470A4 WO2012128470A4 (fr) 2013-01-03
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CN105555393A (zh) * 2013-06-04 2016-05-04 爱科利态株式会社 制造不对称聚偏二氟乙烯中空纤维膜的方法及由其制造的中空纤维膜
CN113877443A (zh) * 2021-11-05 2022-01-04 无锡达魔材料科技有限公司 一种制备表皮致密层无缺陷的具有非对称结构的中空纤维膜纺丝工艺
CN114653219A (zh) * 2022-04-22 2022-06-24 佛山市美的清湖净水设备有限公司 制备铸膜液的方法、用于制备超滤膜的铸膜液、超滤膜
CN115400616A (zh) * 2022-11-01 2022-11-29 富海(东营)新材料科技有限公司 连续一体化聚砜中空纤维膜的制备工艺及其系统
CN115814621A (zh) * 2022-12-26 2023-03-21 有研资源环境技术研究院(北京)有限公司 一种高强度亲水型中空纤维膜及其制备方法和应用

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CN105555393A (zh) * 2013-06-04 2016-05-04 爱科利态株式会社 制造不对称聚偏二氟乙烯中空纤维膜的方法及由其制造的中空纤维膜
CN105555393B (zh) * 2013-06-04 2017-09-05 爱科利态株式会社 制造不对称聚偏二氟乙烯中空纤维膜的方法及由其制造的中空纤维膜
CN113877443A (zh) * 2021-11-05 2022-01-04 无锡达魔材料科技有限公司 一种制备表皮致密层无缺陷的具有非对称结构的中空纤维膜纺丝工艺
CN113877443B (zh) * 2021-11-05 2024-01-26 无锡达魔材料科技有限公司 一种制备表皮致密层无缺陷的具有非对称结构的气体分离用中空纤维膜纺丝方法
CN114653219A (zh) * 2022-04-22 2022-06-24 佛山市美的清湖净水设备有限公司 制备铸膜液的方法、用于制备超滤膜的铸膜液、超滤膜
CN115400616A (zh) * 2022-11-01 2022-11-29 富海(东营)新材料科技有限公司 连续一体化聚砜中空纤维膜的制备工艺及其系统
CN115814621A (zh) * 2022-12-26 2023-03-21 有研资源环境技术研究院(北京)有限公司 一种高强度亲水型中空纤维膜及其制备方法和应用
CN115814621B (zh) * 2022-12-26 2023-08-29 有研资源环境技术研究院(北京)有限公司 一种高强度亲水型中空纤维膜及其制备方法和应用

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