WO2017043233A1 - 非溶剤誘起相分離法用製膜原液およびこれを用いた多孔質中空糸膜の製造方法 - Google Patents

非溶剤誘起相分離法用製膜原液およびこれを用いた多孔質中空糸膜の製造方法 Download PDF

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WO2017043233A1
WO2017043233A1 PCT/JP2016/073134 JP2016073134W WO2017043233A1 WO 2017043233 A1 WO2017043233 A1 WO 2017043233A1 JP 2016073134 W JP2016073134 W JP 2016073134W WO 2017043233 A1 WO2017043233 A1 WO 2017043233A1
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membrane
phase separation
induced phase
solvent
solution
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PCT/JP2016/073134
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English (en)
French (fr)
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孝利 佐藤
健祐 渡辺
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Nok株式会社
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Priority to US15/755,278 priority Critical patent/US20180243700A1/en
Priority to EP16844097.2A priority patent/EP3348323A4/en
Priority to KR1020187006741A priority patent/KR20180048692A/ko
Priority to CA2996769A priority patent/CA2996769A1/en
Priority to CN201680051705.3A priority patent/CN107921379A/zh
Publication of WO2017043233A1 publication Critical patent/WO2017043233A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B01D71/441—Polyvinylpyrrolidone
    • 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
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/268—Drying gases or vapours by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions 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
    • B01D69/08—Hollow fibre membranes
    • 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
    • B01D69/085—Details relating to the spinneret
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B01D71/521—Aliphatic polyethers
    • B01D71/5211—Polyethylene glycol or polyethyleneoxide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04126—Humidifying
    • H01M8/04149—Humidifying by diffusion, e.g. making use of membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D2053/221—Devices
    • B01D2053/223—Devices with hollow tubes
    • B01D2053/224—Devices with hollow tubes with hollow fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0208—Other waste gases from fuel cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a membrane-forming solution for non-solvent induced phase separation and a method for producing a porous hollow fiber membrane using the same. More specifically, a membrane stock solution for non-solvent induced phase separation method used for producing a porous hollow fiber membrane used as a water vapor permeable membrane such as a humidifying membrane for fuel cells, and a method for producing a porous hollow fiber membrane using the same About.
  • Porous hollow fiber membranes have pores of gas separable size, exhibit excellent gas separation among various inorganic membranes, and can be used in environments where heat resistance and chemical resistance are required. It is. From this, in recent years, the application to a water vapor permeable membrane etc. which humidifies the diaphragm of a fuel cell stack using a porous hollow fiber membrane is spreading.
  • the water vapor permeable membrane for humidifying the membrane of the fuel cell stack is prepared from a spinning solution comprising a water soluble organic solvent solution of polyphenyl sulfone resin and hydrophilic polyvinyl pyrrolidone.
  • Hollow fiber membranes have been proposed. Such hollow fiber membranes do not significantly decrease in elongation even after immersion in warm water such as 95 ° C. for 280 hours, and are thus excellent in membrane strength and durability.
  • the performance of the water vapor permeable membrane conventionally proposed tends to decrease in performance as the water vapor permeable membrane as the use progresses.
  • Such a tendency is considered to be caused, for example, by the decrease in hydrophilicity of polyvinyl pyrrolidone used as one component of the membrane-forming solution under high temperature environment. Therefore, further improvement is required to maintain performance even after continuous use in a high temperature environment.
  • An object of the present invention is to provide a non-solvent-induced for use in the production of a highly functional porous hollow fiber membrane that does not show a significant decrease in water vapor transmission performance even after use in a high temperature environment such as 100 to 120 ° C. It is an object of the present invention to provide a membrane-forming solution for phase separation method and a water vapor permeable membrane using the same.
  • the object of the present invention is to use 15 to 40% by weight of polysulfone resin, 5 to 60% by weight of polyvinyl pyrrolidone and 0.1 to 10% by weight of polyoxyethylene sorbitan fatty acid esters in water-soluble organic solvent.
  • Film stock solution for non-solvent induced phase separation dissolved in solution And it is achieved by producing a porous hollow fiber membrane by spinning the aqueous solution as a core solution by non-solvent induced phase separation method using this membrane-forming solution.
  • the porous hollow fiber membrane produced by using the membrane-forming solution according to the present invention can maintain high hydrophilicity inside the pores of the membrane even under high-temperature environment, so it can be used in high-temperature environment such as 120 ° C. Even when the water vapor permeable membrane is used, the effect of reducing the performance is small.
  • polysulfone-based resin examples include polysulfone resin, polyphenylsulfone resin, polyethersulfone resin, polyarylethersulfone resin, bisphenol A-type polysulfone resin and the like, preferably polyphenylsulfone resin.
  • Polyphenyl sulfone resin refers to one having a phenyl sulfone group and an ether bond in the main chain, and a repeating unit shown below That is, it has a biphenylene group and does not have an isopropylidene group, and in fact, a commercially available product, for example, the product of AMOCO product RADEL R series can be used as it is.
  • polyether sulfone resin commercially available products such as those of Solvay Advanced Polymer Co., Ltd., product Radel series, products of BASF Corp. Ultra Zone series, Sumitomo Chemical Co., Ltd. product Sumica Excel PES series can be used.
  • polysulfone-based resins are used at a concentration of about 15 to 40% by weight, preferably about 15 to 30% by weight, in the stock solution.
  • concentration of the polysulfone-based resin is higher than this, the viscosity of the membrane forming solution extremely increases to lower the workability of spinning, or the density of the membrane is too high to lower the water vapor transmission performance.
  • the strength of the membrane will be reduced, and the membrane can not withstand practical use, or the pore diameter of the membrane will be too large to allow gases other than water vapor to permeate, and the performance as a water vapor permeable membrane appears It may not be possible.
  • a film-forming solution containing a polysulfone-based resin as a film-forming component is prepared by adding thereto hydrophilic polyvinyl pyrrolidone, polyoxyethylene sorbitan fatty acid esters and a water-soluble organic solvent.
  • polyvinyl pyrrolidone to be added as a hydrophilic polymer substance those having a molecular weight of about 1000 (K-15) to 1 200 000 (K-90), preferably about 10000 (K-30) to 12 000 000 (K-90) And a concentration of about 5 to 60% by weight, preferably about 15 to 40% by weight, in the stock solution.
  • concentration of the hydrophilic polymer substance is higher than this, the viscosity of the film-forming solution extremely increases and the workability is lowered.
  • polyvinyl pyrrolidone in such a proportion has some influence on the structural control of the surface pore diameter of the porous membrane, etc., but it reduces the air permeation rate of the porous membrane more than that, that is, the gas barrier property The effect of improving the water vapor transmission rate is achieved.
  • polyoxyethylene sorbitan fatty acid esters examples include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and the like, preferably having high hydrophilicity.
  • Polyoxyethylene sorbitan monolaurate is used.
  • the polyoxyethylene sorbitan fatty acid esters are used at a concentration of about 0.1 to 10% by weight, preferably about 0.5 to 5% by weight, in the stock solution.
  • the proportion of polyoxyethylene sorbitan fatty acid esters is lower than this, the performance as a water vapor permeable membrane will be greatly reduced in the use under the high temperature environment of the water vapor permeable membrane, while if higher than this However, the phase state of the membrane forming solution becomes unstable, the dimensions and performance of the membrane become unstable, and the workability of spinning decreases.
  • Patent Document 2 describes a polyphenylsulfone porous membrane by a thermally induced phase separation method of polyphenylsulfone and a solvent, in which case an embodiment using an inorganic particle and polyoxyethylene sorbitan fatty acid ester as a coagulant is also used. Although described, flocculants are said to be used to control the aggregation state of the inorganic particles and to stabilize the molten state of the entire system.
  • Patent Document 3 describes a separation membrane excellent in water permeability, separation characteristics, and low fouling property by an efficient membrane washing method in which the amount of washing liquid used is suppressed, in which case as a pore opening agent
  • a pore opening agent an embodiment in which polyoxyethylene sorbitan fatty acid ester is used is also described, it is stated that this open-pore surfactant is characterized in that it remains in the porous layer and does not decrease in water permeability or inhibition even when dried. It is done. A similar description can also be found in US Pat.
  • Patent Documents 2 to 4 neither teach nor suggest the effect of the present invention that the water vapor transmission performance is not significantly reduced even after use in a high temperature environment of 100 to 120 ° C. .
  • aprotic polar solvents such as methanol, ethanol, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and the like, preferably dimethylacetamide, N-methyl-2-pyrrolidone are used.
  • a homogeneous polymer solution consisting of a polymer and a solvent, which does not contain inorganic particles, causes phase separation due to the change in concentration due to the infiltration of the nonsolvent or the evaporation of the solvent to the external atmosphere
  • a separation membrane can be produced by developing non-solvent-induced phase separation in particular, and a dry-wet spinning method or a wet spinning method is specifically used.
  • the dry-wet spinning using such a membrane-forming solution is carried out using an aqueous solution, generally water as a core solution, and the porous hollow fiber membrane coagulated in water or an aqueous coagulating solution is washed with water and then dried.
  • the washing with water is carried out with normal temperature or warm water, pressurized water with an autoclave (for example, 121 ° C.) or the like.
  • Example 20 parts by weight of polyphenylsulfone resin (Sorvai Specialty Polymers product RADEL R-5000), 15 parts by weight of polyvinylpyrrolidone (genuine chemical product K-30), polyoxyethylene sorbitan monolaurate (Kanto Chemical product tween 20) 1
  • a uniform film-forming stock solution was prepared at room temperature consisting of parts by weight and 64 parts by weight of dimethylacetamide.
  • the prepared membrane stock solution was extruded into a water coagulation bath using water as a core liquid using a double ring structure spinning nozzle, and dry and wet spinning was performed. Thereafter, the membrane was washed in pressurized water at 121 ° C. for 1 hour and then dried in an oven at 60 ° C. to obtain a porous polyphenylsulfone resin hollow fiber membrane having an outer diameter of 1,000 ⁇ m and an inner diameter of 700 ⁇ m.
  • the water vapor permeation rate, the pure water permeation rate, and the air permeation rate were measured for the obtained porous polyphenylsulfone resin hollow fiber membrane.
  • Water vapor transmission rate Three hollow fiber membranes with an effective length of 17 cm are used to make open-ended hollow fiber membrane modules, humidified air with RH 90% from the outside of the membrane, and dry air inside the membrane. The flow rate was measured, and the water vapor transmission rate per time was measured, and the unit membrane area, the unit time, the water vapor partial pressure difference between the outside and the inside of the membrane, and the air permeation amount per 1MPa were calculated.
  • Air permeation rate A hollow fiber membrane with an effective length of 15 cm was made into a loop shape, using a module in which both ends of the loop were fixed to a glass tube , Air at a temperature of 25 ° C and a pressure of 50 kPa from the inside to the outside of the membrane Applied to measure the air permeability per time, unit membrane area, unit time was calculated numerical value in terms of air permeation quantity per 1MPa
  • Comparative Example 1 In the examples, polyoxyethylene sorbitan monolaurate was not used, and the amount of dimethylacetamide was changed to 65 parts by weight and used.
  • Comparative example 2 In the examples, polyvinyl pyrrolidone was not used, and the amount of polyoxyethylene sorbitan monolaurate was changed to 15 parts by weight, and the amount of dimethylacetamide was changed to 65 parts by weight.
  • the porous hollow fiber membrane according to the present invention does not show a significant drop in water vapor permeability even after use in a high temperature environment of 100 to 120 ° C., it can be used as a water vapor permeable membrane or the like used in fuel cells It can be used effectively.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fuel Cell (AREA)

Abstract

製膜原液中、15～40重量％のポリスルホン系樹脂、5～60重量％のポリビニルピロリドンおよび0.1～10重量％のポリオキシエチレンソルビタン脂肪酸エステル類を、水溶性有機溶媒溶液に溶解させた非溶剤誘起相分離法用製膜原液。この製膜原液を用い、水性液を芯液として非溶剤誘起相分離法により紡糸し、多孔質中空糸膜を製造する。得られた高機能な多孔質中空糸膜は、例えば100～120℃といった高温環境下での使用後においても、水蒸気透過性能に大きな低下がみられることがないので、燃料電池の水蒸気透過膜として好適に用いられる。

Description

非溶剤誘起相分離法用製膜原液およびこれを用いた多孔質中空糸膜の製造方法
　本発明は、非溶剤誘起相分離法用製膜原液およびこれを用いた多孔質中空糸膜の製造方法に関する。さらに詳しくは、燃料電池用加湿膜等の水蒸気透過膜として用いられる多孔質中空糸膜の製造に用いられる非溶剤誘起相分離法用製膜原液およびこれを用いた多孔質中空糸膜の製造方法に関する。
　多孔質中空糸膜は、ガス分離可能なサイズの孔を有しており、種々の無機膜の中でもすぐれた気体分離性を示し、耐熱性、耐薬品性が要求される環境下においても使用可能である。このことから、近年では、多孔質中空糸膜を用いて燃料電池スタックの隔膜の加湿を行うといった水蒸気透過膜等への用途が広がってきている。
　燃料電池スタックの隔膜の加湿を行う水蒸気透過膜としては、例えば特許文献１に開示されているように、ポリフェニルスルホン樹脂および親水性ポリビニルピロリドンの水溶性有機溶媒溶液よりなる紡糸原液から作製される中空糸膜が提案されている。かかる中空糸膜は、95℃といった温水に280時間浸漬した後においても、伸度が大幅に低下することがなく、そのため膜強度および耐久性の点ですぐれている。
　ここで、燃料電池は一般的に高温である方が効率がよくなる傾向にあることから、100～120℃といった高温の環境下における性能の維持が求められている。したがって、燃料電池システムに組み込まれている水蒸気透過膜にはかかる温度条件下でその性能を発現することが求められている。
　しかるに、従来より提案されてきた水蒸気透過膜は、120℃の高温水蒸気にさらされる環境下においては、使用が進むにつれて水蒸気透過膜としての性能が低下する傾向にある。かかる傾向は、例えば製膜原液の一成分として用いられているポリビニルピロリドンが高温環境下でその親水性が低下してしまうことが原因であると考えられる。したがって、高温環境下での継続使用後においても性能を維持し得るように、さらなる改良が求められている。
特許４，１００，２１５号公報 特開２００５－１９３１９４号公報 特開２０１２－１４３７４９号公報 特開２００５－２７０７０７号公報
　本発明の目的は、例えば100～120℃といった高温環境下での使用後においても、水蒸気透過性能に大きな低下がみられることがない高機能な多孔質中空糸膜の製造に用いられる非溶剤誘起相分離法用製膜原液およびこれを用いた水蒸気透過膜を提供することにある。
　かかる本発明の目的は、製膜原液中、15～40重量％のポリスルホン系樹脂、5～60重量％のポリビニルピロリドンおよび0.1～10重量％のポリオキシエチレンソルビタン脂肪酸エステル類を、水溶性有機溶媒溶液に溶解させた非溶剤誘起相分離法用製膜原液、
およびこの製膜原液を用い、水性液を芯液として非溶剤誘起相分離法により紡糸し、多孔質中空糸膜を製造することによって達成される。
　本発明に係る製膜原液を用いて製造された多孔質中空糸膜は、高温環境下においても膜の細孔内部の親水性を高く保持できることから、120℃といった高温環境下での使用にあっても、水蒸気透過膜としての性能の低下が小さいといったすぐれた効果を奏する。
　ポリスルホン系樹脂としては、例えばポリスルホン樹脂、ポリフェニルスルホン樹脂、ポリエーテルスルホン樹脂、ポリアリールエーテルスルホン樹脂、ビスフェノールA型ポリスルホン樹脂などが挙げられ、好ましくはポリフェニルスルホン樹脂が用いられる。
　ポリフェニルスルホン樹脂は、主鎖内にフェニルスルホン基およびエーテル結合を有するものをいい、以下に示されるくり返し単位
Figure JPOXMLDOC01-appb-I000001
即ちビフェニレン基を有し、イソプロピリデン基を有しないものであり、実際には市販品、例えばアモコ社製品RADEL Rシリーズのもの等をそのまま使用することができる。
　ポリエーテルスルホン樹脂としては、市販品、例えばソルベイアドバンストポリマー社製品レーデルシリーズ、BASF社製品ウルトラゾーンシリーズ、住友化学工業製品スミカエクセルPESシリーズのもの等を用いることができる。
　これらのポリスルホン系樹脂は、製膜原液中約15～40重量％、好ましくは約15～30重量％を占めるような濃度で用いられる。ポリスルホン系樹脂の濃度がこれより高い場合には、製膜原液の粘度が極端に上昇して紡糸の作業性が低下したり、膜の密度が高すぎて水蒸気透過性能が低下したりするようになり、一方これより低い場合には膜の強度が小さくなり、実用に耐え得なくなったり、膜の孔径が大きくなりすぎて水蒸気以外の気体が透過するようになり、水蒸気透過膜としての性能が発現できなくなる可能性がある。
　ポリスルホン系樹脂を製膜成分とする製膜原液は、そこに親水性ポリビニルピロリドン、ポリオキシエチレンソルビタン脂肪酸エステル類および水溶性有機溶媒が添加されて調製される。
　親水性高分子物質として添加されるポリビニルピロリドンとしては、分子量が約1000(K-15)～1200000(K-90)、好ましくは約10000(K-30)～1200000(K-90)のものが、製膜原液中約5～60重量％、好ましくは約15～40重量％を占めるような濃度で用いられる。親水性高分子物質の濃度がこれより高い場合には、製膜原液の粘度が極端に上昇して作業性が低下するようになる。
　ポリビニルピロリドンのこのような割合での添加は、多孔質膜の表面孔径等の構造制御にも多少の影響はみられるが、それ以上に多孔質膜の空気透過速度を低下させ、すなわちガスバリア性を向上させ、水蒸気透過速度を向上させるという効果を達成させる。
　ポリオキシエチレンソルビタン脂肪酸エステル類としては、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタンモノオレエート等が、好ましくは親水性の高いポリオキシエチレンソルビタンモノラウラートが用いられる。ポリオキシエチレンソルビタン脂肪酸エステル類は、製膜原液中約0.1～10重量％、好ましくは約0.5～5重量％を占めるような濃度で用いられる。ポリオキシエチレンソルビタン脂肪酸エステル類の割合がこれより低い場合には、水蒸気透過膜の高温環境下での使用において、水蒸気透過膜としての性能が大きく低下するようになり、一方これより高い場合には、製膜原液の相状態が不安定になり、膜の寸法や性能が安定しなかったり、紡糸の作業性が低下したりするようになる。
　特許文献２には、ポリフェニルスルホンと溶剤との熱誘起相分離法によるポリフェニルスルホン多孔質膜が記載されており、その際無機粒子および凝集剤としてのポリオキシエチレンソルビタン脂肪酸エステルを用いる態様も記載されているが、凝集剤は無機粒子の凝集状態を制御するためや、系全体の溶融状態の安定化のために用いられると述べられている。
　特許文献３には、使用する洗浄液の量を抑制した効率的な膜の洗浄方法によって、透水性、分離特性、低ファウリング性にすぐれた分離膜が記載されており、その際開孔剤としてポリオキシエチレンソルビタン脂肪酸エステルが用いられる態様も記載されているが、この開孔剤界面活性剤は、多孔質層に残存し乾燥させても透水性、阻止性が低下しないという特徴を有すると述べられている。同様の記載は、特許文献４にもみられる。
　これらの特許文献２～４は、100～120℃といった高温環境下での使用後においても、水蒸気透過性能に大きな低下がみられることがないといった、本発明の効果を決して教示も示唆もしていない。
　水溶性有機溶媒としては、メタノール、エタノール、テトラヒドロフランあるいはジメチルホルムアミド、ジメチルアセトアミド、N-メチル-2-ピロリドン等の非プロトン性極性溶媒、好ましくはジメチルアセトアミド、N-メチル-2-ピロリドンが用いられる。
　非溶剤誘起相分離法では、無機粒子を含有しない、ポリマーと溶媒とからなる均一なポリマー溶液は、非溶媒の進入や溶媒の外部雰囲気への蒸発による濃度変化によって相分離を起し、凝固浴中で非溶剤誘起相分離を発現させることで、分離膜を製造することができ、具体的には乾湿式紡糸法または湿式紡糸法が用いられる。
　このような製膜原液を用いての乾湿式紡糸は、水性液、一般には水を芯液として行われ、水または水性凝固溶中で凝固させた多孔質中空糸膜は水洗後乾燥させる。水洗は、常温あるいは温水、オートクレーブによる加圧水(例えば121℃)などにより行われる。
　次に、実施例について本発明を説明する。
　実施例
　ポリフェニルスルホン樹脂(ソルベイスペシャルティポリマーズ社製品RADEL R-5000)20重量部、ポリビニルピロリドン(純正化学製品K-30)15重量部、ポリオキシエチレンソルビタンモノラウラート(関東化学製品ツイーン20)1重量部およびジメチルアセトアミド64重量部からなる、室温で均一な製膜原液を調製した。
　調製された製膜原液を、二重環状構造の紡糸ノズルを用い、水を芯液として水凝固浴中に押し出し乾湿式紡糸を行った。その後、121℃の加圧水中で1時間洗浄してから60℃のオーブン中で乾燥し、外径1,000μm、内径700μmの多孔質ポリフェニルスルホン樹脂中空糸膜を得た。
　得られた多孔質ポリフェニルスルホン樹脂中空糸膜について、水蒸気透過速度、純水透過速度、空気透過速度の測定が行われた。
　水蒸気透過速度：有効長17cmの中空糸膜を3本を用いて、両端開放型中空糸膜モジュールを作製し、膜の外側からRH 90％の加湿空気を、また膜の内側に乾燥空気をそれぞれ流して、時間当りの水蒸気透過量を測定し、単位膜面積、単位時間、膜の外側と膜内側の水蒸気分圧差、1MPa当りの空気透過量に換算した数値を算出した
　純水透過速度：有効長15cmの両端開放型中空糸膜モジュールを用い、温度25℃、圧力1 MPaの条件下、純水を原水として中空糸膜の内側から外側にろ過(内圧ろ過)して時間当りの透水量を測定し、単位膜面積、単位時間、1 MPa当りの透水量に換算した数値で算出した
　空気透過速度：有効長15cmの中空糸膜をループ状として、ループ両端をガラス管に固定したモジュールを用い、温度25℃、圧力50kPaの空気を膜の内側から外側に向けて印加し、時間当りの空気透過量を測定し、単位膜面積、単位時間、1MPa当りの空気透過量に換算した数値を算出した
　比較例１
　実施例において、ポリオキシエチレンソルビタンモノラウレートが用いられず、またジメチルアセトアミド量が65重量部に変更されて用いられた。
　比較例２
　実施例において、ポリビニルピロリドンが用いられず、またポリオキシエチレンソルビタンモノラウレート量が15重量部に、ジメチルアセトアミド量が65重量部にそれぞれ変更されて用いられた。
　以上の実施例および各比較例で得られた結果は次の表に示される。
 
 
　　　　　　　　　　　　　　　　　　表
　　　　　測定項目　　　　　　　実施例　　 比較例１ 　 比較例２ 
水蒸気透過速度(g/cm2/分/MPa)
　製膜後(90℃)　　　　　　　　　0.282 　　　0.280 　　　0.290
　120℃、50時間保持後　　　　　 0.273　　　 0.241　　　 0.260
　性能低下率　　　　　　 (％)　 　　3　　　　　14　　　　　10
純水透過速度(ml/cm2/時間/MPa)　 　0.0　　　　 0.0　　　　 0.0
空気透過速度　(ml/cm2/分/MPa)　 　0.0　　　　 0.0　　　　 0.0
　本発明に係る多孔質中空糸膜は、100～120℃といった高温環境下での使用後においても、水蒸気透過性能に大きな低下がみられることがないので、燃料電池に用いられる水蒸気透過膜等として有効に使用することができる。

Claims (9)

  1. 　製膜原液中、15～40重量％のポリスルホン系樹脂、5～60重量％のポリビニルピロリドンおよび0.1～10重量％のポリオキシエチレンソルビタン脂肪酸エステル類を、水溶性有機溶媒溶液に溶解させた非溶剤誘起相分離法用製膜原液。
  2. 　ポリスルホン系樹脂がポリフェニルスルホン樹脂である請求項１記載の非溶剤誘起相分離法用製膜原液。
  3. 　ポリオキシエチレンソルビタン脂肪酸エステル類がポリオキシエチレンソルビタンモノラウレートである請求項１記載の非溶剤誘起相分離法用製膜原液。
  4. 　ポリオキシエチレンソルビタン脂肪酸エステル類が0.5～5重量％用いられた請求項１または３記載の非溶剤誘起相分離法用製膜原液。
  5. 　無機粒子を含有しない請求項１、２または３記載の非溶剤誘起相分離法用製膜原液。
  6. 　請求項１、２または３記載の非溶剤誘起相分離法用製膜原液を、二重環状ノズルを用い、水性液を芯液として非溶剤誘起相分離法により紡糸することを特徴とする多孔質中空糸膜の製造方法。
  7. 　請求項６記載の製造方法により製造された水蒸気透過膜。
  8. 　燃料電池用加湿膜として用いられる請求項７記載の水蒸気透過膜。
  9. 　100～120℃の高温環境下で使用される請求項８記載の水蒸気透過膜。
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US11465103B2 (en) 2017-05-08 2022-10-11 Universiteit Twente Aqueous phase separation method
CN111278543A (zh) * 2017-10-27 2020-06-12 Nok株式会社 加湿膜用聚苯砜中空纤维膜的制造方法
KR20200070335A (ko) * 2017-10-27 2020-06-17 에누오케 가부시키가이샤 가습막용 폴리페닐술폰 중공사 막의 제조법
EP3702021A4 (en) * 2017-10-27 2021-12-01 Nok Corporation METHOD OF MANUFACTURING POLYPHENYLSULPHONE HOLLOW FIBER MEMBRANE FOR USE IN A HUMIDIFIER FILM
KR102377158B1 (ko) 2017-10-27 2022-03-23 에누오케 가부시키가이샤 가습막용 폴리페닐술폰 중공사 막의 제조법
CN111278543B (zh) * 2017-10-27 2022-07-08 Nok株式会社 加湿膜用聚苯砜中空纤维膜的制造方法
CN109989126A (zh) * 2017-12-29 2019-07-09 财团法人工业技术研究院 导电弹性纤维及其制造方法
CN112351832A (zh) * 2018-06-26 2021-02-09 Nok株式会社 加湿用多孔质中空纤维膜的制造方法
WO2020096446A1 (en) 2018-11-07 2020-05-14 Universiteit Twente Method for creating a porous film through aqueous phase separation

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