CN116328738A - Application of modified polyvinylidene fluoride material in simultaneous adsorption of microplastic and perfluorinated compounds in water body - Google Patents
Application of modified polyvinylidene fluoride material in simultaneous adsorption of microplastic and perfluorinated compounds in water body Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 34
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- 150000001450 anions Chemical class 0.000 claims description 6
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- FBOSFHSGNSJLLG-UHFFFAOYSA-N 1-butyl-3-ethenyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C=C)C=C1 FBOSFHSGNSJLLG-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
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- 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
- C02F2101/36—Organic compounds containing halogen
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Abstract
The invention discloses an application of a modified polyvinylidene fluoride material in simultaneously adsorbing micro-plastics and perfluorinated compounds in a water body, and the synchronous adsorption of the micro-plastics and perfluorinated compounds in the water body is completed by utilizing the surface wettability and the bonding property of the modified polyvinylidene fluoride material, so that the operation is simple, green and quick. According to the modified polyvinylidene fluoride material, the ionic liquid connected by chemical bonds is uniformly distributed on a polymer material matrix through a chemical modification method of electron beam radiation grafting, the grafted ionic liquid has good hydrophilicity and high surface energy, and meanwhile, a micro-nano hierarchical coarse structure is endowed to the surface of the material through solidification in a water vapor atmosphere, so that the surface adsorption sites are increased, the surface wettability and the bonding performance are improved, and the obtained modified polyvinylidene fluoride material has good micro-plastic and perfluorinated compound adsorption capacity and can realize one-step simultaneous adsorption of the micro-plastic and the perfluorinated compound.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to application of a modified polyvinylidene fluoride material in simultaneous adsorption of microplastic and perfluorinated compounds in water.
Background
The presence of micro-plastics (MPs) and perfluoro compounds (PFCs) in the environment poses a significant hazard to microorganisms, humans, animals and plants. Microplastic refers to plastic chips, particles, fibers, etc. with diameters less than 5 mm, and is a major carrier causing pollution. The perfluoro compounds are organic compounds in which all hydrogen atoms linked with carbon atoms in the molecules of the compounds are replaced by fluorine atoms, mainly comprise perfluorocarboxylic acids (PFCAs), perfluorosulfonic acids (PFSAs), perfluorosulfonamides (PFASs), perfluoro telangiectates (FTOHs) and the like, and are widely applied to the fields of textiles, lubricants, surfactants, food packaging, non-stick pan coatings, electronic products, fireproof clothes, fire-extinguishing foams and the like. PFCs have been classified as novel persistent organic pollutants due to their persistence and bioaccumulation. Several methods are currently available for microplastic cleaning, classified according to the cleaning characteristics: (i) filtration and separation; (ii) capture and surface attachment methods; and (iii) degradation. The removal efficiency is between 58 and 100 percent. As for perfluorinated compounds, research shows that the technology capable of effectively removing high-concentration PFCs in water at the present stage is mainly adsorption.
However, no method for simultaneously adsorbing the microplastic and the perfluorinated compound in the water body is reported at present.
Polyvinylidene fluoride PVDF resin is a chain-like crystalline polymer with-CH 2-CF 2-as a structural unit. The polyvinylidene fluoride resin is similar to other fluorocarbon resins, has strong electronegativity of F atoms, firm C-F bonds, is a strong polar covalent bond, and has high chemical inertness. Polyvinylidene fluoride has an adsorption function, and an adsorbent made from the polyvinylidene fluoride can be used for adsorbing substances such as heavy metal ions and ionic dyes, but cannot be used for adsorbing microplastic in general.
Patent CN201510246195.2, "a nano-structured polyvinylidene fluoride composite material and a preparation method thereof", discloses an ionic liquid modified nano-structured polyvinylidene fluoride composite material, but the ionic liquid modified nano-structured polyvinylidene fluoride composite material does not have conditions or potential for becoming an adsorption material because the ionic liquid modified nano-structured polyvinylidene fluoride composite material does not have a characteristic of graded roughness and lacks adsorption sites, and meanwhile, an ion exchange and micro-plastic adsorption method is not established.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides an application of a modified polyvinylidene fluoride material in simultaneously adsorbing microplastic and perfluorinated compounds in water.
The application of the modified polyvinylidene fluoride material in the simultaneous adsorption of the micro plastic and the perfluorinated compounds in the water body is that the modified polyvinylidene fluoride material is prepared by adopting the following technical scheme:
step (1), respectively placing polyvinylidene fluoride PVDF and ionic liquid IL in a vacuum drying oven, and drying at 60-100 ℃ until the weight is no longer reduced;
the mass ratio of the ionic liquid IL to PVDF is 2-40: 100;
the ionic liquid IL is an ionic liquid containing unsaturated bonds;
preferably, the mass ratio of the ionic liquid IL to PVDF is 20:100, wherein the ionic liquid containing unsaturated bonds is an imidazole ionic liquid, and the cationic structural formula is as follows:
wherein R is 1 Is C 1 ～C 24 Alkyl or C-containing 2 ～C 24 Alkenyl groups; r is R 2 Is C-containing 2 ～C 24 Alkenyl groups;
the anion of the ionic liquid is PF 6 - 、BF 4 - 、Br - 、Cl - 、I - 、NO 3 - 、CF 3 CO 2 - 、CH 3 COO - 、(CF 3 SO 3 ) 2 N - 。
Step (2), mixing the dried polyvinylidene fluoride and the ionic liquid, adding the mixture into a melting and mixing device, and melting and mixing the mixture for 5-10 min at 180-210 ℃;
preferably, the melting and mixing temperature in the step (2) is 190 ℃, and the mixing time is 5min;
preferably, the melt kneading apparatus is an internal mixer, a single screw extruder, a twin screw extruder, or an injector, and the like, which are commonly used in various industries;
step (3), discharging the mixture after melting and mixing from melting and mixing equipment, cooling to normal temperature, and obtaining a film with the thickness of 1-500 mu m through melting and tabletting;
step (4), placing the film prepared in the step (3) into a polyethylene bag, radiating and irradiating at normal temperature under vacuum, and then performing methanol Soxhlet extraction for 72-144 hours to obtain an ionic liquid grafted polyvinylidene fluoride film PVDF-g-IL;
the radiation irradiation is electron beam irradiation, and the absorption dose is 25-75 kGy;
preferably, the absorbed dose is 50kGy;
step (5), at 60-80 ℃, the ionic liquid grafted polyvinylidene fluoride film obtained in the step (4), a pore-forming agent and a solvent are mixed according to the mass ratio of (0.92-0.98): (0.02-0.08): 5, solution blending is carried out for a period of time in proportion;
preferably, the solvent is N, N-Dimethylformamide (DMF);
preferably, the pore-forming agent is polyvinylpyrrolidone PVP-K30;
preferably, the mass ratio is 0.95:0.05:5, a step of;
step (6), uniformly coating the blended solution obtained in the step (5) on a substrate, curing for 1-3 hours in a steam atmosphere with the temperature of 15-25 ℃ and the relative humidity of 60-80%, and drying and molding to obtain a modified polyvinylidene fluoride material;
the substrate comprises various common materials such as metal, ceramic, glass, wood, fabric, etc., preferably a 300 micron thick PVDF film.
The invention has the beneficial effects that:
the invention discloses an application of a modified polyvinylidene fluoride material in simultaneously adsorbing micro-plastics and perfluorinated compounds in a water body, and the synchronous adsorption of the micro-plastics and perfluorinated compounds in the water body is completed by utilizing the surface wettability and the bonding property of the modified polyvinylidene fluoride material, so that the operation is simple, green and quick.
According to the modified polyvinylidene fluoride material, the ionic liquid connected with chemical bonds is uniformly distributed on a polymer material matrix through a chemical modification method of electron beam radiation grafting, the grafted ionic liquid has good hydrophilicity and high surface energy, so that the material can stably maintain a good modification effect for a long time, meanwhile, a micro-nano hierarchical coarse structure is endowed to the surface of the material through solidification under a water vapor atmosphere, the surface adsorption sites are favorably increased, the surface wettability and the bonding performance are improved, and the obtained modified polyvinylidene fluoride material has good micro-plastic and perfluorinated compound adsorption capacity and can realize one-step simultaneous adsorption of the micro-plastic and the perfluorinated compound;
the modified polyvinylidene fluoride material used by the invention has good thermal, mechanical and chemical stability, and can be normally attached under various severe working conditions without failure and falling off; and compared with the common polyvinylidene fluoride material, the polyvinylidene fluoride material has substrate universality, and applicable substrates comprise various common materials such as metal, ceramic, glass, wood, fabric and the like; meanwhile, the preparation of the modified polyvinylidene fluoride material only needs to use common melting and mixing equipment and solution blending equipment, equipment required by radiation is a common irradiation source, the industrial preparation is simple, and the processability is strong.
Drawings
FIG. 1 is a scanning electron micrograph of an ionic liquid modified polyvinylidene fluoride material, wherein a is low magnification (2500 times), b is medium magnification (10000 times), and c is high magnification (20000 times);
FIG. 2 is a schematic diagram of the operation of examples 1-5 and comparative examples 1-2 for adsorbing microplastic and perfluorocompound, wherein A is examples 1-5, B is comparative example 1, and C is comparative example 2;
FIG. 3 is a schematic diagram showing the mechanism of adsorption of microplastic and perfluoro compound in examples 1-5 and comparative examples 1-2, wherein A is examples 1-5, B is comparative example 1, and C is comparative example 2;
FIG. 4 is a graph showing the amount of decrease in microplastic in a water body with adsorption time after the microplastic is adsorbed in example 3 and comparative examples 1-2;
FIG. 5 is a graph showing the percent reduction of microplastic in a body of water 24 hours after the microplastic was adsorbed for examples 1-5 and comparative examples 1-2;
FIG. 6 shows the percent reduction of perfluorooctanoate ions in water 24 hours after adsorption of the microplastic for examples 1-5 and comparative example 2.
Detailed Description
The present invention will be described in detail below with reference to the drawings and the detailed description, but the invention is not limited to the scope of the described detailed description.
The invention provides an application of a modified polyvinylidene fluoride material in simultaneously adsorbing microplastic and perfluorinated compounds in a water body, and the specific implementation scheme of the modified polyvinylidene fluoride material is as follows:
step (1), respectively placing polyvinylidene fluoride and imidazole ionic liquid in a vacuum drying oven, and drying at 60-100 ℃ until the weight is no longer reduced;
the mass ratio of the imidazole ionic liquid to the polyvinylidene fluoride is 2-40: 100; the cationic structural formula of the imidazole ionic liquid is as follows:
wherein R is 1 Is C 1 ～C 24 Alkyl or C-containing 2 ～C 24 Alkenyl groups; r is R 2 Is C-containing 2 ～C 24 Alkenyl groups;
the anion of the ionic liquid is PF 6 - 、BF 4 - 、Br - 、Cl - 、I - 、NO 3 - 、CF 3 CO 2 - 、CH 3 COO - 、(CF 3 SO 3 ) 2 N - 。
Step (2), mixing the dried polyvinylidene fluoride and the ionic liquid, and adding the mixture into a melting and mixing device such as an internal mixer, a single screw extruder, a double screw extruder or an injection machine, and the like, and melting and mixing the mixture for 5-10 min at 180-210 ℃;
step (3), discharging the mixture after melting and mixing from melting and mixing equipment, cooling to normal temperature, and obtaining a film with the thickness of 1-500 mu m through melting and tabletting;
step (4), placing the film prepared in the step (3) into a polyethylene bag, and carrying out electron beam irradiation under normal temperature vacuum, wherein the absorbed dose is 25-75 kGy; then carrying out methanol Soxhlet extraction for 72-144 h to obtain an ionic liquid grafted polyvinylidene fluoride film PVDF-g-IL;
step (5), at 60-80 ℃, the ionic liquid grafted polyvinylidene fluoride film obtained in the step (4), polyvinylpyrrolidone PVP-K30 and N-dimethylformamide DMF are mixed according to the mass ratio (0.92-0.98): (0.02-0.08): 5, solution blending is carried out for a period of time in proportion;
step (6), uniformly coating the blended solution obtained in the step (5) on a substrate, curing for 1-3 hours in a steam atmosphere with the temperature of 15-25 ℃ and the relative humidity of 60-80%, and drying and molding to obtain a modified polyvinylidene fluoride material;
the substrate comprises various common materials such as metal, ceramic, glass, wood, fabric, and the like.
In the examples of the present invention and the comparative examples thereof, a polymer PVDF, manufactured by Wulue chemical Co., ltd., model KF850, was used as the matrix.
In the embodiment of the invention, when the adsorption force test is carried out on the obtained material, the obtained material is cut into square pieces with the concentration of 1cm and 1cm, 4mL of 10mg/L of micro-plastic suspension is immersed, 20ppm of perfluorinated anions are contained in the suspension, the constant temperature oscillation is carried out for a certain period of time, the micro-plastic in the water body is fully adsorbed, the content of the micro-plastic is detected by a turbidimeter, and the content of perfluorinated compounds is detected by a liquid chromatography-mass spectrometer;
the micro plastic is 2000 mesh polypropylene powder (PPPowrers), 2000 mesh polyvinyl chloride powder (PVC Powrers), 3,5 and 10 micron monodisperse polystyrene plastic microspheres (PSMPs), and the perfluoro anions are perfluoro octoate ions.
In the embodiment of the invention, the imidazole ionic liquid containing unsaturated bonds is: 1-vinyl-3-butylimidazole chloride salt.
The specific process in the invention is as follows:
example 1
Step (1) polyvinylidene fluoride and ionic liquid are dried overnight in a vacuum drying oven at 80 ℃ respectively;
sequentially adding 50g of polyvinylidene fluoride and 10g of ionic liquid into an internal mixer, wherein the temperature of the internal mixer is 190 ℃, the rotor speed is 20rpm/min, and the internal mixing is carried out for 2min; then the rotor speed is increased to 50rpm/min, banburying is carried out for 5min, discharging is carried out, and cooling is carried out to normal temperature.
The mixture after the melt mixing is hot-pressed into a film with the thickness of 300 mu m in a hot press with the temperature of 190 ℃, the pressure is 10MPa, and the pressure is maintained for 3min.
Step (2), placing the film in the step (1) into a polyethylene plastic bag for radiation irradiation, and performing normal-temperature radiation at an irradiation dose of 50kGy in electron beam irradiation;
and (3) extracting the film in the step (2) by utilizing a Soxhlet extraction method, wherein the extracting solution is a good solvent methanol of the ionic liquid, the heating temperature is controlled to enable the extracting solution to flow back once every 6-8 min, the extracting time is 72-144 h, the extracting solution is taken out after the extracting is finished, and the extracting solution is dried overnight in a vacuum drying oven at 80 ℃ to obtain the ionic liquid grafted PVDF film.
Step (4) carrying out solution blending on the film in the step (3) and a pore-forming agent polyvinylpyrrolidone PVP-K30 according to a certain proportion, wherein the mass ratio of PVDF-g-IL, PVP-K30 and a solvent is 0.95:0.05:5. the temperature is set to 60-80 ℃ in the process of blending the solution, and the solvent is N, N-Dimethylformamide (DMF);
uniformly coating the solution obtained in the step (4) on a PVDF substrate, curing for 2 hours in a steam atmosphere with the temperature of 15-25 ℃ and the relative humidity of 60-80%, and drying and forming;
cutting the coating obtained in the step (6) into square pieces with the thickness of 1cm and 1cm, immersing 4mL of 10 mg/L2000-mesh polypropylene powder suspension containing 20ppm of perfluorinated anions (perfluorinated octoate ions), oscillating for a certain period of time at constant temperature, fully adsorbing the microplastic in the water body, detecting the content of the microplastic by a turbidimeter, and detecting the content of the perfluorinated compounds by a liquid chromatography-mass spectrometer.
Example 2
Step (1) polyvinylidene fluoride and ionic liquid are dried overnight in a vacuum drying oven at 80 ℃ respectively;
sequentially adding 50g of polyvinylidene fluoride and 10g of ionic liquid into an internal mixer, wherein the temperature of the internal mixer is 190 ℃, the rotor speed is 20rpm/min, and the internal mixing is carried out for 2min; then the rotor speed is increased to 50rpm/min, banburying is carried out for 5min, discharging is carried out, and cooling is carried out to normal temperature.
The mixture after the melt mixing is hot-pressed into a film with the thickness of 300 mu m in a hot press with the temperature of 190 ℃, the pressure is 10MPa, and the pressure is maintained for 3min.
Step (2), placing the film in the step (1) into a polyethylene plastic bag for radiation irradiation, and performing normal-temperature radiation at an irradiation dose of 50kGy in electron beam irradiation;
and (3) extracting the film in the step (2) by utilizing a Soxhlet extraction method, wherein the extracting solution is a good solvent methanol of the ionic liquid, the heating temperature is controlled to enable the extracting solution to flow back once every 6-8 min, the extracting time is 72-144 h, the extracting solution is taken out after the extracting is finished, and the extracting solution is dried overnight in a vacuum drying oven at 80 ℃ to obtain the ionic liquid grafted PVDF film.
Step (4) carrying out solution blending on the film in the step (3) and a pore-forming agent polyvinylpyrrolidone PVP-K30 according to a certain proportion, wherein the mass ratio of PVDF-g-IL, PVP-K30 and a solvent is 0.95:0.05:5. the temperature is set to 60-80 ℃ in the process of blending the solution, and the solvent is N, N-Dimethylformamide (DMF);
uniformly coating the solution obtained in the step (4) on a PVDF substrate, curing for 2 hours in a steam atmosphere with the temperature of 15-25 ℃ and the relative humidity of 60-80%, and drying and forming;
cutting the coating obtained in the step (6) into square pieces with the thickness of 1cm and 1cm, immersing 4mL of 10 mg/L2000-mesh polyvinyl chloride powder suspension, wherein the suspension contains 20ppm of perfluorinated anions (perfluorinated octoate ions), oscillating for a certain period of time at constant temperature, fully adsorbing the microplastic in the water body, detecting the content of the microplastic by a turbidimeter, and detecting the content of the perfluorinated compounds by a liquid chromatography-mass spectrometer.
Example 3
Step (1) polyvinylidene fluoride and ionic liquid are dried overnight in a vacuum drying oven at 80 ℃ respectively;
sequentially adding 50g of polyvinylidene fluoride and 10g of ionic liquid into an internal mixer, wherein the temperature of the internal mixer is 190 ℃, the rotor speed is 20rpm/min, and the internal mixing is carried out for 2min; then the rotor speed is increased to 50rpm/min, banburying is carried out for 5min, discharging is carried out, and cooling is carried out to normal temperature.
The mixture after the melt mixing is hot-pressed into a film with the thickness of 300 mu m in a hot press with the temperature of 190 ℃, the pressure is 10MPa, and the pressure is maintained for 3min.
Step (2), placing the film in the step (1) into a polyethylene plastic bag for radiation irradiation, and performing normal-temperature radiation at an irradiation dose of 50kGy in electron beam irradiation;
and (3) extracting the film in the step (2) by utilizing a Soxhlet extraction method, wherein the extracting solution is a good solvent methanol of the ionic liquid, the heating temperature is controlled to enable the extracting solution to flow back once every 6-8 min, the extracting time is 72-144 h, the extracting solution is taken out after the extracting is finished, and the extracting solution is dried overnight in a vacuum drying oven at 80 ℃ to obtain the ionic liquid grafted PVDF film.
Step (4) carrying out solution blending on the film in the step (3) and a pore-forming agent polyvinylpyrrolidone PVP-K30 according to a certain proportion, wherein the mass ratio of PVDF-g-IL, PVP-K30 and a solvent is 0.95:0.05:5. the temperature is set to 60-80 ℃ in the process of blending the solution, and the solvent is N, N-Dimethylformamide (DMF);
uniformly coating the solution obtained in the step (4) on a PVDF substrate, curing for 2 hours in a steam atmosphere with the temperature of 15-25 ℃ and the relative humidity of 60-80%, and drying and forming;
and (6) cutting the coating obtained in the step (5) into square pieces with the length of 1cm and the length of 1cm, immersing 4mL of 10 mg/L3-micrometer monodisperse polystyrene plastic microsphere suspension, wherein the suspension contains 20ppm of perfluorinated anions (perfluorinated octoate ions), oscillating for a certain period of time at constant temperature, fully adsorbing the microplastic in the water body, detecting the content of the microplastic by using a turbidimeter, and detecting the content of the perfluorinated compound by using a liquid chromatography-mass spectrometer.
Example 4
Step (1) polyvinylidene fluoride and ionic liquid are dried overnight in a vacuum drying oven at 80 ℃ respectively;
sequentially adding 50g of polyvinylidene fluoride and 10g of ionic liquid into an internal mixer, wherein the temperature of the internal mixer is 190 ℃, the rotor speed is 20rpm/min, and the internal mixing is carried out for 2min; then the rotor speed is increased to 50rpm/min, banburying is carried out for 5min, discharging is carried out, and cooling is carried out to normal temperature.
The mixture after the melt mixing is hot-pressed into a film with the thickness of 300 mu m in a hot press with the temperature of 190 ℃, the pressure is 10MPa, and the pressure is maintained for 3min.
Step (2), placing the film in the step (1) into a polyethylene plastic bag for radiation irradiation, and performing normal-temperature radiation at an irradiation dose of 50kGy in electron beam irradiation;
and (3) extracting the film in the step (2) by utilizing a Soxhlet extraction method, wherein the extracting solution is a good solvent methanol of the ionic liquid, the heating temperature is controlled to enable the extracting solution to flow back once every 6-8 min, the extracting time is 72-144 h, the extracting solution is taken out after the extracting is finished, and the extracting solution is dried overnight in a vacuum drying oven at 80 ℃ to obtain the ionic liquid grafted PVDF film.
Step (4) carrying out solution blending on the film in the step (3) and a pore-forming agent polyvinylpyrrolidone PVP-K30 according to a certain proportion, wherein the mass ratio of PVDF-g-IL, PVP-K30 and a solvent is 0.95:0.05:5. the temperature is set to 60-80 ℃ in the process of blending the solution, and the solvent is N, N-Dimethylformamide (DMF);
uniformly coating the solution obtained in the step (4) on a PVDF substrate, curing for 2 hours in a steam atmosphere with the temperature of 15-25 ℃ and the relative humidity of 60-80%, and drying and forming;
and (6) cutting the coating obtained in the step (5) into square pieces with the thickness of 1cm and 1cm, immersing 4mL of 10 mg/L5-micrometer monodisperse polystyrene plastic microsphere suspension, wherein the suspension contains 20ppm of perfluorinated anions (perfluorinated octoate ions), oscillating for a certain period of time at constant temperature, fully adsorbing the microplastic in the water body, detecting the content of the microplastic by using a turbidimeter, and detecting the content of the perfluorinated compound by using a liquid chromatography-mass spectrometer.
Example 5
Step (1) polyvinylidene fluoride and ionic liquid are dried overnight in a vacuum drying oven at 80 ℃ respectively;
sequentially adding 50g of polyvinylidene fluoride and 10g of ionic liquid into an internal mixer, wherein the temperature of the internal mixer is 190 ℃, the rotor speed is 20rpm/min, and the internal mixing is carried out for 2min; then the rotor speed is increased to 50rpm/min, banburying is carried out for 5min, discharging is carried out, and cooling is carried out to normal temperature.
The mixture after the melt mixing is hot-pressed into a film with the thickness of 300 mu m in a hot press with the temperature of 190 ℃, the pressure is 10MPa, and the pressure is maintained for 3min.
Step (2), placing the film in the step (1) into a polyethylene plastic bag for radiation irradiation, and performing normal-temperature radiation at an irradiation dose of 50kGy in electron beam irradiation;
and (3) extracting the film in the step (2) by utilizing a Soxhlet extraction method, wherein the extracting solution is a good solvent methanol of the ionic liquid, the heating temperature is controlled to enable the extracting solution to flow back once every 6-8 min, the extracting time is 72-144 h, the extracting solution is taken out after the extracting is finished, and the extracting solution is dried overnight in a vacuum drying oven at 80 ℃ to obtain the ionic liquid grafted PVDF film.
Step (4) carrying out solution blending on the film in the step (3) and a pore-forming agent polyvinylpyrrolidone PVP-K30 according to a certain proportion, wherein the mass ratio of PVDF-g-IL, PVP-K30 and a solvent is 0.95:0.05:5. the temperature is set to 60-80 ℃ in the process of blending the solution, and the solvent is N, N-Dimethylformamide (DMF);
uniformly coating the solution obtained in the step (4) on a PVDF substrate, curing for 2 hours in a steam atmosphere with the temperature of 15-25 ℃ and the relative humidity of 60-80%, and drying and forming;
and (6) cutting the coating obtained in the step (5) into square pieces with the length of 1cm and the length of 1cm, immersing 4mL of 10 mg/L10-micrometer monodisperse polystyrene plastic microsphere suspension, wherein the suspension contains 20ppm of perfluorinated anions (perfluorinated octoate ions), oscillating for a certain period of time at constant temperature, fully adsorbing the microplastic in the water body, detecting the content of the microplastic by using a turbidimeter, and detecting the content of the perfluorinated compound by using a liquid chromatography-mass spectrometer.
Comparative example 1: two-step process (two-step)
Step (1-5) is the same as in examples 1-5;
cutting the coating obtained in the step (6) into square pieces with the length of 1cm and the length of 1cm, immersing the square pieces in a solution containing enough perfluoro octoate ions, fully performing ion exchange to enrich hydrophobic perfluoro octoate ions on the surface, fully drying, immersing 4mL of 10mg/L micro-plastic suspension without perfluoro octoate ions, oscillating at constant temperature for a certain period of time, fully adsorbing micro-plastics in water, and detecting the content of the micro-plastics by a turbidimeter.
Comparative example 2: does not adsorb perfluoro octoate ion
Step (1-5) is the same as in examples 1-5;
cutting the coating obtained in the step (6) into square tablets with the length of 1cm and the length of 1cm, immersing 4mL of 10mg/L microplastic suspension without perfluoro octoate ions, oscillating for a certain period of time at constant temperature, fully adsorbing the microplastic in the water body, and detecting the microplastic content by a turbidimeter.
The coatings obtained in the examples were examined by scanning electron microscopy under experimental conditions: the result of the metal spraying is shown in fig. 1.
The adsorption experiments were carried out according to the experimental methods described above, and the operation and mechanism of the adsorption experiments are schematically shown in fig. 2 and 3.
The adsorption experiments were performed in accordance with the above experimental methods for example 3 and comparative examples 1 to 2, and the relationship between the reduction amount of the microplastic and the adsorption time was analyzed by taking 3 μm monodisperse polystyrene plastic microspheres as an example. As can be seen from fig. 4, the amount of reduction of the microplastic in the example is significantly higher than that in the comparative example, mainly because, on one hand, the surface of the example is enriched with hydrophobic perfluorooctanoate ions (compared with comparative example 2), so that the microplastic has stronger hydrophobic interaction and the adsorption capacity to the microplastic is enhanced; on the other hand, in the comparative example 1 using the two-step method, after drying, the coating is in a super-hydrophobic state, and an Air cushion layer (Air) can be formed under water to obstruct the adsorption of the micro-plastics on the surface of the coating (the mechanism shown in fig. 3), so that the adsorption capacity is weak; compared with the two-step method, the embodiment 3 adopting the one-step method has better coating surface wettability, fewer air cushions and more sites for micro-plastic adsorption, so that the adsorption capacity to the micro-plastic is stronger.
The adsorption experiments were performed in accordance with the above-described experimental methods for examples 1 to 5 and comparative examples 1 to 2, and the relationship between the reduction rate of microplastic and the type of microplastic was analyzed by taking various microplastics as examples. As can be seen from FIG. 5, the microplastic reduction rate of the examples was superior to that of the comparative examples for all the test microplastics, and the main reason is the same.
The adsorption experiments of examples 1 to 5 and comparative example 2 were performed according to the above-described experimental methods, and the relationship between the reduction rate of perfluorooctanoate ions and the types of microplastic was analyzed by taking various microplastics as examples. As can be seen from FIG. 6, the ratio of reduction of perfluorooctanoate ion was about 80% for all the test microplastics, and about 97% for the comparative example. The reduction of the examples relative to the comparative examples is reduced mainly because the microplastic and the perfluorinated anions form a competing relationship on the surface of the coating, and the examples sacrifice a certain amount of adsorption sites for the perfluorinated anions while adsorbing the microplastic. However, the reduction rate of the embodiment to the two is about 80% as a whole, and the method is a strategy for simultaneously adsorbing the microplastic and the perfluorinated compounds in the water body.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and falls within the scope of the present invention as long as the present invention meets the requirements.
Claims (8)
1. The application of the modified polyvinylidene fluoride material in the simultaneous adsorption of the microplastic and the perfluorinated compound in the water body is characterized in that the preparation method of the modified polyvinylidene fluoride material comprises the following steps:
step (1), respectively placing polyvinylidene fluoride PVDF and ionic liquid IL in a vacuum drying oven, and drying at 60-100 ℃ until the weight is no longer reduced;
the mass ratio of the ionic liquid IL to PVDF is 2-40: 100;
the ionic liquid IL is an ionic liquid containing unsaturated bonds;
step (2), mixing the dried polyvinylidene fluoride PVDF and the ionic liquid IL, adding the mixture into a melting and mixing device, and melting and mixing the mixture for 5-10 min at 180-210 ℃ to obtain a mixture;
step (3), discharging the mixture obtained in the step (2) from a melting and mixing device, cooling to normal temperature, and performing melting and tabletting to obtain a film with the thickness of 1-500 mu m;
step (4), placing the film obtained in the step (3) into a polyethylene bag, radiating and irradiating at normal temperature under vacuum, and then performing methanol Soxhlet extraction for 72-144 hours to obtain an ionic liquid grafted polyvinylidene fluoride film PVDF-g-IL;
the radiation irradiation is electron beam irradiation, and the absorption dose is 25-75 kGy;
step (5), at 60-80 ℃, the ionic liquid grafted polyvinylidene fluoride film obtained in the step (4), a pore-forming agent and a solvent are mixed according to the mass ratio of (0.92-0.98): (0.02-0.08): 5, mixing the solutions in proportion;
and (6) coating the blended solution obtained in the step (5) on a substrate, curing for 1-3 hours in a steam atmosphere with the temperature of 15-25 ℃ and the relative humidity of 60-80%, and drying and molding to obtain the modified polyvinylidene fluoride material.
2. The use according to claim 1, wherein the ionic liquid in step (1) is an imidazole ionic liquid having the following cationic structural formula:
wherein R is 1 Is C 1 ～C 24 Alkyl or C-containing 2 ～C 24 Alkenyl groups; r is R 2 Is C-containing 2 ～C 24 Alkenyl groups;
the anion of the ionic liquid is PF 6 - 、BF 4 - 、Br - 、Cl - 、I - 、NO 3 - 、CF 3 CO 2 - 、CH 3 COO - 、(CF 3 SO 3 ) 2 N - 。
3. The use according to claim 1, wherein in step (2) the melt-kneading temperature is 190℃and the kneading time is 5 minutes.
4. The use according to claim 1, wherein the absorbed dose of the electron beam irradiation in step (4) is 50kGy.
5. The use according to claim 1, wherein the solvent in step (5) is N, N-dimethylformamide DMF.
6. The use according to claim 1, wherein the porogenic agent in step (5) is polyvinylpyrrolidone PVP-K30.
7. The use according to claim 1, wherein the ionic liquid grafted polyvinylidene fluoride film obtained in step (4) in step (5) has a mass ratio of pore-forming agent to solvent of 0.95:0.05:5.
8. the use according to claim 1, wherein the substrate in step (6) is metal, ceramic, glass, wood or fabric.
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