WO2010143647A1 - Membrane à fibres creuses et son procédé de fabrication - Google Patents

Membrane à fibres creuses et son procédé de fabrication Download PDF

Info

Publication number
WO2010143647A1
WO2010143647A1 PCT/JP2010/059749 JP2010059749W WO2010143647A1 WO 2010143647 A1 WO2010143647 A1 WO 2010143647A1 JP 2010059749 W JP2010059749 W JP 2010059749W WO 2010143647 A1 WO2010143647 A1 WO 2010143647A1
Authority
WO
WIPO (PCT)
Prior art keywords
hollow fiber
fiber membrane
polymer
group
ionic
Prior art date
Application number
PCT/JP2010/059749
Other languages
English (en)
Japanese (ja)
Inventor
充 比嘉
敦 直原
Original Assignee
国立大学法人山口大学
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人山口大学, 株式会社クラレ filed Critical 国立大学法人山口大学
Priority to JP2011518551A priority Critical patent/JP5637483B2/ja
Publication of WO2010143647A1 publication Critical patent/WO2010143647A1/fr

Links

Images

Classifications

    • 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
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment

Definitions

  • the present invention relates to a polyvinyl alcohol-based hollow fiber membrane and a method for producing the same.
  • Non-Patent Document 1 J. Membr. Sci., Vol. 231, p109 (2004) describes a charged hollow fiber membrane in the form of particulate ions having a size of 30 ⁇ m or less in a polysulfone membrane matrix.
  • a hollow fiber membrane prepared by dispersing an exchange resin is described.
  • the ion exchange resin over both sides of the membrane there is a problem that the permeation flux of the counter ions is low because the ratio of such ion paths to the whole is small.
  • Non-Patent Document 2 Ind. Eng. Chem. Res., 47, p6204 (2008), after spinning using a poly (2,6-dimethyl-1,4-phenylene oxide) solution, An anion exchangeable hollow fiber membrane prepared by quaternizing a coalescence is described. However, since such a membrane does not have a chemical cross-linking structure, it has a problem of high water content, low counter ion selectivity, and low mechanical strength.
  • the present invention has been made in order to solve the above-described problems, and an object of the present invention is to provide a hollow fiber membrane having a large ion permeation flux, a large selection coefficient, and excellent mechanical strength. is there. Furthermore, it aims at providing the manufacturing method of the hollow fiber membrane which can manufacture such a hollow fiber membrane easily and at low cost.
  • the object is a hollow fiber membrane comprising an ionic polymer selected from a cationic polymer or an anionic polymer; the ionic polymer having an ionic group selected from a cationic group or an anionic group
  • the problem is solved by providing a hollow fiber membrane comprising a polyvinyl alcohol containing or a mixture of a polymer containing the ionic group and a polyvinyl alcohol not containing the ionic group.
  • the ionic monomer content of the ionic polymer is preferably 0.1 to 50 mol%.
  • the hollow fiber membrane preferably has a thickness of 0.1 to 500 ⁇ m.
  • a preferred embodiment of the present invention is a hollow fiber membrane for Donnan dialysis.
  • An object of the present invention is a method for producing a hollow fiber membrane comprising an ionic polymer selected from a cationic polymer or an anionic polymer, wherein a spinning stock solution comprising a solution containing the ionic polymer is spun from an annular nozzle. It is also solved by providing a method for producing a hollow fiber membrane, characterized in that the hollow fiber membrane is formed by taking out, introducing into a coagulating liquid and solidifying. At this time, when the spinning solution is spun from the annular nozzle, the spinning solution is supplied to the annular nozzle and the coagulating solution is supplied to the inside of the annular nozzle, so that the spinning solution and the coagulating solution can be spun simultaneously. preferable. Moreover, after forming the said hollow fiber membrane, it is also preferable to extend
  • the hollow fiber membrane of the present invention has a large ion permeation flux, a large selection coefficient, and excellent mechanical strength, dialysis can be performed efficiently. Furthermore, according to the method for producing a hollow fiber membrane of the present invention, such a hollow fiber membrane can be produced easily and at low cost.
  • Example 4 it is the image which image
  • C GA crosslinking solution
  • Cl - is a graph plotting the selectivity coefficient of alpha - NO 3 against.
  • the permeation flux J of Ca 2+ and Na + is plotted against the glutaraldehyde concentration (C GA ) in the crosslinking treatment solution.
  • it is a graph in which the selectivity coefficient ⁇ of Ca 2+ against Na + is plotted against the glutaraldehyde concentration (C GA ) in the crosslinking treatment solution.
  • NO 3 - is a graph plotting flux J of - and Cl.
  • Cl - is a graph plotting the selectivity coefficient of alpha - NO 3 against.
  • the NO 3 ⁇ permeation flux J is plotted against the NO 3 ⁇ selection coefficient ⁇ against Cl ⁇ .
  • the hollow fiber membrane of the present invention is made of an ionic polymer selected from a cationic polymer or an anionic polymer.
  • the cationic polymer in the present invention is composed of polyvinyl alcohol containing a cationic group or a mixture of a polymer containing a cationic group and polyvinyl alcohol not containing an ionic group.
  • the cationic polymer includes a structural unit containing a cationic group and a vinyl alcohol unit as its structural unit.
  • the polyvinyl alcohol containing the cationic group may be plural kinds.
  • the cationic polymer is a mixture of a polymer containing a structural unit containing a cationic group and polyvinyl alcohol containing no ionic group.
  • Plural kinds of the cationic polymer and / or polyvinyl alcohol not containing an ionic group may be used. These polymers are preferably crosslinkable.
  • the cationic group contained in the cationic polymer used in the present invention may be contained in any of the main chain, side chain, and terminal of the polymer.
  • the cationic group include an ammonium group, an iminium group, a sulfonium group, and a phosphonium group.
  • a polymer containing a functional group that can be converted into an ammonium group or an iminium group in water, such as an amino group or an imino group is also included in the cationic polymer of the present invention.
  • an ammonium group is preferable from the viewpoint of industrial availability.
  • ammonium group any of primary ammonium group (ammonium group), secondary ammonium group (alkyl ammonium group, etc.), tertiary ammonium group (dialkyl ammonium group, etc.), quaternary ammonium group (trialkyl ammonium group, etc.) can be used. Although it can be used, a quaternary ammonium group (such as a trialkylammonium group) is more preferable.
  • the cationic polymer may contain only one type of cationic group or may contain a plurality of types of cationic groups.
  • the counter anion of the cationic group is not particularly limited, and examples thereof include halide ions, hydroxide ions, phosphate ions, and carboxylate ions. Of these, halide ions are preferred and chloride ions are more preferred from the standpoint of availability.
  • the cationic polymer may contain only one type of counter anion or may contain multiple types of counter anions.
  • Examples of the structural unit containing a cationic group in the cationic polymer include those represented by the following general formulas (1) to (8).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 2 , R 3 and R 4 each independently represents a hydrogen atom or an optionally substituted alkyl group, aryl group or aralkyl group having 1 to 18 carbon atoms.
  • R 2 , R 3 and R 4 may be connected to each other to form a saturated or unsaturated cyclic structure.
  • Z represents —O—, —NH—, or —N (CH 3 ) —, and Y represents a divalent linking group having 1 to 8 carbon atoms which may contain an oxygen, nitrogen, sulfur or phosphorus atom.
  • X ⁇ represents an anion.
  • Examples of the anion represented by X ⁇ in the general formula (1) include halide ions, hydroxide ions, phosphate ions, and carboxylate ions.
  • Examples of the cationic polymer containing the structural unit represented by the general formula (1) include 3- (meth) acrylamidepropyltrimethylammonium chloride, 3- (meth) acrylamide-3,3-dimethylpropyltrimethylammonium chloride, and the like.
  • a homopolymer or copolymer of-(meth) acrylamide-alkyltrialkylammonium salt is exemplified.
  • R 5 represents a hydrogen atom or a methyl group.
  • R 2 , R 3 , R 4 and X ⁇ are as defined in general formula (1).
  • Examples of the cationic polymer containing the structural unit represented by the general formula (2) include homopolymers or copolymers of vinylbenzyltrialkylammonium salts such as vinylbenzyltrimethylammonium chloride.
  • a homopolymer or copolymer obtained by cyclopolymerizing a diallyldialkylammonium salt such as diallyldimethylammonium chloride is exemplified.
  • n 0 or 1; R 2 and R 3 have the same meaning as in the general formula (1).
  • Examples of the cationic polymer containing the structural unit represented by the general formula (5) include allylamine homopolymers and copolymers.
  • Examples of the cationic polymer containing the structural unit represented by the general formula (6) include homopolymers or copolymers of allyl ammonium salts such as allylamine hydrochloride.
  • R 5 represents a hydrogen atom or a methyl group
  • A represents —CH (OH) CH 2 —, —CH 2 CH (OH) —, —C (CH 3 ) (OH) CH 2 —, —CH 2 C (CH 3 ) (OH) —, —CH (OH) CH 2 CH 2 —, or —CH 2 CH 2 CH (OH) —
  • E is -N (R 6) 2 or -N + (R 6) 3 ⁇
  • X - represents, R 6 represents a hydrogen atom, a methyl group or an ethyl group.
  • X ⁇ has the same meaning as in the general formula (1).
  • a cationic polymer containing the structural unit represented by the general formula (7) a homopolymer or copolymer of N- (3-allyloxy-2-hydroxypropyl) dimethylamine or a quaternary ammonium salt thereof, N— Examples include (4-allyloxy-3-hydroxybutyl) diethylamine or a quaternary ammonium salt homopolymer or copolymer thereof.
  • R 5 represents a hydrogen atom or a methyl group
  • R 7 represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an i-propyl group
  • R 8 represents a hydrogen atom, a methyl group or an ethyl group, respectively.
  • Cationic polymers containing the structural unit represented by the general formula (8) include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, etc. Is exemplified.
  • the anionic polymer in the present invention is composed of a polyvinyl alcohol containing an anionic group, or a mixture of a polymer containing an anionic group and a polyvinyl alcohol containing no ionic group.
  • the anionic polymer includes a structural unit containing an anionic group as a structural unit and a vinyl alcohol unit.
  • Plural kinds of polyvinyl alcohols containing the anionic group may be used.
  • the anionic polymer is a mixture of a polymer containing a structural unit containing an anionic group and polyvinyl alcohol containing no ionic group.
  • Plural kinds of the anionic polymer and / or polyvinyl alcohol containing no ionic group may be used. These polymers are preferably crosslinkable.
  • the anionic group contained in the anionic polymer used in the present invention may be contained in any of the main chain, side chain, and terminal of the polymer.
  • the anionic group include a sulfonate group, a carboxylate group, and a phosphonate group.
  • a polymer containing a functional group that can be converted into a sulfonate group, a carboxylate group, or a phosphonate group in water, such as a sulfonic acid group, a carboxyl group, and a phosphonic acid group, is also an anionic property of the present invention. Included in the polymer. Of these, a sulfonate group is preferred because of its large ion dissociation constant.
  • the anionic polymer may contain only one type of anionic group or may contain a plurality of types of anionic groups.
  • the counter anion of an anion group is not specifically limited, A hydrogen ion and an alkali metal ion are illustrated. Of these, alkali metal ions are preferred from the viewpoint of less equipment corrosion problems.
  • the anionic polymer may contain only one type of counter anion or may contain a plurality of types of counter anions.
  • Examples of the structural unit containing an anionic group in the anionic polymer include those represented by the following general formulas (9) and (10).
  • R 5 represents a hydrogen atom or a methyl group.
  • G represents —SO 3 H, —SO 3 ⁇ M + , —PO 3 H 2 , —PO 3 H ⁇ M + , —CO 2 H or —CO 2 ⁇ M + .
  • M + represents an ammonium ion or an alkali metal ion.
  • anionic polymer containing the structural unit represented by the general formula (9) examples include 2-acrylamido-2-methylpropanesulfonic acid homopolymer or copolymer.
  • R 5 represents a hydrogen atom or a methyl group
  • T represents a phenylene group or a naphthylene group which may be substituted with a methyl group.
  • G is synonymous with the general formula (9). ]
  • anionic polymer containing the structural unit represented by the general formula (10) examples include homopolymers or copolymers of p-styrene sulfonate such as sodium p-styrene sulfonate.
  • anionic polymer examples include homopolymers or copolymers of monomers having a sulfonic acid group or a salt thereof such as vinyl sulfonic acid and (meth) allyl sulfonic acid, fumaric acid, maleic acid, itaconic acid, Examples also include homopolymers or copolymers of monomers having a carboxyl group such as maleic anhydride and itaconic anhydride, derivatives thereof or salts thereof.
  • G is preferably a sulfonate group, a sulfonic acid group, a phosphonate group, or a phosphonic acid group that gives a higher charge density.
  • examples of the alkali metal ion represented by M + include sodium ion, potassium ion, and lithium ion.
  • the copolymerization component when the ionic polymer is a copolymer a vinyl alcohol component is used.
  • the polymer containing no ionic group may be polyvinyl alcohol having a high affinity with the polymer containing the ionic group. Used. Since polyvinyl alcohol can be easily crosslinked, a high-strength hollow fiber membrane can be obtained.
  • the ionic polymer contains polyvinyl alcohol containing an ionic group selected from a cationic group or an anionic group, or a polymer containing the ionic group and the ionic group. It is important that it consists of a mixture with polyvinyl alcohol that does not.
  • Examples of the polyvinyl alcohol containing a cationic group forming a cationic polymer include a copolymer of allylamine hydrochloride and a polyvinyl alcohol component, a copolymer of methacrylamide alkyltrialkylammonium salt and a polyvinyl alcohol component, and vinylbenzyltrialkyl.
  • Examples include a copolymer of an ammonium salt and a polyvinyl alcohol component, and a copolymer of a diallyldialkylammonium salt and a polyvinyl alcohol component.
  • a mixture of a polymer containing a cationic group and a polyvinyl alcohol not containing a cationic group which is a cationic polymer
  • a mixture of a polymer of the above and polyvinyl alcohol a mixture of a polymer of vinylbenzyltrialkylammonium salt and polyvinyl alcohol, or a mixture of a polymer of diallyldialkylammonium salt and polyvinyl alcohol.
  • the ratio of the number of vinyl alcohol units to the total number of monomer units in the cationic polymer is 50 mol% or more, and it is more preferable that it is 70 mol% or more.
  • Polyvinyl alcohol containing an anionic group forming an anionic polymer includes a copolymer of 2-acrylamido-2-methylpropane sulfonate and a polyvinyl alcohol component, p-styrene sulfonate and a polyvinyl alcohol component.
  • the copolymer of is illustrated.
  • a mixture of a polymer containing an anionic group and a polyvinyl alcohol not containing an anionic group forming an anionic polymer a mixture of a polymer of 2-acrylamido-2-methylpropane sulfonate and polyvinyl alcohol or p.
  • Examples include a mixture of a polymer of styrene sulfonate and polyvinyl alcohol.
  • the ratio of the number of vinyl alcohol units to the total number of monomer units in the anionic polymer Is preferably 50 mol% or more, and more preferably 70 mol% or more.
  • the polyvinyl alcohol containing an ionic group used in the present invention is obtained by copolymerizing an ionic monomer and a vinyl ester monomer, and saponifying this by a conventional method.
  • the vinyl ester monomer can be used as long as it can be radically polymerized. Examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl varenate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate and vinyl versatate. Among these, vinyl acetate is preferable.
  • Examples of the method of copolymerizing the ionic monomer and the vinyl ester monomer include known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these methods, a bulk polymerization method performed without a solvent or a solution polymerization method performed using a solvent such as alcohol is usually employed. When the copolymerization reaction is carried out using the solution polymerization method, examples of the alcohol used as a solvent include lower alcohols such as methanol, ethanol, and propanol.
  • Examples of the initiator used in the copolymerization reaction include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2,4-dimethyl-valeronitrile), 1,1′-azobis.
  • Azo initiators such as (cyclohexane-1-carbonitrile), 2,2′-azobis (N-butyl-2-methylpropionamide); peroxide initiators such as benzoyl peroxide and n-propyl peroxycarbonate
  • known initiators such as an agent.
  • the polymerization temperature for carrying out the copolymerization reaction is not particularly limited, but a range of 5 to 180 ° C. is appropriate.
  • the vinyl ester polymer obtained by copolymerizing an ionic monomer and a vinyl ester monomer then contains an ionic group by saponification in a solvent according to a known method.
  • Polyvinyl alcohol can be obtained.
  • Alkaline substances are usually used as catalysts for saponification reactions of vinyl ester polymers.
  • Examples thereof include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and alkali metal alkoxides such as sodium methoxide. It is done.
  • the saponification catalyst may be added all at once at the initial stage of the saponification reaction, or a part thereof may be added at the initial stage of the saponification reaction and the rest may be added and added during the saponification reaction.
  • the solvent used for the saponification reaction include methanol, methyl acetate, dimethyl sulfoxide, diethyl sulfoxide, and dimethylformamide. Among these, methanol is preferable.
  • the saponification reaction can be carried out by either a batch method or a continuous method.
  • the remaining saponification catalyst may be neutralized as necessary, and usable neutralizing agents include organic acids such as acetic acid and lactic acid, and ester compounds such as methyl acetate.
  • the degree of saponification of polyvinyl alcohol containing an ionic group is not particularly limited, but is preferably 40 to 99.9 mol%. If the degree of saponification is less than 40 mol%, the crystallinity is lowered and the strength of the resulting hollow fiber membrane may be insufficient.
  • the saponification degree is more preferably 60 mol% or more, and further preferably 80 mol% or more. Usually, the saponification degree is 99.9 mol% or less.
  • the saponification degree when the polyvinyl alcohol is a mixture of plural kinds of polyvinyl alcohols refers to the average saponification degree of the whole mixture.
  • the saponification degree of polyvinyl alcohol is a value measured according to JIS K6726.
  • the saponification degree of polyvinyl alcohol containing no ionic group used in the present invention is also preferably in the above range.
  • the viscosity-average polymerization degree of polyvinyl alcohol containing an ionic group (hereinafter sometimes simply referred to as polymerization degree) is not particularly limited, but is preferably 50 to 10,000. If the degree of polymerization is less than 50, there is a possibility that the hollow fiber membrane cannot maintain sufficient strength in practical use. More preferably, the degree of polymerization is 100 or more. If the degree of polymerization exceeds 10,000, the polymer solution used for spinning may be too viscous to handle. The degree of polymerization is more preferably 8000 or less. At this time, the polymerization degree in the case where the polyvinyl alcohol is a mixture of plural kinds of polyvinyl alcohols means an average polymerization degree as the whole mixture.
  • the viscosity average polymerization degree of polyvinyl alcohol is a value measured according to JIS K6726.
  • the polymerization degree of polyvinyl alcohol containing no ionic group used in the present invention is also preferably within the above range.
  • a block copolymer or a graft copolymer containing a polymer component obtained by polymerizing an ionic monomer and a polyvinyl alcohol component is preferably used as the ionic polymer.
  • the ionic polymer is microphase-separated, and the polyvinyl alcohol component that plays a role in improving the strength of the entire hollow fiber membrane, suppressing the swelling degree of the membrane and maintaining the shape, and the cation or anion are permeated.
  • the role of the polymer component obtained by polymerizing the ionic monomer having the function can be shared, and both the degree of swelling and the dimensional stability of the hollow fiber membrane can be achieved.
  • the structural unit of the polymer component obtained by polymerizing the ionic monomer is not particularly limited, but those represented by the general formulas (1) to (10) are exemplified.
  • a cationic polymer a block copolymer containing a polymer component obtained by polymerizing a methacrylamide alkyltrialkylammonium salt and a polyvinyl alcohol component, vinylbenzyltrialkyl, because it is easily available.
  • a block copolymer containing a polymer component obtained by polymerizing p-styrene sulfonate and a polyvinyl alcohol component or 2-acrylamido-2-methylpropane sulfonate is polymerized.
  • Contains a polymer component and a polyvinyl alcohol component Lock copolymer is preferably used.
  • the method for producing a block copolymer containing a polymer component obtained by polymerizing an ionic monomer used in the present invention and a polyvinyl alcohol component is roughly classified into the following two methods.
  • one or more types of monomers are block copolymerized in the presence of polyvinyl alcohol having a mercapto group at the terminal, and then one or more types of polymer in the block copolymer are copolymerized.
  • a block copolymer is produced by radical polymerization of at least one ionic monomer in the presence of polyvinyl alcohol having a mercapto group at the terminal.
  • the method to do is preferable from industrial ease.
  • the kind and amount of each component of the polymer component obtained by polymerizing the polyvinyl alcohol component and the ionic monomer in the block copolymer can be easily controlled, the presence of polyvinyl alcohol having a mercapto group at the terminal
  • a method of producing a block copolymer by radical polymerization of at least one ionic monomer is preferred.
  • a vinyl alcohol polymer having a mercapto group at the terminal used for the production of these block copolymers can be obtained, for example, by the method described in JP-A-59-187003. That is, a method of saponifying a vinyl ester polymer obtained by radical polymerization of a vinyl ester monomer such as vinyl acetate in the presence of thiolic acid can be mentioned.
  • a method for obtaining a block copolymer using the thus obtained polyvinyl alcohol having a mercapto group at the terminal and an ionic monomer for example, the method described in JP-A-59-189113 or the like is used. Can be mentioned.
  • a block copolymer can be obtained by radical polymerization of an ionic monomer in the presence of polyvinyl alcohol having a mercapto group at the terminal.
  • This radical polymerization can be carried out by a known method such as bulk polymerization, solution polymerization, pearl polymerization, emulsion polymerization, etc., but mainly comprises a solvent capable of dissolving polyvinyl alcohol containing a mercapto group at the terminal, such as water or dimethyl sulfoxide. It is preferable to carry out in a solvent.
  • any of a batch method, a semi-batch method, and a continuous method can be employed.
  • the ionic monomer content of the ionic polymer is not particularly limited, the ionic monomer content of the ionic polymer, that is, the ionic monomer amount relative to the total number of monomer units in the ionic polymer
  • the ratio of the number of body units is preferably 0.1 to 50 mol%.
  • the ionic monomer content is less than 0.1 mol%, the effective charge density in the hollow fiber membrane is lowered, and the counter ion selectivity of the membrane may be lowered.
  • the content is more preferably 0.5 mol% or more, and further preferably 1 mol% or more.
  • the ionic monomer content exceeds 50 mol%, the degree of swelling of the hollow fiber membrane increases, and the mechanical strength may be reduced.
  • the content is more preferably 30 mol% or less, and further preferably 20 mol% or less.
  • the ionic monomer content when the ionic polymer is a mixture of plural types of polymers refers to the ratio of the number of ionic monomer units to the total number of monomer units in the mixture.
  • the hollow fiber membrane of the present invention may contain various additives such as an inorganic filler as long as the object of the present invention is not impaired.
  • the inner diameter of the hollow fiber membrane of the present invention is preferably 100 to 2000 ⁇ m. If the inner diameter is less than 100 ⁇ m, clogging with foreign substances in the processing solution may occur.
  • the inner diameter is more preferably 130 ⁇ m or more, and further preferably 150 ⁇ m or more. If the inner diameter exceeds 2000 ⁇ m, the specific surface area of the membrane may be insufficient and dialysis efficiency may be deteriorated.
  • the inner diameter is more preferably 1500 ⁇ m or less, and even more preferably 1000 ⁇ m or less.
  • the outer diameter of the hollow fiber membrane of the present invention is preferably 101 to 3000 ⁇ m. If the outer diameter is less than 101 ⁇ m, the strength of the hollow fiber may be inferior.
  • the outer diameter is more preferably 130 ⁇ m or more, and further preferably 150 ⁇ m or more. If the outer diameter exceeds 3000 ⁇ m, the specific surface area of the membrane may be insufficient and dialysis efficiency may be deteriorated.
  • the outer diameter is more preferably 2500 ⁇ m or less, and further preferably 2000 ⁇ m or less.
  • the thickness of the hollow fiber membrane of the present invention is preferably 0.1 to 500 ⁇ m. If the film thickness is less than 0.1 ⁇ m, the mechanical strength may decrease. The film thickness is more preferably 0.3 ⁇ m or more, and further preferably 1 ⁇ m or more. If the film thickness exceeds 500 ⁇ m, the permeation flux may be reduced. The film thickness is more preferably 300 ⁇ m or less, and further preferably 100 ⁇ m or less.
  • the hollow fiber membrane of the present invention is preferably produced by forming a hollow fiber membrane by spinning a spinning stock solution consisting of a solution containing an ionic polymer from an annular nozzle, introducing the solution into a coagulation liquid and solidifying it. Is done. According to such a production method, the hollow fiber membrane can be produced easily and at low cost.
  • the ionic polymer is dissolved in the spinning dope.
  • the solvent is not particularly limited as long as the ionic polymer is soluble, and water, dimethyl sulfoxide, and dimethylformamide are exemplified, and water is preferable from the viewpoint of safety.
  • the spinning dope is acidified by further dissolving boric acid or a water-soluble salt thereof (for example, borax) and further dissolving another acid selected from inorganic acids and organic acids (for example, acetic acid). By doing so, a boric acid crosslinking reaction occurs between the hydroxyl groups of the polyvinyl alcohol unit in the coagulation liquid, and the hollow fiber membrane can be molded well.
  • it is preferable to defoam the spinning stock solution by allowing it to stand in the spinning stock solution tank for several tens of minutes to several hours before spinning.
  • the spinning solution is spun from an annular nozzle.
  • the inner diameter and outer diameter of the annular nozzle are appropriately selected in consideration of the dimensions of the hollow fiber membrane to be manufactured. It is preferable to heat the spinning dope when spinning from the annular nozzle.
  • a suitable temperature is 50 to 100 ° C. By heating, the viscosity of the spinning dope is lowered and the spinning operation becomes easy.
  • the extrusion pressure at the time of spinning the spinning dope is appropriately selected depending on the viscosity of the spinning dope, but is usually 0.01 to 1 MPa.
  • the spinning dope spun from the annular nozzle is introduced into the coagulation solution. From the viewpoint of controlling the film morphology, it may be introduced into the coagulating liquid after passing through a certain length of air from the outlet of the annular nozzle to the liquid level of the coagulating liquid.
  • the coagulation liquid is not particularly limited as long as it exhibits coagulation properties with respect to the spinning dope, and an aqueous solution is usually used.
  • an alkaline aqueous solution in which an alkali such as sodium hydroxide and / or a salt such as sodium sulfate is dissolved in the case of an anionic hollow fiber membrane, an acid such as sulfuric acid and / or An acidic aqueous solution in which a salt such as sodium sulfate is dissolved is used.
  • the temperature of the coagulation liquid is preferably lower than that of the spinning dope, and is preferably 0 to 50 ° C. The spinning dope introduced into the coagulation liquid is coagulated to form a hollow fiber membrane.
  • the spinning dope is supplied to the annular nozzle and the coagulating solution is supplied to the inside of the annular nozzle to simultaneously spin the spinning dope and the coagulating solution.
  • the coagulation liquid supplied to the inside may be any one that exhibits coagulation properties with respect to the spinning dope. It is possible to use the same coagulation liquid as the spinning dope introduced and coagulated.
  • the hollow fiber membrane thus obtained may then be washed by immersing it in an acidic aqueous solution or the like in order to cut the crosslinking.
  • an acidic aqueous solution an aqueous solution in which an acid such as sulfuric acid and, if necessary, a salt such as sodium sulfate is dissolved is used. Further, after that, in order to remove boric acid and other acids, washing may be performed by dipping in an aqueous solution in which a salt such as sodium sulfate is dissolved.
  • the method for producing a hollow fiber membrane of the present invention it is preferable to perform a stretching treatment after forming the hollow fiber membrane.
  • the stretching treatment By performing the stretching treatment, the molecular chains of PVA are oriented in the stretching direction and crystallization is promoted.
  • ionic groups are excluded from the PVA matrix because they are less likely to be present in the PVA crystallization region. For this reason, an ionic group will localize in a hollow membrane, the density of the charged group in a membrane will increase, and ion selectivity will improve.
  • the method for the stretching treatment is not particularly limited, and a uniaxial stretching machine or the like is generally used.
  • the draw ratio is preferably 2 times or more, and more preferably 3 times or more. If the draw ratio is too high, the hollow fiber membrane may break, so it is usually 10 times or less and preferably 5 times or less.
  • the temperature of the stretching treatment is not particularly limited, but is preferably 0 to 250 ° C. If the temperature of the stretching treatment is less than 0 ° C., the temperature becomes lower than the glass transition point of the PVA matrix, the flexibility is lowered, and the stretchability of the hollow fiber membrane may be insufficient.
  • the temperature is more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. When the temperature of heat processing exceeds 250 degreeC, there exists a possibility that an ionic group may thermally decompose or polyvinyl alcohol may melt
  • the temperature is more preferably 230 ° C. or less, further preferably 220 ° C. or less, and particularly preferably 200 ° C. or less.
  • the stretching treatment is usually performed before the heat treatment and / or crosslinking treatment described later.
  • the method for producing a hollow fiber membrane of the present invention it is preferable to perform heat treatment after forming the hollow fiber membrane.
  • the degree of crystallinity increases, so that the number of physical cross-linking points increases and the mechanical strength of the resulting hollow fiber membrane increases.
  • the ionic groups are concentrated in the amorphous part and the formation of the ion exchange path is promoted, the charge density is increased and the counter ion selectivity is improved.
  • the method of heat treatment is not particularly limited, and a hot air dryer or the like is generally used.
  • the temperature of the heat treatment is not particularly limited, but is preferably 50 to 250 ° C.
  • the temperature of the heat treatment is less than 50 ° C., the mechanical strength of the resulting hollow fiber membrane may be insufficient.
  • the temperature is more preferably 80 ° C. or higher, and further preferably 100 ° C. or higher.
  • the temperature of heat processing exceeds 250 degreeC, there exists a possibility that an ionic group may thermally decompose or a polyvinyl alcohol may melt
  • the temperature is more preferably 230 ° C. or less, further preferably 220 ° C. or less, and particularly preferably 200 ° C. or less.
  • the heat treatment time is usually 1 minute to 10 hours.
  • the heat treatment is desirably performed in an inert gas (eg, nitrogen gas, argon gas, etc.) atmosphere.
  • the method for producing a hollow fiber membrane of the present invention it is preferable to perform a crosslinking treatment after forming the hollow fiber membrane.
  • the method for the crosslinking treatment is not particularly limited as long as it is a method capable of bonding the molecular chains of the polymer by chemical bonding.
  • a method of immersing the hollow fiber membrane in a crosslinking treatment solution containing a crosslinking agent is used.
  • the crosslinking agent include glutaraldehyde, formaldehyde, and glyoxal.
  • the concentration of the crosslinking agent is usually 0.001 to 1% by volume of the volume of the crosslinking agent with respect to the solution.
  • both heat treatment and crosslinking treatment may be performed, or only one of them may be performed.
  • the crosslinking treatment may be performed after the heat treatment, the heat treatment may be performed after the crosslinking treatment, or both may be performed simultaneously. It is preferable from the viewpoint of mechanical strength of the resulting hollow fiber membrane to perform a crosslinking treatment after the heat treatment.
  • the hollow fiber membrane of the present invention can be used for various applications.
  • the hollow fiber membrane of the present invention is suitably used for Donnan dialysis because it has a large ion permeation flux, a large selection coefficient, and excellent mechanical strength.
  • removal of trace ions recovery of useful metals from waste liquids, exchange of counter ions of organic acids, softening of hard water, recovery of acids and alkalis, neutralization dialysis, humidity adjusting members (for humidification, dehumidification, Suitable for moisturizing).
  • FIG. 1 A schematic diagram of the Donnan permeation test apparatus is shown in FIG. In FIG. 1, the flow of the solution (hereinafter referred to as “external solution”) through which the left circulation line passes through the outside of the hollow fiber membrane, Flow).
  • An aqueous solution containing ⁇ 10 -4 M at a concentration of driving force ions at a concentration of 0.1 M was charged so that the total amount of the external solution was 800 mL.
  • the permeation test process was performed in parallel flow, and the internal solution and the external solution were each circulated using a liquid feed pump.
  • the Donnan dialysis test was performed at a temperature of 25 ° C. After starting the test, the internal solution was sampled at a predetermined time, and the concentrations of ions to be removed and driving force ions in the internal solution were measured using an ion chromatograph. The slope of the graph of ion concentration with time as shown in FIG. 4 was obtained by linear approximation, and the initial concentration gradient ( ⁇ Ci / ⁇ t) was calculated.
  • J i V ⁇ ⁇ C i / (S ⁇ ⁇ t)
  • i a (removal target ion) or b (driving force ion).
  • the selection coefficient ⁇ is defined by the following equation.
  • Example 1 Preparation of cationic hollow fiber (C-HF-1) membrane) (Preparation of spinning dope)
  • the acetic acid was weighed, placed in 650 g of deionized water, and heated and dissolved at 90-100 ° C. for 4 hours or longer to obtain a spinning dope.
  • PAAm PAA-HCL-10S manufactured by Nitto Boseki Co., Ltd. was used as PAAm.
  • the “PAAm” has a weight average molecular weight of about 80,000.
  • PVA PVA-124 manufactured by Kuraray Co., Ltd. was used.
  • the polymerization degree of the “PVA-124” is 2400, and the saponification degree of vinyl alcohol units is 98.5 mol%.
  • the acidic bath solution was prepared by adding 20 g of sulfuric acid and 300 g of sodium sulfate to 800 g of deionized water.
  • a cleaning solution was prepared by adding 360 g of sodium sulfate to 800 g of deionized water.
  • Hollow fiber membranes were prepared by dry and wet spinning. A schematic view of the spinning device is shown in FIG. An annular nozzle having an outer diameter of 2.0 mm and an inner diameter of 0.4 mm was used. The spinning dope prepared above was charged into a tank and allowed to stand for about 1 hour for defoaming. The tank was heated so that the temperature of the spinning dope was 80 ° C. during spinning. A coagulation liquid having the same composition as the external coagulation liquid in the coagulation bath was used as the internal coagulation liquid. Both internal and external coagulation solutions were used at 25 ° C.
  • the internal coagulation liquid was started to be supplied to the inside of the annular nozzle at 32 mL / min.
  • the extrusion pressure was basically 0.1 MPa.
  • the spun stock solution thus spun was introduced into an external coagulation liquid in a coagulation bath through a 15 cm air gap.
  • the formed hollow fiber membrane was passed through a pressing rod and then pulled up with a roller, and again entered into the external coagulation liquid, and was allowed to become familiar with the coagulation liquid for about 10 minutes.
  • the winding speed was 1850 cm / min.
  • the hollow fiber membrane thus obtained was taken out from the coagulation bath, and the hollow fiber membrane was wound and fixed on a mold. With the hollow fiber membrane fixed to the mold, it was immersed in an acidic bath solution for 5 minutes to cut the crosslink. It was then immersed in a cleaning solution to remove boric acid and acid. The produced hollow fiber membrane was stored in a saturated sodium sulfate aqueous solution.
  • the hollow fiber membrane obtained above was lightly immersed in ethanol to remove the salt attached to the hollow fiber membrane, and then wound up and fixed to the mold.
  • the fixed hollow fiber membrane was dried in an oven at 80 ° C. under reduced pressure for 5 hours. Thereafter, heat treatment was performed at 160 ° C. for 10 minutes in a reduced pressure state. After heat treatment, the hollow fiber membrane was removed from the mold and stored in a saturated aqueous sodium sulfate solution.
  • a hollow fiber membrane fixed element is referred to as a hollow fiber membrane element
  • a hollow fiber membrane element incorporated into the apparatus and ready for dialysis is referred to as a module.
  • the hollow fiber membrane was dried under reduced pressure, then both ends were hardened with an epoxy resin, and the end of the epoxy resin was cut off so that the solution could pass.
  • one hollow fiber membrane was incorporated into the hollow fiber membrane element.
  • an acrylic rod was incorporated as a reinforcing material to improve operability.
  • the produced hollow fiber membrane element is shown in FIG.
  • the cross-section of the produced hollow fiber membrane was observed in a wet state under atmospheric pressure using a color 3D laser microscope, and the image was taken.
  • the obtained image is shown in FIG. Table 1 shows values of the inner diameter, outer diameter, and film thickness (d) of the hollow fiber membrane calculated from this image.
  • the cross section of the produced hollow fiber membrane was observed using the scanning electron microscope (SEM), and the image was image
  • the obtained image is shown in FIG.
  • Example 2 the glutaraldehyde concentration in the crosslinking treatment liquid was changed to 0.05 volume% (Example 2) and 0.1 volume% (Example 3), and was the same as in Example 1.
  • Example 3 a hollow fiber membrane was produced.
  • the Donan dialysis test of the hollow fiber membrane thus obtained was carried out in the same manner as in Example 1. The obtained results are plotted in FIG. 14 and FIG.
  • Example 4 (Preparation of anionic hollow fiber (AP-2-HF) membrane) (Synthesis of anionic polymer AP-2)
  • a methanol solution containing 2340 g of vinyl acetate, 640 g of methanol, and 25% by mass of sodium 2-acrylamido-2-methylpropanesulfonate.
  • 25.7 g of a methanol solution containing 2340 g of vinyl acetate, 640 g of methanol, and 25% by mass of sodium 2-acrylamido-2-methylpropanesulfonate.
  • the inside of the system was purged with nitrogen under stirring, and then the internal temperature was raised to 60 ° C.
  • 20 g of methanol containing 1.2 g of 2,2′-azobisisobutyronitrile was added to initiate the polymerization reaction.
  • AP-2 which is a polyvinyl alcohol containing 2 mol% of sodium 2-acrylamido-2-methylpropanesulfonate.
  • AP-2 is represented by the following structural formula.
  • the viscosity of the 4% aqueous solution was 33.1 mPa ⁇ s (20 ° C.), the polymerization degree was 1900, and the saponification degree was 99.2 mol%.
  • Example 1 (Production of hollow fiber membrane) In Example 1, instead of using a mixture of polyallylamine hydrochloride (PAAm) which is a cationic polymer and polyvinyl alcohol (PVA), 100 g of “AP-2” which is an anionic polymer was used. In the same manner as in Example 1, an AP-2-HF membrane that is an anionic hollow fiber (A-HF) membrane was produced.
  • PAAm polyallylamine hydrochloride
  • PVA polyvinyl alcohol
  • Example 1 The Donan dialysis test of the anionic hollow fiber membrane thus obtained was performed.
  • NO 3 as the removal target ion - with Ca 2+ ions instead of the ion
  • Cl as a driving force ion - with Na + ions instead of the ion
  • Cl as a counter anion - except using ion implementation
  • the test was conducted in the same manner as in Example 1, and the permeation flux and the selection coefficient were measured.
  • the obtained results are plotted in FIG. 16 (permeation flux) and FIG. 17 (selection coefficient).
  • Example 4 the same procedure as in Example 4 was repeated, except that the glutaraldehyde concentration in the crosslinking treatment solution was changed to 0.05% by volume (Example 5) and 0.1% by volume (Example 6). Thus, a hollow fiber membrane was produced.
  • the Donan dialysis test of the hollow fiber membrane thus obtained was carried out in the same manner as in Example 4. The obtained results are plotted in FIG. 16 (permeation flux) and FIG. 17 (selection coefficient).
  • Example 7 Preparation of cationic hollow fiber (C-HF-2) membrane
  • Reference example synthesis of a polyvinyl alcohol polymer having a mercapto group at the molecular end
  • Polyvinyl alcohol (PVA-1) having an average molecular weight of 1500 and a saponification degree of 98.5 mol% and having a mercapto group at the molecular end was synthesized by the method described in Patent Document 1.
  • the system was purged with nitrogen by bubbling nitrogen into the aqueous solution for 30 minutes.
  • 171 mL of a 2.5% aqueous solution of potassium persulfate was sequentially added to the above aqueous solution over 1.5 hours to start and proceed with block copolymerization, and then the system temperature was maintained at 75 ° C. for 1 hour.
  • the polymerization was further advanced, and then cooled to obtain an aqueous PVA- (b) -p-vinylbenzyltrimethylammonium chloride copolymer aqueous solution having a solid content of 17%.
  • a part of the obtained aqueous solution was dried, dissolved in heavy water, and subjected to 1 H-NMR measurement at 400 MHz.
  • the amount of modification of the vinylbenzyltrimethylammonium chloride unit was 8 mol%.
  • the viscosity of the 4% aqueous solution measured with a B-type viscometer was 18 milliPa ⁇ s (20 ° C.).
  • Example 1 (Production of hollow fiber membrane) In Example 1, instead of using a mixture of the cationic polymer polyallylamine hydrochloride (PAAm) and polyvinyl alcohol (PVA), the above PVA- (b) -p-vinylbenzyltrimethylammonium chloride block copolymer was used. A spinning dope was obtained in the same manner as in Example 1 except that 100 g of the coalescence was used. A cationic hollow fiber (C-HF-2) membrane was produced from the obtained spinning dope by the same dry and wet spinning as in Example 1.
  • PAAm cationic polymer polyallylamine hydrochloride
  • PVA polyvinyl alcohol
  • a cationic hollow fiber (C-HF-2) membrane was produced from the obtained spinning dope by the same dry and wet spinning as in Example 1.
  • Example 7 the glutaraldehyde concentration in the cross-linking solution is 0.05% by volume (Example 8), 0.075% by volume (Example 9), and 0.1% by volume (Example 10).
  • a hollow fiber (C-HF-2) membrane was produced in the same manner as in Example 7 except that The Donnan dialysis test of the obtained hollow fiber membrane was conducted in the same manner as in Example 7. The obtained results are plotted in FIG. 18 (permeation flux) and FIG. 19 (selection coefficient).
  • Example 11 (Preparation of stretched cationic hollow fiber (C-HF-3) membrane) (Production of stretched hollow fiber membrane)
  • PAAm polyallylamine hydrochloride
  • PVA polydiallyldimethylammonium chloride
  • PVA polyvinyl alcohol
  • the hollow fiber membrane thus obtained was installed in a uniaxial stretching machine 11AO (Imoto Seisakusho Co., Ltd.), the distance between chucks was set to 5 cm, and a stretching treatment at a stretching ratio of 2 was performed at a temperature of 50 ° C. A hollow fiber membrane subjected to stretching treatment was produced.
  • the hollow fiber membrane obtained above was lightly immersed in ethanol to remove the salt attached to the hollow fiber membrane, and then wound up and fixed to the mold.
  • the fixed hollow fiber membrane was dried in an oven at 80 ° C. under reduced pressure for 5 hours. Thereafter, heat treatment was performed at 160 ° C. for 10 minutes in a reduced pressure state. After heat treatment, the hollow fiber membrane was removed from the mold and stored in a saturated aqueous sodium sulfate solution.
  • Example 12 a hollow fiber membrane subjected to stretching treatment was produced in the same manner as in Example 11 except that the stretching ratio was changed to 3 times (Example 12) and 4 times (Example 13). did.
  • the Donan dialysis test of the obtained hollow fiber membrane was conducted in the same manner as in Example 11. The obtained results are shown in Table 3.
  • FIG. 20 shows the relationship between nitrate ion permeation flux and selectivity when the draw ratio is changed.
  • Example 14 In Example 11, an unstretched hollow fiber membrane was produced using the same method as in Example 11 except that the stretching process was not performed.
  • the Donan dialysis test of the obtained hollow fiber membrane was conducted in the same manner as in Example 11. The obtained results are shown in Table 3. Also for this unstretched hollow fiber membrane, the relationship between the nitrate ion permeation flux and the selection coefficient is shown in FIG.
  • Example 1 Preparation of PVA hollow fiber (N-HF) membrane
  • Example 1 Preparation of spinning dope
  • PVA-124 100% of polyvinyl alcohol “PVA-124” was used.
  • PVA-HF which is a yarn (N-HF) membrane
  • the cross section of the PVA hollow fiber membrane thus obtained was observed using a color 3D laser microscope in the same manner as in Example 1 to obtain an image.
  • the obtained image is shown in FIG.
  • Table 1 shows values of the inner diameter, outer diameter, and film thickness (d) of the hollow fiber membrane calculated from this image. Furthermore, it observed using the scanning electron microscope (SEM) and obtained the image. The obtained image is shown in FIG.
  • Comparative Examples 2 and 3 Comparative Example 1 was the same as Comparative Example 1 except that the glutaraldehyde concentration in the crosslinking treatment solution was changed to 0.05% by volume (Comparative Example 2) and 0.1% by volume (Comparative Example 3). Thus, a hollow fiber membrane was produced.
  • the Donnan dialysis test for anion dialysis of the PVA hollow fiber membrane thus obtained was carried out in the same manner as in Example 1. The obtained results are plotted in FIG. 14 (permeation flux) and FIG. 15 (selection coefficient).
  • a Donnan dialysis test for cationic dialysis of the obtained PVA hollow fiber membrane was conducted in the same manner as in Example 4. The obtained results are plotted in FIG. 16 (permeation flux) and FIG. 17 (selection coefficient).
  • the C-HF-1 membrane has both permeation flux and selectivity. It turns out that it shows a high value. This is because the charge group (cation group) of the C—HF-1 membrane suppresses the flux of cations (Na + ions) that are side ions, so that nitrate ions are diffused along with the diffusion of chloride ions that are driving force ions. This is thought to be due to the fact that it became easier to transport against the concentration gradient.
  • the moisture content of the membrane decreases when the concentration of glutaraldehyde, which is a cross-linking agent, increases, the permeation flux of both ions to be removed and the driving force ions decreases. It can be seen that as the charge density increases, the selectivity factor ⁇ increases, indicating higher counter-ion selective permeability. Thus, it can be said that the C—HF-1 membrane is more suitable for concentration and separation of NO 3 ⁇ ions than the N—HF membrane.
  • the selectivity coefficient ⁇ was about half that of the commercially available anion exchange membrane (AM-1). This is because the commercial ion exchange membrane has a higher membrane charge density.
  • the permeation flux of the C-HF-1 membrane is about 3 times that of the commercially available membrane, and the hollow fiber membrane can produce a module with a larger membrane area per unit volume. Can be constructed.
  • AP-2-HF membrane which is an anionic hollow fiber membrane, and N-HF membrane made of PVA
  • AP-2-HF membrane has both permeation flux and selectivity coefficient. It turns out that it shows a high value. This is because the charge of the AP-2-HF membrane (anion group) suppresses the flux of the anion (Cl 2 ⁇ ion) as a secondary ion, and therefore, Ca 2+ ions are diffused along with the diffusion of Na + ions as driving force ions. This is because it became easier to transport against the concentration gradient.
  • the selectivity coefficient ⁇ increases as the charge density increases as the concentration of the cross-linking agent increases, and is 1 in the AP-2-HF membrane when using a cross-linking solution having a glutaraldehyde concentration of 0.1% by volume. (A value of 1 or more is an experimental error). That is, it has 100% selective permeability.
  • the AP-2-HF membrane is more suitable for the concentration and separation of polyvalent cations than the N-HF membrane.
  • the permeation flux of the AP-2-HF membrane is about twice that of the commercially available membrane, and the selectivity coefficient ⁇ is such that the glutaraldehyde concentration is 0.1% by volume.
  • the selectivity coefficient ⁇ is such that the glutaraldehyde concentration is 0.1% by volume.
  • FIG. 15 and FIG. 19 show that when the results of the C-HF-1 film and the C-HF-2 film are compared, the C-HF-2 film shows a high selectivity coefficient although the amount of modification is the same. .
  • the C-HF-1 membrane is a blend of PVA and a cationic polymer, so it has a macro layer separation structure, ion channels are non-uniformly present, and communication holes are difficult to form.
  • a C—HF-2 membrane made of a block copolymer of PVA and a cationic polymer has a micro layer separation structure, so that ion channels exist more uniformly and communication holes are easily formed. That is, it can be said that the C-HF-2 membrane is more suitable for the concentration and separation of anions than the C-HF-1 membrane.
  • FIG. 20 shows that when the stretching ratio of the C—HF-3 membrane is increased, the permeation flux of NO 3 ⁇ ions to be removed can be increased and the selectivity coefficient can be increased.
  • the molecular chain of PVA is oriented in the stretching direction and crystallization is promoted.
  • the cationic group is hardly present in the crystallization region of PVA, it is easily excluded from the PVA matrix. For this reason, cation groups are localized in the hollow fiber membrane, which increases the density of charged groups in the membrane and improves the ion selectivity. From these facts, it can be said that the C—HF-2 membrane, which is a block copolymer, is more suitable for the concentration and separation of anions than the C—HF-1 membrane, which is a mixture of PAAm and PVA.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne une membrane à fibres creuses comprenant un polymère ionique choisi parmi des polymères cationiques et des polymères anioniques, dans laquelle ledit polymère ionique comprend soit un alcool polyvinylique contenant un groupe ionique choisi parmi des groupes cationiques et des groupes anioniques, soit un mélange comprenant un polymère contenant ledit groupe ionique et un alcool polyvinylique ne contenant pas ledit groupe ionique. Une membrane à fibres creuses ayant un flux de perméation ionique et un coefficient de sélectivité élevés et une excellente résistance mécanique peut être obtenue en utilisant un tel polymère ionique. Idéalement, la teneur en monomère ionique à l'intérieur du polymère ionique est de 0,1 à 50 % en moles. La membrane à fibres creuses est appropriée pour une utilisation dans une dialyse de Donnan.
PCT/JP2010/059749 2009-06-09 2010-06-09 Membrane à fibres creuses et son procédé de fabrication WO2010143647A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2011518551A JP5637483B2 (ja) 2009-06-09 2010-06-09 中空糸膜およびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009137907 2009-06-09
JP2009-137907 2009-06-09

Publications (1)

Publication Number Publication Date
WO2010143647A1 true WO2010143647A1 (fr) 2010-12-16

Family

ID=43308902

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/059749 WO2010143647A1 (fr) 2009-06-09 2010-06-09 Membrane à fibres creuses et son procédé de fabrication

Country Status (2)

Country Link
JP (1) JP5637483B2 (fr)
WO (1) WO2010143647A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014210056A (ja) * 2013-04-18 2014-11-13 国立大学法人山梨大学 血液浄化器
JP2015164977A (ja) * 2014-02-28 2015-09-17 富士フイルム株式会社 イオン交換性ポリマー、高分子機能性膜および高分子機能性膜の製造方法
JP2015188867A (ja) * 2014-03-28 2015-11-02 次世代型膜モジュール技術研究組合 ガス分離膜

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07236889A (ja) * 1993-04-21 1995-09-12 Nippon Rensui Kk 純水製造装置
JPH11235521A (ja) * 1998-02-23 1999-08-31 Kuraray Co Ltd 延伸二段凝固によるビニルアルコール系重合体分離膜の製造方法
JP2001515407A (ja) * 1997-03-14 2001-09-18 コック メンブラン システムズ インコーポレーテッド 透析膜及びそれらの製造法
JP2001519711A (ja) * 1997-03-14 2001-10-23 エクソン リサーチ アンド エンジニアリング カンパニー ポリアミンポリマーおよびブレンド中にアミノ酸塩を含んでなる膜
JP2006328536A (ja) * 2005-05-25 2006-12-07 Enthone Inc 電解質のイオン濃度を設定する方法及びその装置
JP2008188518A (ja) * 2007-02-02 2008-08-21 Yamaguchi Univ イオンバリヤー膜および該イオンバリヤー膜を使用した分離装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55148210A (en) * 1979-04-30 1980-11-18 Kuraray Co Ltd Preparation of hollow ethylene-vinyl alcohol membrane
JPS58116361A (ja) * 1981-12-28 1983-07-11 株式会社クラレ 血液処理膜の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07236889A (ja) * 1993-04-21 1995-09-12 Nippon Rensui Kk 純水製造装置
JP2001515407A (ja) * 1997-03-14 2001-09-18 コック メンブラン システムズ インコーポレーテッド 透析膜及びそれらの製造法
JP2001519711A (ja) * 1997-03-14 2001-10-23 エクソン リサーチ アンド エンジニアリング カンパニー ポリアミンポリマーおよびブレンド中にアミノ酸塩を含んでなる膜
JPH11235521A (ja) * 1998-02-23 1999-08-31 Kuraray Co Ltd 延伸二段凝固によるビニルアルコール系重合体分離膜の製造方法
JP2006328536A (ja) * 2005-05-25 2006-12-07 Enthone Inc 電解質のイオン濃度を設定する方法及びその装置
JP2008188518A (ja) * 2007-02-02 2008-08-21 Yamaguchi Univ イオンバリヤー膜および該イオンバリヤー膜を使用した分離装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MITSURU HIGA ET AL., JOURNAL OF MEMBRANE SCIENCE, vol. 49, 1990, pages 145 - 149 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014210056A (ja) * 2013-04-18 2014-11-13 国立大学法人山梨大学 血液浄化器
JP2015164977A (ja) * 2014-02-28 2015-09-17 富士フイルム株式会社 イオン交換性ポリマー、高分子機能性膜および高分子機能性膜の製造方法
JP2015188867A (ja) * 2014-03-28 2015-11-02 次世代型膜モジュール技術研究組合 ガス分離膜

Also Published As

Publication number Publication date
JPWO2010143647A1 (ja) 2012-11-22
JP5637483B2 (ja) 2014-12-10

Similar Documents

Publication Publication Date Title
KR101768434B1 (ko) 모자이크 하전 복층막 및 그 제조 방법
WO2010119858A1 (fr) Membrane échangeuse d'ions et procédé de production associé
JP6329184B2 (ja) 両親媒性ブロックを有するコポリマー、及びポリマー濾過膜を製造するためのその使用
KR20090024393A (ko) 개질화된 불소수지막의 제조방법
JP5965307B2 (ja) イオン交換膜、その製造方法および電気透析装置
JP5637483B2 (ja) 中空糸膜およびその製造方法
US9833742B2 (en) Cation exchange membrane and method for producing same
KR101458442B1 (ko) 친수성 고분자로 그라프트된 나노입자를 이용한 여과막 및 그 제조 방법
JP6270094B2 (ja) 減塩醤油の製造方法
JP5965308B2 (ja) イオン交換膜、その製造方法および逆電気透析発電装置
JP2012071286A (ja) モザイク荷電膜の製造方法
JP2014124562A (ja) イオン交換膜、その製造方法および逆電気透析発電装置
JP2016195976A (ja) 正浸透膜およびその製造方法
JP6018005B2 (ja) 硝酸イオンの分離方法
US10752716B2 (en) Copolymers and terpolymers based on chlorotrifluoroethylene and vinyl chloride and uses thereof
JP2014088514A (ja) 陰イオン交換膜及びその製造方法
JP5633847B2 (ja) モザイク荷電膜およびその製造方法
JP2016195977A (ja) 正浸透膜およびその製造方法
JP6202609B2 (ja) 酸の回収方法
WO2021049623A1 (fr) Film composite et procédé de fabrication de film composite
JP6172662B2 (ja) 塩の製造方法
JP6053514B2 (ja) 有機物の脱塩方法
JP2006169457A (ja) 多孔質体の製造方法
JP2000176259A (ja) ポリビニルアルコール系中空繊維膜およびその製造方法
EP3621997A1 (fr) Copolymères et terpolymères à base de chlorotrifluoroéthylène et de chlorure de vinyle et leurs utilisations

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10786178

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2011518551

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10786178

Country of ref document: EP

Kind code of ref document: A1