WO2024239647A1 - 一种co2-光热双重响应型纳米乳液分离膜及其制备方法及其应用 - Google Patents

一种co2-光热双重响应型纳米乳液分离膜及其制备方法及其应用 Download PDF

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WO2024239647A1
WO2024239647A1 PCT/CN2023/141755 CN2023141755W WO2024239647A1 WO 2024239647 A1 WO2024239647 A1 WO 2024239647A1 CN 2023141755 W CN2023141755 W CN 2023141755W WO 2024239647 A1 WO2024239647 A1 WO 2024239647A1
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responsive
separation membrane
nanoemulsion
photothermal
dual
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French (fr)
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董亮亮
汪杨杨
董飞飞
朱博
白云翔
张春芳
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Jiangnan University
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Jiangnan University
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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
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • 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
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/08—Thickening liquid suspensions by filtration
    • B01D17/085—Thickening liquid suspensions by filtration with membranes
    • 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
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B01D67/00791—Different components in separate layers
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • 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
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B01D71/0211—Graphene or derivates thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B01D71/0212—Carbon nanotubes
    • 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
    • B01D71/02—Inorganic material
    • B01D71/04—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/48—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • B01D2325/0282—Dynamic pores-stimuli responsive membranes, e.g. thermoresponsive or pH-responsive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/38—Hydrophobic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/39—Amphiphilic membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil

Definitions

  • the present invention belongs to the technical field of chemical separation, and relates to an oil-water separation membrane, and in particular to a CO 2 -photothermal dual-response nanoemulsion separation membrane, and a preparation method and a use method thereof.
  • Stimuli-responsive separation membranes are a type of intelligent separation membrane that can spontaneously regulate the physicochemical properties of the membrane by "sensing" changes in the surrounding environment to achieve reversible regulation of membrane flux and selectivity. This characteristic makes it flexible and controllable in the actual oil-water separation process.
  • responsive separation membranes Compared with traditional stimulus sources (such as pH, light, heat, redox, etc.), using CO2 as a stimulus source to construct responsive separation membranes has incomparable advantages, such as no membrane pollution, no damage to membrane structure, no accumulation of chemical substances, good response depth, high cycle stability, etc., which is currently a research hotspot in the field of responsive separation membranes.
  • the existing CO2- responsive separation membranes can only be used for the separation of immiscible oil-water mixtures, and it is difficult to achieve efficient separation for various stable emulsion systems.
  • problems such as cumbersome membrane preparation process, low efficiency, and difficulty in large-scale preparation.
  • CO2- stimulated responsive polymers are usually protonated in the presence of CO2 and then deprotonated when an inert gas is introduced.
  • the deprotonation process by introducing an inert gas is time-consuming. This is because the solubility of inert gases in aqueous solutions is low, resulting in a slow deprotonation process on the membrane surface, which causes the membrane to respond to the inert gas for a long time (usually more than 20 minutes), which greatly limits the industrial application of such separation membranes.
  • the technical problem to be solved by the present invention is to provide a nanoemulsion separation membrane that can be rapidly deprotonated and can achieve rapid switching back and forth between hydrophobic/oleophilic and hydrophilic/underwater oleophobic wettability.
  • the first object of the present invention is to provide a CO2 -photothermal dual-responsive nanoemulsion separation membrane, wherein the nanoemulsion separation membrane is woven from fibers having a three-layer structure, wherein the inner core is fibers, the middle layer is a photothermal conversion functional coating, and the outer layer is a CO2 responsive functional coating; the photothermal conversion functional coating is prepared from carbon-based nanomaterials and polyvinyl alcohol; the CO2 responsive functional coating is obtained by free radical polymerization of a CO2 responsive monomer and a hard monomer; and the pore size distribution of the separation membrane is below 0.1 um.
  • the photothermal conversion layer is made of a hydrophilic material and is easily fallen off when exposed to the outside in a water environment. Therefore, it needs to be covered with an outer CO2 response layer to prevent it from falling off.
  • the fiber material comprises PET, polyester, acrylic, nylon, spandex, carbon fiber or glass;
  • the carbon-based nanomaterial includes one or more of carbon black, carbon nanotubes, graphene, graphene oxide and reduced graphene oxide;
  • the CO2- responsive monomer includes N,N-dimethylphenylene (DMSt), dimethylaminoethyl methacrylate (DMAEMA) or diethylaminoethyl methacrylate (DEAEMA);
  • the hard monomers include styrene (ST), hydroxyethyl methacrylate (HEMA), acrylamide (AM), methyl methacrylate (MMA), polyethylene glycol methacrylate (PEGMA), and 2-ethoxyethyl methacrylate (EEMA).
  • ST styrene
  • HEMA hydroxyethyl methacrylate
  • AM acrylamide
  • MMA methyl methacrylate
  • PEGMA polyethylene glycol methacrylate
  • EEMA 2-ethoxyethyl methacrylate
  • the mass ratio of the carbon-based nanomaterial to polyvinyl alcohol is 3:1000-10:1000.
  • the mass ratio of the carbon-based nanomaterial to polyvinyl alcohol is 3:1000.
  • the ratio of the CO2 responsive monomer to the hard monomer is a molar ratio of 1:1-1:2.
  • the ratio of the CO2 responsive monomer to the hard monomer is a molar ratio of 1:1.
  • the second object of the present invention is to provide a method for preparing a CO 2 -photothermal dual-responsive nanoemulsion separation membrane, the steps of which are as follows:
  • photothermal conversion functional coating 7.5-12.5 wt % polyvinyl alcohol and deionized water were added to a flask, and then 0.2-0.5 mg/ml of carbon-based nanomaterial was added, and the mixture was heated and stirred in an oil bath at 90-110° C. for 30-90 min to obtain the photothermal conversion functional coating;
  • Preparation of CO 2 -photothermal dual response fiber Use a sizing machine to evenly coat the photothermal conversion functional coating prepared in S1 on the surface of the PET fiber and heat treat it in an oven at 70-90°C for 2-10 min to obtain the photothermal conversion functional fiber. Then use a sizing machine to evenly coat the CO 2 responsive functional coating prepared in S2 on the surface of the photothermal conversion functional fiber and heat treat it in an oven at 70-90°C for 2-10 min to obtain the CO 2 -photothermal dual response fiber.
  • CO 2 -photothermal dual-responsive nanoemulsion separation membrane Preparation of CO 2 -photothermal dual-responsive nanoemulsion separation membrane: The CO 2 -photothermal dual-responsive fibers prepared in S3 are woven into a membrane using a loom to obtain a CO 2 -photothermal dual-responsive nanoemulsion separation membrane.
  • the CO2 responsive functional coating in step S2 is a transparent material, and the light transmittance of the coating after film formation is 85-92%.
  • the third object of the present invention is to provide an application of a CO 2 -photothermal dual-responsive nanoemulsion separation membrane, wherein the nanoemulsion separation membrane can achieve reversible switching between super-hydrophobic and super-hydrophilic states under CO 2 or photothermal stimulation.
  • the CO 2 stimulation is to place the nanoemulsion separation membrane in a water environment and pass CO 2 for 5 minutes; the photothermal stimulation is to raise the temperature of the nanoemulsion separation membrane to 120-180° C. within 10-20 seconds under the irradiation of a near-infrared light source.
  • the nanoemulsion separation membrane separates an oil-water mixture
  • the hydrophobic/oleophilic membrane in the initial state is used for separation
  • the hydrophobic/oleophilic separation membrane is placed in a water environment and CO2 is introduced for 5 minutes to convert it into a hydrophilic/underwater oleophobic separation membrane before separation
  • the hydrophilic/underwater oleophobic separation membrane is placed in a water environment and irradiated with a 1.2V 808nm near-infrared light source for 1 minute to convert it into a hydrophobic/oleophilic separation membrane again before separation.
  • the separation membrane can achieve reversible switching between superhydrophobic and superhydrophilic states under alternating CO 2 -light stimulation.
  • the water contact angle (WCA) of the membrane is above 150° (superhydrophobic).
  • the WCA drops to 0° (superhydrophilic).
  • the WCA is again increased to above 150° (superhydrophobic).
  • the membrane After the separation membrane provided by the present invention is stimulated by CO2 , the membrane is converted into a hydrophilic state, allowing water to pass through. Since the membrane surface is occupied by water, oil droplets cannot contact and pass through the membrane, thereby achieving the retention of oil droplets; conversely, after being stimulated by near-infrared light, photothermal energy is provided to enable the hydrophilic CO2 polymer to quickly restore to a hydrophobic state, allowing oil to pass through. Since the membrane surface is occupied by oil, water droplets cannot contact and pass through the membrane, thereby achieving the retention of water droplets.
  • the separation membrane of the present invention has excellent photothermal performance. Under the irradiation of near-infrared light, the temperature of the membrane surface can be greatly increased within 15 seconds, thereby realizing the transition of the membrane from protonated to deprotonated state within 1 minute. Compared with inert gas stimulation, the response time of the membrane is shortened by more than 20 times.
  • the separation efficiency of 20nm oil-in-water emulsion in super-hydrophobic state is more than 99.5%
  • the separation efficiency of 20nm water-in-oil emulsion in hydrophilic state is more than 99.5%.
  • the separation membrane of the present invention has a narrow distribution of submicron pores and can achieve separation of nanoemulsions.
  • the separation membrane of the present invention is easy to prepare on a large scale, and a separation membrane with an area of 4800 cm2 can be easily prepared.
  • Figure 1 is a schematic diagram of the membrane preparation process, transitioning from a blank membrane to a photothermal functional coating membrane and then to a CO 2 -photothermal dual response membrane.
  • Figure 2 is a SEM image of a fiber cross-section with a photothermal functional coating and a CO2 responsive functional coating.
  • the inner layer is the photothermal functional coating, in which graphene oxide powder within 2 ⁇ m can be seen, and the outer layer is the CO2 responsive functional coating, which is smoother and more uniform than the inner layer.
  • FIG3 shows SEM images and optical photographs, wherein A is a blank film, B is a photothermal functional coating film, and C is a CO 2 -photothermal dual response film.
  • the carbon-based nanomaterial used in this embodiment is graphene oxide, and the polymer is formed by free radical polymerization of two monomers, CO2- responsive monomer DMAEMA and hard monomer HEMA, in a solvent.
  • the amount of initiator used is 1% of the total mass of DMAEMA monomer and HEMA monomer.
  • the method for preparing the CO 2 -photothermal dual-responsive nanoemulsion separation membrane-1 is characterized by comprising the following specific steps:
  • Preparation of CO 2 -photothermal dual response fiber Use a sizing machine to evenly coat the photothermal conversion functional coating prepared in S1 on the surface of the PET fiber and heat treat it in an oven at 70°C for 2 min to obtain the photothermal conversion functional fiber. Then use a sizing machine to evenly coat the CO 2 responsive functional coating prepared in S2 on the surface of the photothermal conversion functional fiber and heat treat it in an oven at 70°C for 2 min to obtain the CO 2 -photothermal dual response fiber.
  • CO 2 -photothermal dual-responsive nanoemulsion separation membrane Preparation of CO 2 -photothermal dual-responsive nanoemulsion separation membrane: The CO 2 -photothermal dual-responsive fiber prepared in S3 was woven into a membrane using a loom at a sum of warp density and weft density of 300T to obtain CO 2 -photothermal dual-responsive nanoemulsion separation membrane-1.
  • the PPGOM in Figure 1 is a schematic diagram of the membrane prepared in this embodiment, whose core is PET fiber, the middle layer is graphene oxide coating, and the outer layer is copolymer coating;
  • Figure 2 corresponds to the SEM image of the cross-section of the fiber with photothermal functional coating and CO2 response functional coating in this embodiment, whose inner layer is the photothermal functional coating in which graphene oxide flakes within 2 um can be seen, and the outer layer is the CO2 response functional coating, which is smoother and more uniform than the inner layer;
  • Figure 3C corresponds to the SEM image of the membrane prepared in this embodiment. Compared with the membrane without CO2 response coating in Figure 3B, its color is darker and the surface is smoother.
  • the hydrophobic/oleophilic CO 2 -photothermal dual responsive nanoemulsion separation membrane-1 was placed in a water environment and CO 2 was introduced for 5 min to obtain a hydrophilic/underwater oleophobic CO 2 -photothermal dual responsive nanoemulsion separation membrane-1.
  • the water contact angle of the membrane in air was measured using a contact angle meter, and the contact angle was measured to be 0°.
  • the hydrophilic/underwater oleophobic CO 2 -photothermal dual responsive nanoemulsion separation membrane-1 was irradiated with a 1.2V 808nm near-infrared light source for 1 min to obtain the hydrophobic/oleophilic CO 2 -photothermal dual responsive nanoemulsion separation membrane-1 again.
  • the water contact angle of the membrane in the air was measured using a contact angle meter, and the contact angle was measured to be 151.2°.
  • the hydrophobic/oleophilic separation membrane When the mixture type is an oil-in-water nanoemulsion, the hydrophobic/oleophilic separation membrane is placed in a water environment and CO 2 is introduced for 5 min to convert it into a hydrophilic/underwater oleophobic separation membrane, and then separation is performed.
  • the separation performance test data are shown in Table 1;
  • the hydrophilic/underwater oleophobic separation membrane is irradiated with a 1.2V 808nm near-infrared light source for 1 minute and converted back into a hydrophobic/oleophilic separation membrane before separation.
  • the separation efficiency of the prepared separation membrane for isooctane oil-in-water nanoemulsion (20 nm) and oil-in-water nanoemulsion (20 nm) can be maintained above 99%.
  • the carbon-based nanomaterial used in this embodiment is graphene, and the polymer is formed by free radical polymerization of two monomers, DMSt, a CO2- responsive monomer, and HEMA, a hard monomer, in a solvent.
  • the amount of initiator used is 1% of the total mass of the DMSt monomer and the HEMA monomer.
  • the method for preparing the CO 2 -photothermal dual-responsive nanoemulsion separation membrane-2 is characterized by comprising the following specific steps:
  • Preparation of CO 2 -photothermal dual response fiber Use a sizing machine to evenly coat the photothermal conversion functional coating prepared in S1 on the surface of acrylic fiber and heat treat it in an oven at 80°C for 5 min to obtain photothermal conversion functional fiber. Then use a sizing machine to evenly coat the CO 2 responsive functional coating prepared in S2 on the surface of photothermal conversion functional fiber and heat treat it in an oven at 80°C for 5 min to obtain CO 2 -photothermal dual response fiber.
  • CO 2 -photothermal dual-responsive nanoemulsion separation membrane Preparation of CO 2 -photothermal dual-responsive nanoemulsion separation membrane: The CO 2 -photothermal dual-responsive fiber prepared in S3 was woven into a membrane using a loom at a sum of warp density and weft density of 330T to obtain CO 2 -photothermal dual-responsive nanoemulsion separation membrane-2.
  • the hydrophobic/oleophilic CO 2 -photothermal dual responsive nanoemulsion separation membrane-2 was placed in a water environment and CO 2 was introduced for 8 minutes to obtain a hydrophilic/underwater oleophobic CO 2 -photothermal dual responsive nanoemulsion separation membrane-2.
  • the water contact angle of the membrane in the air was measured using a contact angle meter, and the contact angle was measured to be 0°.
  • the hydrophilic/underwater oleophobic CO 2 -photothermal dual responsive nanoemulsion separation membrane-2 was irradiated with a 1.5V 780nm near-infrared light source for 1.5min to obtain the hydrophobic/oleophilic CO 2 -photothermal dual responsive nanoemulsion separation membrane-2 again.
  • the water contact angle of the membrane in the air was measured using a contact angle meter, and the contact angle was measured to be 150.6°.
  • the hydrophobic/oleophilic separation membrane When the mixture type is an oil-in-water nanoemulsion, the hydrophobic/oleophilic separation membrane is placed in a water environment and CO 2 is introduced for 8 min to convert it into a hydrophilic/underwater oleophobic separation membrane, and then separation is performed.
  • the separation performance test data are shown in Table 1;
  • the hydrophilic/underwater oleophobic separation membrane is irradiated with a 1.5V 780nm near-infrared light source for 1.5 minutes and converted back into a hydrophobic/oleophilic separation membrane before separation.
  • the separation efficiency of the prepared separation membrane for isooctane oil-in-water nanoemulsion (20 nm) and oil-in-water nanoemulsion (20 nm) can be maintained above 99%.
  • the carbon-based nanomaterial used in this embodiment is carbon nanotubes, and the polymer is formed by free radical polymerization of two monomers, CO2 - responsive monomer DMSt and hard monomer AEMA, in a solvent.
  • the amount of initiator used is 1% of the total mass of DMSt monomer and AEMA monomer.
  • the method for preparing the CO 2 -photothermal dual-responsive nanoemulsion separation membrane-3 is characterized by comprising the following specific steps:
  • Preparation of CO 2 -photothermal dual response fiber Use a sizing machine to evenly coat the photothermal conversion functional coating prepared in S1 on the surface of nylon fiber and heat treat it in an oven at 90°C for 10 min to obtain photothermal conversion functional fiber. Then use a sizing machine to evenly coat the CO 2 responsive functional coating prepared in S2 on the surface of photothermal conversion functional fiber and heat treat it in an oven at 90°C for 10 min to obtain CO 2 -photothermal dual response fiber.
  • CO 2 -photothermal dual-responsive nanoemulsion separation membrane Preparation of CO 2 -photothermal dual-responsive nanoemulsion separation membrane: The CO 2 -photothermal dual-responsive fiber prepared in S3 was woven into a membrane using a loom at a sum of warp density and weft density of 350T to obtain CO 2 -photothermal dual-responsive nanoemulsion separation membrane-3.
  • the hydrophobic/oleophilic CO 2 -photothermal dual responsive nanoemulsion separation membrane-3 was placed in a water environment and CO 2 was introduced for 10 min to obtain a hydrophilic/underwater oleophobic CO 2 -photothermal dual responsive nanoemulsion separation membrane-3.
  • the water contact angle of the membrane in air was measured using a contact angle meter, and the contact angle was measured to be 0°.
  • the hydrophilic/underwater oleophobic CO 2 -photothermal dual responsive nanoemulsion separation membrane-3 was irradiated with a 2V 900nm near-infrared light source for 2 min to obtain the hydrophobic/oleophilic CO 2 -photothermal dual responsive nanoemulsion separation membrane-3 again.
  • the water contact angle of the membrane in the air was measured using a contact angle meter, and the contact angle was measured to be 152.3°.
  • the hydrophobic/oleophilic separation membrane When the mixture type is an oil-in-water nanoemulsion, the hydrophobic/oleophilic separation membrane is placed in a water environment and CO 2 is introduced for 10 min to convert it into a hydrophilic/underwater oleophobic separation membrane, and then separation is performed.
  • the separation performance test data are shown in Table 1;
  • the hydrophilic/underwater oleophobic separation membrane is irradiated with a 2V 900nm near-infrared light source for 2 minutes to be converted back into a hydrophobic/oleophilic separation membrane before separation.
  • the separation efficiency of the prepared separation membrane for isooctane oil-in-water nanoemulsion (20 nm) and oil-in-water nanoemulsion (20 nm) can be maintained above 99%.
  • the carbon-based nanomaterial used in this embodiment is redox graphene, and the polymer is formed by free radical polymerization of two monomers, CO2- responsive monomer DMAEMA and hard monomer AEMA, in a solvent.
  • the amount of initiator used is 1% of the total mass of DMAEMA monomer and AEMA monomer.
  • the method for preparing the CO 2 -photothermal dual-responsive nanoemulsion separation membrane-4 is characterized by comprising the following specific steps:
  • Preparation of CO 2 -photothermal dual response fiber Use a sizing machine to evenly coat the photothermal conversion functional coating prepared in S1 on the surface of the polyester fiber and heat treat it in an oven at 75°C for 4 min to obtain the photothermal conversion functional fiber. Then use a sizing machine to evenly coat the CO 2 responsive functional coating prepared in S2 on the surface of the photothermal conversion functional fiber and heat treat it in an oven at 75°C for 4 min to obtain the CO 2 -photothermal dual response fiber.
  • the hydrophobic/oleophilic CO 2 -photothermal dual responsive nanoemulsion separation membrane-4 was placed in a water environment and CO 2 was introduced for 5 min to obtain a hydrophilic/underwater oleophobic CO 2 -photothermal dual responsive nanoemulsion separation membrane-4.
  • the water contact angle of the membrane in the air was measured using a contact angle meter, and the contact angle was measured to be 0°.
  • the hydrophilic/underwater oleophobic CO 2 -photothermal dual responsive nanoemulsion separation membrane-4 was irradiated with a 1.2V 808nm near-infrared light source for 1 min to obtain the hydrophobic/oleophilic CO 2 -photothermal dual responsive nanoemulsion separation membrane-4 again.
  • the water contact angle of the membrane in the air was measured using a contact angle meter, and the contact angle was measured to be 151.0°.
  • the hydrophobic/oleophilic separation membrane When the mixture type is an oil-in-water nanoemulsion, the hydrophobic/oleophilic separation membrane is placed in a water environment and CO 2 is introduced for 5 min to convert it into a hydrophilic/underwater oleophobic separation membrane, and then separation is performed.
  • the separation performance test data are shown in Table 1;
  • the hydrophilic/underwater oleophobic separation membrane is irradiated with a 1.2V 808nm near-infrared light source for 1 minute and converted back into a hydrophobic/oleophilic separation membrane before separation.
  • the separation efficiency of the prepared separation membrane for isooctane oil-in-water nanoemulsion (20 nm) and oil-in-water nanoemulsion (20 nm) can be maintained above 99%.
  • the polymer used in this embodiment is prepared by free radical polymerization of two monomers, CO2 - responsive DMAEMA and hard HEMA, in a solvent.
  • the amount of initiator used is 1% of the total mass of DMAEMA and HEMA monomers.
  • the method for preparing the above-mentioned CO2- responsive nanoemulsion separation membrane is characterized by comprising the following specific steps:
  • PVA coating 7.5 wt% polyvinyl alcohol (PVA) and deionized water were added into a flask, and heated and stirred in an oil bath at 95° C. for 30 min to prepare the PVA coating;
  • Preparation of CO2 responsive fibers Use a sizing machine to evenly coat the PVA coating prepared in S1 on the surface of the PET fiber and heat treat it in an oven at 80°C for 5 min to obtain the PVA coated fiber. Then use a sizing machine to evenly coat the CO2 responsive functional coating prepared in S2 on the surface of the PVA coated fiber and heat treat it in an oven at 80°C for 4 min to obtain the CO2 responsive fiber.
  • CO2- responsive nanoemulsion separation membrane The CO2 - responsive fiber prepared in S3 was woven into a membrane using a loom at a sum of warp density and weft density of 300T to obtain a CO2 - responsive nanoemulsion separation membrane.
  • the polymer used in this embodiment is prepared by free radical polymerization of two monomers, CO2 - responsive DMAEMA and hard HEMA, in a solvent.
  • the amount of initiator used is 1% of the total mass of DMAEMA and HEMA monomers.
  • the method for preparing the above-mentioned CO2- responsive nanoemulsion separation membrane is characterized by comprising the following specific steps:
  • PVA coating 10 wt% polyvinyl alcohol (PVA) and deionized water were added into a flask, and heated and stirred in an oil bath at 95° C. for 1 h to prepare the PVA coating;
  • Preparation of CO2 responsive fibers Use a sizing machine to evenly coat the PVA coating prepared in S1 on the surface of the PET fiber and heat treat it in an oven at 70°C for 2 min to obtain the PVA coated fiber. Then use a sizing machine to evenly coat the CO2 responsive functional coating prepared in S2 on the surface of the PVA coated fiber and heat treat it in an oven at 70°C for 2 min to obtain the CO2 responsive fiber.
  • CO2- responsive nanoemulsion separation membrane The CO2 - responsive fiber prepared in S3 was woven into a membrane using a loom at a sum of warp density and weft density of 300T to obtain a CO2 - responsive nanoemulsion separation membrane.
  • the carbon-based nanomaterial used in this embodiment is graphene oxide, and the polymer is formed by free radical polymerization of two monomers, CO2- responsive monomer DMSt and hard monomer AEMA, in a solvent.
  • the amount of initiator used is 1% of the total mass of DMSt monomer and AEMA monomer.
  • Preparation of CO2 -photothermal dual response fiber Use a sizing machine to evenly coat the CO2 response functional coating prepared in S2 on the surface of the PET fiber and heat treat it in an oven at 90°C for 5 min to obtain the CO2 response functional fiber. Then use a sizing machine to evenly coat the photothermal conversion functional coating prepared in S1 on the surface of the photothermal conversion functional fiber and heat treat it in an oven at 90°C for 5 min to obtain the photothermal/ CO2 dual response fiber.
  • Preparation of photothermal/ CO2 dual-responsive nanoemulsion separation membrane Use a loom to weave the photothermal/ CO2 dual-responsive fiber prepared in S3 into a membrane with a sum of warp density and weft density of 350T to obtain a photothermal/ CO2 dual-responsive nanoemulsion separation membrane.
  • Wettability switching When needed, the hydrophobic/oleophilic photothermal/ CO2 dual-responsive nanoemulsion separation membrane is placed in a water environment and CO2 is introduced for 5 minutes to obtain a hydrophilic/underwater oleophobic photothermal/ CO2 dual-responsive nanoemulsion separation membrane; when needed, the hydrophilic/underwater oleophobic photothermal/ CO2 dual-responsive nanoemulsion separation membrane is irradiated with a 1.2V 808nm near-infrared light source for 1 minute to obtain a hydrophobic/oleophilic photothermal/ CO2 dual-responsive nanoemulsion separation membrane again.
  • the carbon-based nanomaterial used in this embodiment is graphene oxide.
  • Preparation of photothermal responsive fiber Use a sizing machine to evenly coat the photothermal conversion functional coating prepared in S1 on the surface of the PET fiber, and heat treat it in an oven at 70°C for 5 minutes to obtain the photothermal responsive fiber.
  • Wettability switching When necessary, the hydrophobic/oleophilic photothermal responsive nanoemulsion separation membrane was placed in a water environment and CO 2 was introduced for 5 min; when necessary, the hydrophilic/underwater oleophobic photothermal responsive nanoemulsion separation membrane was irradiated with a 1.2V 808nm near-infrared light source for 1 min.
  • the photothermal responsive nanoemulsion separation membrane When necessary, the photothermal responsive nanoemulsion separation membrane is placed in a water environment and CO 2 is introduced for 5 minutes. The water contact angle of the membrane in the air is measured using a contact angle meter, and the contact angle is measured to be 0°.
  • the photothermal responsive nanoemulsion separation membrane was irradiated with a 1.2V 808nm near-infrared light source for 1 min, and the water contact angle of the membrane in the air was measured using a contact angle meter, and the contact angle was measured to be 0°.
  • the separation performance test data is shown in Table 1; when the mixture type is water-in-oil nanoemulsion, the hydrophobic/lipophilic separation membrane is placed in a water environment and CO 2 is introduced for 5 minutes before separation, and the separation performance test data is shown in Table 1; when the oil-in-water nanoemulsion needs to be separated again, a 1.2V 808nm near-infrared light source is used for 1 minute of irradiation before separation. After two cycles of separation, the separation efficiency of the prepared separation membrane for isooctane water-in-oil nanoemulsion (20nm) and oil-in-water nanoemulsion (20nm) dropped to less than 90%.
  • the GOM in Figure 1 corresponds to a schematic diagram of the membrane of this comparative example, wherein the core is PET fiber and the outer layer is a graphene oxide coating.
  • Figure 3B corresponds to a SEM image of the membrane prepared in this comparative example, which has a rougher surface and a lighter color than the membrane with a CO 2 responsive coating in Figure 3C.

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Abstract

本发明公开了一种CO2-光热双重响应型纳米乳液分离膜，涉及化工分离技术领域。所述纳米乳液分离膜具有三层结构的纤维织造而成，内核为纤维，中间层为光热转化功能涂层，外层为CO2响应功能涂层；所述光热转化功能涂层是由碳基纳米材料和聚乙烯醇制备得到；所述CO2响应功能涂层是由CO2响应性单体和硬单体自由基聚合反应得到；所述分离膜孔径分布在0.1um以下。具有优异的光热性能，在近红外光的照射下可在15s内大幅提高膜表面的温度，从而在1min内实现膜从质子化到去质子化状态的转变。

Description

一种CO2-光热双重响应型纳米乳液分离膜及其制备方法及其应用 技术领域
本发明属于化工分离技术领域，涉及油水分离膜，尤其涉及一种CO2-光热双重响应型纳米乳液分离膜及其制备方法和使用方法。
背景技术
频繁的石油泄漏事故以及工业和居民生活污水的大量排放造成严重的环境污染，危害人类健康，因此，开发高效油水分离膜材料成为当前的研究热点之一。刺激响应性分离膜是一类可通过“感知”周围环境变化来自发调控膜的物化性质从而实现对膜通量和选择性的可逆调节的智能分离膜。这种特性使其在实际的油水分离过程中具有灵活性与可控性。相比于传统的刺激源(如，pH、光、热、氧化还原等)，利用CO2作为刺激源来构筑响应性分离膜具有无可比拟的优势，如无膜污染、不损害膜结构、不存在化学物质积累、响应深度好、循环稳定性高等，是目前响应性分离膜领域的研究热点。然而，现有的CO2响应型分离膜仅能用于不相溶油水混合物分离，对于各种稳定的乳液体系难以实现高效分离。此外，还存在制膜过程繁琐、效率低下、难以大面积制备等问题。更重要的是CO2刺激响应聚合物通常是在CO2存在情况下实现质子化，随后在通入惰性气体的情况下实现去质子化，然而通入惰性气体去质子化的过程耗时严重，这是因为惰性气体在水溶液中的溶解度较低，导致膜表面的去质子化过程缓慢，从而造成膜对惰性气体的响应时间较长(通常在20min以上)，这极大地限制了此类分离膜的工业化应用。
发明内容
本发明需要解决的技术问题是：提供一种快速去质子化，能实现在疏水/亲油和亲水/水下疏油润湿性之间快速来回切换的纳米乳液分离膜。
本发明的第一个目的在于，提供一种CO2-光热双重响应型纳米乳液分离膜，所述纳米乳液分离膜具有三层结构的纤维织造而成，内核为纤维，中间层为光热转化功能涂层，外层为CO2响应功能涂层；所述光热转化功能涂层是由碳基纳米材料和聚乙烯醇制备得到；所述CO2响应功能涂层是由CO2响应性单体和硬单体自由基聚合反应得到；所述分离膜孔径分布在0.1um以下。
其中光热转化层为亲水材质，暴露在外侧在水环境中容易脱落，因此需要外层的CO2响应层覆盖以防止其脱落。
在一种实施方式中，所述纤维材料包括PET、涤纶、腈纶、锦纶、氨纶、碳纤维或玻璃；
所述碳基纳米材料包括炭黑、碳纳米管、石墨烯、氧化石墨烯和还原氧化石墨烯中的一种或多种；
所述CO2响应性单体包括N，N-二甲基对苯乙烯(DMSt)、甲基丙烯酸二甲氨基乙酯(DMAEMA)或甲基丙烯酸二乙氨基乙酯(DEAEMA)；
所述硬单体包括苯乙烯(ST)、甲基丙烯酸羟乙酯(HEMA)、丙烯酰胺(AM)、甲基丙烯酸甲酯(MMA)、聚乙二醇甲基丙烯酸酯(PEGMA)、甲基丙烯酸-2-乙氧基乙酯(EEMA)。
在一种实施方式中，所述碳基纳米材料和聚乙烯醇的比例为质量比为3:1000-10:1000。
在一种实施方式中，所述碳基纳米材料和聚乙烯醇的比例为质量比为3:1000。
在一种实施方式中，所述CO2响应性单体和硬单体的比例为摩尔比为1:1-1:2。
在一种实施方式中，所述CO2响应性单体和硬单体的比例为摩尔比为1:1。
本发明的第二个目的在于提供一种CO2-光热双重响应型纳米乳液分离膜的制备方法，步骤如下：
S1、光热转化功能涂料的制备:将7.5-12.5wt％聚乙烯醇和去离子水加入烧瓶中，再加入0.2-0.5mg/ml的碳基纳米材料，在90-110℃油浴锅中加热搅拌30-90min制得光热转化功能涂料；
S2、CO2响应功能涂料的制备：将CO2响应性单体和一种硬单体通过在四氢呋喃中自由基聚合反应制备CO2响应聚合物，将制备的CO2响应聚合物溶于乙醇中制备质量分数5～20wt％的CO2响应功能涂料；
S3、CO2-光热双重响应纤维的制备：使用浆纱机将S1制备的光热转化功能涂料均匀涂覆在PET纤维表面并在烘箱中70-90℃热处理2-10min得到光热转化功能纤维，再使用浆纱机将S2制备的CO2响应功能涂料均匀涂覆在光热转化功能纤维表面，并在烘箱中70-90℃热处理2-10min得到CO2-光热双重响应纤维。
S4、CO2-光热双重响应型纳米乳液分离膜的制备：使用织机将S3所制备的CO2-光热双重响应纤维织造成膜，得到CO2-光热双重响应型纳米乳液分离膜。
在一种实施方式中，步骤S2中所述CO2响应功能涂料为透明材料，涂料成膜后的透光量为85-92％。
本发明的第三个目的在于提供一种CO2-光热双重响应型纳米乳液分离膜的应用，所述纳米乳液分离膜在CO2或光热刺激下实现超疏水与超亲水状态的可逆切换。
在一种实施方式中，所述CO2刺激为将纳米乳液分离膜置于水环境中通CO2 5min；所述光热刺激为将纳米乳液分离膜在近红外光源照射下可以在10～20s内，将自身温度提高至120～180℃。
在一种实施方式中，纳米乳液分离膜对油水混合物进行分离时，当混合物类型为油包水纳米乳液时，使用初始状态下的疏水/亲油的膜进行分离；当混合物类型为水包油纳米乳液时，将疏水/亲油的分离膜置于水环境中通入CO2 5min转化为亲水/水下疏油的分离膜后，再进行分离；需要再次对油包水纳米乳液进行分离时，将亲水/水下疏油的分离膜置于水环境中使用1.2V 808nm近红外光源照射1min再次转化为疏水/亲油的分离膜后，再进行分离。
在一种实施方式中，所述分离膜在CO2-光交替刺激下可实现在超疏水和超亲水状态之间的可逆切换，初始状态下膜的水接触角(WCA)在150°以上(超疏水)，将膜置于水环境中通CO2 5min后WCA降至0°(超亲水)，随后使用近红外光源照射膜1min后WCA再次提升至150°以上(超疏水)。
有益效果：
本发明所提供分离膜经CO2刺激后，膜转化为亲水状态，允许水通过，由于膜表面被水占据，油滴无法接触并透过膜，实现了对油滴的截留；反之经近红外光刺激后，光热通过提供能量使亲水的CO2聚合物快速恢复疏水状态，允许油通过，由于膜表面被油占据，水滴无法接触并透过膜，实现对水滴的截留。
本发明所述分离膜具有优异的光热性能，在近红外光的照射下可在15s内大幅提高膜表面的温度，从而在1min内实现膜从质子化到去质子化状态的转变。相比于惰性气体刺激，膜的响应时间缩短了20倍以上。其中在超疏水状态下对20nm油包水乳液分离效率在99.5％以上，在亲水状态下对20nm水包油乳液分离效率在99.5％以上。
本发明所述分离膜具有窄分布亚微米级孔径，可以实现对纳米乳液的分离。
本发明所述分离膜易于大规模制备，能轻松制备出面积4800cm2的分离膜。
附图说明
图1为膜的制备过程示意图，从空白膜过渡为光热功能涂层膜再到CO2-光热双重响应膜。
图2为附有光热功能涂层和CO2响应功能涂层的纤维截面SEM图像，其内层为光热功能涂层能看见2um以内的氧化石墨烯粉末，外层为CO2响应功能涂层，较内层光滑均匀。
图3为SEM图像和光学照片，其中A为空白膜，B为光热功能涂层膜，C为CO2-光热双重响应膜。
具体实施方式
CO2-光热双重响应型纳米乳液分离膜的制备过程如图1所示。
实施例1 CO2-光热双重响应型纳米乳液分离膜-1的制备
在本实施例中所使用的碳基纳米材料为氧化石墨烯，聚合物由CO2响应性单体DMAEMA和硬单体HEMA两种单体在溶剂中自由基聚合而成。引发剂用量为DMAEMA单体和HEMA单体总质量的1％。
用于制备上述CO2-光热双重响应型纳米乳液分离膜-1的方法，其特征在于，包括如下具体步骤：
S1、光热转化功能涂料的制备:将7.5wt％聚乙烯醇(PVA)和去离子水加入烧瓶中，再加入0.2mg/ml的氧化石墨烯，在90℃油浴锅中加热搅拌30min制得光热转化功能涂料；
S2、CO2响应功能涂料的制备：将DMAEMA单体和HEMA单体按1:0.5质量比溶解于四氢呋喃中，加入引发剂偶氮二异丁腈，在氮气氛围中加热搅拌反应24小时，加热温度为65℃，加入过量的正己烷析出聚合物，取出沉淀的聚合物在烘箱中烘干，将制备的CO2响应聚合物溶于溶剂中制备质量分数5wt％的CO2响应功能涂料；涂料成膜后的透光量为92％。
S3、CO2-光热双重响应纤维的制备：使用浆纱机将S1制备的光热转化功能涂料均匀涂覆在PET纤维表面并在烘箱中70℃热处理2min得到光热转化功能纤维，再使用浆纱机将S2制备的CO2响应功能涂料均匀涂覆在光热转化功能纤维表面，并在烘箱中70℃热处理2min得到CO2-光热双重响应纤维。
S4、CO2-光热双重响应型纳米乳液分离膜的制备：使用织机将S3所制备的CO2-光热双重响应纤维按经密纬密之和为300T织造成膜，得到CO2-光热双重响应型纳米乳液分离膜-1。
图1的PPGOM为本实施例中所制备膜的示意图，其内核为PET纤维，中间层为氧化石墨烯涂层，外层为共聚物涂层；图2对应本实施例的附有光热功能涂层和CO2响应功能涂层的纤维截面SEM图像，其内层为光热功能涂层能看见2um以内的氧化石墨烯微片，外层为CO2响应功能涂层，较内层光滑均匀；图3C对应本实施例所制备膜的SEM图像，与图3B没有CO2响应涂层的膜相比，其颜色更深，且表面更加光滑。
实施例2 CO2-光热双重响应型纳米乳液分离膜-1的润湿性切换过程
在需要时，将疏水/亲油的CO2-光热双重响应型纳米乳液分离膜-1置于水环境中通入CO25min得到亲水/水下疏油的CO2-光热双重响应型纳米乳液分离膜-1，使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为0°。
在需要时将亲水/水下疏油的CO2-光热双重响应型纳米乳液分离膜-1使用1.2V 808nm近红外光源照射1min再次得到疏水/亲油的CO2-光热双重响应型纳米乳液分离膜-1，使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为151.2°。
实施例3 CO2-光热双重响应型纳米乳液分离膜-1的性能检测
使用CO2-光热双重响应型纳米乳液分离膜-1对油水混合物进行分离时，当混合物类型为油包水纳米乳液时，使用疏水/亲油的分离膜进行分离，分离性能测试数据如表1所示；
当混合物类型为水包油纳米乳液时，将疏水/亲油的分离膜置于水环境中通入CO2 5min转化为亲水/水下疏油的分离膜后，再进行分离，分离性能测试数据如表1所示；
需要再次对油包水纳米乳液进行分离时，将亲水/水下疏油的分离膜使用1.2V 808nm近红外光源照射1min再次转化为疏水/亲油的分离膜后，再进行分离。
在进行50次循环分离后，所制备的分离膜对异辛烷水包油纳米(20nm)乳液及油包水纳米乳液(20nm)的分离效率均能维持在99％以上。
实施例4 CO2-光热双重响应型纳米乳液分离膜-2的制备
在本实施例中所使用的碳基纳米材料为石墨烯，聚合物由CO2响应性单体DMSt和硬单体HEMA两种单体在溶剂中自由基聚合而成。引发剂用量为DMSt单体和HEMA单体总质量的1％。
用于制备上述CO2-光热双重响应型纳米乳液分离膜-2的方法，其特征在于，包括如下具体步骤：
S1、光热转化功能涂料的制备:将10wt％聚乙烯醇(PVA)和去离子水加入烧瓶中，再加入0.3mg/ml的石墨烯，在100℃油浴锅中加热搅拌1h制得光热转化功能涂料；
S2、CO2响应功能涂料的制备：将DMSt单体和HEMA单体按1:0.5质量比溶解于四氢呋喃中，加入引发剂偶氮二异庚腈，在氮气氛围中加热搅拌反应36小时，加热温度为75℃，加入过量的正己烷析出聚合物，取出沉淀的聚合物在烘箱中烘干，将制备的CO2响应聚合物溶于溶剂中制备质量分数10wt％的CO2响应功能涂料；涂料成膜后的透光量为90％。
S3、CO2-光热双重响应纤维的制备：使用浆纱机将S1制备的光热转化功能涂料均匀涂覆在腈纶纤维表面并在烘箱中80℃热处理5min得到光热转化功能纤维，再使用浆纱机将S2制备的CO2响应功能涂料均匀涂覆在光热转化功能纤维表面，并在烘箱中80℃热处理5min得到CO2-光热双重响应纤维。
S4、CO2-光热双重响应型纳米乳液分离膜的制备：使用织机将S3所制备的CO2-光热双重响应纤维按经密纬密之和为330T织造成膜，得到CO2-光热双重响应型纳米乳液分离膜-2。
实施例5 CO2-光热双重响应型纳米乳液分离膜-2的润湿性切换过程
在需要时，将疏水/亲油的CO2-光热双重响应型纳米乳液分离膜-2置于水环境中通入CO28min得到亲水/水下疏油的CO2-光热双重响应型纳米乳液分离膜-2，使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为0°。
在需要时将亲水/水下疏油的CO2-光热双重响应型纳米乳液分离膜-2使用1.5V 780nm近红外光源照射1.5min再次得到疏水/亲油的CO2-光热双重响应型纳米乳液分离膜-2，使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为150.6°。
实施例6 CO2-光热双重响应型纳米乳液分离膜-2的性能检测
使用CO2-光热双重响应型纳米乳液分离膜-2对油水混合物进行分离时，当混合物类型为油包水纳米乳液时，使用疏水/亲油的分离膜进行分离，分离性能测试数据如表1所示；
当混合物类型为水包油纳米乳液时，将疏水/亲油的分离膜置于水环境中通入CO2 8min转化为亲水/水下疏油的分离膜后，再进行分离，分离性能测试数据如表1所示；
需要再次对油包水纳米乳液进行分离时，将亲水/水下疏油的分离膜使用1.5V 780nm近红外光源照射1.5min再次转化为疏水/亲油的分离膜后，再进行分离。
在进行50次循环分离后，所制备的分离膜对异辛烷水包油纳米(20nm)乳液及油包水纳米乳液(20nm)的分离效率均能维持在99％以上。
实施例7 CO2-光热双重响应型纳米乳液分离膜-3的制备
在本实施例中所使用的碳基纳米材料为碳纳米管，聚合物由CO2响应性单体DMSt和硬单体AEMA两种单体在溶剂中自由基聚合而成。引发剂用量为DMSt单体和AEMA单体总质量的1％。
用于制备上述CO2-光热双重响应型纳米乳液分离膜-3的方法，其特征在于，包括如下具体步骤：
S1、光热转化功能涂料的制备:将12.5wt％聚乙烯醇(PVA)和去离子水加入烧瓶中，再加入0.4mg/ml的碳纳米管，在95℃油浴锅中加热搅拌90min制得光热转化功能涂料；
S2、CO2响应功能涂料的制备：将DMSt单体和AEMA单体按1:1.5质量比溶解于四氢呋喃中，加入引发剂过氧化二苯甲酰，在氮气氛围中加热搅拌反应36小时，加热温度为85℃，加入过量的正己烷析出聚合物，取出沉淀的聚合物在烘箱中烘干，将制备的CO2响应聚合物溶于溶剂中制备质量分数20wt％的CO2响应功能涂料；涂料成膜后的透光量为85％。
S3、CO2-光热双重响应纤维的制备：使用浆纱机将S1制备的光热转化功能涂料均匀涂覆在锦纶纤维表面并在烘箱中90℃热处理10min得到光热转化功能纤维，再使用浆纱机将S2制备的CO2响应功能涂料均匀涂覆在光热转化功能纤维表面，并在烘箱中90℃热处理10min得到CO2-光热双重响应纤维。
S4、CO2-光热双重响应型纳米乳液分离膜的制备：使用织机将S3所制备的CO2-光热双重响应纤维按经密纬密之和为350T织造成膜，得到CO2-光热双重响应型纳米乳液分离膜-3。
实施例8 CO2-光热双重响应型纳米乳液分离膜-3的润湿性切换过程
在需要时，将疏水/亲油的CO2-光热双重响应型纳米乳液分离膜-3置于水环境中通入CO210min得到亲水/水下疏油的CO2-光热双重响应型纳米乳液分离膜-3，使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为0°。
在需要时将亲水/水下疏油的CO2-光热双重响应型纳米乳液分离膜-3使用2V 900nm近红外光源照射2min再次得到疏水/亲油的CO2-光热双重响应型纳米乳液分离膜-3，使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为152.3°。
实施例9 CO2-光热双重响应型纳米乳液分离膜-3的性能检测
使用CO2-光热双重响应型纳米乳液分离膜-3对油水混合物进行分离时，当混合物类型为油包水纳米乳液时，使用疏水/亲油的分离膜进行分离，分离性能测试数据如表1所示；
当混合物类型为水包油纳米乳液时，将疏水/亲油的分离膜置于水环境中通入CO2 10min转化为亲水/水下疏油的分离膜后，再进行分离，分离性能测试数据如表1所示；
需要再次对油包水纳米乳液进行分离时，将亲水/水下疏油的分离膜使用2V 900nm近红外光源照射2min再次转化为疏水/亲油的分离膜后，再进行分离。
在进行50次循环分离后，所制备的分离膜对异辛烷水包油纳米(20nm)乳液及油包水纳米乳液(20nm)的分离效率均能维持在99％以上。
实施例10 CO2-光热双重响应型纳米乳液分离膜-4的制备
在本实施例中所使用的碳基纳米材料为氧化还原石墨烯，聚合物由CO2响应性单体DMAEMA和硬单体AEMA两种单体在溶剂中自由基聚合而成。引发剂用量为DMAEMA单体和AEMA单体总质量的1％。
用于制备上述CO2-光热双重响应型纳米乳液分离膜-4的方法，其特征在于，包括如下具体步骤：
S1、光热转化功能涂料的制备:将10wt％聚乙烯醇(PVA)和去离子水加入烧瓶中，再加入0.4mg/ml的石墨烯，在95℃油浴锅中加热搅拌1h制得光热转化功能涂料；
S2、CO2响应功能涂料的制备：将DMAEMA单体和AEMA单体按1:2质量比溶解于四氢呋喃中，加入引发剂过氧化二苯甲酰，在氮气氛围中加热搅拌反应48小时，加热温度为85℃，加入过量的正己烷析出聚合物，取出沉淀的聚合物在烘箱中烘干，将制备的CO2响应聚合物溶于溶剂中制备质量分数10wt％的CO2响应功能涂料；涂料成膜后的透光量为88％。
S3、CO2-光热双重响应纤维的制备：使用浆纱机将S1制备的光热转化功能涂料均匀涂覆在涤纶纤维表面并在烘箱中75℃热处理4min得到光热转化功能纤维，再使用浆纱机将S2制备的CO2响应功能涂料均匀涂覆在光热转化功能纤维表面，并在烘箱中75℃热处理4min得到CO2-光热双重响应纤维。
S4、CO2-光热双重响应型纳米乳液分离膜的制备：使用织机将S3所制备的CO2-光热双重响应纤维按经密纬密之和为300T织造成膜，得到CO2-光热双重响应型纳米乳液分离膜-4。
实施例11 CO2-光热双重响应型纳米乳液分离膜-4的润湿性切换过程
在需要时，将疏水/亲油的CO2-光热双重响应型纳米乳液分离膜-4置于水环境中通入CO25min得到亲水/水下疏油的CO2-光热双重响应型纳米乳液分离膜-4，使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为0°。
在需要时将亲水/水下疏油的CO2-光热双重响应型纳米乳液分离膜-4使用1.2V 808nm近红外光源照射1min再次得到疏水/亲油的CO2-光热双重响应型纳米乳液分离膜-4，使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为151.0°。
实施例12 CO2-光热双重响应型纳米乳液分离膜-4的性能检测
使用CO2-光热双重响应型纳米乳液分离膜-4对油水混合物进行分离时，当混合物类型为油包水纳米乳液时，使用疏水/亲油的分离膜进行分离，分离性能测试数据如表1所示；
当混合物类型为水包油纳米乳液时，将疏水/亲油的分离膜置于水环境中通入CO2 5min转化为亲水/水下疏油的分离膜后，再进行分离，分离性能测试数据如表1所示；
需要再次对油包水纳米乳液进行分离时，将亲水/水下疏油的分离膜使用1.2V 808nm近红外光源照射1min再次转化为疏水/亲油的分离膜后，再进行分离。
在进行50次循环分离后，所制备的分离膜对异辛烷水包油纳米(20nm)乳液及油包水纳米乳液(20nm)的分离效率均能维持在99％以上。
对比例1 不加碳基纳米材料对去质子化过程的影响
在本实施例中所使用的聚合物由CO2响应性单体DMAEMA和硬单体HEMA两种单体在溶剂中自由基聚合而成。引发剂用量为DMAEMA单体和HEMA单体总质量的1％。
用于制备上述CO2响应型纳米乳液分离膜的方法，其特征在于，包括如下具体步骤：
S1、PVA涂料的制备:将7.5wt％聚乙烯醇(PVA)和去离子水加入烧瓶中，在95℃油浴锅中加热搅拌30min制得PVA涂料；
S2、CO2响应功能涂料的制备：将DMAEMA单体和HEMA单体按1:0.5质量比溶解于四氢呋喃中，加入引发剂偶氮二异丁腈，在氮气氛围中加热搅拌反应24小时，加热温度为65℃，加入过量的正己烷析出聚合物，取出沉淀的聚合物在烘箱中烘干，将制备的CO2响应聚合物溶于溶剂中制备质量分数5wt％的CO2响应功能涂料；
S3、CO2响应纤维的制备：使用浆纱机将S1制备的PVA涂料均匀涂覆在PET纤维表面并在烘箱中80℃热处理5min得到PVA涂层纤维，再使用浆纱机将S2制备的CO2响应功能涂料均匀涂覆在PVA涂层纤维表面，并在烘箱中80℃热处理4min得到CO2响应纤维。
S4、CO2响应型纳米乳液分离膜的制备：使用织机将S3所制备的CO2响应纤维按经密纬密之和为300T织造成膜，得到CO2响应型纳米乳液分离膜。
使用上述的CO2响应纳米乳液分离膜对油水混合物进行分离时，当混合物类型为异辛烷水包油纳米乳液(20nm)时，将疏水/亲油的分离膜置于水环境中通入CO2 5min转化为亲水/水下疏油的分离膜后，再进行分离，分离性能测试数据如表1所示；需要对异辛烷油包水纳米乳液(20nm)进行分离时，将亲水/水下疏油的分离膜使用1.2V 808nm近红外光源照射1min后，再进行分离，结果见表1。
通过与对比例1比较发现不添加碳基纳米材料会导致膜失去光热去质子化能力，导致对油包水乳液分离通量及性能大幅下降。碳基纳米材料光热所产生的热量能直接补充CO2响应聚合物去质子化所需要的能量，使其快速恢复去质子化状态，恢复疏水性。因此不添加碳基纳米材料会使膜恢复疏水性速度降低，降低其对油包水乳液的分离性能。
对比例2 使用N2去质子化对去质子化过程速率的影响
在本实施例中所使用的聚合物由CO2响应性单体DMAEMA和硬单体HEMA两种单体在溶剂中自由基聚合而成。引发剂用量为DMAEMA单体和HEMA单体总质量的1％。
用于制备上述CO2响应型纳米乳液分离膜的方法，其特征在于，包括如下具体步骤：
S1、PVA涂料的制备:将10wt％聚乙烯醇(PVA)和去离子水加入烧瓶中，在95℃油浴锅中加热搅拌1h制得PVA涂料；
S2、CO2响应功能涂料的制备：将DMAEMA单体和HEMA单体按1:0.5质量比溶解于四氢呋喃中，加入引发剂偶氮二异丁腈，在氮气氛围中加热搅拌反应24小时，加热温度为65℃，加入过量的正己烷析出聚合物，取出沉淀的聚合物在烘箱中烘干，将制备的CO2响应聚合物溶于溶剂中制备质量分数5wt％的CO2响应功能涂料；
S3、CO2响应纤维的制备：使用浆纱机将S1制备的PVA涂料均匀涂覆在PET纤维表面并在烘箱中70℃热处理2min得到PVA涂层纤维，再使用浆纱机将S2制备的CO2响应功能涂料均匀涂覆在PVA涂层纤维表面，并在烘箱中70℃热处理2min得到CO2响应纤维。
S4、CO2响应型纳米乳液分离膜的制备：使用织机将S3所制备的CO2响应纤维按经密纬密之和为300T织造成膜，得到CO2响应型纳米乳液分离膜。
使用上述的CO2响应纳米乳液分离膜对油水混合物进行分离时，当混合物类型为异辛烷水包油纳米乳液(20nm)时，将疏水/亲油的分离膜置于水环境中通入CO2 5min转化为亲水/水下疏油的分离膜后，再进行分离，分离性能测试数据如表1所示；需要对异辛烷油包水纳米乳液(20nm)进行分离时，将亲水/水下疏油的分离膜置于水环境中通入N2 1min后，再进行分离，结果见表1。使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为46.3°
通过与对比例2比较发现使用N2去质子化在1min内接触角不能完全恢复至150°以上，不能完全实现去质子化，而使用光热去质子化是接触角能在1min内恢复至150°以上说明使用光热转化去质子化更加迅速效率更高。
对比例3 光热转化层和CO2响应层涂覆的顺序调换对分离效率的影响
在本实施例中所使用的碳基纳米材料为氧化石墨烯，聚合物由CO2响应性单体DMSt和硬单体AEMA两种单体在溶剂中自由基聚合而成。引发剂用量为DMSt单体和AEMA单体总质量的1％。
用于制备上述乳液分离膜的方法，其特征在于，包括如下具体步骤：
S1、光热转化功能涂料的制备:将12.5wt％聚乙烯醇(PVA)和去离子水加入烧瓶中，再加入0.5mg/ml的石墨烯，在95℃油浴锅中加热搅拌90min制得光热转化功能涂料；
S2、CO2响应功能涂料的制备：将DMSt单体和AEMA单体按1:1.5质量比溶解于四氢呋喃中，加入引发剂过氧化二苯甲酰，在氮气氛围中加热搅拌反应36小时，加热温度为85℃，加入过量的正己烷析出聚合物，取出沉淀的聚合物在烘箱中烘干，将制备的CO2响应聚合物溶于溶剂中制备质量分数20wt％的CO2响应功能涂料；
S3、CO2-光热双重响应纤维的制备：使用浆纱机将S2制备的CO2响应功能涂料均匀涂覆在PET纤维表面并在烘箱中90℃热处理5min得到CO2响应功能纤维，再使用浆纱机将S1制备的光热转化功能涂料均匀涂覆在光热转化功能纤维表面，并在烘箱中90℃热处理5min得到光热/CO2双重响应纤维。
S4、光热/CO2双重响应型纳米乳液分离膜的制备：使用织机将S3所制备的光热/CO2双重响应纤维按经密纬密之和为350T织造成膜，得到光热/CO2双重响应型纳米乳液分离膜。
润湿性切换：在需要时，将疏水/亲油的光热/CO2双重响应型纳米乳液分离膜置于水环境中通入CO2 5min得到亲水/水下疏油的光热/CO2双重响应型纳米乳液分离膜；在需要时将亲水/水下疏油的光热/CO2双重响应型纳米乳液分离膜使用1.2V 808nm近红外光源照射1min再次得到疏水/亲油的光热/CO2双重响应型纳米乳液分离膜。
使用上述的光热/CO2双重响应型纳米乳液分离膜对油水混合物进行分离时，当混合物类型为油包水纳米乳液时，使用疏水/亲油的分离膜进行分离，分离性能测试数据如表1所示；当混合物类型为水包油纳米乳液时，将疏水/亲油的分离膜置于水环境中通入CO2 5min转化为亲水/水下疏油的分离膜后，再进行分离，分离性能测试数据如表1所示；需要再次对油包水纳米乳液进行分离时，将亲水/水下疏油的分离膜使用1.2V 808nm近红外光源照射1min再次转化为疏水/亲油的分离膜后，再进行分离。在进行2次循环分离后，所制备的分离膜对异辛烷水包油纳米(20nm)乳液及油包水纳米乳液(20nm)的分离效率降至90％以下。
通过与对比例3比较发现交换光热转化层和CO2响应层涂覆的顺序后，膜的循环性能大幅下降，这是因为光热转化层中的PVA材质是亲水的，因此将光热转化层放在外部在水环境中涂层容易被水溶解脱落，导致膜的孔径增大，分离性能会大幅下降。
对比例4 不添加CO2响应层涂层对分离效率的影响
在本实施例中所使用的碳基纳米材料为氧化石墨烯。
用于制备上述光热响应型纳米乳液分离膜的方法，其特征在于，包括如下具体步骤：
S1、光热转化功能涂料的制备:将10wt％聚乙烯醇(PVA)和去离子水加入烧瓶中，再加入0.3mg/ml的石墨烯，在95℃油浴锅中加热搅拌1h制得光热转化功能涂料；
S2、光热响应纤维的制备：使用浆纱机将S1制备的光热转化功能涂料均匀涂覆在PET纤维表面，并在烘箱中70℃热处理5min得到光热响应纤维。
S4、光热响应型纳米乳液分离膜的制备：使用织机将S2所制备的光热响应纤维按经密纬密之和为350T织造成膜，得到光热响应型纳米乳液分离膜。
润湿性切换：在需要时，将疏水/亲油的光热响应型纳米乳液分离膜置于水环境中通入CO25min；在需要时将亲水/水下疏油的光热响应型纳米乳液分离膜使用1.2V 808nm近红外光源照射1min。
在需要时，光热响应型纳米乳液分离膜置于水环境中通入CO2 5min，使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为0°。
在需要时，将光热响应型纳米乳液分离膜使用1.2V 808nm近红外光源照射1min，使用接触角测量仪测量此时膜在空气中的水接触角，测得接触角为0°。
使用上述的光热响应型纳米乳液分离膜对油水混合物进行分离时，当混合物类型为油包水纳米乳液时，分离性能测试数据如表1所示；当混合物类型为水包油纳米乳液时，将疏水/亲油的分离膜置于水环境中通入CO2 5min后，再进行分离，分离性能测试数据如表1所示；需要再次对油包水纳米乳液进行分离时，将使用1.2V 808nm近红外光源照射1min后，再进行分离。在进行2次循环分离后，所制备的分离膜对异辛烷水包油纳米(20nm)乳液及油包水纳米乳液(20nm)的分离效率降至90％以下。
与对比例4进行比较可以发现当只使用光热转化功能涂层时，膜并不具有可切换的润湿性，对水的接触角一直是0°，这是因为润湿性切换靠的是CO2响应功能层的质子化去去质子化状态切换实现的。同时膜对纳米乳液的分离性能在短时间内会大幅下降，这是因为光热转化涂层是亲水的，没有外层CO2响应涂层的保护，与水直接接触后图层会快速溶解并脱落，导致孔径增大，分离性能下降。
图1中的GOM对应本对比例膜的示意图，其内核为PET纤维，外层为氧化石墨烯涂层。图3B对应本对比例所制备膜的SEM图像，其表面较图3C中有CO2响应涂层的膜粗糙，且颜色更浅。
表1

Claims (8)

  1. 一种CO2-光热双重响应型纳米乳液分离膜，其特征在于，所述纳米乳液分离膜具有三层结构的纤维织造而成，内核为纤维，中间层为光热转化功能涂层，外层为CO2响应功能涂层；所述光热转化功能涂层是由碳基纳米材料和聚乙烯醇制备得到；所述CO2响应功能涂层是由CO2响应性单体和硬单体自由基聚合反应得到；所述分离膜孔径分布在0.1um以下。
  2. 根据权利要求1所述的一种CO2-光热双重响应型纳米乳液分离膜，其特征在于，纤维材料包括PET、涤纶、腈纶、锦纶、氨纶、碳纤维或玻璃；
    所述碳基纳米材料包括炭黑、碳纳米管、石墨烯、氧化石墨烯和还原氧化石墨烯中的一种或多种；
    所述CO2响应性单体包括N，N-二甲基对苯乙烯、甲基丙烯酸二甲氨基乙酯或甲基丙烯酸二乙氨基乙酯；
    所述硬单体包括苯乙烯、甲基丙烯酸羟乙酯、丙烯酰胺、甲基丙烯酸甲酯、聚乙二醇甲基丙烯酸酯、甲基丙烯酸-2-乙氧基乙酯。
  3. 根据权利要求1所述的一种CO2-光热双重响应型纳米乳液分离膜，其特征在于，所述碳基纳米材料和聚乙烯醇的比例为质量比为3:1000-10:1000，优先地为3:1000。
    所述CO2响应性单体和硬单体的比例为摩尔比为1:1-1:2，优选地为1:1。
  4. 根据权利要求1-3中任一所述的一种CO2-光热双重响应型纳米乳液分离膜的制备方法，其特征在于，步骤如下：
    S1、光热转化功能涂料的制备:将7.5-12.5wt％聚乙烯醇和去离子水加入烧瓶中，再加入0.2-0.5mg/ml的碳基纳米材料，在90-110℃油浴锅中加热搅拌30-90min制得光热转化功能涂料；
    S2、CO2响应功能涂料的制备：将CO2响应性单体和一种硬单体通过在四氢呋喃中自由基聚合反应制备CO2响应聚合物，将制备的CO2响应聚合物溶于乙醇中制备质量分数5～20wt％的CO2响应功能涂料；
    S3、CO2-光热双重响应纤维的制备：使用浆纱机将S1制备的光热转化功能涂料均匀涂覆在PET纤维表面并在烘箱中70-90℃热处理2-10min得到光热转化功能纤维，再使用浆纱机将S2制备的CO2响应功能涂料均匀涂覆在光热转化功能纤维表面，并在烘箱中70-90℃热处理2-10min得到CO2-光热双重响应纤维。
    S4、CO2-光热双重响应型纳米乳液分离膜的制备：使用织机将S3所制备的CO2-光热双重响应纤维织造成膜，得到CO2-光热双重响应型纳米乳液分离膜。
  5. 根据权利要求3所述的一种CO2-光热双重响应型纳米乳液分离膜的制备方法，其特征在于，步骤S2中所述CO2响应功能涂料为透明材料，涂料成膜后的透光量为85-92％。
  6. 根据权利要求1-3任一所述的一种CO2-光热双重响应型纳米乳液分离膜或根据权利要求3或4所述方法制备的一种CO2-光热双重响应型纳米乳液分离膜的应用，其特征在于，所述纳米乳液分离膜在CO2刺激或光热刺激下实现超疏水与超亲水状态的可逆切换。
  7. 根据权利要求6所述的一种CO2-光热双重响应型纳米乳液分离膜的应用，其特征在于，所述CO2刺激为将纳米乳液分离膜置于水环境中通CO2 5-10min；
    所述光热刺激为将纳米乳液分离膜在近红外光源照射下可以在10～20s内，将自身温度提高至120～180℃。
  8. 根据权利要求6所述的一种CO2-光热双重响应型纳米乳液分离膜的应用，其特征在于，纳米乳液分离膜对油水混合物进行分离时，当混合物类型为油包水纳米乳液时，使用初始状态下的疏水/亲油的膜进行分离；当混合物类型为水包油纳米乳液时，将疏水/亲油的分离膜置于水环境中通入CO2 5-10min转化为亲水/水下疏油的分离膜后，再进行分离；需要再次对油包水纳米乳液进行分离时，将亲水/水下疏油的分离膜置于水环境中使用1.2-2V，780-900nm近红外光源照射1-2min再次转化为疏水/亲油的分离膜后，再进行分离。
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