WO2018124103A1 - 複合半透膜及びその製造方法 - Google Patents
複合半透膜及びその製造方法 Download PDFInfo
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- WO2018124103A1 WO2018124103A1 PCT/JP2017/046726 JP2017046726W WO2018124103A1 WO 2018124103 A1 WO2018124103 A1 WO 2018124103A1 JP 2017046726 W JP2017046726 W JP 2017046726W WO 2018124103 A1 WO2018124103 A1 WO 2018124103A1
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- Prior art keywords
- composite semipermeable
- semipermeable membrane
- hydrophilic polymer
- group
- membrane
- Prior art date
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- OBLDVSJBFUIHSN-UHFFFAOYSA-N dimethyl-[4-(2-methylprop-2-enoylamino)butyl]-(2-sulfoethyl)azanium;hydroxide Chemical compound [OH-].CC(=C)C(=O)NCCCC[N+](C)(C)CCS(O)(=O)=O OBLDVSJBFUIHSN-UHFFFAOYSA-N 0.000 description 1
- RHEOKMKHDHUBPS-UHFFFAOYSA-N dimethyl-[4-(2-methylprop-2-enoylamino)butyl]-(3-sulfopropyl)azanium;hydroxide Chemical compound [OH-].CC(=C)C(=O)NCCCC[N+](C)(C)CCCS(O)(=O)=O RHEOKMKHDHUBPS-UHFFFAOYSA-N 0.000 description 1
- GGRWRQADAYMJIB-UHFFFAOYSA-N dimethyl-[4-(2-methylprop-2-enoylamino)butyl]-(4-sulfobutyl)azanium;hydroxide Chemical compound [OH-].CC(=C)C(=O)NCCCC[N+](C)(C)CCCCS(O)(=O)=O GGRWRQADAYMJIB-UHFFFAOYSA-N 0.000 description 1
- FDSGLYZNICIDJX-UHFFFAOYSA-N dimethyl-[4-(2-methylprop-2-enoylamino)butyl]-(5-sulfopentyl)azanium;hydroxide Chemical compound [OH-].CC(=C)C(=O)NCCCC[N+](C)(C)CCCCCS(O)(=O)=O FDSGLYZNICIDJX-UHFFFAOYSA-N 0.000 description 1
- LJPJFKJNXPFMNF-UHFFFAOYSA-N dimethyl-[4-(2-methylprop-2-enoyloxy)butyl]-(2-sulfoethyl)azanium;hydroxide Chemical compound [OH-].CC(=C)C(=O)OCCCC[N+](C)(C)CCS(O)(=O)=O LJPJFKJNXPFMNF-UHFFFAOYSA-N 0.000 description 1
- VIOYFUDDYPCCOG-UHFFFAOYSA-N dimethyl-[4-(2-methylprop-2-enoyloxy)butyl]-(3-sulfopropyl)azanium;hydroxide Chemical compound [OH-].CC(=C)C(=O)OCCCC[N+](C)(C)CCCS(O)(=O)=O VIOYFUDDYPCCOG-UHFFFAOYSA-N 0.000 description 1
- JPUXAVBXIALRHN-UHFFFAOYSA-N dimethyl-[4-(2-methylprop-2-enoyloxy)butyl]-(4-sulfobutyl)azanium;hydroxide Chemical compound [OH-].CC(=C)C(=O)OCCCC[N+](C)(C)CCCCS(O)(=O)=O JPUXAVBXIALRHN-UHFFFAOYSA-N 0.000 description 1
- UQSZZRXDHDMOQB-UHFFFAOYSA-N dimethyl-[4-(prop-2-enoylamino)butyl]-(2-sulfoethyl)azanium;hydroxide Chemical compound [OH-].OS(=O)(=O)CC[N+](C)(C)CCCCNC(=O)C=C UQSZZRXDHDMOQB-UHFFFAOYSA-N 0.000 description 1
- UJERDUHBTFCUTD-UHFFFAOYSA-N dimethyl-[4-(prop-2-enoylamino)butyl]-(3-sulfopropyl)azanium;hydroxide Chemical compound [OH-].OS(=O)(=O)CCC[N+](C)(C)CCCCNC(=O)C=C UJERDUHBTFCUTD-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QHHHYLFZGYIBCX-UHFFFAOYSA-N n,n'-bis[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl]methanediimine Chemical compound O1C(C)(C)OCC1CN=C=NCC1OC(C)(C)OC1 QHHHYLFZGYIBCX-UHFFFAOYSA-N 0.000 description 1
- NSBIQPJIWUJBBX-UHFFFAOYSA-N n-methoxyaniline Chemical group CONC1=CC=CC=C1 NSBIQPJIWUJBBX-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004439 roughness measurement Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1214—Chemically bonded layers, e.g. cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/403—Polymers based on the polymerisation of maleic acid or derivatives thereof
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/14—Membrane materials having negatively charged functional groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/16—Membrane materials having positively charged functional groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/34—Molecular weight or degree of polymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the present invention relates to a composite semipermeable membrane having a high amount of permeated water and a high ability to suppress adhesion to membrane contaminants.
- the composite semipermeable membrane obtained by the present invention can be suitably used for desalination of brine or seawater, for example.
- the separation membrane is used to remove substances (for example, salts) dissolved in a solvent (for example, water).
- the fouling phenomenon is a problem in a separation technique using a separation membrane.
- the fouling phenomenon is a phenomenon in which the permeation of the solution is hindered and the separation performance of the separation membrane deteriorates due to the substances contained in the water to be treated being adsorbed on the surface and inner holes of the separation membrane.
- the fouling phenomenon is classified according to the kind of the adhered substance, and includes chemical fouling due to adsorption of organic substances and biofouling due to adsorption of microorganisms.
- the organic matter contained in the water to be treated such as waste water, accumulates on the surface of the separation membrane or is adsorbed inside the separation membrane, causing the separation membrane to become clogged and the amount of permeated water to be treated. This is a phenomenon in which the separation performance deteriorates due to a decrease in.
- biofouling causes clogging of the separation membrane by causing microorganisms contained in the water to be treated to propagate on the surface or inside of the separation membrane using the organic matter adsorbed on the separation membrane by the chemical fouling as a nutrient source. It is a phenomenon. Fouling significantly deteriorates the water permeability of the separation membrane. Therefore, it has been studied to modify the separation membrane to impart adsorption suppression ability.
- Patent Document 1 As a method for modifying the separation membrane and imparting adsorption suppression ability, a method of imparting a hydrophilic polymer such as polyvinyl alcohol to the membrane surface is known (Patent Document 1).
- zwitterionic fouling inhibitors such as phosphorylcholines have also been developed.
- Patent Document 2 a monomer having a phosphorylcholine-like group and a monomer having an alkyl methacrylate or an organosilicon group are copolymerized to form a crosslinked structure by hydrophobic interaction or silane coupling. It is disclosed that a polymer having a phosphorylcholine-like group is adsorbed on the surface of a membrane.
- Patent Document 3 discloses that a polymer having a phosphorylcholine-like group is adsorbed on the surface of a separation membrane by electrostatic interaction by copolymerizing a monomer having a phosphorylcholine-like group and cationic (meth) acrylamide. Yes.
- An object of this invention is to provide the composite semipermeable membrane which can implement
- the present invention proposes a composite semipermeable membrane that exhibits excellent fouling resistance even for water to be treated having a high salt concentration, such as seawater, and a method for producing the same.
- the present invention has the following configuration. ⁇ 1> A composite semipermeable membrane comprising a support membrane comprising a substrate and a porous support layer, and a separation functional layer provided on the porous support layer, A composite semipermeable membrane in which the separation functional layer contains a crosslinked polyamide and a hydrophilic polymer and satisfies the following conditions (A) and (B).
- the hydrophilic polymer includes a functional group having a positive charge and a functional group having a negative charge, and the hydrophilic polymer is negatively charged.
- the hydrophilic polymer is covalently bonded to the crosslinked polyamide.
- a ratio (N1 / N2) of the number of functional groups having positive charge (N1) and the number of functional groups having negative charge (N2) is 15/85 or more and 45
- ⁇ 4> The composite semipermeable membrane according to any one of ⁇ 1> to ⁇ 3>, wherein the hydrophilic polymer has a charge density of 7.5 mmol / g or more and 10.5 mmol / g or less.
- ⁇ 5> The composite semipermeable membrane according to any one of ⁇ 1> to ⁇ 4>, wherein the hydrophilic polymer has a negative charge density of 4.5 mmol / g or more and 8.0 mmol / g or less.
- ⁇ 6> When the bubble contact angle in an aqueous solution at pH 3 is ⁇ A and the bubble contact angle in an aqueous solution at pH 11 is ⁇ B in the separation functional layer, 150 ° ⁇ A , ⁇ B ⁇ 180 ° and ( ⁇ The composite semipermeable membrane according to any one of ⁇ 1> to ⁇ 5>, wherein B ⁇ A )> 5 ° is satisfied.
- the hydrophilic polymer includes a functional group having a charge, and the charge is a negative charge of the monomer P and the monomer Q having a positive charge and a negative charge functional group.
- the ratio (PN: QN) of the number of monomer units derived from the monomer P (PN) and the number of monomer units derived from the monomer Q (QN) contained in the copolymer is 80:20 to 20:
- R 1 is H or CH 3
- R 2 , R 3 , R 6 and R 7 are each independently an alkylene group having 1 to 5 carbon atoms, or An oxyalkylene group having 1 to 5 carbon atoms
- R 4 , R 5 , R 8 , R 9 and R 10 are each independently an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl having 1 to 5 carbon atoms
- X is O, NH or S
- Y is SO 3 ⁇ , OSO 3 ⁇ , or CO 2 — .
- ⁇ 11> The composite semipermeable membrane according to any one of ⁇ 1> to ⁇ 10>, wherein the covalent bond is an amide bond.
- ⁇ 12> (a) a step of forming a crosslinked polyamide on a support film including a substrate and a porous support layer, and (b) a functional group having a positive charge on the crosslinked polyamide obtained in (a) above, A step of covalently binding a negatively charged hydrophilic polymer containing a negatively charged functional group; A method for producing a composite semipermeable membrane.
- the separation functional layer can maintain a sufficient hydration structure even under a high salt concentration. As a result, the composite semipermeable membrane of the present invention is excellent. High fouling resistance.
- condition (B) it is possible to suppress peeling of the hydrophilic polymer from the separation functional layer during operation or cleaning, and to maintain excellent fouling resistance over a long period of time.
- the composite semipermeable membrane of the present invention may be referred to as a support membrane including a substrate and a porous support layer, and a crosslinked polyamide (hereinafter simply referred to as “polyamide”) provided on the porous support layer. And a separation functional layer containing a hydrophilic polymer.
- polyamide crosslinked polyamide
- the separation function layer is a layer that plays a role of separating the solute in the composite semipermeable membrane.
- the composition and thickness of the separation functional layer are set according to the intended use of the composite semipermeable membrane.
- the separation functional layer includes a crosslinked polyamide and a hydrophilic polymer.
- the crosslinked polyamide is obtained by interfacial polycondensation of a polyfunctional amine and a polyfunctional acid halide.
- the polyfunctional amine is preferably at least one amine selected from an aromatic polyfunctional amine and an aliphatic polyfunctional amine.
- the aromatic polyfunctional amine is an aromatic amine having two or more amino groups in one molecule, and is not particularly limited, but includes metaphenylenediamine, paraphenylenediamine, 1,3,5-triamine. Examples include aminobenzene. Examples of the N-alkylated product include N, N-dimethylmetaphenylenediamine, N, N-diethylmetaphenylenediamine, N, N-dimethylparaphenylenediamine, and N, N-diethylparaphenylenediamine. In view of the stability of performance, metaphenylenediamine (hereinafter referred to as “m-PDA”) or 1,3,5-triaminobenzene is particularly preferable.
- m-PDA metaphenylenediamine
- 1,3,5-triaminobenzene is particularly preferable.
- the aliphatic polyfunctional amine is an aliphatic amine having two or more amino groups in one molecule, preferably a piperazine-based amine or a derivative thereof.
- piperazine or 2,5-dimethylpiperazine is preferable from the viewpoint of stability of performance expression.
- These polyfunctional amines may be used alone or in combination of two or more.
- the polyfunctional acid halide is an acid halide having two or more carbonyl halide groups in one molecule, and is not particularly limited as long as it gives a polyamide by reaction with the polyfunctional amine.
- polyfunctional acid halide examples include oxalic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, 1,3,5-cyclohexanetricarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid.
- 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3-benzenedicarboxylic acid, 1,4-benzenedicarboxylic acid and other halides can be used.
- acid chlorides are preferred, and are acid halides of 1,3,5-benzenetricarboxylic acid, particularly in terms of economy, availability, ease of handling, and ease of reactivity.
- Trimesic acid chloride (hereinafter referred to as “TMC”) is preferred.
- TMC Trimesic acid chloride
- the said polyfunctional acid halide may be used individually by 1 type, or may use 2 or more types as a mixture.
- the polyamide has an amide group derived from a polymerization reaction of a polyfunctional amine and a polyfunctional acid halide, an amino group derived from an unreacted terminal functional group, and a carboxy group.
- the amount of these functional groups affects the water permeability and salt removal rate of the composite semipermeable membrane.
- Functional groups in the polyamide can be converted or new functional groups can be introduced into the polyamide, thereby improving the amount of permeated water and the salt removal rate of the composite semipermeable membrane. be able to.
- Functional groups to be introduced include alkyl groups, alkenyl groups, alkynyl groups, halogen groups, hydroxyl groups, amino groups, carboxy groups, ether groups, thioether groups, ester groups, aldehyde groups, nitro groups, nitroso groups, nitrile groups, azo groups. Etc.
- an azo group is preferably introduced so that the ratio of (molar equivalent of azo group) / (molar equivalent of amide group) in the polyamide is 0.1 or more and 1.0 or less. When this ratio is 0.1 or more and 1.0 or less, a high salt removal rate can be obtained.
- the functional group ratio “(molar equivalent of amino group) / (molar equivalent of amide group)” in the separation functional layer relates to the durability of the composite semipermeable membrane, and this “(molar equivalent of amino group) / ( It is preferable to convert the amino group into another functional group so that the amino group ratio represented by “molar equivalent of amide group” is 0.18 or less. When the amino group ratio is 0.18 or less, the fastness of the layer is increased and the durability of the composite semipermeable membrane is improved.
- the amount of functional groups in these polyamides can be determined by, for example, 13 C solid state NMR measurement. Specifically, the substrate is peeled from the composite semipermeable membrane to obtain a separation functional layer and a porous support layer, and then the porous support layer is dissolved and removed to obtain a separation functional layer. The obtained separation functional layer is subjected to DD / MAS- 13 C solid state NMR measurement, and the integrated value of the peak of the carbon atom to which each functional group is bonded is calculated. The amount of each functional group can be identified from this integrated value.
- the hydrophilic polymer is a polymer that dissolves 0.5 g or more in 1 L of water under the condition of 25 ° C.
- the hydrophilic polymer can suppress contamination of the separation functional layer due to its hydration structure. Suppression of fouling by a hydrated structure is effective for any of nonionic, cationic and anionic soils.
- the hydrophilic polymer on the surface of the separation functional layer the dirt is more likely to adhere to the hydrophilic polymer than the polyamide. That is, even if dirt adheres to the surface of the separation functional layer, it is considered that the dirt adheres to a position away from the polyamide by the hydrophilic polymer. Therefore, the performance degradation of the separation membrane can be kept low.
- the hydrophilic polymer is preferably present on the surface of the separation functional layer.
- the separation functional layer includes a first layer mainly composed of polyamide and a second layer mainly composed of a hydrophilic polymer, and the first layer is disposed on the porous support layer side. preferable.
- the hydrophilic polymer includes both a functional group having a positive charge and a functional group having a negative charge. Furthermore, the hydrophilic polymer is negatively charged.
- the functional group having a charge includes a functional group having a charge by being protonated or deprotonated in water.
- the valence of charge in the “functional group having charge” is not particularly limited, but is preferably monovalent.
- the positively charged functional group is a functional group that is ionic due to electron deficiency, and examples thereof include ammonium, pyrrolidinium, pyridinium, imidazolium, sulfonium, and phosphonium.
- the negatively charged functional group is a functional group that is ionic due to an excess of electrons, and examples thereof include a carboxy group, a phosphonic acid group, a sulfonic acid group, a sulfuric acid group, a phosphoric acid group, and a phosphoric acid ester group.
- the hydrophilic polymer contains both a functional group having a positive charge and a functional group having a negative charge, the positive charge and the negative charge work to cancel each other's charge. It becomes smaller and the strength with which the hydrated water is bound to the hydrophilic polymer becomes smaller. As a result, the exchange rate of hydrated water increases to the extent that foulant adhesion can be suppressed. Moreover, it is hard to be influenced by the ionic strength of the water to be treated, and can exhibit excellent fouling resistance even for water to be treated having a high salt concentration such as seawater.
- the fouling resistance may include both of suppressing fouling and suppressing a decrease in performance even if fouling occurs.
- the hydrophilic polymer can have high hydrophilicity and hydrated water amount, and has excellent fau resistance. Shows ring characteristics.
- being positively or negatively charged means that the total amount of positive charges and the total amount of negative charges are different.
- the hydrophilic polymer is positively charged” and the number of negative charges in the entire hydrophilic polymer is positive.
- the hydrophilic polymer is negatively charged”. Specifically, if the functional group having a charge contained in the hydrophilic polymer is only a monovalent functional group, the number of functional groups having a positive charge and the number of functional groups having a negative charge are different. Macromolecules are positively or negatively charged.
- the hydrophilic polymer of the present invention is negatively charged.
- the hydrophilic polymer is negatively charged, more excellent fouling resistance can be exhibited with respect to a dirt substance containing an organic acid such as humic substance.
- the ratio (N1 / N2) between the number of positively charged functional groups (N1) and the number of negatively charged functional groups (N2) is from 15/85 to 45/55. Is preferred. More preferably, (N1 / N2) is 20/80 or more and 40/60 or less. When the ratio of the number of functional groups is 15/85 or more, the effect of improving the exchange rate of hydrated water by charge cancellation can be sufficiently obtained, and when it is 45/55 or less, the amount of hydrated water is higher. be able to.
- the charge density of the hydrophilic polymer is preferably 7.5 mmol / g or more and 10.5 mmol / g or less.
- the charge density is the molar amount of a functional group having a charge per unit mass.
- the charge density is 7.5 mmol / g or more, a higher hydration water amount can be obtained.
- the charge density is 10.5 mmol / g or less, the binding of hydration water by the hydrophilic polymer can be weakened, and the effect of improving the hydration water exchange rate can be further enhanced.
- the charge density is 8.0 mmol / g or more and 10.0 mmol / g or less.
- the hydrophilic polymer has the above composition, the hydrated water of the hydrophilic polymer suppresses the hydrophobic interaction and suppresses the adhesion of the hydrophobic molecule, and is also excellent for charged substances.
- the fouling resistance can be shown.
- the hydrophilic polymer of the present invention is negatively charged, in the hydrophilic polymer, the negative charge density is larger than the positive charge density. Further, the negative charge density is more preferably in the range of 4.5 mmol / g or more and 8.0 mmol / g or less.
- hydrophilic polymers are preferably polymers of monomers having an ethylenically unsaturated group from the chemical stability of the polymer.
- the hydrophilic polymer includes a functional group having a positive charge and a functional group having a negative charge.
- the hydrophilic polymer includes a functional group having a charge, and the charge is a negative charge. It is preferable that it is a copolymer with the monomer Q containing the functional group which has and the functional group which has a negative charge. That is, the monomer P includes a functional group having only a negative charge as a charge, and does not include a functional group having a positive charge.
- the hydrophilic polymer includes both a functional group having a positive charge and a functional group having a negative charge, so that the charge strength of the hydrophilic polymer can be reduced.
- the binding to the hydrophilic polymer is reduced.
- the effect of reducing the charge intensity depends on the distance between the functional groups, and the effect increases as the distance decreases. Therefore, in the hydrophilic polymer, it is preferable that the functional group having a positive charge and the functional group having a negative charge exist in the vicinity.
- a functional group having a positive charge and a functional group having a negative charge exist in the same monomer (monomer Q) because these functional groups are arranged within a short distance.
- the monomer Q containing both the positively charged functional group and the negatively charged functional group may be further copolymerized with another monomer P having a negatively charged functional group alone. preferable.
- examples of the monomer having a carboxy group include the following. Maleic acid, maleic anhydride, acrylic acid, methacrylic acid, itaconic acid, 2- (hydroxymethyl) acrylic acid, 4- (meth) acryloyloxyethyl trimellitic acid and the corresponding anhydride, 10-methacryloyloxydecylmalonic acid, N- (2-Hydroxy-3-methacryloyloxypropyl) -N-phenylglycine and 4-vinylbenzoic acid are preferable. Among them, acrylic acid, methacrylic acid and maleic acid are preferable from the viewpoint of versatility and copolymerization.
- the polymer P is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid and maleic acid.
- monomers having a phosphonic acid group include vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid, 2- Methacrylamidoethylphosphonic acid, 4-methacrylamideamido-4-methyl-phenyl-phosphonic acid, 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid and 2- [2-dihydroxyphosphoryl) -ethoxy And methyl] -acrylic acid-2,4,6-trimethyl-phenyl ester.
- monomers having an ethylenically unsaturated group include 2-methacryloyloxypropyl monohydrogen phosphate, 2-methacryloyloxypropyl dihydrogen phosphate, and 2-methacryloyloxyethyl monohydrogen.
- examples of the monomer having a sulfonic acid group include vinylsulfonic acid, 4-vinylphenylsulfonic acid, and 3- (methacrylamide) propylsulfonic acid.
- the monomer Q containing both a positively charged functional group and a negatively charged functional group a compound represented by the following formula (1) or a formula ( The compound represented by 2) is illustrated. These compounds are examples of compounds each having one functional group having one negative charge and one functional group having one positive charge.
- R 1 is H or CH 3
- R 2 , R 3 , R 6 and R 7 are each independently an alkylene group having 1 to 5 carbon atoms, or carbon An oxyalkylene group having 1 to 5 carbon atoms
- R 4 , R 5 , R 8 , R 9 and R 10 are each independently an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms.
- X is O, NH or S
- Y is SO 3 ⁇ , OSO 3 ⁇ , or CO 2 — .
- the above compounds include [2- (methacryloyloxy) ethyl] -dimethyl- (2-sulfoethyl) -ammonium hydroxide, [2- (methacryloyloxy) ethyl] -dimethyl- (3-sulfopropyl).
- Ammonium hydroxide [2- (methacryloyloxy) ethyl] -dimethyl- (4-sulfobutyl) -ammonium hydroxide, [2- (methacryloyloxy) ethyl] -dimethyl- (5-sulfopentyl) -ammonium hydroxide, [2- (acryloyloxy) ethyl] -dimethyl- (2-sulfoethyl) -ammonium hydroxide, [2- (acryloyloxy) ethyl] -dimethyl- (3-sulfopropyl) -ammonium hydroxide, [2- (acryloyl) Oxy) ethyl] -dimethyl (4-Sulfobutyl) -ammonium hydroxide, [2- (acryloyloxy) ethyl] -dimethyl- (5-sulfopentyl) -ammonium hydroxide, [3
- the ratio (PN: QN) of the number of monomer units derived from monomer P (number of moles) (PN) to the number of monomer units derived from monomer Q (number of moles) (QN) is a specific numerical value. However, it is preferably in the range of 80:20 to 20:80. When the molar ratio of the monomer units is in the range of 80:20 to 20:80, it has a higher amount of hydration water and can sufficiently obtain the effect of improving the exchange rate of hydration water by charge cancellation. . In addition to this condition, as described above, the ratio of the number of functional groups having a positive charge to the number of functional groups having a negative charge is more preferably in a range satisfying 15:85 or more and 45:55 or less.
- the ratio between the number of functional groups having positive charge and the number of functional groups having negative charge is calculated from the monomer ratio when synthesizing the hydrophilic polymer, for example, by using X-ray photoelectron spectroscopy (XPS). It can also be calculated by measuring the elemental composition and chemical bonding state. At this time, if the measurement depth is deep, it is affected by the composition of the polyamide in the separation functional layer. Therefore, it is preferable to measure the outermost surface by an angle decomposition method in which the sample is inclined. Further, depending on the type of functional group, it may be measured after being converted to another functional group by a chemical modification method. For example, by reacting a carboxy group with trifluoroethanol in the presence of a condensing agent, the number of functional groups can be estimated from the abundance ratio of the fluorine atoms.
- XPS X-ray photoelectron spectroscopy
- the hydrophilic polymer may be a binary copolymer of the monomer P containing the negatively charged functional group and the monomer Q containing both the positively charged functional group and the negatively charged functional group. If appropriate, it may be copolymerized with other monomers. Examples of copolymer components include vinyl pyrrolidone, vinyl alcohol, vinyl acetate, ethylene glycol, propylene glycol, polyethylene glycol (meth) acrylate, or block copolymers of these hydrophilic and hydrophobic polymers, graft copolymers. A polymer, a random copolymer, etc. are mentioned. Among the hydrophilic polymers, vinyl pyrrolidone, vinyl alcohol, and vinyl acetate are preferable from the viewpoint of ease of copolymerization and reduction in adhesion to foulants.
- the weight average molecular weight of the hydrophilic polymer of the present invention is preferably 2,000 or more and 1,500,000 or less.
- the weight average molecular weight is 2,000 or more, it is possible to have a more sufficient layer of hydrated water, and when the weight average molecular weight is 1,500,000 or less, the resistance of water that permeates the separation functional layer is increased. And can maintain a higher permeation flow rate. More preferably, it is 3,000 to 1,200,000, and still more preferably 5,000 to 1,000,000.
- the hydrophilic polymer is introduced covalently into the crosslinked polyamide.
- the hydrophilic polymer is attached to the membrane by, for example, electrostatic interaction, the interaction between the hydrophilic polymer and the membrane is inhibited by the foulant having negative charge, so that the hydrophilic polymer becomes the membrane.
- the foulant having negative charge so that the hydrophilic polymer becomes the membrane.
- it is a covalent bond, such peeling is suppressed.
- Covalent bonds include carbon-carbon bonds, ether bonds, ester bonds, amide bonds, imide bonds, urethane bonds, carbonate ester bonds, phosphate ester bonds, sulfate ester bonds, nitrate ester bonds, thioether bonds, thioester bonds, sulfonyls.
- the bond is mentioned, and it is particularly preferable that it is introduced by an amide bond.
- a hydrophilic polymer is introduced into the polyamide, which is the main component of the separation functional layer, by an amide bond via a carboxylic acid or amino group at the terminal of the polyamide.
- the hydrophilic polymer contained in the second layer is preferably amide-bonded to the polyamide contained in the first layer.
- the hydrophilic polymer is increased on the surface of the separation functional layer. It is possible to confirm that it exists.
- the root mean square roughness (hereinafter also referred to as “Rms”) of the surface of the separation functional layer is preferably 60 nm or more.
- the root mean square surface roughness is 60 nm or more, the surface area of the separation functional layer is increased and the amount of permeated water is increased.
- the root mean square surface roughness is less than 60 nm, the permeated water amount decreases.
- the root mean square surface roughness can be measured with an atomic force microscope (hereinafter referred to as “AFM”).
- the root mean square surface roughness is the square root of the value obtained by averaging the squares of deviations from the reference plane to the specified plane.
- the measurement surface is the surface indicated by all measurement data
- the specified surface is the surface that is subject to roughness measurement
- the specific portion specified by the clip of the measurement surface and the reference surface is the specified surface
- Z0 Z0.
- the AFM for example, NanoScope IIIa manufactured by Digital Instruments can be used.
- the root mean square surface roughness of the separation functional layer can be controlled by the monomer concentration and temperature when the separation functional layer is formed by interfacial polycondensation. For example, when the temperature during interfacial polycondensation is low, the root mean square roughness decreases, and when the temperature is high, the root mean square roughness increases.
- the surface of the separation functional layer is modified with a hydrophilic polymer, since the root mean square surface roughness decreases when the hydrophilic polymer layer is thick, the root mean square surface roughness is modified to be 60 nm or more. It is preferable.
- the bubble contact angle in a pH 3 aqueous solution on the surface of the separation functional layer is ⁇ A
- the bubble contact angle in a pH 11 aqueous solution is ⁇ B
- it is preferably in the range of 150 ° ⁇ A and ⁇ B ⁇ 180 °. . It exists in the said range, and can have the outstanding low fouling property in a wide pH range. Further, ( ⁇ B ⁇ A )> 5 ° is preferable.
- the support membrane is for imparting strength to the separation functional layer, and itself has substantially no separation performance for ions and the like.
- the support membrane includes a base material and a porous support layer.
- the size and distribution of pores in the support membrane are not particularly limited. For example, uniform and fine pores, or gradually having larger fine pores from the surface on the side where the separation functional layer is formed to the other surface, and separation.
- a support membrane in which the size of the micropores on the surface on which the functional layer is formed is 0.1 nm or more and 100 nm or less is preferable.
- the support membrane can be obtained, for example, by forming a porous support layer on the base material by casting a polymer on the base material.
- the material used for the support membrane and its shape are not particularly limited.
- the base material examples include a fabric made of at least one selected from polyester and aromatic polyamide. Particular preference is given to using polyesters which are highly mechanically and thermally stable.
- a long fiber nonwoven fabric or a short fiber nonwoven fabric can be preferably used.
- a polymer solution is cast on a substrate, it penetrates by over-penetration, the substrate and the porous support layer peel off, and the membrane is non-uniform due to fluffing of the substrate.
- the long fiber nonwoven fabric can be more preferably used because excellent film-forming properties that do not cause defects such as crystallization and pinholes are required.
- the long fiber nonwoven fabric examples include a long fiber nonwoven fabric composed of thermoplastic continuous filaments.
- the base material is made of a long-fiber nonwoven fabric, it is possible to suppress non-uniformity and membrane defects caused by fluffing caused by fluffing, which occurs when a short-fiber nonwoven fabric is used.
- the fiber orientation in the nonwoven fabric disposed on the side opposite to the porous support layer of the base material is the longitudinal orientation with respect to the film forming direction, thereby maintaining the strength of the base material and preventing film breakage and the like. It is preferable because it is possible.
- the longitudinal orientation means that the fiber orientation direction is parallel to the film forming direction. Conversely, when the fiber orientation direction is perpendicular to the film forming direction, it is referred to as lateral orientation.
- the fiber orientation degree of the nonwoven fabric base material is preferably 0 ° or more and 25 ° or less.
- the degree of fiber orientation is an index indicating the direction of the fibers of the nonwoven fabric substrate constituting the support membrane, and the direction of film formation during continuous film formation is 0 °, that is, the direction perpendicular to the film formation direction, that is, the nonwoven fabric.
- the average angle of the fibers constituting the nonwoven fabric substrate when the width direction of the substrate is 90 °. Accordingly, the closer to 0 ° the fiber orientation, the longer the orientation, and the closer to 90 °, the lateral orientation.
- the manufacturing process of the composite semipermeable membrane and the manufacturing process of the element include a heating step, but a phenomenon occurs in which the support membrane or the composite semipermeable membrane contracts due to heating.
- a phenomenon occurs in which the support membrane or the composite semipermeable membrane contracts due to heating.
- the film tends to shrink in the width direction. Since the support membrane or the composite semipermeable membrane shrinks, there arises a problem in dimensional stability and the like. Therefore, a substrate having a small thermal dimensional change rate is desired.
- the orientation degree difference between the fiber disposed on the side opposite to the porous support layer in the nonwoven fabric substrate and the fiber disposed on the porous support layer side is 10 ° or more and 90 ° or less, the change in the width direction due to heat Is preferable.
- the air permeability of the substrate is preferably 2.0 cc / cm 2 / sec or more.
- the air permeability is within this range, the amount of permeated water of the composite semipermeable membrane becomes higher. This is a process of forming a support film.
- a high molecular weight polymer is cast on a base material and immersed in a coagulation bath, the non-solvent replacement rate from the base material side is increased, thereby increasing the porous support layer. This is thought to be because the internal structure of the resin changes and affects the retention amount and diffusion rate of the monomer in the subsequent step of forming the separation functional layer.
- the air permeability can be measured by a Frazier type tester based on JIS L1096 (2010). For example, a base material is cut out to a size of 200 mm ⁇ 200 mm and used as a sample. This sample is attached to the Frazier type tester, and the suction fan and air hole are adjusted so that the inclined barometer has a pressure of 125 Pa. Based on the pressure indicated by the vertical barometer at this time and the type of air hole used, The amount of air passing through the material, that is, the air permeability can be calculated. As the Frazier type tester, KES-F8-AP1 manufactured by Kato Tech Co., Ltd. can be used.
- the thickness of the substrate is preferably in the range of 10 ⁇ m to 200 ⁇ m, more preferably in the range of 30 ⁇ m to 120 ⁇ m.
- vinyl polymer polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfone, polyphenylene oxide, and the like homopolymers or copolymers alone or blended.
- cellulose acetate and cellulose nitrate can be used as the cellulose polymer
- polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile and the like can be used as the vinyl polymer.
- homopolymers or copolymers such as polysulfone, polyamide, polyester, cellulose acetate, cellulose nitrate, polyvinyl chloride, polyacrylonitrile, polyphenylene sulfide, and polyphenylene sulfide sulfone are preferable. More preferably, cellulose acetate, polysulfone, polyphenylene sulfide sulfone, or polyphenylene sulfone can be mentioned. Among these materials, polysulfone is highly stable chemically, mechanically, and thermally, and is easy to mold. Can be used generally.
- polysulfone composed of repeating units represented by the following formula because the pore diameter of the support membrane is easy to control and the dimensional stability is high.
- an N, N-dimethylformamide (hereinafter referred to as “DMF”) solution of the above polysulfone is cast on a densely woven polyester fabric or polyester nonwoven fabric to a certain thickness, and is wet-coagulated in water.
- DMF N, N-dimethylformamide
- the thickness of the above support membrane affects the strength of the resulting composite semipermeable membrane and the packing density when it is used as an element.
- the thickness of the support membrane is preferably in the range of 30 ⁇ m to 300 ⁇ m, more preferably in the range of 100 ⁇ m to 220 ⁇ m.
- the morphology of the porous support layer can be observed with a scanning electron microscope, a transmission electron microscope, or an atomic microscope.
- a scanning electron microscope after peeling off the porous support layer from the substrate, it is cut by the freeze cleaving method to obtain a sample for cross-sectional observation.
- the sample is thinly coated with platinum, platinum-palladium or ruthenium tetrachloride, preferably ruthenium tetrachloride, and observed with a high resolution field emission scanning electron microscope (UHR-FE-SEM) at an acceleration voltage of 3 to 15 kV.
- UHR-FE-SEM high resolution field emission scanning electron microscope
- an S-900 electron microscope manufactured by Hitachi, Ltd. can be used.
- the support membrane used in the present invention can be selected from various commercially available materials such as “Millipore Filter VSWP” (trade name) manufactured by Millipore, and “Ultra Filter UK10” (trade name) manufactured by Toyo Roshi Kaisha, “Office of Saleen Water Research and Development Progress Report” No. 359 (1968).
- the thickness of the porous support layer is preferably in the range of 20 ⁇ m to 100 ⁇ m. Since the porous support layer has a thickness of 20 ⁇ m or more, good pressure resistance can be obtained and a uniform support film having no defects can be obtained. Therefore, a composite semipermeable membrane provided with such a porous support layer Can exhibit better salt removal performance. If the thickness of the porous support layer exceeds 100 ⁇ m, the remaining amount of unreacted substances at the time of production increases, which may reduce the amount of permeated water and chemical resistance.
- the thickness of the base material and the thickness of the composite semipermeable membrane can be measured with a digital thickness gauge. Moreover, since the thickness of the separation functional layer is very thin compared with the support membrane, the thickness of the composite semipermeable membrane can be regarded as the thickness of the support membrane. Therefore, the thickness of the porous support layer can be easily calculated by measuring the thickness of the composite semipermeable membrane with a digital thickness gauge and subtracting the thickness of the substrate from the thickness of the composite semipermeable membrane. As the digital thickness gauge, PEACOCK manufactured by Ozaki Manufacturing Co., Ltd. can be used. When a digital thickness gauge is used, the average value is calculated by measuring the thickness at 20 locations.
- the thickness may be measured with a scanning electron microscope. Thickness is calculated
- the manufacturing method includes a supporting film forming step and a separation functional layer forming step.
- the support film forming step includes a step of applying a polymer solution to a substrate and a step of immersing the substrate coated with the solution in a coagulation bath to coagulate the polymer. .
- the polymer solution is prepared by dissolving the polymer that is a component of the porous support layer in a good solvent for the polymer.
- the temperature of the polymer solution during application of the polymer solution is preferably 10 ° C. or more and 60 ° C. or less when, for example, polysulfone is used as the polymer. If the temperature of the polymer solution is within this range, the polymer does not precipitate, and the polymer solution is sufficiently impregnated between the fibers of the base material and then solidified. As a result, the porous support layer is firmly bonded to the substrate by the anchor effect, and a good support film can be obtained.
- the preferred temperature range of the polymer solution can be adjusted as appropriate depending on the type of polymer used, the desired solution viscosity, and the like.
- the time from application of the polymer solution on the substrate to immersion in the coagulation bath is 0.1 second or more and 5 seconds or less. If the time until dipping in the coagulation bath is within this range, the organic solvent solution containing the polymer is sufficiently impregnated between the fibers of the base material and then solidified.
- the preferable range of time until it immerses in a coagulation bath can be suitably adjusted with the kind of polymer solution to be used, desired solution viscosity, etc.
- the coagulation bath water is usually used, but any water that does not dissolve the polymer that is a component of the porous support layer may be used.
- the membrane form of the support membrane obtained by the composition of the coagulation bath changes, and the resulting composite semipermeable membrane also changes.
- the temperature of the coagulation bath is preferably ⁇ 20 ° C. or higher and 100 ° C. or lower, more preferably 10 ° C. or higher and 50 ° C. or lower. If the temperature of the coagulation bath is within this range, the vibration of the coagulation bath surface due to thermal motion does not become intense, and the smoothness of the film surface after film formation is maintained. If the temperature is within this range, the solidification rate is appropriate and the film forming property is good.
- the support membrane thus obtained is washed with hot water in order to remove the solvent remaining in the membrane.
- the temperature of the hot water at this time is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 60 ° C. or higher and 95 ° C. or lower. Within this range, the shrinkage of the support membrane does not increase and the amount of permeated water is good. If the temperature is within this range, the cleaning effect is sufficient.
- the formation process of the separation functional layer of the present invention includes: (A) a step of forming a crosslinked polyamide on a support membrane including a substrate and a porous support layer; and (b) the crosslinked polyamide obtained in (a) has a positively charged functional group and a negative charge.
- the step (a) is preferably the following step (a) ′.
- (A) A step of forming a crosslinked polyamide by performing interfacial polycondensation on the surface of the support film using an aqueous solution containing a polyfunctional amine and an organic solvent solution containing a polyfunctional acid halide.
- the step of forming the separation functional layer further includes (C) contacting with a reagent that reacts with a crosslinked polyamide primary amino group to form a diazonium salt or a derivative thereof; May further be included.
- the step (b) may be after the step (a).
- a process (c) may be performed between a process (a) and (b), and may be performed after a process (b).
- a first layer mainly composed of polyamide is formed, and in the subsequent step (b), a second layer mainly composed of a hydrophilic polymer is formed on the surface of the first layer.
- the step (b) is a step of introducing a crosslinked polyamide and a hydrophilic polymer by a covalent bond, and it is considered that the hydrophilic polymer hardly passes through the crosslinked polyamide having a separation function.
- a second layer is formed on the surface.
- the step (c) is a step of converting an amino group to a functional group, and the step (c) is performed after the step (b), so that the step (c) is performed before the step (b).
- Many hydrophilic polymers can be introduced to improve the fouling resistance.
- step (a) the organic solvent that dissolves the polyfunctional acid halide is immiscible with water, does not destroy the support membrane, and does not inhibit the formation reaction of the crosslinked polyamide. Any may be used. Typical examples include liquid hydrocarbons and halogenated hydrocarbons such as trichlorotrifluoroethane.
- octane nonane, decane, undecane, dodecane, tridecane, tetradecane, heptadecane, hexadecane, cyclooctane , Ethylcyclohexane, 1-octene, 1-decene and the like or a mixture thereof is preferably used.
- acylation catalyst for organic solvent solution containing polyfunctional amine aqueous solution or polyfunctional acid halide, acylation catalyst, polar solvent, acid scavenger, surface activity, if necessary, as long as they do not interfere with the reaction between both components
- a compound such as an agent and an antioxidant may be contained.
- the surface of the support membrane is coated with a polyfunctional amine aqueous solution.
- concentration of the aqueous solution containing the polyfunctional amine is preferably 0.1% by weight or more and 20% by weight or less, more preferably 0.5% by weight or more and 15% by weight or less.
- the surface of the supporting membrane may be uniformly and continuously coated with this aqueous solution, and a known coating means, for example, an aqueous solution is coated on the surface of the supporting membrane.
- a method, a method of immersing the support film in an aqueous solution, or the like may be performed.
- the contact time between the support membrane and the polyfunctional amine aqueous solution is preferably in the range of 5 seconds to 10 minutes, and more preferably in the range of 10 seconds to 3 minutes.
- a liquid draining step it is preferable to remove the excessively applied aqueous solution by a liquid draining step.
- a method for draining liquid for example, there is a method in which the film surface is allowed to flow naturally while being held in a vertical direction. After draining, the membrane surface may be dried to remove all or part of the water in the aqueous solution.
- an organic solvent solution containing the above-mentioned polyfunctional acid halide is applied to a support film coated with an aqueous polyfunctional amine solution, and a crosslinked polyamide is formed by interfacial polycondensation.
- the time for performing the interfacial polycondensation is preferably from 0.1 second to 3 minutes, and more preferably from 0.1 second to 1 minute.
- the concentration of the polyfunctional acid halide in the organic solvent solution is not particularly limited, but if it is too low, the formation of the polyamide as the active layer may be insufficient, which may be a disadvantage, and if it is too high, it is disadvantageous from the viewpoint of cost. Therefore, about 0.01% by weight or more and 1.0% by weight or less is preferable.
- the organic solvent solution after the reaction by a liquid draining step.
- a method of removing the excess organic solvent by naturally flowing it by holding the film in the vertical direction can be used.
- the time for gripping in the vertical direction is preferably 1 minute or more and 5 minutes or less, and more preferably 1 minute or more and 3 minutes or less.
- the gripping time is 1 minute or longer, it is easy to obtain a polyamide having the desired function, and when it is 5 minutes or shorter, it is possible to suppress the occurrence of defects due to overdrying of the organic solvent, so it is possible to suppress performance degradation. .
- the polyamide obtained by the above-described method is washed with hot water within a range of 25 ° C. or more and 90 ° C. or less for 1 minute or more and 60 minutes or less, so that the solute blocking performance and the amount of permeated water of the composite semipermeable membrane Can be further improved.
- the hot water cleaning is performed within a range of 25 ° C. or more and 60 ° C. or less.
- the hot water cleaning process is performed at a high temperature of 61 ° C. or higher and 90 ° C. or lower, it is preferable to cool slowly after the hot water cleaning process. For example, there is a method of cooling to room temperature by contacting with low temperature hot water stepwise.
- acid or alcohol may be contained in the hot water.
- an acid or an alcohol it becomes easier to control the formation of hydrogen bonds in the polyamide.
- the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as citric acid and oxalic acid.
- the acid concentration is preferably adjusted to be pH 2 or less, more preferably pH 1 or less.
- the alcohol include monohydric alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, and polyhydric alcohols such as ethylene glycol and glycerin.
- the concentration of the alcohol is preferably 10% by weight or more and 100% by weight or less, more preferably 10% by weight or more and 50% by weight or less.
- a hydrophilic polymer is introduced into the polyamide by a covalent bond.
- the covalent bond is preferably an amide bond since it is easily eliminated by chemical solution washing or the like when introduced by a weak bond or interaction.
- the structure, type, etc. of the hydrophilic polymer introduced in the step (b) are as described above.
- a method in which an aqueous solution containing a hydrophilic polymer and a condensing agent is brought into contact with the polyamide surface is suitably used. Since the functional group on the polyamide surface and the functional group contained in the hydrophilic polymer form an amide bond by a condensation reaction, the hydrophilic polymer is introduced.
- the method for bringing the aqueous solution containing the hydrophilic polymer and the condensing agent into contact with the separation functional layer is not particularly limited.
- the entire composite semipermeable membrane may be immersed in the aqueous solution containing the hydrophilic polymer and the condensing agent.
- an aqueous solution containing a hydrophilic polymer and a condensing agent may be sprayed on the surface of the composite semipermeable membrane, and the method is not limited as long as the polyamide, the hydrophilic polymer and the condensing agent are in contact with each other.
- the hydrophilic polymer to be brought into contact with the polyamide surface may be used alone or as a mixture of several kinds.
- the hydrophilic polymer is preferably used as an aqueous solution having a weight concentration of 10 ppm to 1%.
- concentration of the hydrophilic polymer is 10 ppm or more, the functional group present in the polyamide can be sufficiently reacted with the hydrophilic polymer.
- it exceeds 1% the hydrophilic polymer layer becomes thick, and the amount of water produced may be reduced.
- an alkaline metal compound such as sodium carbonate, sodium hydroxide, or sodium phosphate may be added to promote the reaction between the polyamide surface and the hydrophilic polymer.
- an alkaline metal compound such as sodium carbonate, sodium hydroxide, or sodium phosphate
- monomers such as polyfunctional acid halides and polyfunctional amine compounds, and oligomers produced by the reaction of these monomers remaining in the polyamide, dodecyl sulfate
- a surfactant such as sodium or sodium benzenesulfonate.
- the condensing agent refers to a compound that activates a carboxy group in water and advances a condensation reaction with an amino group of polyamide.
- Such compounds include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1,3-bis (2,2-dimethyl-1,3-dioxolan-4-ylmethyl) carbodiimide, and 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (hereinafter referred to as “DMT-MM”).
- DMT-MM is particularly preferably used because of stability during the condensation reaction and low toxicity of by-products after the condensation reaction.
- the concentration of the condensing agent in the aqueous solution containing the hydrophilic polymer and the condensing agent is not particularly limited as long as it is higher than the concentration of the carboxy group to be activated, and a sufficient effect for condensation with the reactive group can be obtained.
- the pH of the aqueous solution containing the hydrophilic polymer and the condensing agent is preferably 2 or more and 12 or less.
- the pH of the aqueous solution containing the hydrophilic polymer and the condensing agent is preferably 2 or more and 12 or less.
- hydrophilic polymer can be synthesized by mixing a monomer and a polymerization initiator in an aqueous solution and placing them at an appropriate temperature.
- a hydrophilic polymer can be synthesized by mixing a monomer and a polymerization initiator in an aqueous solution and placing them at an appropriate temperature. Examples of the monomer structure are as described above. The monomer ratio may be equal to the target monomer unit ratio.
- the amino group is converted into another functional group by contacting the amino group of the polyamide with a reagent for converting the functional group.
- a reagent for converting the functional group it is preferable to perform functional group conversion by contacting with a reagent that reacts with an amino group to produce a diazonium salt or a derivative thereof.
- the reagent that reacts with an amino group to produce a diazonium salt or a derivative thereof include aqueous solutions of nitrous acid and salts thereof, nitrosyl compounds, and the like. Since aqueous solutions of nitrous acid and nitrosyl compounds have the property of generating gas and decomposing, it is preferable to sequentially generate nitrous acid by the reaction of nitrite and acidic solution.
- nitrite reacts with hydrogen ions to produce nitrous acid (HNO 2 ), but it is efficiently produced when the pH of the aqueous solution is 7 or less, preferably 5 or less, more preferably 4 or less.
- an aqueous solution of sodium nitrite reacted with hydrochloric acid or sulfuric acid in an aqueous solution is particularly preferable because of easy handling.
- the concentration of nitrous acid or nitrite in a reagent that reacts with an amino group to produce a diazonium salt or a derivative thereof is preferably in the range of 0.01 wt% to 1 wt%, more preferably 0.05 wt%. % Or more and 0.5% by weight or less. If the concentration is 0.01% by weight or more, a sufficient effect can be obtained, and if the concentration is 1% by weight or less, the solution can be easily handled.
- the temperature of the nitrous acid aqueous solution is preferably 15 ° C. or higher and 45 ° C. or lower.
- the temperature is 15 ° C. or higher, a sufficient reaction time can be obtained, and when it is 45 ° C. or lower, the decomposition of nitrous acid hardly occurs and handling is easy.
- the contact time with the nitrous acid aqueous solution may be a time at which at least one of the diazonium salt and its derivative is formed, and can be processed in a short time at a high concentration, but a long time is required at a low concentration. . Therefore, the solution having the above concentration is preferably within 10 minutes, more preferably within 3 minutes.
- the contacting method is not particularly limited, and the composite semipermeable membrane may be immersed in the reagent solution or the reagent solution.
- the solvent for dissolving the reagent any solvent may be used as long as the reagent is dissolved and the composite semipermeable membrane is not eroded.
- the solution may contain a surfactant, an acidic compound, an alkaline compound, or the like as long as it does not interfere with the reaction between the amino group and the reagent.
- a part of the formed diazonium salt or derivative thereof is converted into a different functional group.
- a part of the diazonium salt or a derivative thereof is converted into a phenolic hydroxyl group by reacting with water, for example. Also, contact with a solution containing chloride ion, bromide ion, cyanide ion, iodide ion, boroboric acid, hypophosphorous acid, sodium bisulfite, sulfite ion, aromatic amine, hydrogen sulfide, thiocyanic acid, etc. To the corresponding functional group. Further, by contacting with an aromatic amine, a diazo coupling reaction takes place and an aromatic group can be introduced onto the film surface.
- these reagents may be used alone, or may be used by mixing a plurality of them, or may be brought into contact with different reagents a plurality of times.
- Examples of the reagent that causes a diazo coupling reaction include compounds having an electron-rich aromatic ring or heteroaromatic ring.
- Examples of the compound having an electron-rich aromatic ring or heteroaromatic ring include an unsubstituted heteroaromatic ring compound, an aromatic compound having an electron donating substituent, and a heteroaromatic ring compound having an electron donating substituent.
- Examples of the electron donating substituent include an amino group, an ether group, a thioether group, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
- Specific examples of the above compounds include, for example, methoxyaniline bonded to a benzene ring in any positional relationship of aniline, ortho-position, meta-position, and para-position, and two amino groups are ortho-position, meta-position, para-position, and the like.
- Examples include 4-aminobenzylamine, sulfanilic acid, 3,3′-dihydroxybenzidine, 1-aminonaphthalene, 2-aminonaphthalene, and N-alkylated products of these compounds.
- the composite semipermeable membrane of the present invention comprises a plurality of pores together with a raw water channel material such as a plastic net, a permeate channel material such as tricot, and a film for increasing pressure resistance as required. Is wound around a cylindrical water collecting pipe and is suitably used as a spiral composite semipermeable membrane element. Furthermore, a composite semipermeable membrane module in which these elements are connected in series or in parallel and accommodated in a pressure vessel can be obtained.
- the above-described composite semipermeable membrane, its elements, and modules can be combined with a pump for supplying raw water to them, a device for pretreating the raw water, and the like to constitute a fluid separation device.
- a separation device By using this separation device, raw water can be separated into permeated water such as drinking water and concentrated water that has not permeated through the membrane, and water suitable for the purpose can be obtained.
- the operating pressure during permeation is preferably 0.1 MPa or more and 10 MPa or less.
- the salt removal rate decreases as the feed water temperature increases, but the membrane permeation flux also decreases as the feed water temperature decreases, so 5 ° C. or higher and 45 ° C. or lower is preferable.
- scales such as magnesium may be generated in the case of feed water with a high salt concentration such as seawater, and there is a concern about deterioration of the membrane due to high pH operation. Is preferred.
- Examples of the raw water to be treated by the composite semipermeable membrane according to the present invention include liquid mixtures containing 500 mg / L to 100 g / L TDS (Total Dissolved Solids) such as seawater, brine, and wastewater. .
- TDS Total Dissolved Solids
- mass ⁇ volume or “weight ratio”. According to the definition, it can be calculated from the weight of the residue obtained by evaporating the solution filtered through a 0.45 ⁇ m filter at a temperature of 39.5 to 40.5 ° C., but more simply converted from practical salt (S). To do.
- NaCl removal rate 100 ⁇ ⁇ 1 ⁇ (NaCl concentration in permeated water / NaCl concentration in feed water) ⁇
- polyoxyethylene (10) octylphenyl ether POEOPE
- F2 polyoxyethylene (10) octylphenyl ether
- F3 polyoxyethylene (10) octylphenyl ether
- Air permeability The air permeability was measured by a fragile type tester based on JIS L1096 (2010). The base material is cut into a size of 200 mm ⁇ 200 mm, attached to a Frazier type tester, the suction fan and the air hole are adjusted so that the inclined barometer has a pressure of 125 Pa, and the pressure indicated by the vertical barometer at this time The air permeability was determined from the type of air holes used. As the Frazier type tester, KES-F8-AP1 manufactured by Kato Tech Co., Ltd. was used.
- the aqueous solution obtained in each synthesis example was diluted with 20 mM phosphate buffer (pH 7.4) so as to be 1.0 w / v%, and this solution was filtered through a 0.45 ⁇ m membrane filter to obtain a test solution.
- the weight average molecular weight was measured and calculated by gel permeation chromatography).
- Table 1 shows the molar ratio and weight average molecular weight of the copolymers obtained in each synthesis example.
- the measurement conditions for GPC analysis are as follows.
- the membrane was drained vertically and dried by blowing air at 25 ° C. using a blower, followed by washing with pure water at 40 ° C.
- the membrane performance during film formation and the membrane performance after fouling of the composite semipermeable membrane obtained as described above were measured, and the values shown in Table 2 were obtained.
- Comparative Example 2 The composite semipermeable membrane obtained in Comparative Example 1 was immersed in a 0.3 wt% sodium nitrite aqueous solution adjusted to pH 3 and 35 ° C. for 1 minute. The pH of sodium nitrite was adjusted with sulfuric acid. Next, the composite semipermeable membrane of Comparative Example 2 was obtained by immersing in a 0.1 wt% aqueous sodium sulfite solution at 35 ° C. for 2 minutes. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Comparative Example 3 The composite semipermeable membrane obtained in Comparative Example 1 was brought into contact with a solution prepared by adjusting the polymer obtained in Synthesis Example 1 to 400 ppm and DMT-MM to be 0.1% at 20 ° C. for 24 hours. Washed with water. Next, it was immersed for 1 minute in 0.3 weight% sodium nitrite aqueous solution adjusted to pH3 and 35 degreeC. The pH of sodium nitrite was adjusted with sulfuric acid. Further, the composite semipermeable membrane of Comparative Example 3 was obtained by immersing in a 0.1 wt% aqueous sodium sulfite solution at 35 ° C. for 2 minutes. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Comparative Example 4 The composite semipermeable membrane obtained in Comparative Example 1 was brought into contact with a solution prepared by synthesizing the polymer obtained in Synthesis Example 2 to 400 ppm at 20 ° C. for 24 hours, and then washed with water. It was immersed in a 0.3 wt% sodium nitrite aqueous solution adjusted to pH 3 and 35 ° C. for 1 minute. The pH of sodium nitrite was adjusted with sulfuric acid. Next, the composite semipermeable membrane of Comparative Example 4 was obtained by immersing in a 0.1 wt% aqueous sodium sulfite solution at 35 ° C. for 2 minutes. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Comparative Example 5 The composite semipermeable membrane obtained in Comparative Example 1 was brought into contact with a solution prepared by adding 300 ppm of the polymer obtained in Synthesis Example 12 and 0.1% of DMT-MM at 20 ° C. for 24 hours. Washed with water. Next, it was immersed for 1 minute in 0.3 weight% sodium nitrite aqueous solution adjusted to pH3 and 35 degreeC. The pH of sodium nitrite was adjusted with sulfuric acid. Furthermore, the composite semipermeable membrane of Comparative Example 5 was obtained by immersing in a 0.1 wt% aqueous sodium sulfite solution at 35 ° C. for 2 minutes. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Comparative Example 6 Using the polymer obtained in Synthesis Example 11, the treatment was performed in the same manner as in Comparative Example 5 except that the polymer concentration was changed to 500 ppm, whereby a composite semipermeable membrane of Comparative Example 6 was obtained. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Comparative Example 7 Using the polymer obtained in Synthesis Example 14, the treatment was carried out in the same manner as in Comparative Example 5 except that the polymer concentration was changed to 500 ppm, whereby a composite semipermeable membrane of Comparative Example 7 was obtained. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Example 1 The composite semipermeable membrane obtained in Comparative Example 1 was brought into contact with a solution prepared so that the polymer obtained in Synthesis Example 2 was 400 ppm and DMT-MM was 0.1% at 20 ° C. for 24 hours. Washed with water. Next, it was immersed for 1 minute in 0.3 weight% sodium nitrite aqueous solution adjusted to pH3 and 35 degreeC. The pH of sodium nitrite was adjusted with sulfuric acid. Furthermore, the composite semipermeable membrane of Example 1 was obtained by being immersed in a 0.1 wt% aqueous sodium sulfite solution at 35 ° C. for 2 minutes. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Example 2 The treatment was performed in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 3 was used, and the composite semipermeable membrane of Example 2 was obtained. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Example 3 The composite semipermeable membrane of Example 3 was obtained in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 4 was used. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Example 4 The composite semipermeable membrane of Example 4 was obtained in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 5 was used and the polymer concentration was 2000 ppm. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Example 5 The composite semipermeable membrane of Example 5 was obtained in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 6 was used and the polymer concentration was 1000 ppm. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Example 6 The composite semipermeable membrane of Example 6 was obtained in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 7 was used and the polymer concentration was changed to 300 ppm. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Example 7 The composite semipermeable membrane of Example 7 was obtained in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 8 was used and the polymer concentration was changed to 150 ppm. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Example 8 The composite semipermeable membrane of Example 8 was obtained in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 9 was used. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Example 9 The composite semipermeable membrane of Example 9 was obtained in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 10 was used and the polymer concentration was 1000 ppm. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- Example 10 The composite semipermeable membrane of Example 10 was obtained in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 13 was used and the polymer concentration was 250 ppm. When the obtained composite semipermeable membrane was evaluated, the membrane performance was the value shown in Table 2.
- the bubble contact angles of the composite semipermeable membranes produced in the respective comparative examples and examples were the values shown in Table 2.
- the composite semipermeable membrane of the present invention can realize excellent fouling resistance over a long period of time. That is, it has a high adhesion suppressing ability against film contaminants and can maintain high performance stably for a long period of time.
- raw water can be separated into permeated water such as drinking water and concentrated water that has not permeated through the membrane, and water suitable for the purpose can be obtained.
- the composite semipermeable membrane of the present invention can be suitably used particularly for brine or seawater desalination.
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Abstract
Description
本発明は、長期にわたり優れた耐ファウリング性を実現できる複合半透膜及びその製造方法を提供することを目的とする。特に海水などの塩濃度の高い被処理水に対しても、優れた耐ファウリング性を発現する複合半透膜とその製造方法を提案する。
<1> 基材及び多孔性支持層を含む支持膜と、前記多孔性支持層上に設けられた分離機能層とを備える複合半透膜であって、
前記分離機能層が、架橋ポリアミドと親水性高分子とを含み、下記条件(A)及び(B)を満たす複合半透膜。
(A)前記親水性高分子が、正荷電を有する官能基及び負荷電を有する官能基を含み、かつ、前記親水性高分子が負に荷電している。
(B)前記親水性高分子が、前記架橋ポリアミドに共有結合している。
<2> 前記親水性高分子において、前記正荷電を有する官能基の数(N1)と、前記負荷電を有する官能基の数(N2)との比(N1/N2)が15/85以上45/55以下である、前記<1>に記載の複合半透膜。
<3> 前記親水性高分子の重量平均分子量が2,000以上1,500,000以下である、前記<1>又は<2>に記載の複合半透膜。
<4> 前記親水性高分子の荷電密度が7.5mmol/g以上10.5mmol/g以下である、前記<1>~<3>のいずれか1に記載の複合半透膜。
<5> 前記親水性高分子の負荷電密度が4.5mmol/g以上8.0mmol/g以下である、前記<1>~<4>のいずれか1に記載の複合半透膜。
<6> 前記分離機能層において、pH3の水溶液中における気泡接触角をθA、pH11の水溶液中における気泡接触角をθBとしたとき、150°<θA、θB<180°及び(θB-θA)>5°を満たす、前記<1>~<5>のいずれか1に記載の複合半透膜。
<7> 前記親水性高分子が、荷電を有する官能基を含み、前記荷電は負荷電であるモノマーPと、正荷電を有する官能基及び負荷電を有する官能基を含むモノマーQとの共重合体である、前記<1>~<6>のいずれか1に記載の複合半透膜。
<8> 前記共重合体に含まれる前記モノマーP由来のモノマーユニットの数(PN)と前記モノマーQ由来のモノマーユニットの数(QN)との比(PN:QN)が80:20~20:80である、前記<7>に記載の複合半透膜。
<9> 前記モノマーPが、アクリル酸、メタクリル酸及びマレイン酸からなる群から選択される少なくとも1種の化合物である、前記<7>又は<8>に記載の複合半透膜。
<10> 前記モノマーQが下記式(1)又は式(2)で示される少なくとも一方の化合物である、前記<7>~<9>のいずれか1に記載の複合半透膜。
<12> (a)基材及び多孔性支持層を含む支持膜上に架橋ポリアミドを形成する工程、及び
(b)前記(a)で得られた前記架橋ポリアミドに、正荷電を有する官能基及び負荷電を有する官能基を含み、かつ、負に荷電している親水性高分子を共有結合させる工程、
を備える複合半透膜の製造方法。
本発明の複合半透膜は、基材及び多孔性支持層を含む支持膜と、多孔性支持層上に設けられた、架橋ポリアミド(以下、単に「ポリアミド」と称することもある。)と親水性高分子とを含む分離機能層とを備える。
分離機能層は、複合半透膜において溶質の分離機能を担う層である。分離機能層の組成及び厚み等の構成は、複合半透膜の使用目的に合わせて設定される。
分離機能層は、具体的には、架橋ポリアミド及び親水性高分子を含む。
ここで多官能アミンは、芳香族多官能アミン及び脂肪族多官能アミンから選ばれる少なくとも1つのアミンであることが好ましい。
性能発現の安定性から、特にメタフェニレンジアミン(以下、「m-PDA」という)、又は1,3,5-トリアミノベンゼンが好ましい。
例えば、ピペラジン、2,5-ジメチルピペラジン、2-メチルピペラジン、2,6-ジメチルピペラジン、2,3,5-トリメチルピペラジン、2,5-ジエチルピペラジン、2,3,5-トリエチルピペラジン、2-n-プロピルピペラジン、2,5-ジ-n-ブチルピペラジン、エチレンジアミンなどが例示される。
性能発現の安定性から、特に、ピペラジン又は2,5-ジメチルピペラジンが好ましい。
これらの多官能アミンは、1種を単独で用いても、2種類以上を混合物として用いてもよい。
上記多官能酸ハロゲン化物は1種を単独で用いても、2種類以上を混合物として用いてもよい。
また、親水性高分子が分離機能層表面に存在することで、汚れはポリアミドよりも親水性高分子に付着しやすい。つまり、仮に汚れが分離機能層表面に付着しても、親水性高分子によって、汚れはポリアミドから離れた位置に付着すると考えられる。よって、分離膜の性能低下が低く抑えられる。
本発明において、荷電を有する官能基とは、水中にてプロトン化、又は脱プロトン化することにより、荷電を有する官能基も含む。以下では、「荷電を有する官能基」における荷電の価数は特に限定されないが、一価であることが好ましい。
具体的には、親水性高分子に含まれる荷電を持つ官能基が1価の官能基のみであれば、正荷電を有する官能基数と負荷電を有する官能基数が異なっていることで、親水性高分子は正又は負に荷電する。
親水性高分子は、先述したように正荷電を有する官能基と負荷電を有する官能基とを含むものであるが、荷電を有する官能基を含み、前記荷電は負荷電であるモノマーPと、正荷電を有する官能基及び負荷電を有する官能基を含むモノマーQとの共重合体であることが好ましい。つまり、モノマーPは、荷電として負荷電のみを有する官能基を含み、正荷電を有する官能基を含まない。
チル]ジメチルアンモニオ}ペンタノエート、2-{[2-(メタクリロイルアミノ)エチル]ジメチルアンモニオ}エタノエート、3-{[2-(メタクリロイルアミノ)エチル]ジメチルアンモニオ}プロパノエート、4-{[2-(メタクリロイルアミノ)エチル]ジメチルアンモニオ}ブタノエート、5-{[2-(メタクリロイルアミノ)エチル]ジメチルアンモニオ}ペンタノエート、2-{[2-(アクリロイルアミノ)エチル]ジメチルアンモニオ}エタノエート、3-{[2-(アクリロイルアミノ)エチル]ジメチルアンモニオ}プロパノエート、4-{[2-(アクリロイルアミノ)エチル]ジメチルアンモニオ}ブタノエート、5-{[2-(アクリロイルアミノ)エチル]ジメチルアンモニオ}ペンタノエート、2-{[3-(メタクリロイルアミノ)プロピル]ジメチルアンモニオ}エタノエート、3-{[3-(メタクリロイルアミノ)プロピル]ジメチルアンモニオ}プロパノエート、4-{[3-(メタクリロイルアミノ)プロピル]ジメチルアンモニオ}ブタノエート、5-{[3-(メタクリロイルアミノ)プロピル]ジメチルアンモニオ}ペンタノエート、2-{[3-(アクリロイルアミノ)プロピル]ジメチルアンモニオ}エタノエート、3-{[3-(アクリロイルアミノ)プロピル]ジメチルアンモニオ}プロパノエート、4-{[3-(アクリロイルアミノ)プロピル]ジメチルアンモニオ}ブタノエート、5-{[3-(アクリロイルアミノ)プロピル]ジメチルアンモニオ}ペンタノエート、2-{[4-(メタクリロイルアミノ)ブチル]ジメチルアンモニオ}エタノエート、3-{[4-(メタクリロイルアミノ)ブチル]ジメチルアンモニオ}プロパノエート、4-{[4-(メタクリロイルアミノ)ブチル]ジメチルアンモニオ}ブタノエート、5-{[4-(メタクリロイルアミノ)ブチル]ジメチルアンモニオ}ペンタノエート、2-{[4-(アクリロイルアミノ)ブチル]ジメチルアンモニオ}エタノエート、3-{[4-(アクリロイルアミノ)ブチル]ジメチルアンモニオ}プロパノエート、4-{[4-(アクリロイルアミノ)ブチル]ジメチルアンモニオ}ブタノエート、5-{[4-(アクリロイルアミノ)ブチル]ジメチルアンモニオ}ペンタノエート、2-{[5-(メタクリロイルアミノ)ペンチル]ジメチルアンモニオ}エタノエート、3-{[5-(メタクリロイルアミノ)ペンチル]ジメチルアンモニオ}プロパノエート、4-{[5-(メタクリロイルアミノ)ペンチル]ジメチルアンモニオ}ブタノエート、5-{[5-(メタクリロイルアミノ)ペンチル]ジメチルアンモニオ}ペンタノエート、2-{[5-(アクリロイルアミノ)ペンチル]ジメチルアンモニオ}エタノエート、3-{[5-(アクリロイルアミノ)ペンチル]ジメチルアンモニオ}プロパノエート、4-{[5-(アクリロイルアミノ)ペンチル]ジメチルアンモニオ}ブタノエート、及び、5-{[5-(アクリロイルアミノ)ペンチル]ジメチルアンモニオ}ペンタノエートからなる群から選択される1種以上を含むことが好ましいが、これらに制限されるものではない。
分離機能層表面の自乗平均面粗さ(以下、「Rms」ともいう)は、60nm以上であることが好ましい。自乗平均面粗さが60nm以上であることで、分離機能層の表面積が大きくなり、透過水量が高くなる。一方、自乗平均面粗さが60nm未満の場合には透過水量が低下する。
また、(θB-θA)>5°であることが好ましい。ファウリングなどにより透過水量が低下した逆浸透膜に対して、酸やアルカリといった薬品を用いて洗浄することで、透過水量を回復させる方法があるが、上記範囲にあることで、洗浄効率を向上させ、膜の寿命を向上させることができる。より好ましくは(θB-θA)>10°である。
支持膜は、分離機能層に強度を与えるためのものであり、それ自体は、実質的にイオン等の分離性能を有さない。支持膜は、基材と多孔性支持層とを含む。
ここでセルロース系ポリマーとしては酢酸セルロース、硝酸セルロースなど、ビニルポリマーとしてはポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリアクリロニトリルなどが使用できる。
次に、上記複合半透膜の製造方法について説明する。製造方法は、支持膜の形成工程及び分離機能層の形成工程を含む。
支持膜の形成工程は、基材に高分子溶液を塗布する工程及び溶液を塗布した前記基材を凝固浴に浸漬させて高分子を凝固させる工程を含む。
凝固浴の温度は、-20℃以上100℃以下が好ましく、さらに好ましくは10℃以上50℃以下である。凝固浴の温度がこの範囲以内であれば、熱運動による凝固浴面の振動が激しくならず、膜形成後の膜表面の平滑性が保たれる。また温度がこの範囲内であれば凝固速度が適当で、製膜性が良好である。
次に、複合半透膜を構成する分離機能層の形成工程を説明する。本発明の分離機能層の形成工程は、
(a)基材及び多孔性支持層を含む支持膜上に架橋ポリアミドを形成する工程、及び
(b)上記(a)で得られた前記架橋ポリアミドに正荷電を有する官能基及び負荷電を有する官能基を含み、かつ、負に荷電している親水性高分子を共有結合させる工程、
を有する。
(a)’多官能アミンを含有する水溶液と、多官能酸ハロゲン化物を含有する有機溶媒溶液とを用い、支持膜の表面で界面重縮合を行うことにより、架橋ポリアミドを形成する工程。
(c)架橋ポリアミド第一級アミノ基と反応してジアゾニウム塩又はその誘導体を生成する試薬に接触させる工程、
をさらに含んでもよい。
代表例としては、液状の炭化水素、トリクロロトリフルオロエタンなどのハロゲン化炭化水素が挙げられる。オゾン層を破壊しない物質であることや入手のしやすさ、取り扱いの容易さ、取り扱い上の安全性を考慮すると、オクタン、ノナン、デカン、ウンデカン、ドデカン、トリデカン、テトラデカン、ヘプタデカン、ヘキサデカン、シクロオクタン、エチルシクロヘキサン、1-オクテン、1-デセンなどの単体あるいはこれらの混合物が好ましく用いられる。
支持膜と多官能アミン水溶液との接触時間は、5秒以上10分以下の範囲内であることが好ましく、10秒以上3分以下の範囲内であるとさらに好ましい。
この場合、垂直方向に把持する時間としては、1分以上5分以下であることが好ましく、1分以上3分以下であるとより好ましい。把持する時間が1分以上であることで目的の機能を有するポリアミドを得やすく、5分以下であることで有機溶媒の過乾燥による欠点の発生を抑制できるので、性能低下を抑制することができる。
酸としては、塩酸、硫酸、リン酸などの無機酸や、クエン酸、シュウ酸などの有機酸などが挙げられる。酸の濃度は、pH2以下となるように調整することが好ましく、pH1以下であるとより好ましい。
アルコールとしては、メチルアルコール、エチルアルコール、イソプロピルアルコールなどの1価アルコールや、エチレングリコール、グリセリンなどの多価アルコールが挙げられる。アルコールの濃度は、好ましくは10重量%以上100重量%以下であり、より好ましくは10重量%以上50重量%以下である。
工程(b)で導入される親水性高分子の構造、種類等については、上述したとおりである。
分離機能層に親水性高分子及び縮合剤を含む水溶液を接触させる方法は特に限定されず、例えば、複合半透膜全体を親水性高分子と縮合剤とを含む水溶液中に浸漬してもよいし、親水性高分子及び縮合剤を含む水溶液を複合半透膜表面にスプレーしてもよく、ポリアミドと親水性高分子及び縮合剤が接触するのであれば、その方法は限定されない。
親水性高分子は、重量濃度で10ppm以上1%以下の水溶液として使用するのが好ましい。親水性高分子の濃度が10ppm以上であれば、ポリアミドに存在する官能基と親水性高分子を十分に反応させることができる。一方で、1%を超えると親水性高分子層が厚くなるため、造水量が低下するおそれがある。
アミノ基と反応してジアゾニウム塩又はその誘導体を生成する試薬としては、亜硝酸及びその塩、ニトロシル化合物などの水溶液が挙げられる。亜硝酸やニトロシル化合物の水溶液は気体を発生して分解する性質を持つため、亜硝酸塩と酸性溶液との反応によって亜硝酸を逐次生成するのが好ましい。
また、接触させる方法は特に限定されず、該試薬の溶液を塗布しても、該試薬の溶液に該複合半透膜を浸漬させてもよい。該試薬を溶かす溶媒は該試薬が溶解し、該複合半透膜が侵食されなければ、いかなる溶媒を用いてもかまわない。また、溶液には、アミノ基と試薬との反応を妨害しないものであれば、界面活性剤や酸性化合物、アルカリ性化合物などが含まれていてもよい。
本発明の複合半透膜は、プラスチックネットなどの原水流路材と、トリコットなどの透過水流路材と、必要に応じて耐圧性を高めるためのフィルムと共に、多数の孔を穿設した筒状の集水管の周りに巻回され、スパイラル型の複合半透膜エレメントとして好適に用いられる。さらに、このエレメントを直列又は並列に接続して圧力容器に収納した複合半透膜モジュールとすることもできる。
供給水温度は高くなると塩除去率が低下するが、低くなるに従い膜透過流束も減少するので、5℃以上、45℃以下が好ましい。また、供給水pHは、高くなると海水などの高塩濃度の供給水の場合、マグネシウムなどのスケールが発生する恐れがあり、また、高pH運転による膜の劣化が懸念されるため、中性領域での運転が好ましい。
複合半透膜に、温度25℃、pH7、塩化ナトリウム濃度2,000ppmに調整した評価水を操作圧力1.55MPaで供給して膜ろ過処理を行なった。供給水及び透過水の電気伝導度を東亜電波工業株式会社製電気伝導度計で測定して、それぞれの実用塩分、すなわちNaCl濃度を得た。こうして得られたNaCl濃度及び下記式に基づいて、NaCl除去率を算出した。
NaCl除去率(%)=100×{1-(透過水中のNaCl濃度/供給水中のNaCl濃度)}
前項の試験において、供給水(NaCl水溶液)の膜透過水量を測定し、膜面1平方メートル当たり、1日の透水量(立方メートル)に換算した値を膜透過流束(m3/m2/日)とした。
なお、膜性能の測定は以下のように行った。
初めに、25℃、pH7、NaCl濃度が2,000mg/Lである水溶液を1.55MPaの圧力で1時間ろ過したときの透過水量を測定し、初期透過水量(F1)とした。続いてポリオキシエチレン(10)オクチルフェニルエーテル(POEOPE)を100mg/Lの濃度となるように水溶液に加えて1時間ろ過したときの透過水量をF2とし、F2/F1の値を算出した。POEOPEに代えて、ドデシル硫酸ナトリウム(SDS)を用いて同様の測定を行い、SDSを加えて1時間ろ過したときの透過水量をF3とし、F3/F1の値を算出した。
通気度は、JIS L1096(2010)に基づき、フラジール形試験機によって測定した。基材を200mm×200mmの大きさに切り出し、フラジール形試験機に取り付け、傾斜形気圧計が125Paの圧力になるように吸込みファン及び空気孔を調整し、このときの垂直形気圧計の示す圧力と使用した空気孔の種類から通気度を求めた。フラジール形試験機は、カトーテック株式会社製KES-F8-AP1を使用した。
(合成例1)
[(2-メタクリロイルオキシ)エチル]ジメチル(3-スルホプロピル)-アンモニウムヒドロキシド(MEDMSPAH)を、あらかじめ窒素でバブリングを行った純水に溶解した後、開始剤である過硫酸ナトリウムを添加して、70℃で2時間重合反応を行い、ポリマー溶液を得た。
MEDMSPAHとアクリル酸(AA)をモル比1:1で仕込み、窒素でバブリングを行った純水に溶解、混合した後、開始剤である過硫酸ナトリウムを添加して、70℃で2時間重合反応を行い、ポリマー溶液を得た。
MEDMSPAHに代えて(2-メタクリロイルオキシ)エチル[(2-トリメチルアンモニオ)エチル]ホスフェート(METMAEP)を用いた以外は、合成例2と同様にして反応を行い、ポリマー溶液を得た。
MEDMSPAHに代えて3-{[2-(メタクリロイルオキシ)エチル]ジメチルアンモニオ}プロピオネート(MEDMAP)を用いた以外は、合成例2と同様にして反応を行い、ポリマー溶液を得た。
MEDMSPAHとAAのモル比を8:1に変えた以外は、合成例2と同様にして反応を行い、ポリマー溶液を得た。
MEDMSPAHとAAのモル比を4:1に変えた以外は、合成例2と同様にして反応を行い、ポリマー溶液を得た。
MEDMSPAHとAAのモル比を1:4に変えた以外は、合成例2と同様にして反応を行い、ポリマー溶液を得た。
MEDMSPAHとAAのモル比を1:8に変えた以外は、合成例2と同様にして反応を行い、ポリマー溶液を得た。
AAに代えてメタクリル酸(MAA)を用いた以外は、合成例2と同様にして反応を行い、ポリマー溶液を得た。
AAに代えてマレイン酸(MA)を用い、モル比を1:4に変えた以外は、合成例2と同様にして反応を行い、ポリマー溶液を得た。
AAに代えて2-アミノエチルメタクリレート(AEMA)を用いた以外は、合成例2と同様にして反応を行い、ポリマー溶液を得た。
MAAとAEMAをモル比1:1で仕込み、窒素でバブリングを行った純水に溶解、混合した後、開始剤である過硫酸ナトリウムを添加して、70℃で2時間重合反応を行い、ポリマー溶液を得た。
MAAとAEMAのモル比を2:1に変えた以外は、合成例12と同様にして反応を行い、ポリマー溶液を得た。
MAAとAEMAのモル比を1:2に変えた以外は、合成例12と同様にして反応を行い、ポリマー溶液を得た。
各合成例で得られた水溶液を1.0w/v%になるよう20mMリン酸バッファー(pH7.4)で希釈し、この溶液を0.45μmのメンブランフィルターでろ過して試験溶液とし、GPC(ゲル浸透クロマトグラフィー)により重量平均分子量を測定・算出した。各合成例で得られた共重合体のモル比、及び重量平均分子量を表1に示す。なお、GPC分析の測定条件は次の通りである。
カラム;TSKgel PWXL-CP(東ソー株式会社製)、
溶離溶媒;20mMリン酸バッファー(pH7.4)、
標準物質;ポリエチレングリコール(Polymer Laboratories Ltd.製)、
検出;示差屈折計RI-8020(東ソー株式会社製)、
流速;0.5mL/分、
試料溶液使用量;10μL、カラム温度;45℃。
(比較例1)
長繊維からなるポリエステル不織布(通気度2.0mL/cm2/sec)上にポリスルホン(PSf)の15.0重量%DMF溶液を25℃の条件下でキャストし、ただちに純水中に浸漬して5分間放置することによって、多孔性支持層の厚みが40μmである支持膜を作製した。
次に、この支持膜を3.5重量%のm-PDA水溶液に浸漬した後、余分な水溶液を除去し、さらに0.14重量%のTMCとなるように溶解したn-デカン溶液を多孔性支持層の表面が完全に濡れるように塗布した。次に膜から余分な溶液を除去するために、膜を垂直にして液切りを行って、送風機を使い25℃の空気を吹き付けて乾燥させた後、40℃の純水で洗浄した。このようにして得られた複合半透膜の製膜時膜性能、及びファウリング後膜性能を測定したところ、表2に示す値であった。
比較例1で得られた複合半透膜を、pH3、35℃に調整した0.3重量%の亜硝酸ナトリウム水溶液に1分間浸漬した。なお、亜硝酸ナトリウムのpHの調整は硫酸で行った。次に0.1重量%の亜硫酸ナトリウム水溶液に35℃で2分間浸漬することで、比較例2の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
比較例1で得られた複合半透膜を、合成例1で得られたポリマーを400ppm、DMT-MMを0.1%となるよう調整した溶液に、20℃で24時間接触させた後、水洗した。次にpH3、35℃に調整した0.3重量%の亜硝酸ナトリウム水溶液に1分間浸漬した。なお、亜硝酸ナトリウムのpHの調整は硫酸で行った。さらに0.1重量%の亜硫酸ナトリウム水溶液に35℃で2分間浸漬することで、比較例3の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
比較例1で得られた複合半透膜を、合成例2で得られたポリマーを400ppmとなるよう調整した溶液に、20℃で24時間接触させた後、水洗した。pH3、35℃に調整した0.3重量%の亜硝酸ナトリウム水溶液に1分間浸漬した。なお、亜硝酸ナトリウムのpHの調整は硫酸で行った。次に0.1重量%の亜硫酸ナトリウム水溶液に35℃で2分間浸漬することで、比較例4の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
比較例1で得られた複合半透膜を、合成例12で得られたポリマーを300ppm、DMT-MMを0.1%となるよう調整した溶液に、20℃で24時間接触させた後、水洗した。次にpH3、35℃に調整した0.3重量%の亜硝酸ナトリウム水溶液に1分間浸漬した。なお、亜硝酸ナトリウムのpHの調整は硫酸で行った。さらに0.1重量%の亜硫酸ナトリウム水溶液に35℃で2分間浸漬することで、比較例5の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例11で得られたポリマーを用い、ポリマー濃度を500ppmとした以外は比較例5と同様にして処理を行い、比較例6の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例14で得られたポリマーを用い、ポリマー濃度を500ppmとした以外は比較例5と同様にして処理を行い、比較例7の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
比較例1で得られた複合半透膜を、合成例2で得られたポリマーを400ppm、DMT-MMを0.1%となるよう調整した溶液に、20℃で24時間接触させた後、水洗した。次にpH3、35℃に調整した0.3重量%の亜硝酸ナトリウム水溶液に1分間浸漬した。なお、亜硝酸ナトリウムのpHの調整は硫酸で行った。さらに0.1重量%の亜硫酸ナトリウム水溶液に35℃で2分間浸漬することで、実施例1の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例3で得られたポリマーを用いた以外は実施例1と同様にして処理を行い、実施例2の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例4で得られたポリマーを用いた以外は実施例1と同様にして処理を行い、実施例3の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例5で得られたポリマーを用い、ポリマー濃度を2000ppmとした以外は実施例1と同様にして処理を行い、実施例4の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例6で得られたポリマーを用い、ポリマー濃度を1000ppmとした以外は実施例1と同様にして処理を行い、実施例5の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例7で得られたポリマーを用い、ポリマー濃度を300ppmとした以外は実施例1と同様にして処理を行い、実施例6の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例8で得られたポリマーを用い、ポリマー濃度を150ppmとした以外は実施例1と同様にして処理を行い、実施例7の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例9で得られたポリマーを用いた以外は実施例1と同様にして処理を行い、実施例8の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例10で得られたポリマーを用い、ポリマー濃度を1000ppmとした以外は実施例1と同様にして処理を行い、実施例9の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
合成例13で得られたポリマーを用い、ポリマー濃度を250ppmとした以外は実施例1と同様にして処理を行い、実施例10の複合半透膜を得た。得られた複合半透膜を評価したところ、膜性能は表2に示す値であった。
測定するpHに調整した水溶液に複合半透膜を25℃で16時間浸漬し、接触角測定装置(協和界面科学株式会社製DM-301)を用いて、分離膜機能層に付着している気泡接触角を測定した。測定は、気泡が0.5~2.0μLのものを対象としてN=3回で測定した。このとき、気泡の供給はシリンジ針を用いて行った。各比較例、実施例で作製した複合半透膜の気泡接触角は表2に示す値であった。
Claims (12)
- 基材及び多孔性支持層を含む支持膜と、前記多孔性支持層上に設けられた分離機能層とを備える複合半透膜であって、
前記分離機能層が、架橋ポリアミドと親水性高分子とを含み、下記条件(A)及び(B)を満たす複合半透膜。
(A)前記親水性高分子が、正荷電を有する官能基及び負荷電を有する官能基を含み、かつ、前記親水性高分子が負に荷電している。
(B)前記親水性高分子が、前記架橋ポリアミドに共有結合している。 - 前記親水性高分子において、前記正荷電を有する官能基の数(N1)と、前記負荷電を有する官能基の数(N2)との比(N1/N2)が15/85以上45/55以下である、請求項1に記載の複合半透膜。
- 前記親水性高分子の重量平均分子量が2,000以上1,500,000以下である、請求項1又は2に記載の複合半透膜。
- 前記親水性高分子の荷電密度が7.5mmol/g以上10.5mmol/g以下である、請求項1~3のいずれか1項に記載の複合半透膜。
- 前記親水性高分子の負荷電密度が4.5mmol/g以上8.0mmol/g以下である、請求項1~4のいずれか1項に記載の複合半透膜。
- 前記分離機能層において、pH3の水溶液中における気泡接触角をθA、pH11の水溶液中における気泡接触角をθBとしたとき、150°<θA、θB<180°及び(θB-θA)>5°を満たす、請求項1~5のいずれか1項に記載の複合半透膜。
- 前記親水性高分子が、荷電を有する官能基を含み、前記荷電は負荷電であるモノマーPと、正荷電を有する官能基及び負荷電を有する官能基を含むモノマーQとの共重合体である、請求項1~6のいずれか1項に記載の複合半透膜。
- 前記共重合体に含まれる前記モノマーP由来のモノマーユニットの数(PN)と前記モノマーQ由来のモノマーユニットの数(QN)との比(PN:QN)が80:20~20:80である、請求項7に記載の複合半透膜。
- 前記モノマーPが、アクリル酸、メタクリル酸及びマレイン酸からなる群から選択される少なくとも1種の化合物である、請求項7又は8に記載の複合半透膜。
- 前記共有結合がアミド結合である、請求項1~10のいずれか1項に記載の複合半透膜。
- (a)基材及び多孔性支持層を含む支持膜上に架橋ポリアミドを形成する工程、及び
(b)前記(a)で得られた前記架橋ポリアミドに、正荷電を有する官能基及び負荷電を有する官能基を含み、かつ、負に荷電している親水性高分子を共有結合させる工程、
を備える複合半透膜の製造方法。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021117631A1 (ja) | 2019-12-11 | 2021-06-17 | 日東電工株式会社 | 複合半透膜 |
CN113019141A (zh) * | 2021-04-02 | 2021-06-25 | 哈尔滨工业大学 | 具有电荷Janus结构的单价选择性阳离子交换膜的制备方法 |
CN115108607A (zh) * | 2021-03-23 | 2022-09-27 | 株式会社东芝 | 含胺水浓缩***及装置以及二氧化碳回收*** |
EP4249106A1 (en) | 2022-03-24 | 2023-09-27 | Nitto Denko Corporation | Composite semipermeable membrane and spiral membrane element |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05507233A (ja) * | 1990-06-06 | 1993-10-21 | ネーデルランドセ・オルガニザテイエ・フール・テゲパスト―ナトウールベテンシヤツペリーク・オンデルツエク・テイエヌオー | 半透性複合膜 |
CN102580585A (zh) * | 2012-02-22 | 2012-07-18 | 富阳梅伊韦尔环保设备有限公司 | 一种耐污染低压纳滤膜的制备方法 |
KR20130080619A (ko) * | 2012-01-05 | 2013-07-15 | 주식회사 엘지화학 | 양쪽성 이온 고분자를 포함하는 코팅층이 형성된 역삼투막 및 그 제조방법 |
JP2014510621A (ja) * | 2012-01-05 | 2014-05-01 | エルジー・ケム・リミテッド | 耐汚染性に優れた逆浸透膜及びその製造方法 |
CN104028119A (zh) * | 2014-05-16 | 2014-09-10 | 浙江大学 | 一种羧酸甜菜碱型络合物改性聚酰胺纳滤膜的制备方法 |
WO2015046582A1 (ja) * | 2013-09-30 | 2015-04-02 | 東レ株式会社 | 複合半透膜およびその製造方法 |
WO2016084958A1 (ja) * | 2014-11-28 | 2016-06-02 | 東レ株式会社 | 積層半透膜 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4618533A (en) * | 1984-11-30 | 1986-10-21 | Millipore Corporation | Porous membrane having hydrophilic surface and process |
JP3379963B2 (ja) | 1996-03-18 | 2003-02-24 | 日東電工株式会社 | 逆浸透複合膜及びこれを用いた水の逆浸透処理方法 |
JP2006239636A (ja) | 2005-03-04 | 2006-09-14 | Kazuhiko Ishihara | ファウリング防止材及び該ファウリング防止材で表面処理された分離膜 |
AU2007200609B2 (en) | 2007-02-13 | 2008-11-20 | Saehan Industries Incorporation | Selective membrane having a high fouling resistance |
KR101273334B1 (ko) * | 2011-07-13 | 2013-06-11 | 한남대학교 산학협력단 | 내염소성 및 내오염성 폴리아미드 역삼투 복합막 및 이의 제조방법 |
JP6158720B2 (ja) | 2014-02-19 | 2017-07-05 | 国立大学法人神戸大学 | 表面処理剤、表面処理ポリアミド逆浸透膜及びその製造方法 |
JP6303837B2 (ja) | 2014-06-06 | 2018-04-04 | 栗田工業株式会社 | 逆浸透膜の耐汚染化処理方法 |
-
2017
- 2017-12-26 KR KR1020197016784A patent/KR102337641B1/ko active IP Right Grant
- 2017-12-26 JP JP2017567833A patent/JP7167442B2/ja active Active
- 2017-12-26 WO PCT/JP2017/046726 patent/WO2018124103A1/ja active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05507233A (ja) * | 1990-06-06 | 1993-10-21 | ネーデルランドセ・オルガニザテイエ・フール・テゲパスト―ナトウールベテンシヤツペリーク・オンデルツエク・テイエヌオー | 半透性複合膜 |
KR20130080619A (ko) * | 2012-01-05 | 2013-07-15 | 주식회사 엘지화학 | 양쪽성 이온 고분자를 포함하는 코팅층이 형성된 역삼투막 및 그 제조방법 |
JP2014510621A (ja) * | 2012-01-05 | 2014-05-01 | エルジー・ケム・リミテッド | 耐汚染性に優れた逆浸透膜及びその製造方法 |
CN102580585A (zh) * | 2012-02-22 | 2012-07-18 | 富阳梅伊韦尔环保设备有限公司 | 一种耐污染低压纳滤膜的制备方法 |
WO2015046582A1 (ja) * | 2013-09-30 | 2015-04-02 | 東レ株式会社 | 複合半透膜およびその製造方法 |
CN104028119A (zh) * | 2014-05-16 | 2014-09-10 | 浙江大学 | 一种羧酸甜菜碱型络合物改性聚酰胺纳滤膜的制备方法 |
WO2016084958A1 (ja) * | 2014-11-28 | 2016-06-02 | 東レ株式会社 | 積層半透膜 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021117631A1 (ja) | 2019-12-11 | 2021-06-17 | 日東電工株式会社 | 複合半透膜 |
KR20220093212A (ko) | 2019-12-11 | 2022-07-05 | 닛토덴코 가부시키가이샤 | 복합 반투막 |
CN115108607A (zh) * | 2021-03-23 | 2022-09-27 | 株式会社东芝 | 含胺水浓缩***及装置以及二氧化碳回收*** |
CN113019141A (zh) * | 2021-04-02 | 2021-06-25 | 哈尔滨工业大学 | 具有电荷Janus结构的单价选择性阳离子交换膜的制备方法 |
EP4249106A1 (en) | 2022-03-24 | 2023-09-27 | Nitto Denko Corporation | Composite semipermeable membrane and spiral membrane element |
KR20230138883A (ko) | 2022-03-24 | 2023-10-05 | 닛토덴코 가부시키가이샤 | 복합 반투막 및 스파이럴형 막 엘리먼트 |
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