WO2014002613A1 - Membrane semi-perméable composite et procédé de production associé - Google Patents

Membrane semi-perméable composite et procédé de production associé Download PDF

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Publication number
WO2014002613A1
WO2014002613A1 PCT/JP2013/062917 JP2013062917W WO2014002613A1 WO 2014002613 A1 WO2014002613 A1 WO 2014002613A1 JP 2013062917 W JP2013062917 W JP 2013062917W WO 2014002613 A1 WO2014002613 A1 WO 2014002613A1
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Prior art keywords
group
compound
ethylenically unsaturated
groups
composite semipermeable
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PCT/JP2013/062917
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English (en)
Japanese (ja)
Inventor
宏樹 峰原
晴季 志村
洋樹 富岡
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東レ株式会社
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Priority to JP2013524177A priority Critical patent/JP6201754B2/ja
Publication of WO2014002613A1 publication Critical patent/WO2014002613A1/fr

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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
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • 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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis

Definitions

  • the present invention relates to a composite semipermeable membrane excellent in durability against oxidizing agents, separation performance, and stability during continuous operation, and a method for producing the same.
  • a separation functional layer made of different materials is provided on a microporous support membrane, and this separation functional layer substantially provides membrane separation performance.
  • Membranes are known. Most of the composite semipermeable membranes marketed so far are those in which a separation functional layer made of polyamide is formed by interfacial polycondensation on a porous support membrane.
  • Patent Document 1 discloses a composite semipermeable membrane using polyamide.
  • the composite semipermeable membrane using polyamide has an amide bond in the main chain, durability against an oxidizing agent is still insufficient.
  • the desalting performance and selective separation performance of the composite semipermeable membrane using polyamide are remarkably deteriorated by treatment with chlorine, hydrogen peroxide or the like used for sterilization of the membrane.
  • Patent Document 2 and Patent Document 3 disclose a separation functional layer obtained by polymerizing an ethylenically unsaturated compound.
  • the composite semipermeable membrane produced using an ethylenically unsaturated compound is excellent in chemical resistance, either or both of water permeability and separation performance is not sufficient.
  • Patent Document 4 discloses a water treatment film having a chemical-resistant silane compound on the surface.
  • a polymer emulsion is applied on a nonwoven fabric and irradiated with energy rays to be cured to obtain a porous film.
  • the pore diameter of the formed porous membrane is about several hundreds of nanometers, and considering that the hydration radius of general ions and the radius of oxidant molecules are 1 nm or less, this technique aims to prevent salt permeation. Cannot be achieved.
  • Patent Document 5 discloses a technique for imparting hydrophilicity to the film surface by coating with a silane compound.
  • the pore diameter on the membrane surface is several tens of nanometers or more, which is larger than the radius of hydrated ions and oxidant molecules. Therefore, even this technique cannot achieve the purpose of blocking salt permeation.
  • An object of the present invention is to provide a composite semipermeable membrane having high durability against an oxidizing agent, high separation performance, and stability during continuous water flow operation.
  • a compound having two or more thiol groups can crosslink between compounds having an ethylenically unsaturated group. Therefore, as a means for reducing and homogenizing the pore size of the membrane, it is possible to improve the salt removal rate by crosslinking using a compound having two or more thiol groups and at the same time increase the strength of the separation functional layer. . That is, the present inventor has conceived that by using a compound having two or more thiol groups, high durability not found in a conventional composite semipermeable membrane can be realized, and the following invention has been achieved.
  • a compound having a reactive group having an ethylenically unsaturated group and an acidic group (B), a compound having two or more reactive groups having a thiol group (C), and a reactive group having an ethylenically unsaturated group A mixture of compounds (A), (B), (C), and (D) containing compound (D) having two or more compounds, and condensation of hydrolyzable groups possessed by compound (A), as well as compound Polymerization of ethylenically unsaturated groups possessed by (A), (B) and (D), and ethylenically unsaturated compounds possessed by thiol groups and compounds (A), (B) and (D) possessed by compounds (C) A compound half formed by an addition reaction with a group Film.
  • R 3 Represents a hydrogen atom or an alkyl group, and m and n are integers satisfying m + n ⁇ 4, and satisfy m ⁇ 1 and n ⁇ 1, and two or more functional groups in each of R 1 , R 2 and R 3 When they are bonded to a silicon atom, they may be the same or different.
  • a mixture of A), (B), (C), and (D) is applied to condense the hydrolyzable group of compound (A), and ethylene of compounds (A), (B), and (D)
  • the composite semipermeable membrane is formed by polymerization of the unsaturated group and addition reaction between the thiol group of the compound (C) and the ethylenically unsaturated group of the compounds (A), (B) and (D).
  • the composite semipermeable membrane of the present invention includes a separation functional layer having a fluid separation function such as desalting performance and water permeation performance, a microporous support membrane for supporting the separation functional layer, and the separation functional layer and microporosity. It consists of a base material for supporting the support membrane.
  • the microporous support membrane according to the present invention gives strength to the composite semipermeable membrane of the present invention as a support membrane of the separation functional layer.
  • the separation functional layer is provided on at least one side of the microporous support membrane. Therefore, a microporous support membrane can be provided on the substrate, and a separation functional layer can be provided on the microporous support membrane. It is also possible to provide a separation functional layer on the substrate and further provide a microporous support membrane on the separation functional layer. Although one microporous support membrane can support a plurality of separation functional layers, it is usually sufficient to have one separation functional layer on one side of one microporous support membrane.
  • the layers are generally laminated in order from the coarser layer to the finer layer. Therefore, a configuration in which a microporous support membrane is provided on a substrate and a separation functional layer is further provided on the microporous support membrane is often employed.
  • the pore diameter on the surface of the microporous support membrane used in the present invention is preferably in the range of 1 nm to 100 nm. If the pore diameter on the surface of the microporous support membrane is in this range, a separation functional layer having sufficiently few defects can be formed on the surface of the microporous support membrane by a chemical reaction. Further, if the pore diameter on the surface of the microporous support membrane is in the above range, the resulting composite semipermeable membrane has a high pure water permeation flux, and the separation functional layer of the microporous support membrane is in the pressurization operation. The structure can be maintained without falling into the pores.
  • the pore diameter of the surface of the microporous support membrane can be calculated from an electron micrograph.
  • the surface of the microporous support membrane is photographed with an electron micrograph, the diameters of all the observable pores are measured, and the pore diameter can be obtained by arithmetic averaging.
  • a circle having an area equal to the area of the pores can be obtained by an image processing apparatus or the like, and the equivalent circle diameter can be obtained by the method of setting the diameter of the pores.
  • the pore diameter can be determined by differential scanning calorimetry (DSC) using the principle that water in minute pores has a lower melting point than ordinary water. The details are described in literature (Ishikiriyama et al., Journal of Colloid and Interface Science, Vol. 171, p103, Academic Press Incorporated (1995)).
  • the thickness of the microporous support membrane is preferably in the range of 1 ⁇ m to 5 mm, and more preferably in the range of 10 ⁇ m to 100 ⁇ m. If the thickness is smaller than 1 ⁇ m, the strength of the microporous support membrane tends to decrease, and as a result, the strength of the composite semipermeable membrane tends to decrease. On the other hand, when the thickness is larger than 5 mm, it becomes difficult to handle when the microporous support membrane and the composite semipermeable membrane obtained therefrom are bent. In order to increase the strength of the composite semipermeable membrane, the microporous support membrane may be reinforced with cloth, nonwoven fabric, paper, or the like. The preferable thickness of these reinforcing materials is usually 50 ⁇ m or more and 150 ⁇ m or less.
  • the material used for the microporous support membrane is not particularly limited.
  • homopolymers or copolymers such as polysulfone, polyethersulfone, polyamide, polyester, cellulose polymer, vinyl polymer, polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfone, and polyphenylene oxide can be used. These polymers can be used alone or blended.
  • examples of the cellulose polymer include cellulose acetate and cellulose nitrate.
  • Preferred examples of the vinyl polymer include polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile and the like.
  • homopolymers and copolymers such as polysulfone, polyethersulfone, polyamide, polyester, cellulose acetate, cellulose nitrate, polyvinyl chloride, polyacrylonitrile, polyphenylene sulfide, and polyphenylene sulfide sulfone are preferable. Furthermore, among these materials, it is particularly preferable to use polysulfone or polyethersulfone that has excellent chemical stability, high mechanical strength, excellent thermal stability, and easy molding.
  • the thickness of the separation functional layer in the composite semipermeable membrane of the present invention is preferably in the range of 5 nm to 500 nm.
  • the lower limit is more preferably 10 nm. More preferably, the upper limit is 200 nm.
  • the separation functional layer thus thinned can improve water permeability.
  • the separation functional layer of the present invention is formed by the following reaction on the microporous support membrane. That is, a compound (A) in which a reactive group having an ethylenically unsaturated group and a hydrolyzable group are bonded to a silicon atom on a microporous support membrane, a reactive group having an ethylenically unsaturated group, and an acidic group A mixture containing a compound (B) having a thiol group and a compound (C) having two or more reactive groups having a thiol group is applied.
  • a separation function is realized by a network of siloxane bonds formed by hydrolysis of a hydrolyzable group bonded to a silicon atom of the compound (A), and appropriate water permeability is imparted by an acidic group of the compound (B).
  • Two or more thiol groups possessed by the compound (C) are cross-linked between molecules having a double bond to reduce and homogenize the pore size, thereby improving the salt removal rate and at the same time increasing the strength of the separation functional layer, Realizes high durability.
  • the separation function can be improved by the presence of the network formed by the group polymerization reaction.
  • the reactive group having an ethylenically unsaturated group is directly bonded to the silicon atom.
  • reactive groups include vinyl groups, allyl groups, methacryloxyethyl groups, methacryloxypropyl groups, acryloxyethyl groups, acryloxypropyl groups, and styryl groups. From the viewpoint of polymerizability, a methacryloxypropyl group, an acryloxypropyl group, and a styryl group are preferable.
  • a condensation reaction occurs in which a compound is bonded by a siloxane bond through a process such that a hydrolyzable group directly bonded to a silicon atom is changed to a hydroxyl group, resulting in a polymer.
  • the hydrolyzable group include an alkoxy group, an alkenyloxy group, a carboxy group, a ketoxime group, an aminohydroxy group, a halogen atom and an isocyanate group.
  • an alkoxy group a C1-C10 thing is preferable, More preferably, it is a C1-C2 thing.
  • the alkenyloxy group preferably has 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and further preferably 3 carbon atoms.
  • the carboxy group those having 2 to 10 carbon atoms are preferable, and those having 2 carbon atoms, that is, an acetoxy group is preferable.
  • the ketoxime group include a methyl ethyl ketoxime group, a dimethyl ketoxime group, and a diethyl ketoxime group.
  • the aminohydroxy group is one in which an amino group is bonded to a silicon atom via an oxygen atom via oxygen. Examples of such include dimethylaminohydroxy group, diethylaminohydroxy group, and methylethylaminohydroxy group.
  • halogen atom a chlorine atom is preferably employed.
  • a compound in which a part of the hydrolyzable group is hydrolyzed and has a silanol structure can be used.
  • the compound (A) is preferably represented by the following general formula (a). Si (R 1 ) m (R 2 ) n (R 3 ) 4-mn— General formula (a) (R 1 represents a reactive group containing an ethylenically unsaturated group. R 2 represents any of an alkoxy group, an alkenyloxy group, a carboxy group, a ketoxime group, an aminohydroxy group, a halogen atom or an isocyanate group.
  • R 3 Represents a hydrogen atom or an alkyl group, and m and n are integers satisfying m + n ⁇ 4, and satisfy m ⁇ 1 and n ⁇ 1, and two or more functional groups in each of R 1 , R 2 and R 3 When they are bonded to a silicon atom, they may be the same or different.
  • R 1 is a reactive group containing an ethylenically unsaturated group, and is as described above.
  • R 2 is a hydrolyzable group, which is as described above.
  • the number of carbon atoms of the alkyl group to be R 3 is preferably 1 or more and 10 or less, and more preferably 1 or 2.
  • an alkoxy group is preferably used in forming the separation functional layer because the reaction solution has a viscosity and pot life suitable for film formation.
  • Such compounds (A) include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxy.
  • Silane methacryloxypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxypropyltrimethoxysilane, (acryloxymethyl)
  • An example is phenethyltrimethoxysilane.
  • a compound having no hydrolyzable group which does not have a reactive group having an ethylenically unsaturated group, can be used together with the compound (A).
  • Such a compound can be represented by the following general formula (b), and examples thereof include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.
  • R 1 represents any of an alkoxy group, an alkenyloxy group, a carboxy group, a ketoxime group, an aminohydroxy group, a halogen atom or an isocyanate group.
  • R 2 represents a hydrogen atom or an alkyl group.
  • M represents 1 ⁇ m ⁇ 4. (In the case where two or more functional groups are bonded to a silicon atom in each of R 1 and R 2, they may be the same or different.)
  • the ethylenically unsaturated group has addition polymerizability.
  • Examples of the compound having an ethylenically unsaturated group include ethylene, propylene, methacrylic acid, acrylic acid, styrene, and derivatives thereof.
  • the compound (B) is an alkali-soluble compound having an acidic group in order to increase the selective permeability of water and increase the salt rejection when the composite semipermeable membrane is used for separation of an aqueous solution.
  • Preferred acids are carboxylic acid, phosphonic acid, phosphoric acid and sulfonic acid, and these acid structures may exist in any form of acid form, ester compound, and metal salt.
  • These compounds (B) having an ethylenically unsaturated group may contain two or more acidic groups, and among them, compounds containing one or two acidic groups are preferable.
  • compounds having a carboxylic acid group include maleic acid, maleic anhydride, acrylic acid, methacrylic acid, 2- (hydroxymethyl) acrylic acid, 4- ( Mention may be made of (meth) acryloyloxyethyl trimellitic acid and the corresponding anhydride, 10-methacryloyloxydecylmalonic acid, N- (2-hydroxy-3-methacryloyloxypropyl) -N-phenylglycine and 4-vinylbenzoic acid.
  • compounds having a phosphonic acid group include vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid.
  • the phosphoric acid ester compounds include 2-methacryloyloxypropyl monohydrogen phosphate, 2-methacryloyloxypropyl dihydrogen phosphate, 2-methacryloyloxyethyl monoester.
  • compounds having a sulfonic acid group include vinyl sulfonic acid, allyl sulfonic acid, 3- (acryloyloxy) propane-1-sulfonic acid, and 3- (methacryloyl).
  • Examples include 3- (methacrylamide) propylsulfonic acid and salts thereof.
  • a compound (C) having two or more reactive groups having a thiol group it is important to add a compound (C) having two or more reactive groups having a thiol group.
  • the thiol group forms a thioether structure by addition reaction with a reactive group having an ethylenically unsaturated group.
  • This reaction has a mechanism through generation of a thio radical or a mechanism by nucleophilic reaction of a thiol group. In any reaction mechanism, even if oxygen coexists in the reaction system, the thioether structure is rapidly formed.
  • the said addition reaction advances preferentially rather than the radical polymerization of ethylenically unsaturated groups, and suppresses radical polymerization. Therefore, there is a concern that the molecular weight of the obtained polymer is lowered.
  • the compound (C) is allowed to coexist with the radical polymerization reaction of the compounds (A) and (B) or the compounds (A), (B) and (D), the molecular chain produced by the reaction between vinyl groups has a low molecular weight.
  • the compound (C) since branching based on the compound (C) occurs, the effect of crosslinking by the siloxane bond derived from the compound (A) is increased. As a result, the compound (C) is obtained by reducing and homogenizing the pore diameter by crosslinking between the polymer chains formed by the compounds (A) and (B) or the compounds (A), (B) and (D). Improves the salt removal rate and at the same time increases the strength of the separation functional layer. As a result, the composite semipermeable membrane of the present invention achieves high durability not found in conventional siloxane compound-containing composite semipermeable membranes.
  • the molar equivalent of the thiol group with respect to the ethylenically unsaturated group is 0.01 to 1 equivalent, preferably 0.05 to 0.5 equivalent. Blend as follows. If the molar equivalent of the thiol group relative to the ethylenically unsaturated group is less than 0.01 equivalent, the addition reaction may not proceed efficiently. When the molar equivalent of the thiol group with respect to the ethylenically unsaturated group is more than 1 equivalent, the polymerization between the ethylenically unsaturated groups may not proceed efficiently, and it may adversely affect the formation of the crosslinked structure, which is not preferable. .
  • Examples of the compound (C) include diethylene glycol dimercaptopropionate, 4-t-butyl-1,2-benzenedithiol, bis- (2-mercaptoethyl) sulfide, 4,4′-thiodibenzenethiol, benzenedithiol, Glycol dimercaptoacetate, glycol dimercaptopropionate ethylene bis (3-mercaptopropionate), polyethylene glycol dimercaptoacetate, polyethylene glycol di- (3-mercaptopyropionate), 2,2-bis (mercaptomethyl) 1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, bisphenofluorene bis (ethoxy-3-mercaptopropionate), 4,8-bis (mercaptomethyl) -3,6 , 9-Trithia 1,11-undecanedithiol, 2-mercaptomethyl-2-methyl-1,3-propanedithiol, 1,8-dimercap
  • a compound (D) having two or more reactive groups having an ethylenically unsaturated group can also be used as an additive.
  • the compound (C) having two or more reactive groups having a thiol group reduces the pore size by crosslinking the polymer chains formed by the compound (A), the compound (B), and the compound (D).
  • the salt removal rate is improved, and at the same time, the strength of the separation functional layer is increased.
  • the composite semipermeable membrane of the present invention achieves high durability not found in conventional siloxane compound-containing composite semipermeable membranes.
  • L (R) n general formula (c) (R represents any one of a vinyl group, an acryl group, and a methacryl group. L represents an arbitrary atomic group. N is a positive integer of 2 or more.) R is an unsaturated group responsible for polymerization, and L is a linker connecting them.
  • L examples include linear alkyl groups, branched alkyl groups, fluoroalkyl groups and derivatives thereof, oligooxyethylene and derivatives thereof, polyhydric alcohol derivatives, polycarboxylic acid derivatives, sugar derivatives, alkylamines and derivatives thereof, phosphorus
  • n ⁇ 3 include tris (2-acryloyloxyethyl) cyanurate, tris (2-acryloyloxyethyl) isocyanurate, 1,3,5-triacryloyltriazine, 1,3,5-triacryloyl Hexahydro-1,3,5-triazine, trimethylolpropane triacrylate, gallic acid triacrylate, pentaerythritol triacrylate, pyrogallol triacrylate, cyanuric acid tris (2-methacryloyloxyethyl), isocyanuric acid tris ( 2-methacryloyloxyethyl), 1,3,5-trimethacryloyltriazine, 1,3,5-trimethacryloylhexa
  • the separation functional layer may be hydrolyzed using hot alkali, and then the low molecular weight component may be separated to perform nuclear magnetic resonance, mass spectrometry, or the like.
  • a reaction liquid containing compounds (A), (B) and (C) or compounds (A), (B), (C) and (D) is applied.
  • condensation of the hydrolyzable group and addition reaction between the thiol group and the ethylenically unsaturated group may occur simultaneously.
  • the reaction liquid containing the compounds (A), (B) and (C) or the compounds (A), (B), (C) and (D) is brought into contact with the microporous support membrane.
  • a reaction solution usually contains a solvent.
  • a solvent is not particularly limited as long as it does not destroy the microporous support membrane and dissolves the compounds (A), (B), (C), (D) and a polymerization initiator added as necessary. . 1 to 10 molar equivalents, preferably 1 to 5 molar equivalents, of water with respect to the number of moles of compound (A) is added to the reaction solution together with an inorganic acid or an organic acid. It is preferable to promote hydrolysis of the compound (A).
  • a solvent of the reaction solution containing the compounds (A), (B) and (C) or the compounds (A), (B), (C) and (D) water, alcohol-based organic solvents, ether-based organic solvents A ketone organic solvent and a mixture thereof are preferable.
  • an alcohol organic solvent methanol, ethoxymethanol, ethanol, propanol, butanol, amyl alcohol, cyclohexanol, methylcyclohexanol, ethylene glycol monomethyl ether (2-methoxyethanol), ethylene glycol monoacetate, diethylene glycol monomethyl ether
  • examples include diethylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol monoacetate, dipropylene glycol monoethyl ether, and methoxybutanol.
  • ether organic solvents include methylal, diethyl ether, dipropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl ether, trioxane, dioxane and the like.
  • ketone organic solvents acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl cyclohexyl ketone, diethyl ketone, ethyl butyl ketone, trimethylnonanone, acetonitrile acetone, dimethyl oxide, phorone, cyclohexanone, dye Acetone alcohol etc. are mentioned.
  • the amount of the solvent added is preferably 50% by weight to 99% by weight and more preferably 80% by weight to 99% by weight with respect to the total weight of the reaction solution.
  • the amount of the solvent added is more than 99% by weight, there is a tendency that a defect that deteriorates the film performance tends to occur in the film, and when it is less than 50% by weight, the water permeability of the obtained composite semipermeable membrane tends to be lowered.
  • the contact between the microporous support membrane and the reaction liquid containing the compounds (A), (B) and (C) or the compounds (A), (B), (C) and (D) It is preferable to carry out uniformly and continuously on the surface.
  • a method of coating the reaction solution on a microporous support film using a coating device such as a spin coater, a wire bar, a flow coater, a die coater, a roll coater, or a spray.
  • a coating device such as a spin coater, a wire bar, a flow coater, a die coater, a roll coater, or a spray.
  • the method of immersing a microporous support membrane in the said reaction liquid can be mentioned.
  • the contact time between the microporous support membrane and the reaction solution is preferably within a range of 0.5 minutes to 10 minutes, and preferably 1 minute to 3 minutes. More preferably within the following range.
  • Liquid draining methods include a method in which the microporous support membrane after contact with the reaction liquid is vertically gripped to allow the excess reaction liquid to flow down naturally, or air such as nitrogen is blown from an air nozzle to force the liquid. A cutting method or the like can be used. In addition, after draining, the membrane surface can be dried to remove a part of the solvent in the reaction solution.
  • the heating temperature at this time is required to be lower than the temperature at which the microporous support membrane melts and the performance as a separation membrane decreases.
  • the condensation reaction temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower. If the reaction temperature is 0 ° C.
  • the hydrolysis and condensation reaction proceed rapidly, and if it is 150 ° C. or lower, the hydrolysis and condensation reaction are easily controlled. Further, by adding a catalyst that promotes hydrolysis or condensation, the reaction can proceed even at a lower temperature. Furthermore, in the present invention, the heating condition and the humidity condition are selected so that the separation functional layer has pores, and the condensation reaction is appropriately performed.
  • electromagnetic waves include ultraviolet rays, X-rays, ⁇ -rays and the like.
  • the polymerization method may be appropriately selected as appropriate, but polymerization by electromagnetic wave irradiation is preferred from the viewpoint of running cost, productivity and the like.
  • electromagnetic waves ultraviolet irradiation is more preferable from the viewpoint of simplicity.
  • these light sources need not selectively generate only light in the ultraviolet wavelength region, but may be any material that contains electromagnetic waves in the ultraviolet wavelength region.
  • the intensity of these ultraviolet rays is higher than electromagnetic waves in other wavelength regions.
  • Electromagnetic waves can be generated from halogen lamps, xenon lamps, UV lamps, excimer lamps, metal halide lamps, rare gas fluorescent lamps, mercury lamps, and the like.
  • the energy of the electromagnetic wave is not particularly limited as long as it can be polymerized, but the ultraviolet thin film formation property is particularly high.
  • Such ultraviolet rays can be generated by a low-pressure mercury lamp or an excimer laser lamp.
  • the thickness and form of the separation functional layer according to the present invention may vary greatly depending on the respective polymerization conditions. In the case of polymerization using electromagnetic waves, the thickness and form of the separation functional layer according to the present invention may vary greatly depending on the wavelength of electromagnetic waves, the intensity, the distance to the irradiated object, and the processing time. Therefore, these conditions need to be optimized as appropriate.
  • the polymerization initiator and the polymerization accelerator are not particularly limited, and are appropriately selected according to the structure of the compound to be used, the polymerization technique, and the like.
  • the polymerization initiator is exemplified below.
  • an initiator for polymerization by electromagnetic waves benzoin ether, dialkylbenzyl ketal, dialkoxyacetophenone, acylphosphine oxide or bisacylphosphine oxide, ⁇ -diketone (for example, 9,10-phenanthrenequinone), diacetylquinone, furylquinone, anisylquinone, Examples are 4,4'-dichlorobenzylquinone and 4,4'-dialkoxybenzylquinone, and camphorquinone.
  • Initiators for thermal polymerization include azo compounds (eg, 2,2′-azobis (isobutyronitrile) (AIBN) or azobis- (4-cyanovaleric acid), or peroxides (eg, dibenzoyl peroxide).
  • azo compounds eg, 2,2′-azobis (isobutyronitrile) (AIBN) or azobis- (4-cyanovaleric acid
  • peroxides eg, dibenzoyl peroxide
  • Peroxides and ⁇ -diketones are preferably used in combination with aromatic amines to accelerate the initiation of polymerization.
  • This combination is also called a redox system.
  • examples of such systems include benzoyl peroxide or camphorquinone and amines (eg, N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine, ethyl p-dimethyl-aminobenzoate). And combinations thereof with esters or derivatives thereof.
  • a system containing a peroxide in combination with ascorbic acid, barbiturate or sulfinic acid as a reducing agent is also preferable in order to accelerate the initiation of polymerization.
  • reaction solution containing the microporous support membrane and the compounds (A), (B) and (C) or the compounds (A), (B), (C) and (D) is added as necessary.
  • an agent that accelerates the polymerization such as a polymerization initiator or a polymerization accelerator and polymerizing the ethylenically unsaturated group by an appropriate polymerization means, it is heated at about 100 to 200 ° C. for about 10 minutes to 3 hours.
  • a composite semipermeable membrane of the present invention in which a polycondensation reaction occurs and a separation functional layer is formed on the surface of the microporous support membrane can be obtained.
  • the heating temperature depends on the material of the microporous support membrane, if it is too high, dissolution occurs and the pores of the microporous support membrane are blocked, resulting in a decrease in the amount of water produced in the composite semipermeable membrane.
  • the heating temperature is too low, the polycondensation reaction becomes insufficient, and the salt removal rate decreases due to elution of the separation functional layer.
  • the polymerization step of the reactive group having an ethylenically unsaturated group may be performed before or after the condensation step with a hydrolyzable group. Moreover, you may perform a polycondensation reaction and a polymerization reaction simultaneously.
  • the composite semipermeable membrane thus obtained can be used as it is, but it is preferable to hydrophilize the surface of the membrane with, for example, an alcohol-containing aqueous solution or an alkaline aqueous solution before use.
  • a composite semipermeable membrane excellent in strength, dimensional stability, and unevenness forming ability can be obtained.
  • a fibrous substrate can be used in terms of strength, unevenness forming ability, and fluid permeability.
  • both a long fiber nonwoven fabric and a short fiber nonwoven fabric can be used preferably.
  • the long fiber nonwoven fabric has excellent film-forming properties, when the polymer solution is cast, the solution penetrates by over-penetration, the microporous support membrane peels off, Furthermore, it can suppress that a film
  • the base material is made of a long-fiber non-woven fabric composed of thermoplastic continuous filaments, it suppresses non-uniformity and membrane defects during casting of a polymer solution caused by fuzz that occurs when a short-fiber non-woven fabric is used. be able to.
  • tensile_strength is applied with respect to the film forming direction, it is preferable to use the long-fiber nonwoven fabric which is more excellent in dimensional stability for a base material.
  • the long-fiber nonwoven fabric When a long-fiber nonwoven fabric is used as the base material, the long-fiber nonwoven fabric has a fiber on the surface layer on the side opposite to the microporous support membrane in terms of moldability and strength. Is also preferably longitudinally oriented. According to such a structure, not only a high effect of preventing membrane breakage and the like by realizing strength is realized, but also the microporous support membrane and the base material when the unevenness is imparted to the composite semipermeable membrane. The moldability as a laminated body is also improved, and the uneven shape on the surface of the composite semipermeable membrane is stabilized, which is preferable.
  • the fiber orientation degree in the surface layer on the side opposite to the microporous support membrane of the long-fiber nonwoven fabric is preferably 0 ° to 25 °, and the fibers in the surface layer on the microporous support membrane side
  • the difference in orientation degree from the orientation degree is preferably 10 ° to 90 °.
  • a heating process is included, but the phenomenon that the microporous support membrane or the separation functional layer contracts due to the heating occurs. This is particularly noticeable in the width direction where no tension is applied in continuous film formation. Since shrinkage causes problems in dimensional stability and the like, a substrate having a small rate of thermal dimensional change is desired.
  • the difference between the fiber orientation degree on the surface layer opposite to the microporous support membrane and the fiber orientation degree on the microporous support membrane side surface layer is 10 ° to 90 °, the change in the width direction due to heat is suppressed. Can also be preferred.
  • the fiber orientation degree is an index indicating the fiber direction of the nonwoven fabric base material, and the direction of film formation during continuous film formation is 0 °, and the direction perpendicular to the film formation direction, that is, the width of the nonwoven fabric base material. It means the average angle of the fibers constituting the nonwoven fabric substrate when the direction is 90 °. Accordingly, the closer to 0 ° the fiber orientation, the longer the orientation, and the closer to 90 °, the lateral orientation.
  • the degree of fiber orientation was obtained by randomly collecting ten small sample samples from a nonwoven fabric, photographing the surface of the sample with a scanning electron microscope at a magnification of 100 to 1000 times, and measuring 10 fibers from each sample for a total of 100 fibers. Measure the angle when the longitudinal direction (longitudinal direction, film forming direction) is 0 ° and the width direction (lateral direction) of the nonwoven fabric is 90 °, and round off the average value to the first decimal place. To determine the degree of fiber orientation.
  • the initial performance of the NaCl removal rate of the composite semipermeable membrane is the following equation (d)
  • the initial performance of the membrane permeation flux of the composite semipermeable membrane is the following equation (e)
  • the pure water permeability coefficient is the following equation ( f)
  • the solute permeability coefficient is calculated by the following formula (m)
  • the pure water permeability coefficient change rate is calculated by the following formula (n)
  • the solute permeability coefficient change rate is calculated by the following formula (p).
  • NaCl removal rate (%) ⁇ (NaCl concentration of the feed solution ⁇ NaCl concentration of the permeate) / NaCl concentration of the feed solution ⁇ ⁇ 100
  • Membrane permeation flux of solution (m 3 / m 2 / day) (Amount of permeate per day) / (Membrane area)
  • Pure water permeability coefficient (m 3 / m 2 / sec / Pa) (membrane permeation flux of solution) / (pressure difference on both sides of membrane ⁇ osmotic pressure difference on both sides of membrane ⁇ solute reflection coefficient)
  • the solute reflection coefficient can be obtained by the following method.
  • the following equation is known as a transport equation of the reverse osmosis method based on non-equilibrium thermodynamics.
  • J v L p ( ⁇ P ⁇ ⁇ ⁇ ) Equation (g)
  • J s P (C m ⁇ C p ) + (1 ⁇ ) C ⁇ J v Formula (h)
  • Jv is the membrane permeation flux of the solution (m 3 / m 2 / s)
  • L p is the pure water permeability coefficient (m 3 / m 2 / s / Pa)
  • ⁇ P is the pressure difference (Pa )
  • ⁇ is the solute reflection coefficient
  • ⁇ is the osmotic pressure difference (Pa) on both sides of the membrane
  • Js is the solute permeability through the membrane (mol / m 2 / s)
  • P is the solute permeability coefficient (m / s)
  • Solute permeability coefficient (m / sec) (solute membrane permeation flux ⁇ (1 ⁇ solute reflection coefficient) ⁇ average concentration on both sides of membrane ⁇ membrane permeation flux of solution) / (solute film surface concentration ⁇ membrane permeate concentration) )
  • Formula (m) Change rate of pure water permeability coefficient (day ⁇ 1 ) (pure water permeability coefficient after passing for 23 hours ⁇ pure water permeability coefficient after passing for 3 hours) / (pure water permeability coefficient after passing for 3 hours ⁇ passage water) (Time) ...
  • Example 1 A 15.7% by weight dimethylformamide solution of polysulfone on a polyethylene terephthalate nonwoven fabric was cast at a thickness of 200 ⁇ m at room temperature (25 ° C.), and immediately immersed in pure water and allowed to stand for 5 minutes to form a microporous support membrane. Produced.
  • the microporous support membrane thus obtained had a surface pore size of 21 nm and a thickness of 150 ⁇ m.
  • the microporous support membrane was brought into contact with this solution for 1 minute, and nitrogen was blown from an air nozzle to remove excess solution from the surface of the support membrane to form a layer of the solution on the microporous support membrane.
  • a UV irradiation device TOSCURE (registered trademark) 752 manufactured by Harrison Toshiba Lighting Co. which can irradiate 365 nm ultraviolet light
  • the irradiation intensity when using a UV integrated light meter UIT-250 manufactured by USHIO is 20 mW / cm 2.
  • a composite semipermeable membrane having a separation functional layer formed on the surface of the microporous support membrane was prepared by irradiating with ultraviolet rays for 15 minutes.
  • the obtained composite semipermeable membrane is held in a hot air dryer at 120 ° C. for 2 hours to condense the compound (A), and a dry composite semipermeable membrane having a separation functional layer on the microporous support membrane is obtained. Obtained. Thereafter, the dried composite semipermeable membrane was hydrophilized by immersing it in a 10 wt% isopropyl alcohol aqueous solution for 10 minutes. 500 ppm saline adjusted to pH 6.5 was supplied to the composite semipermeable membrane thus obtained under the conditions of 0.75 MPa and 25 ° C., and pressure membrane filtration operation was performed.
  • the membrane removal rate calculated from the formula (d) and the membrane structure obtained by dividing the permeated water amount per day by the membrane area were obtained.
  • the amount of water is shown in Table 1. Further, the pressure membrane filtration operation under the above conditions was continued, and the performance evaluation was similarly performed 23 hours after the start of the operation. Table 1 also shows the pure water permeability coefficient change rate calculated from the equation (n) using the performances 3 hours and 23 hours after the start of water flow and the solute permeability coefficient change rate calculated from the equation (p).
  • Example 2 A composite semipermeable membrane was prepared in the same manner as in Example 1 except that the Karenz MTBD1 (manufactured by Showa Denko KK) of the compound (C) used in Example 1 was replaced with Karenz MTNR1 (manufactured by Showa Denko KK). .
  • the obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 3 The compound half-column compound (C) Karenz MTBD1 (manufactured by Showa Denko KK) used in Example 1 was replaced with 1,3,5-triazine-2,4,6-trithiol in the same manner as in Example 1 except that A permeable membrane was prepared. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 4 A composite semipermeable membrane was prepared in the same manner as in Example 1, except that the compound (C) Karenz MTBD1 (manufactured by Showa Denko KK) used in Example 1 was replaced with Karenz MTPE1 (manufactured by Showa Denko KK). The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 5 A composite semipermeable membrane was prepared in the same manner as in Example 2 except that glycerol diacrylate corresponding to the compound (D) was added to the solution applied on the microporous support membrane in Example 2 so as to have a concentration of 10 mM. Produced. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 6 The same procedure as in Example 2 was conducted except that tris (2-acryloyloxyethyl) isocyanurate corresponding to compound (D) was added to the solution applied on the microporous support membrane in Example 2 so as to have a concentration of 10 mM. Thus, a composite semipermeable membrane was produced. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 7 A composite semipermeable membrane in the same manner as in Example 2 except that pentaerythritol tetramethacrylate corresponding to the compound (D) was added to the solution applied on the microporous support membrane in Example 2 to 10 mM. Was made. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 1 A composite semipermeable membrane was produced in the same manner as in Example 2 except that the compound (C) Karenz MTNR1 (manufactured by Showa Denko KK) used in Example 2 was not added. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 2 A composite semipermeable membrane was produced in the same manner as in Example 2 except that the compound (C) Karenz MTNR1 (manufactured by Showa Denko KK) used in Example 2 was replaced with hexanethiol. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 3 A composite semipermeable membrane was prepared in the same manner as in Example 5 except that the compound (C) Karenz MTNR1 (manufactured by Showa Denko KK) used in Example 5 was not added. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 4 A composite semipermeable membrane was prepared in the same manner as in Example 6 except that the compound (C) Karenz MTNR1 (manufactured by Showa Denko KK) used in Example 6 was not added. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 5 A composite semipermeable membrane was produced in the same manner as in Example 7 except that the compound (C) Karenz MTNR1 (manufactured by Showa Denko KK) used in Example 7 was not added. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 6 A composite semipermeable membrane was prepared in the same manner as in Example 1 except that 3-acryloxypropyltrimethoxysilane of the compound (A) used in Example 1 was replaced with 4-hydroxybutyl acrylate. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Example 7 A composite semipermeable membrane was produced in the same manner as in Example 1 except that sodium 4-vinylphenylsulfonate of compound (B) used in Example 1 was replaced with p-methylstyrene. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
  • Table 1 shows that the composite semipermeable membranes obtained in Examples 1 to 7 have a higher NaCl removal rate than the composite semipermeable membranes obtained in Comparative Examples 1 to 7. Further, when comparing the rate of change of the pure water permeability coefficient after passing water, the composite semipermeable membranes shown in Examples 1 to 7 are continuously operated compared to the composite semipermeable membranes obtained in Comparative Examples 1 to 7. It can be seen that the change in performance due to is small. In addition, the NaCl removal rate of Comparative Examples 3, 4, and 5 is relatively high, and the pure water permeability coefficient change rate is relatively small. However, the amount of membrane water formation in these Comparative Examples 3, 4, and 5 is higher than that in Examples 1 and 3. The water production performance is poor.
  • the addition of compound (C) is effective in improving the solute removal rate and improving the stability during continuous operation.
  • the composite semipermeable membrane of Comparative Example 6 to which no compound (A) was added had a very low NaCl removal rate, a high pure water permeability coefficient change rate, and obvious performance degradation due to continuous operation.
  • the composite semipermeable membrane of Comparative Example 7 in which the compound (B) was not added has an NaCl removal rate extremely low and is at a level equal to no water production performance. That is, the composite semipermeable membrane of the present invention produced from a substance containing compound (A), (B), (C) or compound (A), (B), (C), (D) has high separation performance. It can be seen that it has stability during continuous water flow operation.
  • the composite semipermeable membrane of the present invention includes solid-liquid separation, liquid separation, filtration, purification, concentration, sludge treatment, seawater desalination, drinking water production, pure water production, waste water reuse, waste water volume reduction, valuable material recovery, etc. In addition to being used in the field of water treatment, it can also be used in the field of osmotic pressure power generation.

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

Abstract

La présente invention concerne une membrane semi-perméable composite qui possède une durabilité élevée à l'égard des oxydants, des propriétés d'élimination élevées de corps dissous et une stabilité en fonctionnement continu. Une couche à fonction de séparation à former sur un film de soutien microporeux utilise, comme matériau de départ, un mélange de composés (A), (B) et (C), ledit mélange contenant un composé (A) dans lequel un groupe hydrolysable et un groupe réactif possédant un groupe à insaturation éthylénique sont liés à un atome de silicium, un composé (B) qui possède un groupe acide et un groupe réactif possédant un possédant un groupe à insaturation éthylénique, et un composé (C) qui possède au moins deux groupes réactifs possédant un groupe thiol. La couche à fonction de séparation est formée par condensation du groupe hydrolysable du composé (A), polymérisation entre les groupes à insaturation éthylénique des composés (A) et (B), et une réaction d'addition entre groupes à insaturation éthylénique des composés (A) et (B) et le groupe thiol du composé (C).
PCT/JP2013/062917 2012-06-28 2013-05-08 Membrane semi-perméable composite et procédé de production associé WO2014002613A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010029985A1 (fr) * 2008-09-12 2010-03-18 東レ株式会社 Film semi-transparent composite et son procédé de fabrication
WO2011136029A1 (fr) * 2010-04-28 2011-11-03 国立大学法人神戸大学 Membrane composite semi-perméable
WO2012077619A1 (fr) * 2010-12-07 2012-06-14 東レ株式会社 Membrane semi-perméable composite et son procédé de fabrication
JP2012210582A (ja) * 2011-03-31 2012-11-01 Toray Ind Inc 複合半透膜およびその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005111429A (ja) * 2003-10-10 2005-04-28 Toray Ind Inc 複合半透膜およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010029985A1 (fr) * 2008-09-12 2010-03-18 東レ株式会社 Film semi-transparent composite et son procédé de fabrication
WO2011136029A1 (fr) * 2010-04-28 2011-11-03 国立大学法人神戸大学 Membrane composite semi-perméable
WO2012077619A1 (fr) * 2010-12-07 2012-06-14 東レ株式会社 Membrane semi-perméable composite et son procédé de fabrication
JP2012210582A (ja) * 2011-03-31 2012-11-01 Toray Ind Inc 複合半透膜およびその製造方法

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