WO2020066521A1 - Membrane composite semi-perméable et son procédé de fabrication - Google Patents

Membrane composite semi-perméable et son procédé de fabrication Download PDF

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Publication number
WO2020066521A1
WO2020066521A1 PCT/JP2019/034876 JP2019034876W WO2020066521A1 WO 2020066521 A1 WO2020066521 A1 WO 2020066521A1 JP 2019034876 W JP2019034876 W JP 2019034876W WO 2020066521 A1 WO2020066521 A1 WO 2020066521A1
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Prior art keywords
copolymer
weight
composite semipermeable
semipermeable membrane
porous support
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PCT/JP2019/034876
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English (en)
Japanese (ja)
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清彦 高谷
修治 古野
芳機 西口
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東レ株式会社
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Priority to JP2019548761A priority Critical patent/JPWO2020066521A1/ja
Publication of WO2020066521A1 publication Critical patent/WO2020066521A1/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
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/28—Polymers of vinyl aromatic compounds
    • 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
    • B01D71/28—Polymers of vinyl aromatic compounds
    • B01D71/281—Polystyrene
    • 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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • 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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B01D71/421—Polyacrylonitrile

Definitions

  • the present invention relates to a composite semipermeable membrane useful for selective separation of a liquid mixture and a method for producing the same.
  • the composite semipermeable membrane obtained by the present invention can be suitably used for, for example, desalination of brine and purification of tap water.
  • the membrane used in the membrane separation method includes a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, and the like. These membranes are used, for example, for obtaining drinking water from seawater, brackish water, water containing harmful substances, and for producing industrial ultrapure water, wastewater treatment, recovering valuable resources, and purifying tap water. I have.
  • Patent Literature 1 discloses a composite semipermeable membrane including a support membrane including a base material and a porous support, and a separation functional layer provided on the porous support. Further, as a thermoplastic resin contained in the porous support, polysulfone, polyacrylamide, polyethersulfone, cellulose ester, polyacrylonitrile, polyvinyl chloride and the like are disclosed. Patent Document 2 discloses a copolymer based on polyacrylonitrile as a material for a support.
  • the present inventors studied a copolymer of a vinyl cyanide-based monomer and an aromatic vinyl-based monomer as a material for a porous support, and in the present invention, an object of the present invention is to improve the water permeability.
  • a composite semipermeable membrane comprising a support film having a substrate and a porous support on the substrate, and a separation functional layer on the porous support, wherein the porous support is cyan.
  • Composite semi-permeable material containing a copolymer of a vinyl chloride-based monomer and an aromatic vinyl-based monomer, and having a pore volume having a radius of 10.6 nm or more and 93.5 nm or less of 0.100 cm 3 / g or more. film.
  • a method for producing a composite semipermeable membrane comprising: [8] The production method according to [7], wherein the good solvent is dimethyl sulfoxide. [9] The method according to [7] or [8], wherein the copolymer is a copolymer of acrylonitrile and styrene.
  • the composite semipermeable membrane has high water permeability (permeation flow rate: Flux).
  • FIG. 1 is a cross-sectional photograph of the porous support of Example 4 observed at a magnification of 30,000 by a scanning electron microscope (SEM).
  • FIG. 2 is a cross-sectional photograph of Comparative Example 1 observed at a magnification of 30,000 by SEM.
  • the composite semipermeable membrane according to the present invention comprises a support membrane having a substrate and a porous support disposed on the substrate, and a separation functional layer disposed on the porous support.
  • the separation function layer has substantially separation performance
  • the support membrane has substantially no separation performance of ions and the like, and can provide strength to the separation function layer.
  • the support film has a substrate and a porous support disposed on the substrate.
  • Base Material examples include a polyester polymer, a polyamide polymer, a polyolefin polymer, and a mixture or copolymer thereof. Above all, a polyester polymer cloth having high mechanical and thermal stability is particularly preferable.
  • a long-fiber nonwoven fabric, a short-fiber nonwoven fabric, or a woven or knitted fabric can be preferably used.
  • the long fiber nonwoven fabric refers to a nonwoven fabric having an average fiber length of 300 mm or more and an average fiber diameter of 3 to 30 ⁇ m.
  • the substrate preferably has an air permeability of 0.5 cc / cm 2 / sec or more and 5.0 cc / cm 2 / sec.
  • the air permeability of the base material is within the above range, the polymer solution serving as the porous support impregnates the base material, so that the adhesiveness with the base material is improved and the physical stability of the support film is increased. be able to.
  • the air permeability can be measured by a Frazier-type tester based on JIS L1096 (2010). For example, a base material is cut out to a size of 200 mm ⁇ 200 mm to obtain a sample. This sample was mounted on a Frazier tester, and the suction fan and air holes were adjusted so that the pressure of the inclined barometer was 125 Pa. Based on the pressure indicated by the vertical barometer and the type of air holes used, It is possible to calculate the amount of air passing through the material, that is, the air permeability. As the Frazier-type testing machine, KES-F8-AP1 manufactured by Kato Tech Co., Ltd. can be used.
  • the thickness of the substrate is preferably 20 ⁇ m or more, more preferably 40 ⁇ m or more, and preferably 200 ⁇ m or less, more preferably 120 ⁇ m or less.
  • the thickness of the substrate can be measured with a dial thickness gauge or a digital thickness gauge.
  • a dial thickness gauge or a digital thickness gauge products of PEACACK of Ozaki Seisakusho Co., Ltd. or Teklock Co., Ltd. can be used.
  • a dial thickness gauge or a digital thickness gauge is used, the thickness is measured at any 20 locations, the arithmetic average thereof is calculated, and the arithmetic average is used as the thickness of the base material.
  • the thickness may be measured with an optical microscope or a scanning electron microscope.
  • the porous support includes a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer (that is, a vinyl copolymer).
  • the porous support is preferably made of a thermoplastic resin.
  • the thermoplastic resin is a resin that is made of a chain-like polymer material and has a property of being deformed or flowed by an external force when heated.
  • the pore volume V of the porous support is preferably 0.100 cm 3 / g or more. When the pore volume V is in this range, high water permeability can be obtained.
  • the pores in the pore volume V mean pores having a radius of 10.6 nm to 93.5 nm, and the pore volume V is calculated by the following equation (1).
  • Pore volume V (total volume V1 of pores having a radius of 10.6 nm to 93.5 nm) / (weight of porous support Wp / weight of composite semipermeable membrane Wc) (1)
  • the total volume V1 can be determined by the gas adsorption method as follows. Specifically, the composite semipermeable membrane cut into a predetermined area is thoroughly washed with warm water and air-dried at room temperature. After air drying, it is further dried in a vacuum dryer. The sample after vacuum drying is cut into a 2 mm square and filled in a glass tube. For the sample in the glass tube, the adsorption isotherm of nitrogen gas is measured by a constant volume gas adsorption method using a pore distribution measuring device. By analyzing the nitrogen gas adsorption isotherm data obtained by the measurement by the BJH method (Barrett-Joyner-Halenda), the volume of the pores corresponding to the radius is obtained.
  • BJH method Barrett-Joyner-Halenda
  • the total volume V1 of the pores having a radius of 10.6 nm to 93.5 nm is obtained.
  • a high-precision specific surface area / pore distribution measuring device BELSORP-mini II manufactured by Microtrac BEL can be used.
  • the obtained volume V1 is the value per unit weight of the sample, that is, the unit weight of the composite semipermeable membrane.
  • pores having a radius of 10.6 nm or more and 93.5 nm or less are localized in the porous support. Therefore, as shown in the above formula (1), by dividing the volume V1 by the ratio of the weight of the porous support to the weight of the sample subjected to the gas adsorption method, the weight other than the porous support (particularly the weight of the base material) is obtained. Correction to remove the effect of
  • the weight Wp of the porous support and the weight Wc of the composite semipermeable membrane can be determined by the following method.
  • the composite semipermeable membrane cut into a predetermined area is thoroughly washed with warm water and air-dried at room temperature. After air-drying, it is completely dried with a vacuum dryer. The weight after drying (that is, the weight Wc of the composite semipermeable membrane) is measured.
  • the composite semipermeable membrane is brought into contact with a solvent that dissolves the porous support. Examples of the solvent include acetone and the like. Thereby, the porous support is dissolved, and the separation functional layer is dispersed in the solvent without being dissolved in the solvent.
  • the substrate keeps its shape, the substrate is extracted from the solvent. After the extracted substrate is thoroughly washed with a solvent, the substrate is subjected to air drying and vacuum drying, and the weight Ws of the substrate is measured.
  • the separation functional layer can be separated from the solvent in which the porous support is dissolved. After the filtrate is thoroughly washed with a solvent, it is subjected to air drying and vacuum drying, and then the weight Wf of the separation functional layer is measured.
  • the weight Wf of the separation function layer is very small compared to the weight (Wp + Ws) of the support membrane and is about 0.05 to 0.25% by weight in the composite semipermeable membrane, and may be ignored.
  • the measurement of the weight of the separation function layer can be omitted. That is, the value obtained by subtracting the weight Ws of the substrate from the weight Wc of the composite semipermeable membrane may be applied to the formula (1) as the weight Wp of the porous support.
  • FIG. 1 shows a cross-sectional photograph of the porous support of Example 4 of the present invention observed at 30,000 ⁇ by SEM, and the porous support of Comparative Example 1 at the same magnification as a comparative object.
  • 2 is shown in FIG. 1 and 2, a shown by an arrow indicates the surface of the porous support, b shows a pore structure, and c shows a void.
  • a hole having a major axis of 1 ⁇ m or more is called a void.
  • a portion surrounding the void, that is, a portion having small holes is referred to as a “pore structure” for convenience of description.
  • the pores included in the pore structure b are small and the number of pores is large. This corresponds to the pore volume V satisfying the above range.
  • Such a structure has high continuity (communication) by connecting pores.
  • many pores are also found on the wall of the void c, and high communication is also seen between the void and the pore.
  • the holes other than the void c are relatively large and the number of holes is small as compared with FIG. In the structure of FIG. 2, the number of holes in the wall of the void c is small.
  • the separation functional layer is formed by interfacial polycondensation between a polyfunctional amine aqueous solution and a polyfunctional acidic halide solution.
  • polycondensation proceeds by supplying the polyfunctional amine impregnated in the support film to the interface between the solutions. Since the space (pores, voids) in the porous support is a path for supplying the polyfunctional amine to the polymerization site, the polyfunctional amine is sufficiently supplied due to the high communicability, and the folds in the separation functional layer are provided. It is thought that it can grow greatly.
  • the pore volume V is 0.120cm 3 / g or more, further preferably 0.200 cm 3 / g or more. Further, the pore volume V is preferably 0.350 cm 3 / g or less. When it is 0.350 cm 3 / g or less, good pressure resistance can be obtained.
  • the ratio of the cyano group to the benzene ring in the porous support that is, the ratio of the cyano group is preferably 1.50 or less, more preferably 1.35 or less, and even more preferably 1.10 or less. Further, the cyano group ratio is preferably 0.20 or more.
  • the cyano group ratio is preferably 1.50 or less, the water permeability of the composite semipermeable membrane can be improved. It is not clear why the water permeation performance is improved, but the low ratio of cyano groups increases the hydrophobicity of the porous support, and the polyfunctional amine is sufficiently supplied during the formation of the separation functional layer by interfacial polycondensation. This is considered to be due to the fact that the folds in the separation function layer grow large.
  • the cyano group ratio can be determined by the following method. First, the support membrane or the composite semipermeable membrane cut into a predetermined area is washed with warm water and air-dried at room temperature. Next, only the porous support is dissolved by contacting with acetone, and the obtained solution is filtered through a metal mesh (wire diameter 0.03 mm, 300 mesh) to remove the substrate and the separation function layer. Subsequently, acetone is removed from the obtained filtrate using an evaporator or the like to obtain an insoluble matter. After that, the insoluble material was dissolved again in acetone so as to have a concentration of about 10% by weight, and the obtained solution was applied on a glass substrate to a thickness of 15 mil (381 ⁇ m) using an applicator.
  • a metal mesh wire diameter 0.03 mm, 300 mesh
  • a film-like sample is obtained by allowing the sample to stand for 12 hours or more in the atmosphere described above.
  • the obtained sample was dried in a vacuum dryer at 60 ° C. for 5 hours to completely remove acetone, and the dried sample (porous support) was subjected to absorbance analysis using a Fourier transform infrared spectrophotometer (FT-IR). (Transmission method).
  • FT-IR Fourier transform infrared spectrophotometer
  • vinyl cyanide-based monomer examples include acrylonitrile, methacrylonitrile, etaacrylonitrile, and the like. Acrylonitrile is particularly preferred as the vinyl cyanide monomer.
  • the vinyl cyanide-based monomer contained in the copolymer may be one type or two or more types.
  • aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, and o, p-dichlorostyrene. Is mentioned. Styrene and ⁇ -methylstyrene are particularly preferred as the aromatic vinyl monomer, and styrene is more preferred.
  • the aromatic vinyl monomer contained in the copolymer may be one kind or two or more kinds.
  • the copolymer of the vinyl cyanide monomer and the aromatic vinyl monomer is more preferably a copolymer of acrylonitrile and styrene.
  • the proportion of the vinyl cyanide monomer in the vinyl monomer constituting the vinyl copolymer is preferably 10% by weight or more, more preferably 15% by weight or more, even more preferably 18% by weight or more. Further, the ratio is preferably 30% by weight or less, more preferably 28% by weight or less. When the proportion is 10% by weight or more, the moldability of the porous support is improved. Further, when the above ratio is 30% by weight or less, the cyano group ratio can be 1.50 or less.
  • the ratio of the aromatic vinyl monomer in the vinyl monomer constituting the vinyl copolymer is preferably 70% by weight or more, more preferably 72% by weight or more. Further, the ratio is preferably 90% by weight or less, more preferably 85% by weight or less, and still more preferably 82% by weight or less.
  • the proportion of the aromatic vinyl monomer is 70% by weight or more, the porous support and the separation functional layer are firmly adhered to each other, so that the occurrence of defects is suppressed.
  • the weight-average molecular weight (Mw) of the tetrahydrofuran (THF) -soluble component in the porous support is determined based on the copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer contained in the porous support. It has the same value as the weight average molecular weight (Mw).
  • the value of the weight average molecular weight (Mw) is preferably 180,000 or more, more preferably 220,000 or more, and still more preferably 320,000 or more. When Mw is 180,000 or more, the pore volume of the porous support can be increased, and the pressure resistance of the porous support can be improved. Further, Mw is preferably 1,000,000 or less. By setting Mw to 1,000,000 or less, the moldability of the porous support is improved.
  • the weight average molecular weight (Mw) of the THF-soluble component in the porous support can be measured by the following method. First, the support membrane or the composite semipermeable membrane cut into a predetermined area is thoroughly washed with warm water and air-dried at room temperature. Next, only the porous support is dissolved by contacting with THF, and the obtained solution is filtered through a metal mesh (wire diameter: 0.03 mm, mesh: 300, manufactured by Kansai Wire Mesh Co., Ltd.) to separate the substrate and the substrate. The functional layer is removed. Subsequently, the obtained filtrate is centrifuged at 8,800 rpm (10,000 G or more) for 40 minutes, and the supernatant is collected. The obtained supernatant is measured by gel permeation chromatography (GPC) using THF as a solvent and polystyrene as a standard substance to determine a weight average molecular weight.
  • GPC gel permeation chromatography
  • the thickness of the porous support is preferably 10 ⁇ m or more and 100 ⁇ m or less. If it is less than 10 ⁇ m, the substrate may be exposed and a defect may occur. If it exceeds 100 ⁇ m, the water permeability may decrease due to the resistance due to the thickness of the porous support.
  • the thickness of the porous support is determined by the type of solvent used to dissolve the materials used in forming the porous support, the viscosity of the solution containing the materials, the concentration of the materials in the solution, the coagulation bath temperature, and the thickness of the solution applied to the substrate. Can be controlled by
  • the thickness of the porous support can be measured by cross-sectional observation using a scanning electron microscope (SEM) or an optical microscope.
  • SEM scanning electron microscope
  • the composite semipermeable membrane or the supporting membrane is cut by a freeze splitting method to prepare a section sample, and the section sample is observed with a SEM at a magnification of 100 to 500 times.
  • the thickness at any 10 points is measured using a scale or calipers.
  • the thickness at 10 locations at 10 ⁇ m intervals In the direction perpendicular to the thickness direction of the film (in the direction of the surface of the film), it is preferable to measure the thickness at 10 locations at 10 ⁇ m intervals. The same operation is performed on five section samples, and the arithmetic mean of 50 pieces of data is calculated to be the thickness of the porous support.
  • the sample Before observation by SEM, the sample is thinly coated with platinum or platinum-palladium or ruthenium tetroxide.
  • SEM an S-5500 scanning electron microscope manufactured by Hitachi High-Technologies Corporation can be used, and observation is performed at an acceleration voltage of 3 to 6 kV.
  • the thickness of the support film and the porous support can also be measured with a dial thickness gauge or a digital thickness gauge as in the case of the substrate. Since the thickness of the separation functional layer is very thin compared to the base material and the porous support, the thickness of the composite semipermeable membrane can be regarded as the total thickness of the base material and the porous support (the thickness of the support film). it can. Therefore, the thickness of the porous support can be easily calculated by measuring the thickness of the composite semipermeable membrane with a dial thickness gauge or a digital thickness gauge and subtracting the thickness of the substrate from the thickness of the composite semipermeable membrane. it can. When a dial thickness gauge or a digital thickness gauge is used, the thickness is measured at any 20 locations, and the arithmetic mean thereof is calculated.
  • the thickness of the support membrane affects the strength of the composite semipermeable membrane and the packing density when it is used as an element.
  • the total thickness of the support film is preferably 30 ⁇ m or more, more preferably 80 ⁇ m or more, and preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less.
  • the pure water permeability coefficient of the support membrane at 25 ° C. is preferably 0.8 ⁇ 10 ⁇ 9 m 3 / m 2 ⁇ s ⁇ Pa or more.
  • the separation function layer has a thin film mainly composed of polyamide obtained by a polycondensation reaction between a polyfunctional amine and a polyfunctional acid halide.
  • the main component refers to a component that accounts for 50% by mass or more of the components of the separation function layer.
  • the ratio occupied by the polyamide in the separation function layer may be 90% by mass or more, or the separation function layer may be composed of only the polyamide.
  • the separation functional layer can be formed by interfacial polycondensation between a polyfunctional amine and a polyfunctional acid halide.
  • a polyfunctional amine and a polyfunctional acid halide it is preferable that at least one of the polyfunctional amine and the polyfunctional acid halide contains a compound having three or more functional groups.
  • the polyfunctional amine means an amine having at least two amino groups of at least one of a primary amino group and a secondary amino group in one molecule.
  • Polyfunctional aromatic amine 1,3,5-triaminobenzene, 1,2,4-triaminoben Emissions, 3,5-diaminobenzoic acid, 3-amino-benzylamine, such a polyfunctional aromatic amines such as 4-aminobenzyl amine.
  • piperazine, m-phenylenediamine, p-phenylenediamine, 1,3,5-triaminobenzene, and 2-methylpiperazine are preferably used in consideration of the selective separation property, permeability and heat resistance of the membrane.
  • These polyfunctional amines may be used alone or in combination of two or more.
  • the polyfunctional acid halide refers to an acid halide having at least two carbonyl halide groups in one molecule.
  • trifunctional acid halides include trimesic acid chloride, 1,3,5-cyclohexanetricarboxylic acid trichloride, 1,2,4-cyclobutanetricarboxylic acid trichloride and the like.
  • Bifunctional dicarboxylic acid halides include biphenyldicarboxylic acid Aromatic difunctional acid halides such as acid dichloride, azobenzene dicarboxylic dichloride, terephthalic acid chloride, isophthalic acid chloride, naphthalene dicarboxylic acid chloride, etc., aliphatic bifunctional acid halides such as adipoyl chloride, sebacoyl chloride, cyclopentane Alicyclic difunctional acid halides such as dicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, tetrahydrofurandicarboxylic acid dichloride and the like can be mentioned.
  • the polyfunctional acid halide is preferably a polyfunctional aromatic acid chloride. It is preferably a polyfunctional aromatic acid chloride having 2 to 4 carbonyl chloride groups. Among these, trimesic acid chloride, terephthalic acid chloride, and isophthalic acid chloride are more preferable from the viewpoint of availability and ease of handling. These polyfunctional aromatic acid halides may be used alone or in combination of two or more.
  • the thickness of the separation function layer is preferably at least 0.01 ⁇ m, more preferably at least 0.1 ⁇ m. Further, the thickness is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less.
  • the pore size of the separation function layer is 2 nm or less, preferably 1 nm or less.
  • a method for manufacturing a composite semipermeable membrane will be described.
  • the manufacturing method includes a step of forming a support film and a step of forming a separation functional layer.
  • the composite semipermeable membrane of the present invention is not limited to the manufacturing method and the method for forming each layer described in this document.
  • the method for producing a composite semipermeable membrane includes the following steps (a) to (c).
  • (A) a step of disposing a solution in which a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer is dissolved in a good solvent, on a substrate; (B) a step of obtaining a porous support of the copolymer by contacting the solution with a coagulation bath containing a non-solvent of the copolymer; (C) a step of forming a separation functional layer on the porous support. Details of the manufacturing method including the steps represented by (a) to (c) will be described below, divided into a support film forming step and a separation function layer forming step.
  • the support film forming step includes the above steps (a) and (b).
  • the chemical structure of the copolymer in the above step (a) is as described above.
  • the concentration of the copolymer in the solution in the above step (a) is preferably 10% by weight or more, more preferably 14% by weight or more. Further, the copolymer concentration is preferably 25% by weight or less, more preferably 22% by weight or less. When the copolymer concentration is 10% by weight or more and 25% by weight or less, a support film having a strength that can be practically used is obtained.
  • the solvent that dissolves the copolymer is a good solvent for the copolymer, and has a polarity parameter dP of the Hansen solubility parameter of 11.0 or more and 17.0 or less and a hydrogen bond term dH of 7.0 or more and 12.0 or less. Is preferred.
  • the good solvent for the copolymer is one that dissolves the copolymer. Examples of the solvent include N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), dimethylacetamide (DMAC), dimethylformamide (DMF), ⁇ -butyrolactone (GBL), and dimethylsulfoxide is preferable.
  • a solvent in which the polarity term dP of the Hansen solubility parameter is 11.0 or more and 17.0 or less and the hydrogen bond term dH is 7.0 or more and 12.0 or less by mixing these solvents may be used.
  • DMSO, a mixed solvent of DMSO and DMF, and a mixed solvent of DMSO and GBL are preferable.
  • the pore volume of the porous support can be increased.
  • the ratio of DMSO is preferably set to 80% by weight or more.
  • the weight average molecular weight Mw of the copolymer is 220,000 or more and 1,000,000 or less;
  • the good solvent contains dimethyl sulfoxide (DMSO), It is preferable that at least one of the above is satisfied, and it is more preferable that both are satisfied.
  • DMSO dimethyl sulfoxide
  • the copolymer solution may contain an additive for adjusting the pore size, porosity, hydrophilicity, elastic modulus, etc. of the porous support.
  • additives for adjusting the pore size and porosity include water, alcohols, water-soluble polymers such as polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, and polyacrylic acid or salts thereof, and further include lithium chloride, sodium chloride, and chloride. Examples thereof include inorganic salts such as calcium and lithium nitrate, and formamide, but are not limited thereto.
  • Various surfactants can be used as additives for adjusting hydrophilicity and elastic modulus. By mixing these materials, a solution of the copolymer can be prepared.
  • a spin coater for example, a spin coater, a flow coater, a roll coater, a spray, a comma coater, a bar coater, a gravure coater, a slit die coater, or the like can be used.
  • the temperature of the solution at the time of coating the copolymer solution is preferably in the range of 5 to 60 ° C, more preferably 10 ° C or higher, and more preferably 40 ° C or lower. Within this range, the organic solvent solution of the copolymer is sufficiently impregnated into the space between the fibers of the substrate without being precipitated, and then solidified. As a result, it is possible to obtain a support film in which the porous support is firmly bonded to the substrate by the anchor effect.
  • the base material is impregnated with the copolymer solution.
  • the impregnation of the base material with the copolymer solution generation of defects can be suppressed.
  • the viscosity may be adjusted by controlling the temperature or concentration of the solution, and these conditions may be combined.
  • the time from application of the copolymer solution on the substrate to immersion in the coagulation bath is preferably in the range of usually 0.1 to 10 seconds.
  • the time until immersion in the coagulation bath is within this range, the copolymer solution is sufficiently impregnated between the fibers of the base material and then solidified.
  • the preferred range of the time until immersion in the coagulation bath may be adjusted according to the viscosity of the copolymer solution used.
  • the coagulation bath contains a non-solvent having a lower solubility than the good solvent for the copolymer.
  • Non-solvents include, for example, pure water, hexane, pentane, benzene, toluene, methanol, ethanol, trichloroethylene, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, low molecular weight polyethylene glycol And the like, aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic alcohols, and mixed solvents thereof. Generally, pure water is used.
  • the temperature of the coagulation bath is preferably ⁇ 20 ° C. or higher, more preferably 0 ° C. or higher, and is preferably 50 ° C. or lower, more preferably 40 ° C. or lower.
  • the temperature is preferably ⁇ 20 ° C. or higher, more preferably 0 ° C. or higher, and is preferably 50 ° C. or lower, more preferably 40 ° C. or lower.
  • the support membrane obtained above is washed with pure water to remove the solvent remaining in the support membrane.
  • the temperature of the pure water at this time is preferably 25 to 80 ° C.
  • a method for producing the copolymer constituting the porous support will be described.
  • a method for producing the vinyl copolymer it can be produced by any polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization. Two or more of these may be combined. There are no particular restrictions on the method of charging each monomer.Initial batch charging, or continuous or divided charging and polymerization of part or all of the charged monomers in order to know the composition distribution of the copolymer. You may.
  • the suspension polymerization method or the bulk polymerization method is preferred, and the suspension polymerization method is most preferred in view of the ease of polymerization control and the ease of post-treatment.
  • suspension stabilizer used for suspension polymerization examples include inorganic suspension stabilizers such as clay, barium sulfate, and magnesium hydroxide, and organic solvents such as polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, and methyl methacrylate / acrylamide copolymer. And a suspension stabilizer. Two or more of these may be used. Among these, an organic suspension stabilizer is preferable in terms of thermal coloring stability at the time of melting, and a methyl methacrylate / acrylamide copolymer is more preferable.
  • the initiator used for the polymerization is not particularly limited, and a peroxide, an azo compound or a persulfate is used.
  • peroxide examples include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butylperoxyacetate, t-butylperoxybenzoate, t-butyl isopropyl carbonate, di-t-butyl peroxide, t-butyl peroctate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t -Butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexanoate and the like.
  • azo compound examples include azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propylazo Formamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 1-t-butylazo-2 -Cyanobutane, 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane and the like.
  • persulfate examples include potassium persulfate, sodium persulfate, ammonium persulfate and the like.
  • the initiator can also be used in a redox system.
  • the polymerization temperature is not particularly limited, but from the viewpoint that the weight average molecular weight of the vinyl copolymer is easily adjusted to the above range, from the viewpoint of suspension stability.
  • the polymerization is started at 60 to 80 ° C., and when the degree of polymerization reaches 50 to 70%, the temperature is raised, and finally the temperature is preferably 100 to 120 ° C.
  • the weight average molecular weight of the vinyl copolymer can be easily adjusted by using the above-mentioned initiator and chain transfer agent, and setting the polymerization temperature in the above-mentioned preferable range.
  • chain transfer agent examples include mercaptans such as n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, and terpenes such as terpinolene. Two or more of these may be used. Of these, n-octyl mercaptan and t-dodecyl mercaptan are preferably used.
  • Step of Forming Separation Function Layer an aqueous solution containing the above-described polyfunctional amine and an organic solvent immiscible with water containing the polyfunctional acid halide are mentioned.
  • the polyamide skeleton can be formed by performing interfacial polycondensation on the surface of the support film using a solution.
  • the concentration of the polyfunctional amine in the aqueous polyfunctional amine solution is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and preferably 15% by weight or less, more preferably 10% by weight. It is as follows. Within this range, sufficient water permeability and solute removal performance can be obtained.
  • additives such as a surfactant, an alkaline compound, an acylation catalyst, and an antioxidant are added. be able to.
  • surfactant for example, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium lauryl sulfate and the like can be mentioned.
  • alkaline compound examples include sodium hydroxide, trisodium phosphate, triethylamine and the like.
  • the above-mentioned aqueous solution of a polyfunctional amine is brought into contact with the support membrane.
  • the contact is preferably performed uniformly and continuously on the surface of the support film.
  • a method of coating a polyfunctional amine aqueous solution on a support film or a method of dipping the support film in a polyfunctional amine aqueous solution can be used.
  • the contact time between the support membrane and the aqueous polyfunctional amine solution is preferably 1 second or more, more preferably 3 seconds or more, and preferably 10 minutes or less, more preferably 3 minutes or less.
  • Examples of the draining method include a method in which the support film after contact with the polyfunctional amine aqueous solution is vertically held and an excessive aqueous solution flows naturally, or a gas stream such as nitrogen is blown from an air nozzle to forcibly remove the liquid. A cutting method or the like can be used. After draining, the film surface may be dried to partially remove the water content of the aqueous solution.
  • a water-immiscible organic solvent solution containing a polyfunctional acid halide is brought into contact with the support film after contact with the aqueous solution of a polyfunctional amine, and a separation functional layer is formed by interfacial polycondensation.
  • the concentration of the polyfunctional acid halide in the water-immiscible organic solvent solution is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and preferably 3% by weight or less, It is more preferably at most 2% by weight.
  • concentration of the polyfunctional acid halide is 0.01% by weight or more, a sufficient reaction rate can be obtained.
  • concentration is 3% by weight or less, generation of a side reaction can be sufficiently suppressed.
  • the organic solvent that is immiscible with water is preferably one that dissolves the polyfunctional acid halide and does not destroy the support film, and is inert to the polyfunctional amine compound and the polyfunctional acid halide.
  • a hydrocarbon solvent may be mentioned, and it may be a simple substance or a mixture.
  • the organic solvent include saturated hydrocarbons such as hexane, heptane, octane, nonane, and decane; IP solvent 1620, IP clean LXIP solvent 2028, and isoparaffins such as ISOPAR E, ISOPAR G, ISOPAR H, ISOPAR L manufactured by ExxonMobil. Naphthene solvents such as Exol D30, Exol D40, Exol D60 and Exol D80 manufactured by ExxonMobil.
  • the organic solvent solution may contain other polyfunctional amine-reactive monomers, organic solvents, acylation catalysts, surfactants, solubilizing agents, complexing agents, and the like.
  • other polyfunctional amine-reactive monomers include compounds containing at least one, preferably from 2 to 4, amine-reactive functional groups selected from sulfonyl halides and acid anhydrides, and at least one carboxy group.
  • Compounds containing at least one acyl halide are included.
  • the organic solvent include benzene, toluene, acetone, ethyl acetate and the like.
  • the acylation catalyst include DMF.
  • the method of bringing the organic solvent solution containing the polyfunctional acid halide into contact with the support film may be performed in the same manner as the method of coating the support film with a polyfunctional amine aqueous solution.
  • the support film is sufficiently covered with the crosslinked polyamide thin film and that the polyfunctional acid halide solution is left on the support film. Therefore, the time for performing the interfacial polycondensation is preferably from 0.1 seconds to 3 minutes, more preferably from 0.1 seconds to 1 minute. Since the time for performing the interfacial polycondensation is 0.1 second or more and 3 minutes or less, the support film can be sufficiently covered with the crosslinked polyamide thin film, and the polyfunctional acid halide solution is held on the support film. can do.
  • the method of draining includes, for example, a method of vertically removing the excess organic solvent by grasping the membrane in a vertical direction, a method of drying and removing the organic solvent by blowing air with a blower, a mixed fluid of water and air A method of removing excess organic solvent with (two fluids) can be used.
  • the composite semipermeable membrane of the present invention is suitably used as a spiral composite semipermeable membrane element. Further, a composite semipermeable membrane module in which these elements are connected in series or in parallel and housed in a pressure vessel can be provided.
  • the above-described composite semipermeable membrane, its elements and modules can be combined with a pump for supplying raw water thereto, a device for pre-treating the raw water, and the like to constitute a fluid separation device. By using this separation device, raw water can be separated into permeated water intended for drinking water and the like and concentrated water not permeated through the membrane to obtain water suitable for the purpose.
  • the operating pressure at the time of permeating the treated water is preferably from 0.2 MPa to 4.1 MPa.
  • the salt removal property decreases, but as the temperature decreases, the membrane permeation flux also decreases.
  • the pH of the feed water is high, in the case of feed water having a high salt concentration such as seawater, scale such as magnesium may be generated, and the membrane may be deteriorated due to high pH operation. Operation in the region is preferred.
  • Raw water treated by the composite semipermeable membrane includes a liquid mixture containing 500 mg / L to 100 g / L of TDS (Total Dissolved Solids: total dissolved solids) such as seawater, brackish water, and wastewater.
  • TDS Total Dissolved Solids: total dissolved solids
  • the solution filtered through a 0.45 ⁇ m filter can be evaporated at a temperature of 39.5 to 40.5 ° C. and can be calculated from the weight of the residue.
  • the weight after vacuum drying was measured with an electronic balance and divided by the unit area to obtain the weight of the composite semipermeable membrane per unit area (g / m 2 ).
  • the porous support was dissolved by immersing the composite semipermeable membrane in acetone at 25 ° C.
  • the remaining base material was further thoroughly washed with acetone, air-dried at 25 ° C. for 10 hours or more, and dried at 40 ° C. in a vacuum dryer for 6 hours.
  • the weight after vacuum drying was measured and divided by the unit area to calculate the substrate weight (g / m 2 ).
  • the weight (g / m 2 ) of the porous support was determined by subtracting the weight of the substrate from the weight of the composite semipermeable membrane.
  • the composite semipermeable membrane (area 0.1 m 2 ) washed with pure water at 70 ° C. for 1 hour or more is air-dried at 25 ° C. for 10 hours or more, and further dried in a vacuum dryer at 40 ° C. for 6 hours or more, and is 2 mm square size Cut into pieces.
  • the sample was filled in a glass tube, and the sample weight was measured from the difference between the empty glass tube weight measured in advance and the glass tube weight after filling the sample (the sum of the sample weight and the glass tube weight).
  • the glass tube filled with the sample was set in a pore distribution measuring device, and the adsorption isotherm of nitrogen gas was measured.
  • the adsorption isotherm data obtained by the measurement was analyzed by the BJH method, a volume corresponding to the pore radius was determined, and the pore volume was determined using the equation (1).
  • Apparatus Microtrac BEL high-precision specific surface area / pore distribution measurement apparatus BELSORP-mini II Measurement method: Constant volume gas adsorption method
  • the insoluble matter was dissolved again in acetone so as to be 10% by weight.
  • the resulting solution was applied on a glass substrate with a thickness of 15 mil (381 ⁇ m) using an applicator, and left in an atmosphere of a temperature of 25 ° C. and a humidity of 50% for 12 hours or more to obtain a film sample.
  • the obtained sample was dried in a vacuum dryer at 60 ° C. for 5 hours to completely remove acetone, and the dried sample was subjected to absorbance analysis with a Fourier transform infrared spectrophotometer (FT-IR) (transmission method).
  • FT-IR Fourier transform infrared spectrophotometer
  • the cyano group ratio was determined from the formula (2).
  • 1605 cm -1 peak attributed to vibration of benzene nucleus derived from aromatic vinyl monomer
  • FT-IR IR Traxer-100 manufactured by Shimadzu Corporation
  • Measurement conditions apodization function Happ-Genzel, resolution 4 cm ⁇ 1 , number of scans 32, measurement range 600 to 4000 cm ⁇ 1
  • Baseline correction was performed with three points at 2200, 2600, and 3800 cm ⁇ 1 as zero absorption intensity, and then the peak absorption intensity was read.
  • Pure water permeability coefficient Pure water permeability / (membrane area x water sampling time x supply pressure)
  • the conductivity was converted to calculate the NaCl concentration, and the NaCl removal rate was determined from the NaCl concentration.
  • the value obtained by subtracting the NaCl removal rate at 1.03 MPa from the NaCl removal rate at 3.0 MPa (change amount) is used as an index of pressure resistance.
  • B was determined to be 0.5% or less and more than -1.5%, and C was determined to have a change of -1.5% or less.
  • aqueous solution 35 parts by weight of sodium hydroxide and 15,000 parts by weight of ion-exchanged water were added to obtain a 0.6% by weight aqueous solution of a copolymer of methyl methacrylate and acrylamide. After stirring at 70 ° C. for 2 hours for saponification, the mixture was cooled to room temperature to obtain an aqueous solution of a medium for suspension polymerization.
  • the reaction temperature was raised to 65 ° C. over 30 minutes, and then to 100 ° C. over 3 hours. Thereafter, the inside of the system was cooled to room temperature, and the polymer was separated, washed and dried to obtain a vinyl copolymer A.
  • the weight average molecular weight Mw of the vinyl copolymer A was 100,000.
  • Vinyl copolymer B was obtained in the same manner as in Production Example 2, except that the amount of t-dodecyl mercaptan was changed to 0.30 parts by weight. The weight average molecular weight Mw of this vinyl copolymer B was 140,000.
  • Vinyl copolymer (C) A vinyl copolymer C was obtained in the same manner as in Production Example 2, except that t-dodecyl mercaptan was changed to 0.20 part by weight. The weight average molecular weight Mw of this vinyl copolymer C was 180,000.
  • Vinyl copolymer (D) A vinyl copolymer D was obtained in the same manner as in Production Example 2, except that the amount of t-dodecyl mercaptan was changed to 0.15 parts by weight. The weight average molecular weight Mw of this vinyl copolymer D was 220,000.
  • Vinyl copolymer (E) A vinyl copolymer E was obtained in the same manner as in Production Example 2, except that the amount of t-dodecyl mercaptan was changed to 0.10 parts by weight. The weight average molecular weight Mw of this vinyl copolymer E was 320,000.
  • Vinyl copolymer (F) A vinyl copolymer F was obtained in the same manner as in Production Example 2, except that styrene was changed to 63 parts by weight and acrylonitrile was changed to 37 parts by weight. The weight average molecular weight Mw of this vinyl copolymer F was 110,000.
  • Vinyl copolymer (G) A vinyl copolymer G was obtained in the same manner as in Production Example 2, except that styrene was changed to 69 parts by weight and acrylonitrile was changed to 31 parts by weight. The weight average molecular weight Mw of this vinyl copolymer G was 110,000.
  • Vinyl copolymer (H) A vinyl copolymer H was obtained in the same manner as in Production Example 2, except that styrene was changed to 76 parts by weight and acrylonitrile was changed to 24 parts by weight.
  • the weight average molecular weight Mw of the vinyl copolymer H was 100,000.
  • Vinyl copolymer (I) A vinyl copolymer I was obtained in the same manner as in Production Example 2 except that styrene, 76 parts by weight, acrylonitrile 24 parts by weight, and t-dodecyl mercaptan were changed to 0 parts by weight. The weight average molecular weight Mw of this vinyl copolymer I was 340,000.
  • Vinyl copolymer (J) A vinyl copolymer J was obtained in the same manner as in Production Example 2, except that 80 parts by weight of styrene, 20 parts by weight of acrylonitrile, and 0 parts by weight of t-dodecyl mercaptan were used. The weight average molecular weight Mw of this vinyl copolymer J was 260,000.
  • a resin solution was prepared by adding the vinyl copolymer A obtained in Production Example 2 to DMF so as to be 16% by weight and heating and holding at 70 ° C. for 3 hours while stirring with a mechanical stirrer.
  • the prepared resin solution was cooled to 25 ° C. and filtered using a metal mesh (wire diameter 0.03 mm, mesh 400, manufactured by Kansai Wire Mesh Co., Ltd.). Thereafter, a 100 ⁇ m-thick resin solution was applied onto a nonwoven fabric (thickness: about 90 ⁇ m, air permeability: 1.0 cc / cm 2 / sec) made of polyester fiber manufactured by a papermaking method.
  • the support was immersed in pure water at 20 ° C. for 10 seconds to separate phases, and then washed with pure water at 70 ° C. for 5 minutes to obtain a support film.
  • the obtained support membrane was immersed in a 2.0% by weight aqueous solution of m-phenylenediamine (m-PDA) prepared with pure water for 10 seconds, and then slowly pulled up so that the membrane surface became vertical. After removing excess aqueous solution from the surface of the support film by blowing nitrogen from an air nozzle, the support film is placed so that the film surface is horizontal, and a 25 ° C. n-decane solution containing trimesic acid chloride (0.07% by weight) is applied to the film. It was applied so that the surface was completely wetted. After allowing to stand for 30 seconds, the film surface was held vertically for 1 minute to remove excess solution from the film, drained, and dried by blowing air at 25 ° C. using a blower. Thereafter, by washing with pure water at 70 ° C. for 5 minutes, a composite semipermeable membrane was obtained. Table 1 shows the membrane performance of the obtained composite semipermeable membrane.
  • Comparative Example 1 differs from Comparative Example 1 in that B was used in Comparative Example 2, C was used in Example 1, D was used in Example 2, and E was used in Example 3 instead of vinyl copolymer A. Similarly, the composite semipermeable membranes of Comparative Example 2 and Examples 1 to 3 were obtained. Table 1 shows the membrane performance of the obtained composite semipermeable membrane.
  • Example 4 In Comparative Example 1, a composite semipermeable membrane of Example 4 was obtained in the same manner as in Comparative Example 1 except that DMSO was used instead of DMF. Table 1 shows the membrane performance of the obtained composite semipermeable membrane.
  • Example 5 In Comparative Example 2, a composite semipermeable membrane of Example 5 was obtained in the same manner as in Comparative Example 2 except that DMSO was used instead of DMF. Table 1 shows the membrane performance of the obtained composite semipermeable membrane.
  • Example 6 A composite semipermeable membrane of Example 6 was obtained in the same manner as in Example 1 except that DMSO was used instead of DMF. Table 1 shows the membrane performance of the obtained composite semipermeable membrane.
  • Example 7 A composite semipermeable membrane of Example 7 was obtained in the same manner as in Example 2 except that DMSO was used instead of DMF. Table 2 shows the membrane performance of the obtained composite semipermeable membrane.
  • Example 8 A composite semipermeable membrane of Example 8 was obtained in the same manner as in Example 3, except that DMSO was used instead of DMF. Table 2 shows the membrane performance of the obtained composite semipermeable membrane.
  • Example 9 A composite semipermeable membrane of Example 9 was obtained in the same manner as in Example 8, except that the concentration of the vinyl copolymer E was changed to 20% by weight. Table 1 shows the membrane performance of the obtained composite semipermeable membrane.
  • Example 4 F was used in Example 10, G was used in Example 11, H was used in Example 12, I was used in Example 13, and J was used in Example 14 instead of the vinyl copolymer A. Except for the above, the composite semipermeable membranes of Examples 10 to 14 were obtained in the same manner as in Example 4. Table 2 shows the membrane performance of the obtained composite semipermeable membrane.
  • a composite semipermeable membrane having a high permeation flux was obtained by setting the pore volume of the porous support to 0.100 cm 3 / g or more. Further, from Examples 10 to 14, a composite semipermeable membrane having a high permeation flux was obtained by setting the ratio of cyano groups in the porous support to 1.50 or less. From the above, it was confirmed that a composite semipermeable membrane having high water permeability was obtained by the present invention.
  • the composite semipermeable membrane of the present invention can be suitably used particularly for desalination of brine and purification of tap water.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne une membrane composite semi-perméable comprenant : un film de support qui comprend un matériau de base et un corps de support poreux sur le matériau de base ; et une couche à fonction de séparation sur le corps de support poreux. Le corps de support poreux contient un copolymère d'un monomère de vinyle cyanuré et d'un monomère de vinyle aromatique, et le volume des pores ayant un rayon de 10,6 nm à 93,5 nm dans le corps de support poreux est d'au moins 0,100 cm3/g.
PCT/JP2019/034876 2018-09-28 2019-09-04 Membrane composite semi-perméable et son procédé de fabrication WO2020066521A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55149330A (en) * 1979-03-28 1980-11-20 Monsanto Co Anisotropic membrane and its manufacture
JPS60202701A (ja) * 1984-03-23 1985-10-14 Toray Ind Inc 分離膜
JPS63248405A (ja) * 1986-05-30 1988-10-14 Mitsubishi Rayon Co Ltd 多孔質膜
JP2006205067A (ja) * 2005-01-28 2006-08-10 Toray Ind Inc 多孔質膜
US20120181228A1 (en) * 2011-01-18 2012-07-19 Samsung Electronics Co., Ltd. Polyacrylonitrile Copolymer, Method For Manufacturing Membrane Including The Same, Membrane Including The Same, And Water Treatment Module Using The Membrane
WO2014192883A1 (fr) * 2013-05-30 2014-12-04 東レ株式会社 Membrane semiperméable composite
WO2017222063A1 (fr) * 2016-06-24 2017-12-28 東レ株式会社 Membrane composite à fibres creuses poreuses, module composite de membranes à fibres creuses poreuses et procédé de fonctionnement pour module composite de membranes à fibres creuses poreuses.

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55149330A (en) * 1979-03-28 1980-11-20 Monsanto Co Anisotropic membrane and its manufacture
JPS60202701A (ja) * 1984-03-23 1985-10-14 Toray Ind Inc 分離膜
JPS63248405A (ja) * 1986-05-30 1988-10-14 Mitsubishi Rayon Co Ltd 多孔質膜
JP2006205067A (ja) * 2005-01-28 2006-08-10 Toray Ind Inc 多孔質膜
US20120181228A1 (en) * 2011-01-18 2012-07-19 Samsung Electronics Co., Ltd. Polyacrylonitrile Copolymer, Method For Manufacturing Membrane Including The Same, Membrane Including The Same, And Water Treatment Module Using The Membrane
WO2014192883A1 (fr) * 2013-05-30 2014-12-04 東レ株式会社 Membrane semiperméable composite
WO2017222063A1 (fr) * 2016-06-24 2017-12-28 東レ株式会社 Membrane composite à fibres creuses poreuses, module composite de membranes à fibres creuses poreuses et procédé de fonctionnement pour module composite de membranes à fibres creuses poreuses.

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