JP6014881B2 - 高空隙容積を有する荷電多孔質ポリマー膜 - Google Patents
高空隙容積を有する荷電多孔質ポリマー膜 Download PDFInfo
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- JP6014881B2 JP6014881B2 JP2014256512A JP2014256512A JP6014881B2 JP 6014881 B2 JP6014881 B2 JP 6014881B2 JP 2014256512 A JP2014256512 A JP 2014256512A JP 2014256512 A JP2014256512 A JP 2014256512A JP 6014881 B2 JP6014881 B2 JP 6014881B2
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- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 210000000265 leukocyte Anatomy 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005649 polyetherethersulfone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920006214 polyvinylidene halide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- KCTGOQZIKPDZNK-UHFFFAOYSA-N tetrapentyl silicate Chemical compound CCCCCO[Si](OCCCCC)(OCCCCC)OCCCCC KCTGOQZIKPDZNK-UHFFFAOYSA-N 0.000 description 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/08—Flat membrane modules
- B01D63/081—Manufacturing thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/08—Specific temperatures applied
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2181—Inorganic additives
- B01D2323/21813—Metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/021—Pore shapes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
- B01D2325/02833—Pore size more than 10 and up to 100 nm
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Water Supply & Treatment (AREA)
Description
[0001]様々な流体をろ過するためにポリマー膜が使用される。しかしながら、高いスループット能力を実現する膜が求められている。
[0003]本発明のある実施形態は、第1の微多孔質表面、第2の微多孔質表面、及び第1の微多孔質表面と第2の微多孔質表面との間の多孔質バルクを有する単一層を含む膜であって、バルクが、導入された溶解性シリカナノ粒子を除去することにより調製されて外縁を有する細孔の第1のセットであり、第1の制御された細孔径を有する細孔の第1のセットと、細孔の第1のセットの外縁に連結している細孔の第2のセットであり、第2の制御された細孔径を有する細孔の第2のセットと、細孔の第1のセットを支持しているポリマーマトリックスとを含み、第1の制御された細孔径が第2の制御された細孔径よりも大きく、第1の及び/又は第2の微多孔質表面が、電荷が中和した、負に荷電した又は正に荷電した微多孔質表面を含む、膜を提供する。
[0012]本発明のある実施形態によれば膜が提供され、膜は、第1の微多孔質表面、第2の微多孔質表面、及び第1の微多孔質表面と第2の微多孔質表面との間の多孔質バルクを有する単一層を含み、バルクは、導入された溶解性シリカナノ粒子を除去することにより調製されて外縁を有する細孔の第1のセットであって、第1の制御された細孔径を有する細孔の第1のセットと、細孔の第1のセットの外縁に連結している細孔の第2のセットであって、第2の制御された細孔径を有する細孔の第2のセットと、細孔の第1のセットを支持しているポリマーマトリックスとを含み、第1の制御された細孔径が第2の制御された細孔径よりも大きく、第1の及び/又は第2の微多孔質表面が、電荷が中和した表面、負に荷電した表面又は正に荷電した表面を含む。
実施例1
実施例2
実施例3
実施例4
実施例5
実施例6
Claims (10)
- (a)第1の微多孔質表面、
(b)第2の微多孔質表面、
(c)第1の多孔質バルクが含まれる第1の荷電ゾーンであって、前記第1の多孔質バルクが、外縁を有する細孔の第1のセットであり、第1の制御された細孔径を有する細孔の第1のセットと、前記細孔の第1のセットの前記外縁に連結している細孔の第2のセットであり、第2の制御された細孔径を有する細孔の第2のセットと、前記細孔の第1のセットを支持しているポリマーマトリックスとを含み、前記第1の制御された細孔径が前記第2の制御された細孔径よりも大きく、前記第1の及び/又は前記第2の微多孔質表面が、電荷が中和した、負に荷電した又は正に荷電した表面を含み、及び
(d)外縁を有する細孔の第3のセットであって、第3の制御された細孔径を有する細孔の第3のセットと、前記細孔の第3のセットの前記外縁に連結している細孔の第4のセットであって、第4の制御された細孔径を有する細孔の第4のセットと、前記細孔の第3のセットを支持している第2のポリマーマトリックスとを含む第2の多孔質バルクが含まれる第2の荷電したゾーンを含み、
前記第2の多孔質バルクにおける前記第3の制御された細孔径が前記第1の多孔質バルクにおける前記第1の制御された細孔径よりも小さく、
(i)前記第1の多孔質バルクが負に荷電したバルクを含む場合、前記第2の多孔質バルクが、電荷が中和した又は正に荷電したバルクを含み、
(ii)前記第1の多孔質バルクが正に荷電したバルクを含む場合、前記第2の多孔質バルクが、電荷が中和した又は負に荷電したバルクを含み、及び
(iii)前記第1の多孔質バルクが電荷が中和したバルクを含む場合、前記第2の多孔質バルクが、負に荷電した又は正に荷電したバルクを含む、
微多孔質膜。 - 前記細孔の第1のセットが、約50nm〜約1000nmの範囲の制御された細孔径を有する、請求項1に記載の微多孔質膜。
- 前記第1の多孔質バルクが、電荷が中和した、負に荷電した又は正に荷電したバルクを含む、請求項1又は2に記載の微多孔質膜。
- 前記微多孔質膜が、外縁を有する細孔の第5のセットであって、第5の制御された細孔径を有する細孔の第5のセットと、前記細孔の第5のセットの前記外縁に連結している細孔の第6のセットであって、第6の制御された細孔径を有する細孔の第6のセットと、前記細孔の第5のセットを支持している第3のポリマーマトリックスとを含む少なくとも1つの第3の多孔質バルクを更に含み、前記第5の制御された細孔径が前記第6の制御された細孔径よりも大きく、前記第3の多孔質バルクが前記第1の多孔質バルク又は前記第2の多孔質バルクと異なる電荷を含む、請求項1〜3のいずれか一項に記載の膜。
- 前記微多孔質膜が追加の層を更に含み、前記追加の層が、
(i)第1の多孔質表面、
(ii)第2の多孔質表面、及び
(iii)前記追加の層の前記第1の多孔質表面と前記第2の多孔質表面との間の多孔質バルクを有し、前記多孔質バルクが繊維状マトリックスを含む、
又は
(iv)第1の微多孔質表面、
(v)第2の微多孔質表面、及び
(vi)前記追加の層の前記第1の微多孔質表面と前記第2の微多孔質表面との間の多孔質バルクを有し、当該多孔質バルクが、
(a)導入された溶解性シリカナノ粒子を除去することにより調製されて外縁を有する細孔の第1のセットであって、第1の制御された細孔径を有する細孔の第1のセットと、前記細孔の第1のセットの前記外縁に連結している細孔の第2のセットであって、第2の制御された細孔径を有する細孔の第2のセットと、前記細孔の第1のセットを支持しているポリマーマトリックスとを含み、前記第1の制御された細孔径が前記第2の制御された細孔径よりも大きい、又は
(b)繊維状マトリックスを含む、請求項1〜4のいずれか一項に記載の膜。 - 膜を製造する方法であって、
(a)非荷電ポリマー又は荷電ポリマーを含む溶解性シリカナノ粒子含有ポリマー溶液を含む第1の溶液を基材に流延するステップ、
(b)非荷電ポリマー又は荷電ポリマーを含む溶解性シリカナノ粒子含有ポリマー溶液を含む第2の溶液を基材に流延するステップ[ただし、(i)前記第1の溶液が負に荷電したポリマーを含む場合、前記第2の溶液が、電荷が中和した又は正に荷電したポリマーを含み、(ii)前記第1の溶液が正に荷電したポリマーを含む場合、前記第2の溶液が、電荷が中和した又は負に荷電したポリマーを含み、及び(iii)前記第1の溶液が電荷が中和したポリマーを含む場合、前記第2の溶液が、負に荷電した又は正に荷電したポリマーを含む]、
(c)前記ナノ粒子含有ポリマー溶液の相反転を実行して膜を形成するステップ、
(d)前記ナノ粒子を溶解させ、第1の荷電ゾーン及び第2の荷電ゾーンを含むナノ粒子空乏膜を得るステップ、及び
(e)前記ナノ粒子空乏膜を洗浄するステップ
を含む方法。 - (a)が、前処理剤又は剥離剤で前処理した基材に前記第1の溶液を流延するステップを含む、請求項6に記載の方法。
- 前記前処理した基材に前記第1の溶液を流延する前に、前記前処理剤又は前記剥離剤を前記基材上で乾燥させる、請求項7に記載の方法。
- (c)が、前記ナノ粒子含有ポリマー溶液を約1分〜約2時間の範囲の期間にわたり約40℃〜約80℃の範囲の温度に曝すステップを含む、請求項6〜8のいずれか一項に記載の方法。
- 流体をろ過する方法であって、前記流体を請求項1〜5のいずれか一項に記載の膜に通すステップを含む方法。
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