WO2017140279A1 - 高分子材料、膜、涂层及其制备方法与应用 - Google Patents

高分子材料、膜、涂层及其制备方法与应用 Download PDF

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WO2017140279A1
WO2017140279A1 PCT/CN2017/079914 CN2017079914W WO2017140279A1 WO 2017140279 A1 WO2017140279 A1 WO 2017140279A1 CN 2017079914 W CN2017079914 W CN 2017079914W WO 2017140279 A1 WO2017140279 A1 WO 2017140279A1
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oil
water
polymer material
polymer
coating
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PCT/CN2017/079914
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English (en)
French (fr)
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靳健
高守建
张丰
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中国科学院苏州纳米技术与纳米仿生研究所
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Priority to US16/071,177 priority Critical patent/US20200353423A1/en
Priority to EP17752711.6A priority patent/EP3417924A4/en
Publication of WO2017140279A1 publication Critical patent/WO2017140279A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/78—Graft polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/147—Microfiltration
    • 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
    • B01D67/00111—Polymer pretreatment in the casting solutions
    • 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
    • B01D67/0013—Casting processes
    • 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
    • B01D67/0016—Coagulation
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/28—Polymers of vinyl aromatic compounds
    • B01D71/281—Polystyrene
    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B01D71/522—Aromatic polyethers
    • B01D71/5221—Polyaryletherketone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09D171/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/06—Polysulfones; Polyethersulfones
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/34—Arrangements for separating materials produced by the well
    • E21B43/36—Underwater separating arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/36—Introduction of specific chemical groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/46—Impregnation
    • 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
    • B01D2325/14—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
    • B01D2325/20—Specific permeability or cut-off range
    • 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

Definitions

  • the present application specifically relates to a polymer material, a film or coating based on the polymer material, and a preparation method and application thereof.
  • the main methods for separating and collecting oil from oil-water mixtures are fence method, adsorption method, and oil mop method. Continuous and effective separation and recovery of leaked oil has always been a challenge and a challenge due to the damage caused by oil easy adhesion and pollution recovery equipment.
  • the main object of the present application is to provide a polymer material based on a film or coating of the polymer material and a preparation method and application thereof to overcome the deficiencies in the prior art.
  • the technical solution adopted by the present application includes:
  • the embodiment of the present application provides a polymer material which is formed by phase inversion of a polymer compound containing an ionizable hydrophilic group and ionization of the hydrophilic group contained therein.
  • the polymer material has a strong hydration ability, and a stable hydration layer is formed on the surface of the material in water to protect the material from oil adhesion and super oleophobic property.
  • the polymeric material has a static contact angle of more than 140° for various oil phase systems in water and an adhesion of less than 10 ⁇ N.
  • the polymer compound includes at least one or two groups modified with at least a sulfonic acid group, a phosphoric acid group, a carboxyl group, an amide group, an alcoholic hydroxyl group, a quaternary ammonium salt, an amine group, an alcohol amine group, a cyano group and the like. More than one type of aliphatic polymer or aromatic polymer.
  • Embodiments of the present application also provide a film or coating composed of the polymer material.
  • Embodiments of the present application also provide a method of preparing the film or coating, comprising:
  • the polymer compound layer is sufficiently impregnated with an alkaline solution to effect phase transformation of the polymer compound, while ionizing the hydrophilic group in the polymer compound to form the film or coating on the substrate. layer,
  • the polymer compound in the polymer compound layer is subjected to a wet phase transformation, and then sufficiently impregnated with an alkaline solution to ionize a hydrophilic group in the polymer compound to form a substrate on the substrate. Film or coating.
  • the embodiment of the present application further provides the polymer material for preparing an oil-water separation structure, an oil-repellent coating structure, a high-viscosity oil collecting device in water, a dye separating device, a protein separating device, a heavy metal ion separating device, a food processing device, and blood. Use in processing equipment, wastewater treatment equipment, and the like.
  • the polymer material provided contains an ionized hydrophilic group, which has a strong hydration ability, and a stable hydration layer is formed on the surface of the material in water, protecting the material from oil adhesion and having super oleophobic property.
  • the polymer material provided has underwater super-sparing properties and oil-resistance functions not only for light, low-viscosity oil or organic reagents which are immiscible with water, but also for petroleum, heavy oil, silicone oil, heavy diesel oil, etc.
  • the viscosity oil has underwater super-sparing properties and oil-resistant adhesion function;
  • the film, coating, etc. formed by the provided polymer material have underwater oil resistance, oil pollution and self-cleaning effect on high viscosity oil, and are resistant to oil adhesion, oil pollution, oil/water separation. , oil-proof coating, marine oil spill treatment and high-viscosity oil separation and collection in water, and many other fields are widely used.
  • Example 1 is an optical photograph of a polymer material (separation membrane) prepared in Example 1 of the present application and oil in water Photograph of the contact angle on the polymer separation membrane.
  • Example 2 is a SEM photograph of a polymer material (separation membrane) prepared in Example 1 of the present application.
  • Example 3 is a graph showing the underwater petroleum adhesion test of a polymer material (separation membrane) prepared in Example 1 of the present application, and contacting, extruding, leaving the oil-repellent and adhering oil-resistance of the oil droplets. Optical photo with film attached.
  • Example 4 is an optical photograph of different substrates coated with a polymer material in Example 3 of the present application and a contact angle photograph of water in water coated on different substrates coated with the oil-resistant adsorption and adhesion-resistant material. .
  • FIG. 5 is a photograph of the self-cleaning of the glove coated with the polymer material in the water after being contaminated by petroleum in the third embodiment and the fifteenth embodiment of the present application, and the right glove of the uncoated polymer material is contaminated by petroleum after Photographed in water.
  • 6a to 6f are SEM photographs of a copper mesh coated with a polymer material in Example 3 of the present application.
  • FIG. 7 is a separation flux test chart of a plurality of petroleum/water mixtures separated by a copper mesh coated with a polymer material in Examples 6 and 16 of the present application, a test chart of the oil content in the water after separation, and a package after completion of separation.
  • FIG. 8 is a schematic structural view of a water-oil separation device in some exemplary embodiments of the present application, wherein: 1-oil-water mixture, 2-oil-water separation membrane or oil-water separation device, 3-water, 4-oil.
  • One aspect of the present application provides a polymer material that does not adsorb and adhere to high viscosity oil/grease (such as petroleum, heavy oil, silicone oil, heavy diesel oil, etc.) in water, and the polymer material contains a hydrophilic functional group.
  • Polymer composition, hydrophilic The whole or part of the sexual functional group is a positively charged, or negatively charged, or positively and negatively charged hydrophilic functional group or at least formed by an ionization process to form the above hydrophilic functional group.
  • the present application provides a polymeric material formed from a polymer compound containing an ionizable hydrophilic group after phase inversion and ionization of the hydrophilic group contained therein.
  • the polymer material has the specific structure described above, the polymer material has hydrophilic properties and synergistic effect on the light oil and high viscosity oil phase system in water by the synergistic action of the hydrophilic functional group and the functional group ionization. Both exhibited static contact angles greater than 140° and adhesions less than 10 ⁇ N.
  • the polymer material has a strong hydration ability, and a high stability hydration can be formed on the surface of the polymer material.
  • the protective layer can protect the polymer material from being directly contacted by high-viscosity oil molecules or other molecules, so that the high-viscosity oil is difficult to adsorb and adhere to the polymer material. Therefore, the polymer material and the substrate coated with the polymer material have underwater super-sparing properties and oil-resistant adhesion functions to high-viscosity oil.
  • the polymer compound includes at least a group modified with a sulfonic acid group, a phosphoric acid group, a carboxyl group, an amide group, an alcoholic hydroxyl group, a quaternary ammonium salt, an amine group, an alcohol amine group, a cyano group or the like. Any one or two or more kinds of aliphatic polymers or aromatic polymers, but are not limited thereto.
  • the aliphatic polymer includes any one or a combination of two or more of polyethylene, polypropylene, polyacrylonitrile, polyvinylidene fluoride, and polyhexafluoropropylene, but is not limited thereto.
  • aromatic polymer includes any one or a mixture of two or more of polyether sulfone, polyether ketone, polypyrrole, polypyrrole, and polycarbazole, but is not limited thereto.
  • the polymer compound is selected from the group consisting of sulfonated polyethersulfone, diethanolamine grafted polycarbazole, polyacrylonitrile, methylimidazole modified polyphenylene ether, polyacrylamide grafted polystyrene-diphenyl Ethylene copolymer, phosphate grafted polyether ketone, polyacrylic acid grafted polyvinylidene fluoride, polyvinyl sulfonic acid grafted polyether sulfone, polyacrylic acid grafted polycarbonate, polymaleic anhydride graft Any one or a combination of two or more of polyvinylidene fluorides is not limited thereto.
  • the solvent in the polymer solution comprises N-methylpyrrolidone, chloroform, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, m-cresol Any one or a combination of two or more of diphenyl sulfone, diphenyl ether, tetrahydrofuran, and dimethyl sulfoxide;
  • the concentration of the polymer solution is 0.001 wt% to 40 wt%, and may be, for example, 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%.
  • 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt% may preferably be 1 wt% to 40 wt%, further preferably 1 wt% to 10 wt%, still more preferably It is 2 wt% to 8 wt%.
  • the hydrophilic group of the polymer compound is ionized after the polymer compound is sufficiently impregnated with an alkaline solution.
  • the alkaline substance contained in the alkaline solution includes, but is not limited to, NaOH, KOH, ammonia water or Na 2 CO 3 .
  • the solvent contained in the alkaline solution is a poor solvent of the polymer compound, and includes water, methanol, ethanol, ethylene glycol, isopropyl alcohol or n-butanol, but is not limited thereto.
  • the concentration of the alkaline solution is 0.001 mol/L to 10 mol/L, and may be, for example, 0.001 mol/L, 0.005 mol/L, 0.01 mol/L, 0.02 mol/L, 0.09 mol/L, 0.05 mol. /L, 0.1 mol/L, 0.5 mol/L, 1 mol/L, 5 mol/L, 10 mol/L, for example, preferably 0.01 mol/L to 10 mol/L, further preferably 0.01 mol/L to 1 mol/L, It is still more preferably 0.05 mol/L to 0.1 mol/L.
  • the phase inversion is performed in one step with the ionization; or the ionization is performed in an alkaline solution after phase inversion of the polymer material is completed.
  • the conditions required for the aforementioned phase inversion process may depend on the type of the polymer compound, etc., which are known to those skilled in the art, and may be found in many literatures in the field. Therefore, it will not be elaborated here.
  • the aforementioned phase inversion and ionization processes can be performed at room temperature.
  • the polymer material described in the present application can be used for preparing an oil-water separation structure, an oil-repellent coating structure, a high-viscosity oil collecting device in water, a dye separating device, a protein separating device, a heavy metal ion separating device, a food processing device, a blood processing device, Wastewater treatment equipment, etc., therefore in oil-water separation, oil-repellent coating, marine oil spill, oil spill treatment, high-viscosity oil collection in water, molecular separation, food processing, medical and medical treatment, wastewater treatment, and other microfiltration, ultrafiltration, nano It can be applied in fields such as filtration.
  • the polymeric material of the present application may exist in the form of a separation membrane or coating.
  • a film or coating composed of the polymeric material is also provided in some embodiments.
  • These membranes and coatings exhibit completely non-adsorbing and non-adhesive properties to high-viscosity oils such as petroleum, heavy oil, silicone oil, and heavy diesel oil in water, as follows: high-viscosity oil in water cannot adsorb and adhere to the above. On the polymer material, or even if the polymer material is adhered to the high-viscosity oil in the air, once it is placed in the water, the oil will automatically detach from the polymer material to achieve oil pollution resistance and self-cleaning. effect.
  • the film or coating may be a porous film, a porous coating or a non-porous coating.
  • the polymer compound layer is sufficiently impregnated with an alkaline solution to phase-convert the polymer compound, and the hydrophilic group in the polymer compound is ionized to form the film or coating on the substrate.
  • the organic solvent in which the polymer compound is dissolved can be diffused into the alkaline solution by sufficiently impregnating the polymer compound layer with an alkaline solution, but the polymer compound is not compatible with the alkaline poor solvent.
  • Mutual dissolution and precipitation molding the phase conversion of the polymer compound is achieved, and the hydrophilic group in the polymer compound is ionized by reacting with a basic substance in the alkaline solution to form the film on the substrate. Or coating.
  • the polymer compound in the polymer compound layer may be wet phase-transformed, and then fully impregnated with an alkaline solution to ionize the hydrophilic group in the polymer compound, thereby The film or coating is formed on the substrate.
  • a method of preparing a film or coating coated on a surface of a substrate may include: dissolving the polymer material and coating the surface of the substrate or immersing the substrate in the polymer.
  • the raw material solution is coated or adsorbed on the surface of the substrate, and then immersed in an alkaline solution to complete the phase inversion process of the polymer material and the reaction to form an ionized hydrophilic group.
  • a method of preparing a film or coating coated on a surface of a substrate may also include: dissolving the polymer material and applying it to a surface of the substrate or immersing the substrate in a high The surface of the molecular raw material solution is coated or adsorbed with a polymer raw material, and after being wet phase-transformed, it is immersed in an alkaline solution to complete a reaction for forming an ionized hydrophilic group.
  • the aforementioned polymer raw material may be at least selected from the group consisting of a sulfonic acid group, a phosphoric acid group, a carboxyl group, an amide group, an alcoholic hydroxyl group, a quaternary ammonium salt, an amine group, an alcohol amine group, and a cyano modified aliphatic polymer (including polyethylene, polypropylene).
  • polyacrylonitrile polyvinylidene fluoride, polyhexafluoropropylene and copolymers thereof
  • aromatic polymers including polyethersulfone, polyetherketone, polypyrrole, polypyrrole, polycarbazole and copolymers thereof
  • Any one of the other polymers whose groups are different from the main chain but is not limited thereto.
  • the polymer raw material may be at least selected from the group consisting of sulfonated polyethersulfone, diethanolamine grafted polycarbazole, polyacrylonitrile, methylimidazole modified polyphenylene ether, and polyacrylamide grafted polyphenylene.
  • the solvent in the polymer raw material solution may be at least selected from the group consisting of N-methylpyrrolidone, chloroform, dioxane, N,N-dimethylformamide, N,N-dimethyl B. Any one of amide, m-cresol, diphenyl sulfone, diphenyl ether, tetrahydrofuran, and dimethyl sulfoxide, but is not limited thereto.
  • the concentration of the polymer raw material solution is 0.001 wt% to 40 wt%, for example, 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 2wt%, 5wt%, 8wt%, 10wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt%, for example, may preferably be 1 wt% to 40 wt%, further preferably 1 wt% to 10 wt%, still more preferably 2 wt% to 8 wt%.
  • the substrate may be at least selected from the group consisting of glass, metal, plastic, wire mesh, sheet, and fabric.
  • the alkaline solution may be at least selected from any one of NaOH, KOH, ammonia water, and sodium carbonate solution.
  • concentration of the alkaline solution is 0.001 mol/L to 10 mol/L, and may be, for example, 0.001 mol/L, 0.005 mol/L, 0.01 mol/L, 0.02 mol/L, 0.09 mol/L, 0.05 mol.
  • /L 0.1 mol/L, 0.5 mol/L, 1 mol/L, 5 mol/L, 10 mol/L, for example, preferably 0.01 mol/L to 10 mol/L, further preferably 0.01 mol/L to 1 mol/L, It is still more preferably 0.05 mol/L to 0.1 mol/L.
  • the solvent of the alkaline solution is a poor solvent of the polymer raw material, and may be at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, isopropanol, n-butanol and the like. And is not limited to this.
  • At least one of a ruthenium film method, a coating film method, a film injection method, and a doctor blade method can be used to realize the film formation process.
  • the polymer material described in the present application can exist in various forms such as a coating layer, a porous film or a porous web.
  • the substrate coated with the material when the polymeric material is in the form of an oil-repellent coating, the substrate coated with the material also has underwater oleophobic properties for high viscosity oils (oil contact angle > 140°) And low adhesion ( ⁇ 10 ⁇ N).
  • high viscosity oils oil contact angle > 140°
  • low adhesion ⁇ 10 ⁇ N
  • the high-viscosity oil in the water cannot adhere to the polymer coating, or even if the polymer coating is adhered to the high-viscosity oil in the air, once it is placed in the water, the high-viscosity oil will automatically The polymer coating is removed, so that the substrate coated with the polymer coating has water-resistant adhesion and self-cleaning properties in water.
  • the separation membrane when the polymeric material is present in the form of a separation membrane, the separation membrane has excellent oil contamination resistance when separating an unemulsified oil-water mixture or an emulsified oil-water mixture (oil-water emulsion). Specifically, after the simple water cleaning, the water flux of the separation membrane is restored to 80% or more.
  • the embodiment of the present application further provides the polymer material or the film or coating for preparing an oil-water separation structure, an oil-repellent coating structure, a high-viscosity oil collecting device in water, a dye separating device, and a protein separating device.
  • an oil-water separation structure an oil-repellent coating structure
  • a high-viscosity oil collecting device in water a dye separating device
  • a protein separating device Use in heavy metal ion separation devices, food processing devices, blood treatment devices, wastewater treatment devices, or other microfiltration, ultrafiltration, and nanofiltration devices.
  • a water-oil separation device including:
  • a water-and-oil separation element comprising a substrate, at least a part of the surface of the substrate being coated with a coating formed of the polymer material;
  • the oil-water separation membrane and the oil-water separation element are formed with pores through which the water phase in the oil-water mixture passes to block the oil phase, and at least a partial pore wall of the pore is formed of the polymer material.
  • the oil-water separation element may include a mesh structure formed by intersecting grid lines whose surface is coated with the polymer material.
  • the substrate may include a mesh, a woven fabric, a nonwoven fabric, a plate, or the like, and is not limited thereto.
  • the oil-water separation device may further include a support structure, and the support structure is fixedly connected to the oil-water separation membrane or the oil-water separation element.
  • the support structure With the support structure, the oil-water separation membrane or the oil-water separation element can be made to withstand a fluid flow at a certain flow rate.
  • These support structures can be of any suitable form known in the art.
  • the oil-water mixture comprises a non-emulsified oil-water mixture or an oil-water emulsion.
  • a high viscosity oil collection device in water comprising:
  • the oil-water separation element includes a substrate, and at least a part of the surface of the substrate is coated with a coating layer formed of the polymer material.
  • the oil-water separation membrane and the oil-water separation element are formed with pores through which water or an aqueous solution can pass to retain oil, and at least a partial pore wall of the pore is formed of the polymer material.
  • the pore diameter of the pore is smaller than 500 ⁇ m;
  • the oil-water separation element includes a mesh structure formed by intersecting grid lines whose surface is coated with the polymer material.
  • the substrate includes a wire mesh, a woven fabric, a non-woven fabric or a plate material, etc., but is not limited thereto.
  • the high-viscosity oil collecting device in water may further include a supporting structure, and the supporting structure is fixedly connected to the oil-water separation film or the oil-water separating element.
  • the high viscosity oil includes petroleum, heavy oil, silicone oil or heavy diesel oil, etc., but is not limited thereto.
  • a microfiltration device comprising:
  • a microfiltration element comprising a substrate, at least a partial surface of the substrate being coated with a coating formed of the polymer material
  • An ultrafiltration channel is formed in the microfiltration membrane or the microfiltration element, and at least a partial inner wall of the microfiltration channel is formed of the polymer material.
  • the microfiltration channel has a pore diameter of 0.01 ⁇ m to 500 ⁇ m.
  • an ultrafiltration device characterized by comprising:
  • an ultrafiltration element comprising a substrate, at least a partial surface of the substrate being coated with a coating formed of the polymer material
  • An ultrafiltration channel is formed in the ultrafiltration membrane or ultrafiltration element, and at least a partial inner wall of the ultrafiltration passage is formed of the polymer material.
  • the ultrafiltration channel has a pore diameter of 0.002 ⁇ m to 0.1 ⁇ m.
  • a nanofiltration device comprising:
  • a nanofiltration element comprising a substrate, at least part of the surface of the substrate being coated with a coating formed of the polymer material
  • a nanofiltration channel is formed in the nanofiltration membrane or the nanofiltration element, and at least a partial inner wall of the nanofiltration channel is formed of the polymer material.
  • the nanofiltration channel has a pore diameter of less than 0.002 ⁇ m.
  • the aforementioned ultrafiltration or nanofiltration separation device can be used for protein separation, heavy metal ion and dye separation, food processing, blood treatment, wastewater treatment, etc., and has good anti-pollution property.
  • Adhesion The residual force field of a solid surface adheres to the solid or liquid particles in close contact with it.
  • the nature of the adhesion phenomenon is the same as the adsorption, which is the result of the surface force between the two substances.
  • the adhesion can be manifested by the friction during the relative sliding of the two solid phases, the aggregation and sintering of the solid powder.
  • Separation membrane a membrane-type material with selective permeability. It can be divided into microfiltration membrane, ultrafiltration membrane, nanofiltration membrane, reverse osmosis membrane, pervaporation membrane, ion exchange membrane, etc. according to the separation mechanism and application range. .
  • the solid continuous film obtained by one application of the coating is a thin layer applied on a substrate such as metal, fabric or plastic for protection, insulation, decoration and the like.
  • the coating can be in a gaseous, liquid, or solid state, and the type and state of the coating is typically determined by the substrate to be sprayed.
  • Phase inversion refers to the process in which the solvent system of the casting solution is a polymer solution of the continuous phase and is converted into a swollen three-dimensional macromolecular network gel in which the polymer is a continuous phase. This gel constitutes a phase inversion film or coating.
  • Contact angle refers to the angle ⁇ between the tangential line of the gas-liquid interface made at the intersection of gas, liquid and solid three-phase, and the solid-liquid boundary line, which is a measure of the degree of wetting.
  • Adhesion refers to the ability of a material to adhere to the surface of another material.
  • the attached material generally refers to a liquid or powdery solid, and the attached body refers to an object having a certain surface.
  • the amount of adhesion depends not only on the molecular structure and chemical composition of the adherent material, but also on the surface properties of the adherend, as well as on the external conditions under which adhesion occurs, such as temperature, humidity, radiation, vibration, wind speed, etc. Wait.
  • Aliphatic polymer The aliphatic compound is a generic term for chain hydrocarbons (open chain hydrocarbons) and cyclic hydrocarbons other than aromatic compounds and derivatives thereof. Aliphatic carbocyclic compounds are also known as alicyclic compounds. Aliphatic compounds encompass all varieties of organic compounds, such as alkenes, alkanes, alcohols, ethers, ketones, aldehydes, esters, and the like.
  • the aliphatic polymer is an organic polymer in which a plurality of aliphatic compounds are covalently bonded to each other to form a compound having a relatively large molecular weight and having a repeating structural unit.
  • Aromatic polymer An aromatic compound is a type of organic compound having at least one benzene ring having a delocalized bond in a hydrocarbon molecule and having a unique property (called aromaticity) different from that of an open-chain compound or an alicyclic hydrocarbon.
  • the aromatic polymer is an organic polymer in which a plurality of aromatic compounds are covalently bonded to each other to form a compound having a relatively large molecular weight and having a repeating structural unit.
  • Example 1 The sulfonated polyethersulfone was weighed and dissolved in N,N-dimethylformamide to prepare a polymer raw material solution having a concentration of 10% by weight.
  • the above polymer raw material solution was uniformly coated on the surface of the cleaned glass substrate by a doctor blade method, and then transferred to a NaOH aqueous solution having a concentration of 0.01 mol/L to carry out a phase transformation and a reaction for forming an ionized hydrophilic functional group. After 10 minutes, it is taken out from the NaOH aqueous solution, and the excess NaOH is washed away with water to obtain a finished polymer material (separation membrane).
  • the optical photograph and surface morphology can be seen in Fig. 1 and Fig. 2, and the underwater oil contact is obtained.
  • the angle is 166° (see Figure 1)
  • the underwater oil roll angle is 2.4°
  • the underwater oil adhesion is about 0 ⁇ N (see Figure 3).
  • Example 2 A sulfonated polyethersulfone was weighed and dissolved in N,N-dimethylformamide to prepare a polymer raw material solution having a concentration of 10% by weight.
  • the polymer raw material solution was uniformly coated on the surface of the cleaned glass substrate by a doctor blade method, and then transferred to a water bath for phase transformation. After 10 minutes, it was taken out and transferred to a 0.1 mol/L NaOH aqueous solution to generate ionization.
  • the reaction of the hydrophilic functional group is taken out from the aqueous NaOH solution after 5 minutes, and the excess NaOH is washed away with water to obtain a finished oil-resistant adhesion separation membrane.
  • the membrane underwater oil contact angle is 165°
  • the underwater oil rolling angle is 2.7°
  • the underwater petroleum adhesion is about 0 ⁇ N.
  • Example 3 Diethanolamine-grafted polycarbazole was weighed and dissolved in chloroform to prepare a polymer raw material solution having a concentration of 1% by weight.
  • the copper mesh, the foamed nickel, the non-woven fabric, the polypropylene plastic plate, the latex glove and the like are respectively immersed in the polymer raw material solution for 5 hours to adsorb the polymer raw material on the surface of the substrate, and then immersed in the concentration of 0.01.
  • the phase transformation and the formation of the ionized hydrophilic functional group are carried out in a mol/L aqueous solution of NaOH.
  • Adhesive coating See Figure 4 for its optical photo and underwater oil contact angle.
  • the underwater oil contact angle of the various substrates coated with the oil-resistant adhesion coating is greater than 150°, the underwater oil rolling angle is less than 10°, and the underwater petroleum adhesion is less than 10 ⁇ N.
  • Copper mesh coated with the oil-resistant coating See Figure 6a - Figure 6f for the surface topography.
  • Example 4 Diethanolamine-grafted polycarbazole was weighed and dissolved in chloroform to prepare a solution having a concentration of 1% by weight.
  • the copper mesh, the foamed nickel, the non-woven fabric, the polypropylene plastic plate, the latex glove and the like are respectively immersed in the polymer raw material solution for 5 hours, the polymer raw material is adsorbed on the surface of the substrate, and then transferred into a water bath for phase transformation. After 10 minutes, it was taken out and transferred to a 0.1 mol/L aqueous solution of NaOH to carry out a reaction for forming an ionized hydrophilic functional group.
  • the underwater oil contact angle of the various substrates coated with the oil-resistant adhesion coating is greater than 150°, the underwater oil rolling angle is less than 10°, and the underwater petroleum adhesion is less than 10 ⁇ N.
  • Example 5 A methyl imidazole-modified polyphenylene ether was weighed and dissolved in N,N-dimethylacetamide to prepare a solution having a concentration of 1% by weight.
  • the copper mesh, foamed nickel, non-woven fabric, polypropylene plastic plate, latex glove and other substrates were immersed in the polymer raw material solution for 5 hours to adsorb the polymer raw material on the surface of the substrate, and then immersed in a concentration of 0.01 mol.
  • the underwater oil contact angle of the various substrates coated with the oil-resistant adhesion coating is greater than 150°, the underwater oil rolling angle is less than 10°, and the underwater petroleum adhesion is less than 10 ⁇ N.
  • Example 6 Polyacrylic acid grafted polyvinylidene fluoride was weighed and dissolved in N,N-dimethylformamide to prepare a solution having a concentration of 1% by weight.
  • the copper mesh, the foamed nickel, the non-woven fabric, the polypropylene plastic plate, the latex glove and the like are respectively immersed in the polymer raw material solution for 5 hours, the polymer raw material is adsorbed on the surface of the substrate, and then transferred into a water bath for phase transformation. After 10 minutes, it was taken out and transferred to a 0.1 mol/L aqueous solution of NaOH to carry out a reaction for forming an ionized hydrophilic functional group.
  • the underwater oil contact angle of the various substrates coated with the oil-resistant adhesion coating is greater than 150°, the underwater oil rolling angle is less than 10°, and the underwater petroleum adhesion is less than 10 ⁇ N.
  • Example 7 Phosphate-grafted polyether ketone was weighed and dissolved in N-methylpyrrolidone to prepare a solution having a concentration of 10% by weight. The above solution was uniformly applied to the surface of the cleaned glass substrate by a doctor blade method, and then transferred to a water bath for phase transformation. After 10 minutes, it was taken out and transferred to a 0.1 mol/L aqueous solution of NaOH to form an ionized hydrophilic functional group. The reaction was taken out from the aqueous NaOH solution after 5 minutes, and the excess NaOH was washed away with water to obtain a finished oil-resistant adhesion separation membrane.
  • the membrane underwater oil contact angle is 164°
  • the underwater oil rolling angle is 2.6°
  • the underwater petroleum adhesion is about 0 ⁇ N.
  • Example 8 Polyacrylamide-grafted polystyrene-stilbene copolymer was weighed and dissolved in dimethyl sulfoxide to prepare a solution having a concentration of 10% by weight, and the above solution was uniformly coated on the surface of a clean stainless steel plate. Then, it is immersed in a NaOH aqueous solution having a concentration of 0.01 mol/L to carry out a phase inversion reaction and a reaction for forming an ionized hydrophilic functional group, and after 10 minutes, it is removed from the reaction. The aqueous solution of NaOH was taken out, and excess NaOH was washed away with water to obtain an oil-resistant adhesive coating coated on the surface of the stainless steel plate.
  • the stainless steel plate coated with the oil-resistant coating has an underwater oil contact angle of 167°, an underwater oil rolling angle of 2.4°, and an underwater petroleum adhesion of about 0 ⁇ N.
  • Example 9 Weighing polymaleic anhydride grafted polyether ketone in N-methylpyrrolidone to prepare a solution having a concentration of 10% by weight, uniformly coating the above solution on the surface of a clean stainless steel plate, and then immersing it The phase inversion and the formation of the ionized hydrophilic functional group were carried out in an aqueous solution of NaOH having a concentration of 0.01 mol/L. After 10 minutes, the solution was taken out from the aqueous NaOH solution, and the excess NaOH was washed away with water to obtain a stainless steel plate. An oil resistant coating on the surface. The stainless steel plate coated with the oil-resistant coating has an underwater oil contact angle of 164°, an underwater oil rolling angle of 2.7°, and an underwater petroleum adhesion of about 0 ⁇ N.
  • Comparative Example 1 Polyacrylamide-grafted polystyrene-stilbene copolymer was weighed and dissolved in dimethyl sulfoxide to prepare a solution having a concentration of 10% by weight, and the above solution was uniformly coated on the surface of a clean stainless steel plate. Then, it is immersed in water for phase transformation, and after 10 minutes, it is taken out to obtain a polymer coating coated on the surface of the stainless steel plate.
  • Comparative Example 2 The polymaleic anhydride grafted polyether ketone was weighed and dissolved in N-methylpyrrolidone to prepare a solution having a concentration of 10% by weight, and the above solution was uniformly coated on the surface of a clean stainless steel plate, and then immersed therein. The phase transformation was carried out in water, and after 10 minutes, it was taken out to obtain a polymer coating coated on the surface of the stainless steel plate.
  • Comparative Example 3 Polyacrylamide-grafted polyvinylidene fluoride was weighed and dissolved in N-methylpyrrolidone to prepare a solution having a concentration of 10% by weight, and the above solution was uniformly coated on the surface of a clean stainless steel plate, and then immersed therein. The phase transformation was carried out in water, and after 10 minutes, it was taken out to obtain a polymer coating coated on the surface of the stainless steel plate.
  • Comparative Example 4 The polystyrene-stilbene copolymer was weighed and dissolved in dimethyl sulfoxide to prepare a solution having a concentration of 10% by weight, and the above solution was uniformly coated on the surface of a clean stainless steel plate, and then immersed in The phase inversion and the reaction were carried out in an aqueous solution of NaOH having a concentration of 0.01 mol/L. After 10 minutes, it was taken out from the aqueous NaOH solution, and excess NaOH was washed away with water to obtain a polymer coating coated on the surface of the stainless steel plate.
  • Comparative Example 5 The polyether ketone was weighed and dissolved in N-methylpyrrolidone to prepare a solution having a concentration of 10% by weight, and the above solution was uniformly coated on the surface of a clean stainless steel plate, and then immersed in a concentration of 0.01 mol/L. Into the NaOH solution The phase transformation and reaction were carried out, and after 10 minutes, it was taken out from the aqueous NaOH solution, and excess NaOH was washed away with water to obtain a polymer coating coated on the surface of the stainless steel plate.
  • Example 8 Comparative example 1 Underwater oil contact angle 167° 154° Underwater oil rolling angle 2.4° >90° Underwater oil adhesion 0 ⁇ N 11.4 ⁇ N
  • Example 9 Comparative example 2 Underwater oil contact angle 164° 147° Underwater oil rolling angle 2.7° >90° Underwater oil adhesion 0 ⁇ N 13.2 ⁇ N
  • Example 10 Comparative example 3 Underwater oil contact angle 166° 151° Underwater oil rolling angle 2.5° >90° Underwater oil adhesion 0 ⁇ N 12.7 ⁇ N
  • Example 8 The coatings in Examples 8, 9, 10 and Comparative Examples 4, 5, and 6 were compared, and the underwater oil contact angle and rolling of the obtained coating were respectively performed using an OCA20 contact angle tester and a Dataphysics surface/interfacial tension meter DCAT21. The angle and adhesion were tested and each test for each sample was tested 3 times and averaged.
  • Example 8 Comparative example 4 Underwater oil contact angle 167° 132° Underwater oil rolling angle 2.4° >90°
  • Example 10 Comparative example 6 Underwater oil contact angle 166° 119° Underwater oil rolling angle 2.5° >90°
  • the films, coatings and the like of the foregoing Examples 1-10 also exhibit non-adhesion properties under water for heavy oil, silicone oil or other highly adherent oils such as heavy diesel oil and edible oils.
  • Example 12 Polyacrylonitrile was weighed and dissolved in N,N-dimethylformamide to prepare a solution having a concentration of 8 wt%. The above solution was uniformly applied to the surface of the cleaned glass substrate by a doctor blade method, and then transferred to a water bath for phase transformation. After 10 minutes, it was taken out and transferred to a 0.1 mol/L aqueous solution of NaOH to form an ionized hydrophilic functional group. The reaction was taken out from the NaOH aqueous solution after 1 minute, and the excess NaOH was washed away with water to obtain a finished oil-resistant adhesion separation membrane.
  • the oil-resistant adhesion separation membrane has an underwater oil contact angle of 166°, an underwater oil rolling angle of 2.7°, and an underwater petroleum adhesion of about 0 ⁇ N.
  • Example 13 Polyacrylamide-grafted polyvinylidene fluoride was weighed and dissolved in N,N-dimethylformamide to prepare a solution having a concentration of 2% by weight. Soaking a clean polymer film (such as polytetrafluoroethylene) or a ceramic film (such as zirconia film, anodized aluminum film, etc.) in the above polymer raw material solution for 5 hours to adsorb the polymer raw material on the surface of the substrate, and then It is immersed in an ammonia aqueous solution having a concentration of 5 mol/L to carry out phase transformation and to generate an ionized hydrophilic functional group.
  • a clean polymer film such as polytetrafluoroethylene
  • a ceramic film such as zirconia film, anodized aluminum film, etc.
  • the underwater oil contact angle of the polymer film or ceramic film coated with the oil-resistant adhesion coating is greater than 150°, the underwater oil rolling angle is less than 10°, and the underwater petroleum adhesion is less than 10 ⁇ N.
  • Example 14 Polyacrylic acid grafted polyvinylidene fluoride was weighed and dissolved in N,N-dimethylformamide to prepare a solution having a concentration of 9 wt%.
  • the above polymer raw material solution is uniformly coated on the surface of a clean polymer film (such as a polytetrafluoroethylene film) or a ceramic film (such as a zirconia film, an anodized aluminum film, etc.) by a doctor blade method, and then transferred to a water bath. After phase conversion, 10 minutes later, it was taken out and transferred to a KOH aqueous solution having a concentration of 0.001 mol/L to carry out a reaction for forming an ionized hydrophilic functional group.
  • a clean polymer film such as a polytetrafluoroethylene film
  • a ceramic film such as a zirconia film, an anodized aluminum film, etc.
  • a polymer film or a ceramic film having a surface coated with an oil-resistant adhesive coating (the pore diameter of the polymer film or the ceramic film may be selected from the range of 0.001 ⁇ m to 100 ⁇ m).
  • the underwater oil contact angles of the polymer film and the ceramic film coated with the oil-resistant adhesion coating are both greater than 150°, the underwater oil rolling angle is less than 10°, and the underwater petroleum adhesion is less than 10 ⁇ N.
  • Example 15 Oil was poured onto a latex glove coated with an oil-resistant adhesive coating on Example 3; the oil was poured onto the same latex glove with no oil-resistant adhesion coating on the surface. Its contamination was used as a control.
  • the two gloves are placed in the same pure water at the same time, the oil on the latex gloves coated with the oil-resistant adhesive coating is automatically peeled off, the gloves are self-cleaning; the surface is not coated with the oil-resistant adhesive coating on the latex gloves. The oil is still firmly adhered to the surface of the glove, and it does not fall off at all, and the glove cannot be self-cleaned.
  • the self-cleaning performance of latex gloves coated with an oil-resistant adhesive coating in water is shown in Figure 5.
  • the inventors of the present invention also refer to the embodiments of Examples 1-15 at concentrations of 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 15 wt%, 20 wt%, 25 wt. %, 30wt%, 35wt%, 40wt%
  • the polymer solution is used as a raw material to prepare a film or a coating which also has oil-resistant adhesion properties.
  • Example 16 Oil and water were mixed at a volume ratio of 1:1 to form an oil-water mixture which was separated by an oil-water separation comprising a 400-mesh copper mesh of the surface-coated oil-resistant adhesion coating of Example 6. The device is separated, and the surface of the copper mesh coated with the oil-resistant adhesion coating has a pore diameter of 25 ⁇ m to 30 ⁇ m. The structure of the oil-water separation device and its working principle can be seen in FIG. Through separation, the oil is effectively entrapped and recovered by the copper mesh coated with the oil-resistant adhesion coating on the surface, and the water is coated with a copper mesh resistant to the oil-adhesive coating and purified, and the surface is coated with oil-resistant adhesive.
  • the coated copper mesh is self-cleaning in water and can be reused for a long time.
  • the water flux during the separation process is 47000 ⁇ 3000 L / (m 2 hbar), and the oil content in the purified water after separation is 0.5 ppm by mass organic carbon analyzer (ie, the mass fraction is 0.5 parts per million).
  • the oil-water separation performance of the copper mesh coated with the oil-resistant adhesion coating is shown in Fig. 8.
  • Example 17 Diesel and water were mixed at a mass ratio of 1:9, and sodium dodecylbenzenesulfonate having a concentration of 0.1 g/L was added as an emulsifying agent, and stirred at 2000 rpm for 2 hours to prepare an oil-water emulsion.
  • the oil-water emulsion was separated by an oil-water separation apparatus (the structure and principle of which is also referred to Fig. 8) comprising the oil-resistant adhesion separation membrane of Example 11, and the effective pore diameter of these membranes was about 0.01 ⁇ m.
  • the emulsified diesel oil is effectively trapped by the oil-resistant adhesion separation membrane and is enriched and recovered, and the water is separated by an oil-resistant adhesion separation membrane and purified.
  • the water flux during the separation was 550 L/(m 2 hbar), and the oil content in the purified water after separation was determined to be 3 ppm (ie, 3 parts per million by mass) by the total organic carbon analyzer.
  • Example 18 The dye Coomassie Brilliant Blue was dissolved in water to a solution having a concentration of 50 mg/L, and the solution was separated by a separation apparatus comprising the oil-resistant separation membrane of Example 12, and the effective pore diameter of these membranes was about 0.002 ⁇ m.
  • Coomassie Brilliant Blue is effectively trapped by the oil-resistant adhesion separation membrane, and water is passed through the separation membrane for purification.
  • the water flux during the separation process was 130 L/(m 2 hbar), and the effective rejection of Coomassie Brilliant Blue in the purified water after separation was determined by UV-Vis spectrophotometer to be 98.0%.
  • the dye trapped on the separation membrane after separation can be removed by simple water washing.
  • Example 19 A bovine serum albumin was dissolved in water to a solution having a concentration of 5 g/L, and the solution was separated by a separation apparatus comprising the oil-resistant adhesive film of Example 13, and the effective pore diameter of these films was about 0.002 ⁇ m. .
  • bovine serum albumin is effectively retained by the oil-resistant adhesion separation membrane, and water is passed through the separation membrane and purified.
  • the water flux during the separation process was 125 L/(m 2 hbar), and the effective rejection of bovine serum albumin in the purified water after separation was 98.5% as determined by UV-Vis spectrophotometry.
  • the protein trapped on the separation membrane after separation can be removed by simple water washing.
  • Example 20 CuSO 4 was dissolved in water to a solution having a concentration of 2000 ppm, and the solution was separated by a separating apparatus comprising the anodized aluminum film coated with the oil-resistant adhesion coating in Example 14.
  • the water flux during the separation was 120 L/(m 2 hbar), and the rejection of Na 2 SO 4 in the water after separation was 56.2% as determined by conductivity meter.

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Abstract

一种高分子材料、膜、涂层及其制备方法与应用，该高分子材料由含可离子化的亲水基团的高分子化合物经相转化且所含亲水基团被离子化后形成，同时该高分子材料在水中对油相体系的静态接触角大于140°，粘附力小于10μΝ。

Description

高分子材料、膜、涂层及其制备方法与应用 技术领域
本申请具体涉及一种高分子材料，基于所述高分子材料的膜或涂层及其制备方法与应用。
背景技术
海洋漏油、溢油在石油开采、运输过程中时常发生，每年都有大量的石油泄漏到自然界水环境中，不仅造成资源浪费，还造成严重的环境污染、毒杀大量的动植物、危害人类自身健康。不恰当的石油泄漏处理方式如原地燃烧和抛洒化学处理剂等还会进一步带来二次污染。将泄漏的石油分离、回收才是符合可持续发展观点的正确途径。目前，从油水混合物中分离、收集石油的主要方法有围栏法、吸附法、油拖把法等。由于石油易粘附和污染回收设备对其功能造成破坏，连续、有效地分离、回收泄漏的石油一直以来都是个难题，也是个挑战。此外，工业生产过程中产生的其他高粘度油(如重油、硅油、重柴油)和水的混合物同样危害严重，其排放量大，成分复杂，COD值高，易粘附、污染周围环境和处理设备，也十分难分离和回收。
为解决油水分离和油回收的问题，研究人员通过反复试验，发展了一系列超亲水-水下超疏油的分离膜和防油涂层，这些超亲水-水下超疏油分离膜或涂层对轻质、低黏度的油(如汽油、轻柴油、食用油以及众多与水不互溶的有机试剂)表现出水下超疏性质和很低的粘附力，但对高粘度的油却不具有超疏性质和抗粘附效果。在实际应用中，这些材料非常容易被石油、重油、硅油、重柴油等高粘度油粘附和污染，导致其失去特殊浸润性、抗油污染功能或油水分离功能。
发明内容
本申请的主要目的在于提供一种高分子材料，基于所述高分子材料的膜或涂层及其制备方法与应用，以克服现有技术中的不足。
为实现前述发明目的，本申请采用的技术方案包括：
本申请实施例提供了一种高分子材料，其由含可离子化的亲水基团的高分子化合物经相转化且所含亲水基团被离子化后形成。
所述高分子材料具有极强的水合能力，在水中该材料表面会形成稳定的水合层，保护该材料不受油黏附、并具有超疏油的性质。例如，所述高分子材料在水中对多种油相体系的静态接触角大于140°，粘附力小于10μN。
进一步的，所述高分子化合物包括至少修饰有磺酸基、磷酸基、羧基、酰胺基、醇羟基、季铵盐、胺基、醇胺基、氰基等基团中的任意一种或两种以上的脂肪族聚合物或芳香族聚合物。
本申请实施例还提供了由所述的高分子材料组成的膜或涂层。
本申请实施例还提供了一种制备所述膜或涂层的方法，其包括：
提供高分子溶液，包括含可离子化的亲水基团的高分子化合物；
以所述高分子溶液涂覆或浸渍基材，使其中的所述高分子化合物涂敷或吸附于所述基体上，形成高分子化合物层；
以碱性溶液充分浸渍所述高分子化合物层而使高分子化合物实现相转化，同时使所述高分子化合物中的亲水基团离子化，从而于所述基材上形成所述膜或涂层，
或者，将所述高分子化合物层中的高分子化合物湿法相转化，之后再以碱性溶液充分浸渍而使高分子化合物中的亲水基团离子化，从而于所述基材上形成所述膜或涂层。
本申请实施例还提供了所述的高分子材料于制备油水分离结构、防油涂层结构、水中高粘度油收集装置、染料分离装置、蛋白分离装置、重金属离子分离装置、食品加工装置、血液处理装置、废水处理装置等中的用途。
与现有技术相比，本申请的优点包括：
(1)提供的高分子材料含有离子化的亲水基团，其具有极强的水合能力，在水中该材料表面会形成稳定的水合层，保护该材料不受油黏附、并具有超疏油的性质；
(2)提供的高分子材料不仅对轻质、低粘度的油或与水不互溶的有机试剂具有水下超疏性质和抗油粘附功能，还对石油、重油、硅油、重柴油等高黏度油具有水下超疏性质和抗油粘附功能；
(3)由提供的高分子材料形成的膜、涂层等对高黏度油具有水下抗油粘附、抗油污染和自清洁效果，在抗油粘附、抗油污染、油/水分离、防油涂层、海洋溢油处理以及水中高粘度油分离收集等诸多领域广泛应用前景。
附图说明
图1是本申请实施例1中制备的一种高分子材料(分离膜)的光学照片及水中石油在该 高分子分离膜上的接触角照片。
图2是本申请实施例1中制备的一种高分子材料(分离膜)的SEM照片。
图3是本申请实施例1中制备的一种高分子材料(分离膜)的水下石油粘附力测试曲线图以及石油液滴接触、挤压、离开该抗油吸附和粘附抗油粘附膜时的光学照片。
图4是本申请实施例3中包覆有高分子材料的不同基材的光学照片和水中石油在包覆有抗油粘附该抗油吸附和粘附材料的不同基材上的接触角照片。
图5左为本申请实施例3和实施例15中包覆有高分子材料的手套在被石油污染后在水中自清洁的照片，右为未包覆高分子材料的手套在被石油污染后在水中清洗的照片。
图6a-图6f是本申请实施例3中包覆有高分子材料的铜网的SEM照片。
图7是本申请实施例6和实施例16中包覆有高分子材料的铜网多次分离石油/水混合物时的分离通量测试图、分离后水中石油含量测试图以及完成分离后，包覆有高分子材料的铜网在水中自清洁的照片。
图8是本申请一些典型实施例中一种油水分离装置的结构示意图，其中：1-油水混合物、2-油水分离膜或油水分离器件、3-水、4-油。
具体实施方式
体现本申请特征与优点的典型实施例将在以下的说明中详细叙述。应理解的是本申请能够在不同的实施例上具有各种的变化，其皆不脱离本申请的范围，且其中的说明及图示在本质上是当作说明之用，而非用以限制本申请。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。
如前所述，对于实际应用中的诸多问题，例如原油泄漏事故中仪器设备的抗原油污染问题和高粘度油的分离、收集问题，仅仅凭借现有的具有超疏油性质的材料是远远不能解决的，而应降低材料对高粘度油的粘附力，克服其粘附、污染问题，如此才能保证分离、收集过程中仪器设备的持续、正常运行。而这也是业界长期渴求解决的技术难题。本案发明人经长期研究和大量实践，得以提出本申请的技术方案，并很好的解决了这些问题，如下将予以更为详细的说明。
本申请的一个方面提供了一种在水中对高粘度油/油脂(例如石油、重油、硅油、重柴油等)不吸附和不粘附的高分子材料，该高分子材料由含有亲水性官能团的高分子构成，亲水 性官能团的全体或部分为带正电荷，或带负电荷，或带正负电荷的亲水性官能团或者至少通过离子化工艺生成上述的亲水性官能团。
在一些实施例中，本申请提供了一种高分子材料，该材料由含可离子化的亲水基团的高分子化合物在经相转化且所含亲水基团被离子化后形成。
因所述高分子材料具有前述的特殊结构，通过其所含亲水官能团和官能团离子化的协同作用，使所述高分子材料具有亲水性质并在水中对轻质油和高粘度油相体系均展现出大于140°的静态接触角和小于10μN的粘附力。
更进一步的讲，因所述高分子材料中亲水官能团和官能团离子化的协同作用，使所述高分子材料具有很强的水合能力，在所述高分子材料表面可形成高稳定性的水合保护层，该水合保护层能保护所述高分子材料不被高黏度油分子或其他分子直接接触，从而使高黏度油难以吸附和黏附到所述高分子材料上。因此，所述高分子材料和涂覆有所述高分子材料的基底具有对高黏度油的水下超疏性质和抗油粘附功能。
在前述的一些实施例中，所述高分子化合物包括至少修饰有磺酸基、磷酸基、羧基、酰胺基、醇羟基、季铵盐、胺基、醇胺基、氰基等基团中的任意一种或两种以上的脂肪族聚合物或芳香族聚合物，但不限于此。
进一步的，所述脂肪族聚合物包括聚乙烯、聚丙烯、聚丙烯腈、聚偏氟乙烯、聚六氟丙烯中的任意一种或两种以上的共聚物，但不限于此。
进一步的，所述芳香族聚合物包括聚醚砜、聚醚酮、聚吡咯、聚吡咯、聚咔唑中的任意一种或两种以上的共聚物，但不限于此。
优选的，所述高分子化合物选自磺化聚醚砜、二乙醇胺接枝的聚咔唑、聚丙烯腈、甲基咪唑修饰的聚苯醚、聚丙烯酰胺接枝的聚苯乙烯-二苯乙烯共聚物、磷酸酯接枝的聚醚酮、聚丙烯酸接枝的聚偏氟乙烯、聚乙烯基磺酸接枝的聚醚砜、聚丙烯酸接枝的聚碳酸酯、聚马来酸酐接枝的聚偏氟乙烯中的任意一种或两种以上的组合，但不限于此。
优选的，所述高分子溶液中的溶剂包括N-甲基吡咯烷酮、三氯甲烷，二氧六环、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、间甲酚、二苯砜、二苯醚、四氢呋喃、二甲基亚砜中的任意一种或两种以上的组合；
进一步的，所述高分子溶液的浓度为0.001wt％～40wt％，例如可以为0.001wt％、0.005wt％、0.01wt％、0.05wt％、0.1wt％、0.5wt％、1wt％、2wt％、5wt％、8wt％、10wt％、15wt％、20wt％、25wt％、30wt％、35wt％或40wt％，例如可优选为1wt％～40wt％，进一步优选为1wt％～10wt％，更进一步优选为2wt％～8wt％。
在前述的一些实施例中，所述高分子化合物的亲水基团是在所述高分子化合物被碱性溶液充分浸渍后而被离子化的。
较为优选的，所述碱性溶液中所含的碱性物质包括NaOH、KOH、氨水或Na2CO3等，但不限于此。
进一步的，所述碱性溶液中所含的溶剂为所述高分子化合物的不良溶剂，包括水、甲醇、乙醇、乙二醇、异丙醇或正丁醇等，但不限于此。
进一步的，所述碱性溶液的浓度为0.001mol/L～10mol/L，例如可以为0.001mol/L、0.005mol/L、0.01mol/L、0.02mol/L、0.09mol/L、0.05mol/L、0.1mol/L、0.5mol/L、1mol/L、5mol/L、10mol/L，例如可优选为0.01mol/L～10mol/L，进一步优选为0.01mol/L～1mol/L，更进一步优选为0.05mol/L～0.1mol/L。
在前述的一些实施例中，所述相转化是与所述离子化一步完成的；或者，所述离子化是在高分子原料相转化完成后于碱性溶液中进行的。
在本申请中，前述的相转化过程所需的条件如温度、时间等可取决于所述高分子化合物的类型等，这是本领域技术人员所知悉的，并可见诸本领域的诸多文献，因而此处不再予以详细阐述。例如，在一些实施案例中，前述的相转化与离子化过程均可在室温条件下完成。
本申请所述的高分子材料可以用于制备油水分离结构、防油涂层结构、水中高粘度油收集装置、染料分离装置、蛋白分离装置、重金属离子分离装置、食品加工装置、血液处理装置、废水处理装置等，因此在油水分离、防油涂层、海洋漏油、溢油处理、水中高粘度油收集、分子分离、食品加工、医药医疗、废水处理、以及其他微滤、超滤、纳滤等领域中均可应用。
例如，本申请的所述高分子材料可以以分离膜或涂层的形式存在。因此，在一些实施例中还提供了由所述高分子材料组成的膜或涂层。这些膜、涂层在水中对石油、重油、硅油、重柴油等高粘度油均表现出完全不吸附和不粘附的性质，具体表现为：在水中高粘度油无法吸附和粘附到所述高分子材料上，或即使所述高分子材料在空气中被高粘度油粘附后，一旦将其置于水中，油会自动从所述高分子材料上脱离下来，达到抗油污染和自清洁效果。
其中，所述膜或涂层可以为多孔膜，多孔涂层或无孔涂层。
在一些实施例中还提供了一种膜或涂层的制备方法，其包括：
提供高分子溶液，其中包括含可离子化的亲水基团的高分子化合物(高分子原料)；
以所述高分子溶液涂覆或浸渍基材，使其中的所述高分子化合物涂敷或吸附于所述基体上，形成高分子化合物层；
以碱性溶液充分浸渍所述高分子化合物层而使高分子化合物相转化，并使高分子化合物中的亲水基团离子化，从而于所述基材上形成所述膜或涂层。
在前述的这些实施例中，通过以碱性溶液充分浸渍所述高分子化合物层，可以使溶解所述高分子化合物的有机溶剂扩散进碱性溶液，但高分子化合物因与碱性不良溶剂不互溶而析出成型，使高分子化合物实现相转化，同时所述高分子化合物中的亲水基团与碱性溶液中的碱性物质反应而离子化，从而于所述基材上形成所述膜或涂层。
或者，在一些实施例中，也可以将所述高分子化合物层中的高分子化合物湿法相转化，之后再以碱性溶液充分浸渍而使高分子化合物中的亲水基团离子化，从而于所述基材上形成所述膜或涂层。
在一些较为具体的实施例中，一种制备包裹在基材表面的膜或涂层的方法可以包括：将所述的高分子原料溶解后涂敷在基材表面或将基材浸泡于高分子原料溶液中使基材表面涂敷或吸附高分子原料，然后将其浸没在碱性溶液中一步完成高分子材料的相转化过程和生成离子化亲水基团的反应。
在一些较为具体的实施例中，一种制备包裹在基材表面的膜或涂层的方法也可以包括：将所述的高分子原料溶解后涂敷在基材表面或将基材浸泡于高分子原料溶液中使其表面涂敷或吸附高分子原料，通过湿法相转化之后将其浸没于碱性溶液中完成生成离子化亲水基团的反应。
前述的高分子原材料至少可选自磺酸基、磷酸基、羧基、酰胺基、醇羟基、季铵盐、胺基、醇胺基、氰基修饰的脂肪族聚合物(包括聚乙烯、聚丙烯、聚丙烯腈、聚偏氟乙烯、聚六氟丙烯及其共聚物)或芳香族聚合物(包括聚醚砜、聚醚酮、聚吡咙、聚吡咯、聚咔唑及其共聚物)中的任意一种或基团相近主链不同的其他高分子，但不限于此。
作为优选方案之一，前述高分子原料至少可选自磺化聚醚砜、二乙醇胺接枝的聚咔唑、聚丙烯腈、甲基咪唑修饰的聚苯醚、聚丙烯酰胺接枝的聚苯乙烯-二苯乙烯共聚物、磷酸酯接枝的聚醚酮、聚丙烯酸接枝的聚偏氟乙烯、聚乙烯基磺酸接枝的聚醚砜、聚丙烯酸接枝的聚碳酸酯、聚马来酸酐接枝的聚偏氟乙烯中的任意一种，但不限于此。
在前述实施例中，高分子原料溶液中的溶剂至少可选自N-甲基吡咯烷酮、三氯甲烷，二氧六环、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、间甲酚、二苯砜、二苯醚、四氢呋喃、二甲基亚砜中任意一种，但不限于此。
较为优选的，所述高分子原料溶液的浓度为0.001wt％～40wt％，例如可以为0.001wt％、0.005wt％、0.01wt％、0.05wt％、0.1wt％、0.5wt％、1wt％、2wt％、5wt％、8wt％、10wt％、 15wt％、20wt％、25wt％、30wt％、35wt％或40wt％，例如可优选为1wt％～40wt％，进一步优选为1wt％～10wt％，更进一步优选为2wt％～8wt％。
在前述实施例中，所述基材至少可选自玻璃、金属、塑料、丝网、板材、织物中的任意一种。
在前述实施例中，所述碱性溶液至少可选自NaOH、KOH、氨水、碳酸钠溶液中的任意一种。优选的，所述碱性溶液的浓度为0.001mol/L～10mol/L，例如可以为0.001mol/L、0.005mol/L、0.01mol/L、0.02mol/L、0.09mol/L、0.05mol/L、0.1mol/L、0.5mol/L、1mol/L、5mol/L、10mol/L，例如可优选为0.01mol/L～10mol/L，进一步优选为0.01mol/L～1mol/L，更进一步优选为0.05mol/L～0.1mol/L。
在前述实施例中，所述碱性溶液的溶剂为高分子原料的不良溶剂，至少可选自水，甲醇，乙醇，乙二醇，异丙醇，正丁醇等中的一种或多种，且不限于此。
在前述实施例中，当制备膜时，至少可选用甩膜法、涂膜法、注膜法，刮膜法中的任意一种而实现成膜过程。
如前述所述，本申请所述的高分子材料能以涂层、多孔膜或多孔网等多种形式存在。
例如，在一些实施例中，当所述高分子材料以防油涂层形式存在时，涂覆有该材料的基材对高粘度油同样具有水下疏油性质(油接触角>140°)和低粘附力(<10μN)。具体表现为，在水中高粘度油无法粘附到该高分子涂层上，或即使该高分子涂层在空气中被高粘度油粘附后，一旦将其置于水中，高粘度油会自动脱离该高分子涂层，从而使涂覆有该高分子涂层的基材具有水中抗油粘附和自清洁性能。
例如，在一些实施例中，当所述高分子材料以分离膜形式存在时，该分离膜在分离未乳化的油水混合物或乳化的油水混合物(油水乳液)时具有优异的抗油污染性能。具体体现在，简单水清洗后，该分离膜的水通量恢复到80％以上。
相应的，本申请实施例还提供了所述的高分子材料或所述的膜或涂层于制备油水分离结构、防油涂层结构、水中高粘度油收集装置、染料分离装置、蛋白分离装置、重金属离子分离装置、食品加工装置、血液处理装置、废水处理装置或者其他微滤、超滤、纳滤装置中的用途。
例如，在一些实施例中还提供了一种油水分离装置，包括：
所述高分子材料形成的油水分离膜，
或者，油水分离元件，包括基材，所述基材的至少局部表面覆设有由所述高分子材料形成的涂层；
所述油水分离膜、油水分离元件中形成有可供油水混合物中的水相通过而阻隔油相的孔道，至少是所述孔道的局部的孔壁由所述高分子材料形成。
进一步的，所述油水分离元件可以包含有由表面包覆有所述高分子材料的网格线交叉形成的网格结构。
进一步的，所述基材可以包括丝网、织物、无纺布或板材等，且不限于此。
进一步的，所述的油水分离装置还可包括支撑结构，所述支撑结构与所述油水分离膜或油水分离元件固定连接。藉由所述支撑结构，可以使所述油水分离膜或油水分离元件能够耐受一定流速的流体冲击。这些支撑结构可以是业界已知的任何合适形式的。
进一步的，所述油水混合物包括非乳化的油水混合物或油水乳液。
例如，在一些实施例中还提供了一种水中高粘度油收集装置，其特征在于包括：
由所述高分子材料形成的油水分离膜，
或者，油水分离元件，包括基材，所述基材的至少局部表面覆设有由所述高分子材料形成的涂层，
所述油水分离膜、油水分离元件中形成有可供水或水溶液通过而截留油的孔道，至少是所述孔道的局部的孔壁由所述高分子材料形成，优选的，所述孔道的孔径小于500μm；
以及，容置空间，至少用以容置所述油水分离膜或油水分离元件截留的油。
进一步的，所述油水分离元件包含有由表面包覆有所述高分子材料的网格线交叉形成的网格结构。
进一步的，所述基材包括丝网、织物、无纺布或板材等，但不限于此。
进一步的，所述的水中高粘度油收集装置还可包括支撑结构，所述支撑结构与所述油水分离膜或油水分离元件固定连接。
进一步的，所述高粘度油包括石油、重油、硅油或重柴油等，但不限与此。
例如，在一些实施例中还提供了一种微滤装置，其特征在于包含：
由所述高分子材料形成的微滤膜，
或者，微滤元件，包括基材，所述基材的至少局部表面覆设有由所述高分子材料形成的涂层，
所述微滤膜或微滤元件中形成有超微滤通道，至少是所述微滤通道的局部的内壁由所述高分子材料形成。优选的，所述微滤通道的孔径为0.01μm～500μm。
例如，在一些实施例中还提供了一种超滤装置，其特征在于包含：
由所述高分子材料形成的超滤膜，
或者，超滤元件，包括基材，所述基材的至少局部表面覆设有由所述高分子材料形成的涂层，
所述超滤膜或超滤元件中形成有超滤通道，至少是所述超滤通道的局部的内壁由所述高分子材料形成。优选的，所述超滤通道的孔径为0.002μm～0.1μm。
例如，在一些实施例中还提供了一种纳滤装置，其特征在于包含：
由所述高分子材料形成的纳滤膜，
或者，纳滤元件，包括基材，所述基材的至少局部表面覆设有由所述高分子材料形成的涂层，
所述纳滤膜或纳滤元件中形成有纳滤通道，至少是所述纳滤通道的局部的内壁由所述高分子材料形成。优选的，所述纳滤通道的孔径为小于0.002μm。
前述的超滤或纳滤分离装置可用于蛋白分离、重金属离子和染料分离、食品加工、血液处理、废水处理等中，并且具有较好的抗污染性。
本申请说明书中述及的一些名词的释义如下，当然，本领域技术人员依据业界的知识亦可有其它合适的理解：
粘附：固体表面剩余力场与其紧密接触的固体或液体的质点相互吸引发生粘附。粘附现象的本质和吸附一样，都是两种物质之间表面力作用的结果。粘附作用可通过两固相相对滑动时的摩擦、固体粉末的聚集和烧结等现象表现出来。
分离膜：一种具有选择性透过能力的膜型材料，通常按分离机理和适用范围可分为微滤膜，超滤膜，纳滤膜，反渗透膜，渗透蒸发膜，离子交换膜等。
涂层：由涂料一次施涂所得到的固态连续膜，是为了防护，绝缘，装饰等目的，涂布于金属，织物，塑料等基体上的薄层。涂料可以为气态、液态、固态，通常根据需要喷涂的基质决定涂料的种类和状态。
相转化：是指铸膜液的溶剂体系为连续相的一个高分子溶液，转变为高分子是连续相的一个溶胀的三维大分子网络式凝胶的过程。这种凝胶就构成了相转化膜或涂层。
接触角：是指在气、液、固三相交点处所作的气-液界面的切线穿过液体与固-液交界线之间的夹角θ，是润湿程度的量度。
粘附力：粘附力指某种材料附着于另一种材料表面的能力。附着材料一般指液体或粉状固体，被附着体指具有一定表面的物体。粘附力的大小，不仅取决于粘附材料的分子结构和化学成分和被粘附体的表面特性，还与发生粘附的外在条件有关，如温度，湿度，辐射，振动，风速，等等。
脂肪族聚合物：脂肪族化合物是链状烃类(开链烃类)及除芳香族化合物以外的环状烃类及其衍生物的总称。属于脂肪族的碳环化合物又称脂环族化合物。脂肪族化合物涵盖有机化合物的所有品种，如烯类、烷烃类、醇类、醚类、酮类、醛类、酯类等。脂肪族聚合物是由众多脂肪族化合物彼此以共价键结合形成相对分子质量特别大、具有重复结构单元的有机高分子。
芳香族聚合物：芳香族化合物是指碳氢化合物分子中至少含有一个带离域键的苯环，具有与开链化合物或脂环烃不同的独特性质(称芳香性)的一类有机化合物。芳香族聚合物是由众多芳香族化合物彼此以共价键结合形成相对分子质量特别大、具有重复结构单元的有机高分子。
下面结合若干较佳实施例以及对比例对本申请的技术方案做进一步的说明，但本申请的保护范围并不限于以下实施例的内容。
实施例1：称取磺化聚醚砜溶解于N，N-二甲基甲酰胺中，配制浓度为10wt％的高分子原料溶液。通过刮膜法将上述高分子原料溶液均匀涂敷在清洁的玻璃基板表面，后转入浓度为0.01mol/L的NaOH水溶液中进行相转化和生成离子化亲水官能团的反应。10分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得成品高分子材料(分离膜)，其光学照片和表面形貌可参阅图1和图2，其水下石油接触角为166°(参阅图1)，水下石油滚动角为2.4°，水下石油粘附力约为0μN(参阅图3)。
实施例2：称取磺化聚醚砜溶解于N，N-二甲基甲酰胺中，配制浓度为10wt％的高分子原料溶液。通过刮膜法将上述高分子原料溶液均匀涂敷在清洁的玻璃基板表面，后转入水浴中进行相转化，10分钟后取出并转入浓度为0.1mol/L的NaOH水溶液中进行生成离子化亲水官能团的反应，5分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得成品抗油粘附分离膜。该膜水下石油接触角为165°，水下石油滚动角为2.7°，水下石油粘附力约为0μN。
实施例3：称取二乙醇胺接枝的聚咔唑溶解于三氯甲烷中，配制浓度为1wt％的高分子原料溶液。分别将铜网、泡沫镍、无纺布、聚丙烯塑料板、乳胶手套等基材浸泡于该高分子原料溶液中5小时，使基材表面吸附高分子原料，然后将其浸没在浓度为0.01mol/L的NaOH水溶液中进行相转化和生成离子化亲水官能团的反应，10分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得到包覆在基材表面的抗油粘附涂层。其光学照片和水下石油接触角参阅图4。表面包覆有该抗油粘附涂层的各种基材的水下石油接触角均大于150°，水下石油滚动角均小于10°，水下石油粘附力均小于10μN。表面包覆有该抗油粘附涂层的铜网 的表面形貌参阅图6a-图6f。
实施例4：称取二乙醇胺接枝的聚咔唑溶解于三氯甲烷中，配制浓度为1wt％的溶液。分别将铜网、泡沫镍、无纺布、聚丙烯塑料板、乳胶手套等基材浸泡于高分子原料溶液中5小时，使基材表面吸附高分子原料，然后转入水浴中进行相转化，10分钟后取出并转入浓度为0.1mol/L的NaOH水溶液中进行生成离子化亲水官能团的反应，5分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得包覆在基材表面的抗油粘附涂层。表面包覆有该抗油粘附涂层的各种基材的水下石油接触角均大于150°，水下石油滚动角均小于10°，水下石油粘附力均小于10μN。
实施例5：称取甲基咪唑修饰的聚苯醚溶解于N,N-二甲基乙酰胺中，配制浓度为1wt％的溶液。分别将铜网、泡沫镍、无纺布、聚丙烯塑料板、乳胶手套等基材浸泡于高分子原料溶液中5小时，使基材表面吸附高分子原料，然后将其浸没在浓度为0.01mol/L的NaOH水溶液中进行相转化和生成离子化亲水官能团的反应，10分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得包覆在基材表面的抗油粘附涂层。表面包覆有该抗油粘附涂层的各种基材的水下石油接触角均大于150°，水下石油滚动角均小于10°，水下石油粘附力均小于10μN。
实施例6：称取聚丙烯酸接枝的聚偏氟乙烯溶解于N,N-二甲基甲酰胺中，配制浓度为1wt％的溶液。分别将铜网、泡沫镍、无纺布、聚丙烯塑料板、乳胶手套等基材浸泡于高分子原料溶液中5小时，使基材表面吸附高分子原料，然后转入水浴中进行相转化，10分钟后取出并转入浓度为0.1mol/L的NaOH水溶液中进行生成离子化亲水官能团的反应，5分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得包覆在基材表面的抗油粘附涂层。表面包覆有该抗油粘附涂层的各种基材的水下石油接触角均大于150°，水下石油滚动角均小于10°，水下石油粘附力均小于10μN。
实施例7：称取磷酸酯接枝的聚醚酮溶解于N-甲基吡咯烷酮中，配制浓度为10wt％的溶液。通过刮膜法将上述溶液均匀涂敷在清洁的玻璃基板表面，后转入水浴中进行相转化，10分钟后取出并转入浓度为0.1mol/L的NaOH水溶液中进行生成离子化亲水官能团的反应，5分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得成品抗油粘附分离膜。该膜水下石油接触角为164°，水下石油滚动角为2.6°，水下石油粘附力约为0μN。
实施例8：称取聚丙烯酰胺接枝的聚苯乙烯-二苯乙烯共聚物溶解于二甲基亚砜中，配制浓度为10wt％的溶液，将上述溶液均匀涂敷在清洁的不锈钢板表面，然后将其浸没在浓度为0.01mol/L的NaOH水溶液中进行相转化和生成离子化亲水官能团的反应，10分钟后将其从 NaOH水溶液中取出，用清水洗去多余的NaOH，即得包覆在不锈钢板表面的抗油粘附涂层。该表面包覆有该抗油粘附涂层的不锈钢板的水下石油接触角为167°，水下石油滚动角为2.4°，水下石油粘附力约为0μN。
实施例9：称取聚马来酸酐接枝的聚醚酮溶解于N-甲基吡咯烷酮中，配制浓度为10wt％的溶液，将上述溶液均匀涂敷在清洁的不锈钢板表面，然后将其浸没在浓度为0.01mol/L的NaOH水溶液中进行相转化和生成离子化亲水官能团的反应，10分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得包覆在不锈钢板表面的抗油粘附涂层。该表面包覆有该抗油粘附涂层的不锈钢板的水下石油接触角为164°，水下石油滚动角为2.7°，水下石油粘附力约为0μN。
实施例10：称取聚丙烯酰胺接枝的聚偏氟乙烯溶解于N-甲基吡咯烷酮中，配制浓度为10wt％的溶液，将上述溶液均匀涂敷在清洁的不锈钢板表面，然后转入水浴中进行相转化，10分钟后取出并转入浓度为0.1mol/L的NaOH水溶液中进行生成离子化亲水官能团的反应，5分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得包覆在不锈钢板表面的抗油粘附涂层。该表面包覆有该抗油粘附涂层的不锈钢板的水下石油接触角为166°，水下石油滚动角为2.5°，水下石油粘附力约为0μN。
对比例1：称取聚丙烯酰胺接枝的聚苯乙烯-二苯乙烯共聚物溶解于二甲基亚砜中，配制浓度为10wt％的溶液，将上述溶液均匀涂敷在清洁的不锈钢板表面，然后将其浸没在水中进行相转化，10分钟后将其取出，即得包覆在不锈钢板表面的高分子涂层。
对比例2：称取聚马来酸酐接枝的聚醚酮溶解于N-甲基吡咯烷酮中，配制浓度为10wt％的溶液，将上述溶液均匀涂敷在清洁的不锈钢板表面，然后将其浸没在水中进行相转化，10分钟后将其取出，即得包覆在不锈钢板表面的高分子涂层。
对比例3：称取聚丙烯酰胺接枝的聚偏氟乙烯溶解于N-甲基吡咯烷酮中，配制浓度为10wt％的溶液，将上述溶液均匀涂敷在清洁的不锈钢板表面，然后将其浸没在水中进行相转化，10分钟后将其取出，即得包覆在不锈钢板表面的高分子涂层。
对比例4：称取聚苯乙烯-二苯乙烯共聚物溶解于二甲基亚砜中，配制浓度为10wt％的溶液，将上述溶液均匀涂敷在清洁的不锈钢板表面，然后将其浸没在浓度为0.01mol/L的NaOH水溶液中进行相转化和反应，10分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得包敷在不锈钢板表面的高分子涂层。
对比例5：称取聚醚酮溶解于N-甲基吡咯烷酮中，配制浓度为10wt％的溶液，将上述溶液均匀涂敷在清洁的不锈钢板表面，然后将其浸没在浓度为0.01mol/L的NaOH水溶液中进 行相转化和反应，10分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得涂敷在不锈钢板表面的高分子涂层。
对比例6：称取聚偏氟乙烯溶解于N-甲基吡咯烷酮中，配制浓度为10wt％的溶液，将上述溶液均匀涂敷在清洁的不锈钢板表面，然后转入水浴中进行相转化，10分钟后取出并转入浓度为0.1mol/L的NaOH水溶液中进行反应，5分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得涂敷在不锈钢板表面的高分子涂层。
取实施例8、9、10及对比例1、2、3中所得涂层进行对比，采用OCA20接触角测试仪和Dataphysics表面/界面张力仪DCAT21分别对所得涂层的水下石油接触角、滚动角以及粘附力进行测试，每个样品的每项测试均测试3次并取平均值，测试结果如下表1、2、3所示。
表1.实施例8和对比例1所得涂层的水下疏油性和粘附力测试结果
  实施例8 对比例1
水下石油接触角 167° 154°
水下石油滚动角 2.4° >90°
水下石油粘附力 0μN 11.4μN
表2.实施例9和对比例2所得涂层的水下疏油性和粘附力测试结果
  实施例9 对比例2
水下石油接触角 164° 147°
水下石油滚动角 2.7° >90°
水下石油粘附力 0μN 13.2μN
表3.实施例10和对比例3所得涂层的水下疏油性和粘附力测试结果
  实施例10 对比例3
水下石油接触角 166° 151°
水下石油滚动角 2.5° >90°
水下石油粘附力 0μN 12.7μN
从表1、2、3所示实施例8-9和对比例1-3所得涂层的对比中可以看出，在原料相同的条件下，通过本申请公开的制备方法和通过普通相转化方法得到的材料对石油这类高粘度油 的水下疏油性和粘附力差别很大，通过本申请公开的制备方法得到的高分子材料在水中对高粘度油具有超疏和超低粘附的性能，通过普通相转化方法得到的材料不具备这种性能。
取实施例8、9、10及对比例4、5、6中所涂层进行对比，采用OCA20接触角测试仪和Dataphysics表面/界面张力仪DCAT21分别对所得涂层的水下石油接触角、滚动角以及粘附力进行测试，每个样品的每项测试均测试3次并取平均值。
对比例4、5、6中所得涂层的水下石油粘附力太大，通过Dataphysics表面/界面张力仪DCAT21测试时，直至油滴拉断，粘附在该涂层上油滴也无法脱离涂层表面，因而无法测出粘附力值(超出该仪器测试范围，因而远大于实施例8、9、10中所得到涂层的水下石油粘附力)。涂层的水下石油接触角、滚动角测试结果如下表4、5、6所示。
表4.实施例8和对比例4所得涂层的水下疏油性测试结果
  实施例8 对比例4
水下石油接触角 167° 132°
水下石油滚动角 2.4° >90°
表5.实施例9和对比例5所得涂层的水下疏油性测试结果
  实施例9 对比例5
水下石油接触角 164° 125°
水下石油滚动角 2.7° >90°
表6.实施例10和对比例6所得涂层的水下疏油性测试结果
  实施例10 对比例6
水下石油接触角 166° 119°
水下石油滚动角 2.5° >90°
同样的，前述实施例1-10的膜、涂层等对于重油、硅油或重柴油等其它高粘附性油和食用油等也均表现出在水下不粘附的特性。
实施例11：称取质量比为1：2的聚丙烯酸接枝的聚偏氟乙烯和聚偏氟乙烯溶解于N,N-二甲基甲酰胺中，配制总浓度为10wt％的溶液。通过刮膜法将上述溶液均匀涂敷在清洁的玻璃基板表面，后转入水浴中进行相转化，10分钟后取出并转入浓度为10mol/L的Na2CO3水 溶液中进行生成离子化亲水官能团的反应，1分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得成品抗油粘附分离膜。该抗油粘附分离膜的水下石油接触角为165°，水下石油滚动角为2.9°，水下石油粘附力约为0μN。
实施例12：称取聚丙烯腈溶解于N,N-二甲基甲酰胺中，配制浓度为8wt％的溶液。通过刮膜法将上述溶液均匀涂敷在清洁的玻璃基板表面，后转入水浴中进行相转化，10分钟后取出并转入浓度为0.1mol/L的NaOH水溶液中进行生成离子化亲水官能团的反应，1分钟后将其从NaOH水溶液中取出，用清水洗去多余的NaOH，即得成品抗油粘附分离膜。该抗油粘附分离膜的水下石油接触角为166°，水下石油滚动角为2.7°，水下石油粘附力约为0μN。
实施例13：称取聚丙烯酰胺接枝的聚偏氟乙烯溶解于N,N-二甲基甲酰胺中，配制浓度为2wt％的溶液。将清洁的高分子膜(如聚四氟乙烯)或陶瓷膜(如氧化锆膜、阳极氧化铝膜等)浸泡于上述高分子原料溶液中5小时，使基材表面吸附高分子原料，然后将其浸没在浓度为5mol/L的氨水溶液中进行相转化和生成离子化亲水官能团的反应，10分钟后将其从氨水溶液中取出，用清水洗去多余的氨水，即得表面包覆抗油粘附涂层的高分子膜或陶瓷膜(膜孔径在0.001μm～100μm范围内可选)。表面包覆抗油粘附涂层的高分子膜或陶瓷膜的水下石油接触角均大于150°，水下石油滚动角均小于10°，水下石油粘附力均小于10μN。
实施例14：称取聚丙烯酸接枝的聚偏氟乙烯溶解于N,N-二甲基甲酰胺中，配制浓度为9wt％的溶液。将上述高分子原料溶液通过刮膜法均匀涂敷在清洁的高分子膜(如聚四氟乙烯膜)或陶瓷膜(如氧化锆膜、阳极氧化铝膜等)表面，然后转入水浴中进行相转化，10分钟后取出并转入浓度为0.001mol/L的KOH水溶液中进行生成离子化亲水官能团的反应，5分钟后将其从KOH水溶液中取出，用清水洗去多余的KOH，即得表面包覆抗油粘附涂层的高分子膜或陶瓷膜(高分子膜或陶瓷膜的孔径在0.001μm～100μm范围内可选)。表面包覆抗油粘附涂层的高分子膜和陶瓷膜的水下石油接触角均大于150°，水下石油滚动角均小于10°，水下石油粘附力均小于10μN。
实施例15：将石油倾倒在实施例3中的表面包覆抗油粘附涂层的乳胶手套上将其污染；同时将石油倾倒在表面未涂覆抗油粘附涂层的相同乳胶手套上将其污染作为对照。将两个手套同时放到相同的纯水中，表面包覆抗油粘附涂层的乳胶手套上的石油自动脱落，手套实现自清洁；表面未包覆抗油粘附涂层的乳胶手套上的石油仍牢牢粘附在手套表面，未有丝毫脱落，手套不能实现自清洁。表面包覆抗油粘附涂层的乳胶手套在水中的自清洁性能参阅图5。
此外，本案发明人还参照实施例1-15的实施方案，以浓度为0.001wt％、0.005wt％、0.01wt％、0.05wt％、0.1wt％、0.5wt％、15wt％、20wt％、25wt％、30wt％、35wt％、40wt％的 高分子溶液作为原料制备了膜或涂层，其也均具有抗油粘附的性能。
实施例16：将石油和水按照体积比为1：1混合，形成油水混合物，将该油水混合物通过包含实施例6中表面包覆抗油粘附涂层的400目铜网的一种油水分离装置进行分离，表面包覆抗油粘附涂层的铜网的孔径为25μm～30μm。该油水分离装置的结构及其工作原理可以参阅图8。通过分离，石油被表面包覆抗油粘附涂层的铜网有效截留并实现富集和回收，水通过表面包覆抗油粘附涂层的铜网并实现纯化，表面包覆抗油粘附涂层的铜网在水中可实现自清洁并长期重复利用。分离过程中水通量为47000±3000L/(m2hbar)，分离后纯化水中的油含量通过总有机碳测定仪测定为0.5ppm(即质量分数百万分之零点五)。表面包覆抗油粘附涂层的铜网的油水分离性能参阅图8。
实施例17：将柴油和水按照质量比为1：9混合，加入浓度为0.1g/L的十二烷基苯磺酸钠作为乳化性剂，在2000rpm的转速下搅拌2小时，配置油水乳液，将该油水乳液通过包含实施例11中抗油粘附分离膜的一种油水分离装置(其结构和原理亦可参阅图8)进行分离，这些膜的有效孔径约为0.01μm。通过分离，乳化的柴油被抗油粘附分离膜有效截留并实现富集和回收，水通过抗油粘附分离膜并实现纯化。分离过程中水通量为550L/(m2hbar)，分离后纯化水中的油含量通过总有机碳测定仪测定为3ppm(即质量分数百万分之三)。
实施例18：将染料考马斯亮蓝溶于水配置成浓度为50mg/L的溶液，将该溶液通过包含实施例12中抗油粘附分离膜的分离装置进行分离，这些膜的有效孔径约为0.002μm。通过分离，考马斯亮蓝被抗油粘附分离膜有效截留，水通过分离膜并实现纯化。分离过程中水通量为130L/(m2hbar)，分离后纯化水中的考马斯亮蓝的有效截留率通过紫外可见分光光度仪测定为98.0％。分离后被截留在分离膜上的染料可通过简单水洗除去。
实施例19：将牛血清蛋白溶于水配置成浓度为5g/L的溶液，将该溶液通过包含实施例13中抗油粘附膜的分离装置进行分离，这些膜的有效孔径约为0.002μm。通过分离，牛血清蛋白被抗油粘附分离膜有效截留，水通过分离膜并实现纯化。分离过程中水通量为125L/(m2hbar)，分离后纯化水中的牛血清蛋白的有效截留率通过紫外可见分光光度仪测定为98.5％。分离后被截留在分离膜上的蛋白可通过简单水洗除去。
实施例20：将CuSO4溶于水配置成浓度为2000ppm的溶液，将该溶液通过包含实施例14中表面包覆抗油粘附涂层的阳极氧化铝膜的分离装置进行分离。分离过程中水通量为120L/(m2hbar)，分离后水中的Na2SO4的截留率通过电导率仪测定为56.2％。
从以上对比结果中可以看出，在使用非本申请公开的原料时，或原料中不含本申请公开的特定的修饰基团时，即使通过本申请公开的制备方法也无法得到对高粘度油具有水中超疏 和超低粘附性能的高分子材料。
应当理解，本申请所揭示的乃较佳实施例的一种或多种，凡是局部的变更或修饰而源于本申请的技术思想而为熟悉该项技术的人所易于推知的，俱不脱离本申请的专利权范围。

Claims (40)

  1. 一种高分子材料，其特征在于：所述高分子材料由含可离子化的亲水基团的高分子化合物经相转化且所含亲水基团被离子化后形成，同时所述高分子材料在水中对油相体系的静态接触角大于140°，粘附力小于10μN。
  2. 根据权利要求1所述的高分子材料，其特征在于：所述高分子化合物的亲水基团是在所述高分子化合物被碱性溶液充分浸渍后而被离子化的。
  3. 根据权利要求2所述的高分子材料，其特征在于：所述碱性溶液中所含的碱性物质包括NaOH、KOH、氨水或Na2CO3。
  4. 根据权利要求2所述的高分子材料，其特征在于：所述碱性溶液中所含的溶剂为所述高分子化合物的不良溶剂。
  5. 根据权利要求4所述的高分子材料，其特征在于：所述溶剂包括水、甲醇、乙醇、乙二醇、异丙醇或正丁醇。
  6. 根据权利要求2所述的高分子材料，其特征在于：所述碱性溶液的浓度为0.001mol/L～10mol/L。
  7. 根据权利要求1所述的高分子材料，其特征在于：所述高分子化合物包括至少修饰有磺酸基、磷酸基、羧基、酰胺基、醇羟基、季铵盐、胺基、醇胺基、氰基中的任意一种或两种以上的脂肪族聚合物或芳香族聚合物。
  8. 根据权利要求7所述的高分子材料，其特征在于：所述脂肪族聚合物包括聚乙烯、聚丙烯、聚丙烯腈、聚偏氟乙烯、聚六氟丙烯中的任意一种或两种以上的共聚物。
  9. 根据权利要求7所述的高分子材料，其特征在于：所述芳香族聚合物包括聚醚砜、聚醚酮、聚吡咙、聚吡咯、聚咔唑中的任意一种或两种以上的共聚物。
  10. 根据权利要求7所述的高分子材料，其特征在于：所述高分子化合物选自磺化聚醚砜、二乙醇胺接枝的聚咔唑、聚丙烯腈、甲基咪唑修饰的聚苯醚、聚丙烯酰胺接枝的聚苯乙烯-二苯乙烯共聚物、磷酸酯接枝的聚醚酮、聚丙烯酸接枝的聚偏氟乙烯、聚乙烯基磺酸接枝的聚醚砜、聚丙烯酸接枝的聚碳酸酯、聚马来酸酐接枝的聚偏氟乙烯中的任意一种或两种以上的组合。
  11. 根据权利要求1-10中任一项所述的高分子材料，其特征在于：所述相转化是与所述离子化是一步完成的。
  12. 根据权利要求1-10中任一项所述的高分子材料，其特征在于：所述离子化是在所述 相转化完成后于碱性溶液中进行的。
  13. 由权利要求1-12中任一项所述的高分子材料组成的膜或涂层。
  14. 根据权利要求13所述的膜或涂层，其特征在于：所述膜或涂层为多孔膜，多孔涂层或无孔涂层。
  15. 一种膜或涂层的制备方法，其特征在于包括：
    提供高分子化合物溶液，其中包括含可离子化的亲水基团的高分子化合物；
    以所述高分子化合物溶液涂覆或浸渍基材，使所述高分子化合物涂敷或吸附于所述基体上，形成高分子化合物层；
    以碱性溶液充分浸渍所述高分子化合物层而使高分子化合物实现相转化，同时使所述高分子化合物中的亲水基团离子化，从而于所述基材上形成所述膜或涂层，
    或者，将所述高分子化合物层中的高分子化合物湿法相转化，之后再以碱性溶液充分浸渍而使高分子化合物中的亲水基团离子化，从而于所述基材上形成所述膜或涂层。
  16. 根据权利要求15所述的制备方法，其特征在于：所述碱性溶液中所含的碱性物质包括NaOH、KOH、氨水或碳酸钠。
  17. 根据权利要求15所述的制备方法，其特征在于：所述碱性溶液中所含的溶剂为所述高分子化合物的不良溶剂。
  18. 根据权利要求17所述的制备方法，其特征在于：所述溶剂包括水、甲醇、乙醇、乙二醇、异丙醇或正丁醇。
  19. 根据权利要求15所述的制备方法，其特征在于：所述碱性溶液的浓度为0.001mol/L～10mol/L。
  20. 根据权利要求15所述的制备方法，其特征在于：所述高分子化合物包括至少修饰有磺酸基、磷酸基、羧基、酰胺基、醇羟基、季铵盐、胺基、醇胺基、氰基中的任意一种或两种以上的脂肪族聚合物或芳香族聚合物。
  21. 根据权利要求20所述的制备方法，其特征在于：所述脂肪族聚合物包括聚乙烯、聚丙烯、聚丙烯腈、聚偏氟乙烯、聚六氟丙烯中的任意一种或两种以上的共聚物。
  22. 根据权利要求20所述的制备方法，其特征在于：所述芳香族聚合物包括聚醚砜、聚醚酮、聚吡咙、聚吡咯、聚咔唑中的任意一种或两种以上的共聚物。
  23. 根据权利要求20所述的制备方法，其特征在于：所述高分子化合物选自磺化聚醚砜、二乙醇胺接枝的聚咔唑、聚丙烯腈、甲基咪唑修饰的聚苯醚、聚丙烯酰胺接枝的聚苯乙烯-二苯乙烯共聚物、磷酸酯接枝的聚醚酮、聚丙烯酸接枝的聚偏氟乙烯、聚乙烯基磺酸接枝的 聚醚砜、聚丙烯酸接枝的聚碳酸酯、聚马来酸酐接枝的聚偏氟乙烯中的任意一种或两种以上的组合。
  24. 根据权利要求15所述的制备方法，其特征在于：所述高分子化合物溶液中的溶剂包括N-甲基吡咯烷酮、三氯甲烷，二氧六环、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、间甲酚、二苯砜、二苯醚、四氢呋喃、二甲基亚砜中的任意一种或两种以上的组合。
  25. 根据权利要求15所述的制备方法，其特征在于：所述高分子溶液的浓度为0.001wt％～40wt％。
  26. 根据权利要求15所述的制备方法，其特征在于：所述基材包括丝网、织物、无纺布、板材中的任意一种。
  27. 权利要求1-12中任一项所述的高分子材料或权利要求13-14中任一项所述的膜或涂层于制备油水分离结构、防油涂层结构、水中高粘度油收集装置、染料分离装置、蛋白分离装置、重金属离子分离装置、食品加工装置、血液处理装置或者废水处理装置中的用途。
  28. 一种油水分离装置，其特征在于包括：
    由权利要求1-12中任一项所述高分子材料形成的油水分离膜，
    或者，油水分离元件，包括基材，所述基材的至少局部表面覆设有由权利要求1-12中任一项所述高分子材料形成的涂层；
    所述油水分离膜、油水分离元件中形成有可供油水混合物中的水相通过而阻隔油相的孔道，至少是所述孔道的局部的孔壁由所述高分子材料形成。
  29. 根据权利要求28所述的油水分离装置，其特征在于：所述油水分离元件包含有由表面包覆有所述高分子材料的网格线交叉形成的网格结构。
  30. 根据权利要求28-29中任一项所述的油水分离装置，其特征在于：所述基材包括丝网、织物、无纺布或板材。
  31. 根据权利要求28所述的油水分离装置，其特征在于还包括支撑结构，所述支撑结构与所述油水分离膜或油水分离元件固定连接。
  32. 根据权利要求28所述的油水分离装置，其特征在于：所述油水混合物包括非乳化的油水混合物或油水乳液。
  33. 一种水中高粘度油收集装置，其特征在于包括：
    由权利要求1-12中任一项所述高分子材料形成的油水分离膜，
    或者，油水分离元件，包括基材，所述基材的至少局部表面覆设有由权利要求1-12中任一项所述高分子材料形成的涂层，
    所述油水分离膜、油水分离元件中形成有可供水或水溶液通过而截留油的孔道，至少是所述孔道的局部的孔壁由所述高分子材料形成；优选的，所述孔道的孔径大于0而小于500μm；
    以及，容置空间，至少用以容置所述油水分离膜或油水分离元件截留的油。
  34. 根据权利要求33所述的水中高粘度油收集装置，其特征在于：所述油水分离元件包含有由表面包覆有所述高分子材料的网格线交叉形成的网格结构。
  35. 根据权利要求33-34中任一项所述的水中高粘度油收集装置，其特征在于：所述基材包括丝网、织物、无纺布或板材。
  36. 根据权利要求33所述的水中高粘度油收集装置，其特征在于还包括支撑结构，所述支撑结构与所述油水分离膜或油水分离元件固定连接。
  37. 根据权利要求33所述的水中高粘度油收集装置，其特征在于：所述高粘度油包括石油、重油、硅油或重柴油。
  38. 一种微滤装置，其特征在于包含：
    由权利要求1-12中任一项所述高分子材料形成的微滤膜，
    或者，微滤元件，包括基材，所述基材的至少局部表面覆设有由权利要求1-12中任一项所述高分子材料形成的涂层，
    所述微滤膜或微滤元件中形成有微滤通道，至少是所述微滤通道的局部的内壁由所述高分子材料形成；优选的，所述微滤通道的孔径为0.01μm～500μm。
  39. 一种超滤装置，其特征在于包含：
    由权利要求1-12中任一项所述高分子材料形成的超滤膜，
    或者，超滤元件，包括基材，所述基材的至少局部表面覆设有由权利要求1-12中任一项所述高分子材料形成的涂层，
    所述超滤膜或超滤元件中形成有超滤通道，至少是所述超滤通道的局部的内壁由所述高分子材料形成；优选的，所述超滤通道的孔径为0.002μm～0.1μm。
  40. 一种纳滤装置，其特征在于包含：
    由权利要求1-12中任一项所述高分子材料形成的纳滤膜，
    或者，纳滤元件，包括基材，所述基材的至少局部表面覆设有由权利要求1-12中任一项所述高分子材料形成的涂层，
    所述纳滤膜或纳滤元件中形成有纳滤通道，至少是所述纳滤通道的局部的内壁由所述高分子材料形成；优选的，所述纳滤通道的孔径大于0而小于0.002μm。
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