CN110743202A - Emulsified water coalescence material and preparation method and application thereof - Google Patents
Emulsified water coalescence material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an emulsified water coalescent material and a preparation method and application thereof. The fluorinated polyurethane coating disclosed by the invention contains a hydrophobic fluorinated chain segment and a hydrophilic chain segment, has hydrophobic oleophylic characteristics in air, has a contact angle with a water drop of 100-120 degrees, a contact angle with an oil drop of 50-80 degrees, and a contact angle with water under oil is dynamically changed and is reduced from 120-150 degrees to 50-80 degrees within 2min, so that favorable conditions are provided for demulsification and combination of liquid drops in a water-oil emulsion, compared with other fluorocarbon materials in the prior art, the fluorinated polyurethane coating has an obviously better coalescence-separation effect on emulsified water, is suitable for separation of water-oil emulsions containing surfactants of different types and different concentrations, and the water-oil separation efficiency is up to 91-98%.
Description
Technical Field
The invention relates to the technical field of oil-water separation materials, in particular to an emulsified water coalescence material and a preparation method and application thereof.
Background
The automotive diesel oil gradually adopts the national V standard, and the sulfur content in the diesel oil is greatly reduced. The diesel oil is subjected to hydrodesulfurization treatment to reduce the lubricity and stability, so that substances with surface activity, such as a lubricant, an antiwear agent, a stabilizer, a preservative and the like, can be artificially added into the ultra-low sulfur diesel oil. When the temperature difference between day and night is large in the process of diesel oil transportation or diesel oil storage, water easily enters into an oil phase, and forms relatively stable emulsified water which is difficult to separate on an engine through shearing of an oil transfer pump and diffusion of a surfactant to an oil-water interface. The surfactant in the diesel oil moves to an oil-water interface, so that the oil-water interfacial tension is reduced, the deformability of the emulsified water is enhanced, and the emulsified water can stably exist in an oil phase. Under the shearing action of high-pressure and low-pressure pumps of diesel engine, the diameter of emulsified water in the diesel oil is about 3-45 micrometers. Since the water drops with the diameter less than 100 μm are difficult to be rapidly settled by the action of gravity, the emulsified water after shearing can be stably dispersed in the oil phase, and the difficulty of oil-water separation is increased. In a compression ignition system of a diesel engine, a high-pressure common rail system with the pressure of 200MPa sprays fuel into a combustion chamber to be fully combusted, and a fuel injection nozzle is only 2-5 mu m, so that the existence of emulsified water can cause corrosion and blockage of the fuel injection nozzle, reduce the self lubricating property of diesel oil and shorten the service life of the engine. In addition, under cold conditions, the emulsified water freezes to ice, causing clogging of the particulate filter, resulting in engine misfire due to fuel not reaching the combustion chamber, and therefore, it is important to remove the emulsified water from the diesel fuel.
The oil-water separation mainly adopts the methods of gravity settling, centrifugation, distillation, coalescence separation and the like. The gravity settling can not separate the emulsified water on the diesel engine in time, the centrifugal separation operation is inconvenient and has high cost, and the distillation and other means can not be used on the engine, so the oil-water separation on the engine is usually simple and low-cost coalescence separation or screening separation or the combination of the two. These separation materials are usually made of natural or synthetic fibers, or a mixture of both, by different technical means. The coalescence separation method uses a porous material with deep filtration to coalesce small drops of emulsified water in the diesel oil, and then realizes oil-water separation by a gravity settling method. According to the coalescence-separation principle, when the contact angle between emulsified water and the surface of the coalescence material is between 90 and 140 degrees, water drops can roll on the solid surface, and the water drops collide with each other, coalesce and grow, and are released along the flowing direction of diesel oil. The radius of the water drops after coalescence is more than 100 μm, the water drops sink under the action of gravity, and oil-water separation is realized by the density difference of two phases.
CN105964014B discloses that spraying a dopamine-mediated layer on a stainless steel net to perform amidation coupling reaction, so that a stable hydrophilic polymer film is formed on the surface of the stainless steel net, and the method has a remarkable effect on oil-water separation, but the influence of the type and concentration of a surfactant on the stability of an oil-water emulsion is not considered.
CN105926020B discloses super-hydrophilic titanium foam for oil-water separation, which has remarkable oil-water separation effect, but does not consider the problem that the existence of a surfactant at an oil-water interface is not beneficial to oil-water separation.
In the water-oil-solid system, the surfactant is free to move in the oil phase and self-assembles to form micelles at higher concentrations. When water drops enter the oil phase, the surfactant can move to the oil-water interface, and the tension of the oil-water interface is reduced. During filtration, the emulsion contacts the surface of the filtering solid, the surfactant can be adsorbed on the surface of the solid, and the adsorption of the surfactant on the surface of the solid can weaken the action of the surfactant on the oil-water interface. In the current oil-water separation example, the effect of specific analysis of the surfactant on oil-water separation is less studied.
Therefore, there is a need for the development of an emulsified water coalescing material that efficiently separates emulsified water from a surfactant-containing oil-water emulsion.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide an emulsified water coalescing material that efficiently separates emulsified water in a surfactant-containing oil-water emulsion.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an emulsified water coalescing material comprising a substrate and a coating layer of a fluorinated polyurethane coated on a surface of the substrate.
The essence of the fluorinated polyurethane coating is that a fluorinated carbon chain is introduced into organic polymer polyurethane, the fluorinated polyurethane coating contains a hydrophobic fluorinated chain segment and a hydrophilic chain segment, the material shows special physical and chemical properties, the surface energy is obviously lower than that of the polyurethane, and emulsified water shows a special wetting phenomenon on the fluorinated polyurethane coating, thereby being beneficial to coalescence and separation of a surfactant-containing dispersion liquid. Under oil, the wettability change of water drops on the surface and the adsorption effect of the water drops on the surface of the water drops on the surfactant provide favorable conditions for demulsification and combination among the water drops, and particularly greatly improve the oil-water separation efficiency of the surfactant with higher concentration.
The term "comprising" as used herein means that it may include, in addition to the components, other components which impart different characteristics to the emulsified water-containing coalescing material. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed.
The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.
Preferably, the substrate comprises a filter material.
Preferably, the filter material is selected from any one or a combination of at least two of stainless steel felt, cellulose fiber, glass microfiber, glass wool, melt-blown polymer fiber, nylon nanofiber and polyvinylidene fluoride fiber; for example, a pure cellulose fiber filter medium, a glass microfiber or glass wool filter medium, a mixed filter medium of cellulose fibers and micron-sized glass fibers or glass wool, a self-supporting melt-blown PET or PBT filter medium, a composite material of melt-blown PET/PBT and a cellulose fiber filter medium, a composite filter medium of melt-blown PET/PBT and glass microfibers, a composite filter medium of melt-blown PET/PBT and cellulose fibers and glass microfibers, other melt-blown polymer fine fiber filter media, a composite porous filter medium formed by electrospinning nylon nanofibers, polyvinylidene fluoride fibers and other filter media.
Preferably, the pore size of the substrate is 0.5 to 20 μm, such as 0.5 μm, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, or 20 μm.
Preferably, the substrate has a thickness of 0.05 to 100mm, such as 0.05mm, 0.1mm, 0.5mm, 1mm, 2mm, 5mm, 10mm, 20mm, 50mm, 80mm, or 100mm, and the like.
Preferably, -C in the fluorine-containing polyurethane coatingxF2x+1- (fluorine-containing repeating segment) and-CH2CH2The molar ratio of O- (ethoxy repeating segment) is (2-8): 1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1 or 8:1, and preferably (4-5): 1.
Preferably, the contact angle between the fluorine-containing polyurethane coating and a water drop is 100-200 degrees, such as 100 degrees, 110 degrees, 120 degrees, 130 degrees, 140 degrees, 150 degrees, 160 degrees, 170 degrees, 180 degrees, 190 degrees or 200 degrees.
In a second aspect, the present invention provides a method for preparing an emulsified water coalescing material according to the first aspect, comprising the steps of:
(1) preparing a fluorine-containing polyurethane emulsion: mixing fluorine-containing alcohol, an organic solvent and a catalyst, adding polyisocyanate, prepolymerizing to obtain a prepolymer, adding a coupling agent and a hydrophilic polymer, continuing to react to obtain a pre-emulsion, adding water to dilute, and removing the organic solvent to obtain a fluorine-containing polyurethane emulsion;
(2) adding a solvent into the fluorinated polyurethane emulsion obtained in the step (1) for dilution to obtain a coating liquid;
(3) and (3) coating the coating liquid obtained in the step (2) on the surface of a base material, and curing to obtain the emulsified water coalescence material.
Preferably, the fluorine-containing alcohol in the step (1) has a structural formula of X-Y-N (R) -R' OH;
wherein X is a fluoroalkyl chain having 3-10 carbon atoms, and the number of carbon atoms can be 3, 4, 5, 6, 7, 8, 9 or 10; y is selected from any one or a combination of at least two of alkylene, alkyleneoxy, sulfenyl or sulfoxy; r and R' are alkyl chains with 1-10 carbon atoms, and the number of the carbon atoms can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Wherein, the fluorine-containing alcohol is short-chain alcohol without biological accumulated toxicity, and Y is used as a transition group to adjust the connection characteristic between the fluorine-containing chain segment and the main chain segment and optimize the separation effect of the oil-water emulsion.
Preferably, the number of carbon atoms of X is 3 to 5.
Preferably, Y is sulfoxy;
preferably, the organic solvent in step (1) comprises any one or a combination of at least two of acetone, butanone, cyclohexanone or 4-methyl-2-pentanone, wherein typical but non-limiting combinations are: a combination of acetone and butanone, a combination of cyclohexanone and 4-methyl-2-pentanone, a combination of acetone, butanone and cyclohexanone, a combination of butanone, cyclohexanone and 4-methyl-2-pentanone, a combination of acetone, butanone, cyclohexanone and 4-methyl-2-pentanone;
preferably, the catalyst of step (1) comprises a tin-containing catalyst, preferably dibutyltin dilaurate and/or dibutyltin diacetate.
Preferably, the polyisocyanate of step (1) comprises any one of diphenylmethane diisocyanate (MDI), toluene-2, 4-diisocyanate (TDI) or Hexamethylene Diisocyanate (HDI) or a combination of at least two thereof; typical but non-limiting combinations among these are: the combination of MDI and TDI, the combination of MDI and HDI, the combination of TDI and HDI, the combination of MDI, TDI and HDI, or the dimer, trimer and the like of MDI, TDI and HDI. The degree of reaction progress and the structure of the synthesized product can be controlled by adjusting the percentage content of NCO groups in the polyisocyanate.
Preferably, the prepolymerization conditions in step (1) are as follows: reacting at 40-80 ℃ for 1-2 h, for example, the prepolymerization temperature is 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, and the like, and the time is 1h, 1.2h, 1.5h, 1.8h or 2h, and the like; preferably 50-70 ℃ for 1-2 h.
Preferably, in the step (1), the mass ratio of the fluorine-containing alcohol to the polyisocyanate is (1-6) to (2-8), for example, 1:2, 1:5, 1:8, 3:2, 3:3, 3:8, 6:2, 6:5, or 6: 8.
Preferably, the coupling agent in step (1) comprises a silane coupling agent, preferably any one or a combination of at least two of aminopropyltriethoxysilane, aminoethyltriethoxysilane or aminopropyltrimethoxysilane; typical but non-limiting combinations among these are: aminopropyltriethoxysilane in combination with aminoethyltriethoxysilane, aminopropyltriethoxysilane in combination with aminopropyltrimethoxysilane, aminoethyltriethoxysilane in combination with aminopropyltrimethoxysilane, preferably aminopropyltriethoxysilane, aminoethyltriethoxysilane in combination with aminopropyltrimethoxysilane.
Preferably, the hydrophilic polymer in step (1) comprises a polyoxyethylene alcohol hydrophilic polymer, preferably polyethylene glycol or a derivative thereof, further preferably polyethylene glycol monomethyl ether and/or polyethylene glycol dimethyl ether.
Preferably, the conditions for continuing the reaction in step (1) are as follows: reacting for 0.5-1 h at 60-80 ℃; for example, the reaction temperature is 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃ or 80 ℃, and the reaction time is 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1 h.
Preferably, in the step (1), the mass ratio of the fluorine-containing alcohol to the coupling agent to the hydrophilic polymer is (1-6): (1-5): 2-6, for example, 1:1:2, 1:5:2, 1:1:6, 1:5:6, 2:3:2, 2:5:4, 6:1:2, 6:5:2, 6:1:6, or 6:5: 2.
Preferably, the water of step (1) comprises deionized water.
Preferably, in the step (1), the mass ratio of the fluorine-containing alcohol to the water is (1-6) to (5-8), for example, 1:5, 1:7, 1:8, 3:5, 3:8, 6:5, 6:6, or 6: 8.
Preferably, the method for removing the organic solvent in the step (1) comprises rotary evaporation.
Preferably, the solvent of step (2) comprises an organic solvent and/or water.
Preferably, the organic solvent comprises any one of isopropanol, N-dimethylformamide, N-methylpyrrolidone or acetone, or a combination of at least two thereof, wherein typical but non-limiting combinations are: a combination of isopropanol and N, N-dimethylformamide, a combination of N-methylpyrrolidone and acetone, a combination of isopropanol, N-dimethylformamide and N-methylpyrrolidone, a combination of isopropanol, N-dimethylformamide, N-methylpyrrolidone and acetone.
Preferably, the content of the fluorinated polyurethane emulsion in the coating liquid of step (2) is 5 to 30 wt%, such as 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, or 30 wt%.
Preferably, when the solvent in the step (2) is a mixture of an organic solvent and water, the mass ratio of the organic solvent to the water is 1 (10-17), such as 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, or 1: 17.
Preferably, the curing conditions in step (3) are as follows: curing at 60-350 ℃ for 5 min-4 h; for example, the curing temperature is 60 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃, 250 ℃, 280 ℃, 300 ℃, 320 ℃ or 350 ℃, and the curing time is 5min, 15min, 30min, 45min, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h or 4 h.
Preferably, the curing of step (3) is performed in a drying oven or a muffle furnace.
As a preferable technical scheme of the invention, the preparation method of the emulsified water coalescence material comprises the following steps:
(1) preparing a fluorine-containing polyurethane emulsion: mixing fluorine-containing alcohol, an organic solvent and a catalyst, adding polyisocyanate, and carrying out prepolymerization reaction at 40-80 ℃ for 1-2 h to obtain a prepolymer, wherein the structural formula of the fluorine-containing alcohol is X-Y-N (R) -R' OH; x is a fluoroalkyl chain with 3-10 carbon atoms; y is selected from any one or a combination of at least two of alkylene, alkyleneoxy, sulfenyl or sulfoxy; r and R' are alkyl chains with 1-10 carbon atoms respectively and independently; the polyisocyanate comprises any one or the combination of at least two of diphenylmethane diisocyanate, toluene-2, 4-diisocyanate or hexamethylene diisocyanate; the mass ratio of the fluorine-containing alcohol to the polyisocyanate is (1-6) to (2-8);
adding a coupling agent and a hydrophilic polymer, wherein the hydrophilic polymer comprises polyethylene glycol or derivatives thereof, reacting for 0.5-1 h at 60-80 ℃ to obtain a pre-emulsion, diluting with water, and removing an organic solvent by rotary evaporation to obtain a fluorinated polyurethane emulsion, wherein the mass ratio of fluorinated alcohol to hydrophilic polymer is (1-6) - (1-5) - (2-6);
(2) adding a solvent into the fluorinated polyurethane emulsion obtained in the step (1) for dilution to obtain a coating liquid, wherein the content of the fluorinated polyurethane emulsion in the coating liquid is 5-30 wt%;
(3) and (3) coating the coating liquid obtained in the step (2) on the surface of a base material, and curing for 5 min-4 h at the temperature of 60-350 ℃ in a drying box or a muffle furnace to obtain the emulsified water coalescence material.
In a third aspect, the present invention provides the use of an emulsified water coalescing material according to the first aspect for oil-water separation of a diesel emulsion.
Preferably, the diesel oil emulsion contains a surfactant, preferably a fat-soluble surfactant, and further preferably a high-purity trimer acid and/or glycerol monooleate. The fluorine-containing polyurethane coating can enhance the adsorption of the surfactant in the diesel on the surface of the material and ensure that the surface has special wettability to water under oil. Under the condition of 0-400 ppm of surfactant concentration, the emulsified water coalescence material still has high separation efficiency.
Preferably, the concentration of surfactant in the diesel emulsion is 0 to 400ppm, such as 0ppm, 10ppm, 20ppm, 50ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, or the like.
Preferably, the diesel emulsion comprises a diesel emulsion in a diesel engine.
Compared with the prior art, the invention has at least the following beneficial effects:
1. the fluorinated polyurethane coating disclosed by the invention contains a hydrophobic fluorinated chain segment and a hydrophilic chain segment, has hydrophobic oleophylic characteristics in air, has a contact angle with a water drop of 100-120 degrees, a contact angle with an oil drop of 50-80 degrees, and a contact angle with water under oil is dynamically changed and is reduced from 120-150 degrees to 50-80 degrees within 2min, so that favorable conditions are provided for demulsification and combination among liquid drops in a water-oil emulsion, and compared with other fluorocarbon materials in the prior art, the fluorinated polyurethane coating has an obviously better coalescence-separation effect on emulsified water;
2. due to the fluorinated polyurethane coating, the emulsified water coalescence material is suitable for separating water-oil emulsions containing different types of surfactants with different concentrations, and the water-oil separation efficiency is up to 91-98%;
3. the fluorinated polyurethane coating has water-repellent and anti-fouling effects to a certain extent, so that the fluorinated polyurethane coating has a self-cleaning effect and has potential application in the fields of building industry, daily use and the like;
4. the raw materials used in the preparation method are easy to degrade in nature, and the product is green and environment-friendly.
Drawings
FIG. 1 is an SEM photograph of a stainless steel felt coated with a fluorinated polyurethane coating in example 1 of the present invention;
FIG. 2 is an SEM image of an uncoated stainless steel felt of comparative example 1 of the present invention;
FIG. 3 is a SEM photograph at a low magnification showing the surface of the fluorine-containing polyurethane coating layer in example 1 of the present invention;
FIG. 4 is a SEM photograph at a high magnification showing the surface of the fluorine-containing polyurethane coating layer in example 1 of the present invention;
FIG. 5 is a contact angle of a water droplet on the surface of a fluorine-containing polyurethane coating layer in example 1 of the present invention;
FIG. 6 is a graph showing contact angle change curves of emulsified water drops in diesel fuel containing 200ppm of glyceryl monooleate according to the present invention on the surfaces of the coatings of example 1, comparative example 2 and comparative example 4;
FIG. 7 is a graph comparing the separation efficiency of emulsified water from ultra low sulfur diesel fuel containing different concentrations of high purity trimer acid with emulsified water coalescent materials of example 1, comparative example 2, and comparative example 4 according to the present invention;
FIG. 8 is a graph showing the separation efficiency of the emulsified water coalescer according to the present invention in ultra low sulfur diesel fuel containing glycerol monooleate at various concentrations in example 1, comparative example 2 and comparative example 4.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
In the specific implementation mode of the invention, the oil-water separation efficiency of each example and each comparative example is measured by the following method:
a diesel oil emulsion was prepared using apparatus EMCEE MSEP (ASTM D7261) and subjected to a filtration experiment, and 50. mu.L of ultrapure water was added to 50mL of surfactant-containing diesel oil in a 60mL syringe, and stirred at a high speed of 25000r/min to give a diesel oil emulsion having a droplet size of 4 to 35 μm. The emulsified water coalescing materials of each example and comparative example were separately placed in a filter, and the filter was mounted on the head of a syringe, which was then placed on a holder of an EMCEE device. When the EMCEE equipment is operated, the lever pushes the plunger piston to enable the emulsion to pass through the stainless steel felt containing the coating, and the filtered diesel oil is obtained. The filtrate was collected and the water content of the filtrate was measured using a karl fischer moisture analyzer. The oil-water separation efficiency was calculated from the following formula:
wherein, C0Is the initial mass fraction of water in the oil phase, CfIs the mass fraction of water not separated in the filtrate.
Example 1
An emulsified water-agglomerating material comprises a stainless steel felt with a pore diameter of 8 μm and a fluorine-containing polyurethane coating coated on the surface of the stainless steel felt, wherein-C in the fluorine-containing polyurethane coating3F7-and-CH2CH2The molar ratio of O-is 6: 1.
The preparation steps are as follows:
(1) preparing a fluorine-containing polyurethane emulsion: in a nitrogen atmosphere, under the condition of constant temperature of 60 ℃, adding 6 parts by weight of fluorine-containing alcohol (the structure of the fluorine-containing alcohol is X-Y-N (R) -R 'OH, wherein the carbon atom number of a fluorine-containing alkyl chain X is 3, a transition group Y is a sulfoxy group, R and R' are respectively alkyl chains with the carbon atom numbers of 3 and 5), acetone and dibutyltin diacetate into a reaction container, fully mixing, then adding 5 parts of HDI, stirring for 2 hours at constant temperature of 60 ℃, and fully reacting to obtain a product; continuously stirring the product at constant temperature for 1h, adding 3 parts of aminopropyl trimethoxy silane and then adding 2 parts of polyethylene glycol, and fully reacting to obtain a fluorine-containing polyurethane product; adding 6 parts of deionized water into the product, stirring to form emulsion, and removing the organic solvent from the mixture by using a rotary evaporator to obtain fluorine-containing polyurethane emulsion;
(2) diluting the fluorine-containing polyurethane polymer, isopropanol and ultrapure water according to the mass ratio of 10%, 20% and 70% to obtain a coating liquid;
(3) respectively coating the fluorine-containing polyurethane coating solution on a glass sheet and a stainless steel felt, selecting a stainless steel felt with the aperture of 8 mu m, and putting the coated glass sheet and the coated stainless steel felt into a 130 ℃ drying oven for curing for 2h to obtain the glass sheet and the stainless steel felt with the fluorine-containing polyurethane coating. An SEM image of a stainless steel felt coated with a fluorinated polyurethane coating is shown in fig. 1, and a low magnification SEM image of the surface of the fluorinated polyurethane coating is shown in fig. 3; a high magnification SEM image of the surface of the fluorinated polyurethane coating is shown in fig. 4.
The coating on the glass plate was used only to test the contact angle of the fluorine-containing polyurethane coating with water and oil, and as shown in fig. 5, the resulting contact angle of the fluorine-containing polyurethane coating with water was 111.2 °. The contact angle of the resulting fluorinated polyurethane coating with oil was 70 °. Within 2min, the contact angle of the drop of oil drops decreased from 118 ° to 60 ° (fig. 6). For diesel emulsions containing 50ppm, 100ppm, 200ppm high purity trimer acid, the oil-water separation efficiency was 94.3%, 92.1%, 81.6% using uncoated stainless steel felt, and the oil-water separation efficiency was 94.3%, 95.0%, 96.0% using this fluorinated polyurethane coated stainless steel felt (fig. 7). For diesel fuel containing 50ppm, 100ppm and 200ppm of oleic acid ester surfactant, the oil-water separation efficiency of uncoated stainless steel felt was 94.7%, 50.8% and 45.1%, and the oil-water separation efficiency of stainless steel felt coated with fluorinated polyurethane was 94.4%, 92.3% and 91.5% (fig. 8).
Example 2
An emulsified water coalescence material comprises a melt-blown polymer fiber filter medium with the pore diameter of 10 mu m and a fluorine-containing polyurethane coating coated on the surface of the melt-blown polymer fiber filter medium. In the coating of fluorine-containing polyurethane-C4F9-and-CH2CH2The molar ratio of O-is 4: 1.
The preparation steps are as follows:
(1) preparing a fluorine-containing polyurethane emulsion: under the atmosphere of nitrogen, at the constant temperature of 70 ℃,4 parts of fluorine-containing alcohol (the structure of the fluorine-containing alcohol is X-Y-N (R) -R 'OH, wherein the carbon atom number of a fluorine-containing alkyl chain X is 4, a transition group Y is a sulfoxy group, R and R' are respectively alkyl chains with the carbon atom numbers of 3 and 5), acetone and dibutyltin diacetate are added into a reaction container in parts by weight, and after the mixture is fully mixed, 2 parts of TDI is added, and the mixture is stirred at the constant temperature of 70 ℃ for 1 hour to fully react to obtain a product; continuously stirring the product at constant temperature for 0.8h, adding 3 parts of aminopropyltriethoxysilane, adding 5 parts of polyethylene glycol alkyl ether, and fully reacting to obtain a fluorine-containing polyurethane product; adding 8 parts of deionized water into the product, and stirring to obtain emulsion; removing the organic solvent from the mixture by using a rotary evaporator to obtain a fluorine-containing polyurethane emulsion;
(2) diluting fluorine-containing polyurethane polymer, N, N-dimethylformamide and ultrapure water according to the mass ratio of 20%, 20% and 60% to obtain coating liquid;
(3) respectively coating the fluorine-containing polyurethane coating solution on a glass sheet and a melt-blown polymer fiber filter medium, selecting the pore diameter of the melt-blown polymer fiber filter medium to be 10 mu m, and putting the coated glass sheet and the melt-blown polymer fiber filter medium into a drying oven at 110 ℃ for curing for 4h to obtain the glass sheet with the fluorocarbon coating and the melt-blown polymer fiber filter medium.
The coating on the glass sheet was used only to test the contact angle of the fluorinated polyurethane coating with water and oil, the resulting fluorinated polyurethane coating had a contact angle with water of 113 ° with oil of 74 °, and the contact angle of a drop of water under oil dropped within 2min dropped from 150 ° to 80 °. For diesel oil emulsion containing 50ppm, 100ppm and 200ppm high-purity trimer acid, the oil-water separation efficiency of uncoated melt-blown polymer fiber filter medium is 95.1%, 93.4% and 86.7%, and the oil-water separation efficiency of melt-blown polymer fiber filter medium using the fluorinated polyurethane coating is 95.4%, 93.2% and 94.7%. For diesel oil emulsion containing 50ppm, 100ppm and 200ppm of glycerol monooleate, the oil-water separation efficiency of uncoated melt-blown polymer fiber filter medium is 92.7%, 46.5% and 39.6%, and the oil-water separation efficiency of melt-blown polymer fiber filter medium using the fluorinated polyurethane coating is 93.5%, 92.7% and 92.1%.
Example 3
An emulsified water coalescing material comprising a stainless steel felt having a pore size of 12 μm and a fluorine-containing polyurethane coating layer coated on the surface of the stainless steel felt. Fluorine-containing polyurethane coating Medium-C5F11-and-CH2CH2The molar ratio of O-is 4: 1.
The preparation steps are as follows:
(1) preparing a fluorine-containing polyurethane emulsion: under the atmosphere of nitrogen, at the constant temperature of 55 ℃, in parts by weight, adding 2 parts of fluorine-containing alcohol (the structure of the fluorine-containing alcohol is X-Y-N (R) -R 'OH, wherein the carbon atom number of a fluorine-containing alkyl chain X is 5, a transition group Y is a sulfoxy group, R and R' are respectively alkyl chains with the carbon atom numbers of 3 and 5), butanone and dibutyltin dilaurate into a reaction container, fully mixing, then adding 5 parts of TDI, stirring for 2 hours at the constant temperature of 55 ℃, and fully reacting to obtain a product; continuously stirring the product at constant temperature for 2 hours, adding 3 parts of aminoethyl triethoxysilane, adding 3 parts of polyethylene glycol alkyl ether, and fully reacting to obtain a fluorine-containing polyurethane product; adding 7 parts of deionized water into the product, and stirring to obtain emulsion; removing the organic solvent from the mixture by using a rotary evaporator to obtain a fluorine-containing polyurethane emulsion;
(2) diluting the fluorine-containing polyurethane polymer and N-methyl pyrrolidone according to the mass ratio of 25% to 75% to obtain a coating liquid;
(3) respectively coating the fluorine-containing polyurethane coating solution on a glass sheet and a stainless steel felt, selecting the stainless steel felt with the aperture of 12 mu m, and curing the coated glass sheet and the coated stainless steel felt in a 180 ℃ muffle furnace for 40min to obtain the glass sheet with the fluorocarbon coating and the stainless steel felt.
The coating on the glass sheet was used only to test the contact angle of the fluorinated polyurethane coating with water and oil, the resulting fluorinated polyurethane coating had a contact angle with water of 100 ° with oil of 80 °, and the contact angle of a drop of water under oil dropped within 2min dropped from 145 ° to 75 °. For diesel oil emulsion containing 50ppm, 100ppm and 200ppm high purity trimer acid, the oil-water separation efficiency of uncoated stainless steel felt is 93.1%, 90.4% and 81.1%, and the oil-water separation efficiency of stainless steel felt coated with the fluorine-containing polyurethane is 93.7%, 93.5% and 91.4%. For diesel emulsions containing 50ppm, 100ppm, and 200ppm glycerol monooleate, the oil-water separation efficiency was 94.2%, 35.8%, and 22.7% for uncoated stainless steel felts, and 94.6%, 91.8%, and 92.6% for the fluorinated polyurethane-coated stainless steel felts.
Example 4
An emulsified water coalescing material comprising a glass microfiber filter media having a pore size of 10 μm and a fluorinated polyurethane coating coated on a surface of the glass microfiber filter media. Fluorine-containing polyurethane coating Medium-C3F7-and-CH2CH2The molar ratio of O-is 4: 1.
The preparation steps are as follows:
(1) preparing a fluorine-containing polyurethane emulsion: under the atmosphere of nitrogen, at the constant temperature of 80 ℃, in parts by weight, adding 2 parts of fluorine-containing alcohol (the structure of the fluorine-containing alcohol is X-Y-N (R) -R 'OH, wherein the carbon atom number of a fluorine-containing alkyl chain X is 3, a transition group Y is a sulfoxy group, R and R' are respectively alkyl chains with the carbon atom numbers of 2 and 4), cyclohexanone and dibutyltin dilaurate into a reaction container, fully mixing, then adding 3 parts of MDI, stirring at the constant temperature of 65 ℃ for 1h, and fully reacting to obtain a product; continuously stirring the product at constant temperature for 0.5h, adding 3 parts of aminoethyl triethoxysilane, adding 2 parts of polyethylene glycol alkyl ether, and fully reacting to obtain a fluorine-containing polyurethane product; adding 5 parts of deionized water into the product, and stirring to obtain emulsion; removing the organic solvent from the mixture by using a rotary evaporator to obtain a fluorine-containing polyurethane emulsion;
(2) diluting fluorine-containing polyurethane polymer, isopropanol and ultrapure water according to the mass ratio of 15%, 10% and 75% to obtain coating liquid;
(3) respectively coating the fluorine-containing polyurethane coating solution on a glass sheet and a glass microfiber filter medium, wherein the pore diameter of the glass microfiber filter medium is 10 microns, and curing the coated glass sheet and the glass microfiber filter medium in a 120 ℃ drying oven for 2.5 hours to obtain the glass sheet with the fluorocarbon coating and the glass microfiber filter medium.
The coating on the glass sheet was used only to test the contact angle of the fluorinated polyurethane coating with water and oil, the resulting fluorinated polyurethane coating had a contact angle with water of 116 ° with oil of 83 °, and the contact angle of a drop of water under oil dropped within 2min decreased from 140 ° to 80 °. For diesel oil emulsions containing 50ppm, 100ppm, 200ppm high purity trimer acid, the oil-water separation efficiency using uncoated glass microfiber filter media was 94.6%, 92.9%, 86.5%, and the oil-water separation efficiency using glass microfiber filter media coated with this fluorinated polyurethane was 94.5%, 95.4%, 93.3%. For diesel emulsions containing 50ppm, 100ppm, 200ppm glycerol monooleate, the oil-water separation efficiency was 94.7%, 55.9%, 46.0% using uncoated glass microfiber filter media and 91.7%, 93.4%, 92.9% using this fluorinated polyurethane coated glass microfiber filter media.
Example 5
An emulsified water-coalescing material comprising a cellulose fiber filter medium having a pore size of 8 μm and a fluorine-containing polyurethane coating layer coated on the surface of the cellulose fiber filter medium, wherein-C is contained in the fluorine-containing polyurethane coating layer4F9-and-CH2CH2The molar ratio of O-is 5: 1.
The preparation steps are as follows:
(1) preparing a fluorine-containing polyurethane emulsion: under the atmosphere of nitrogen, at the constant temperature of 70 ℃,4 parts of fluorine-containing alcohol (the structure of the fluorine-containing alcohol is X-Y-N (R) -R 'OH, wherein the carbon atom number of a fluorine-containing alkyl chain X is 4, a transition group Y is a sulfoxy group, R and R' are respectively alkyl chains with the carbon atom numbers of 2 and 4), cyclohexanone and dibutyltin dilaurate are added into a reaction container in parts by weight, and after the mixture is fully mixed, 3 parts of MDI is added, and the mixture is stirred at the constant temperature of 70 ℃ for 1.5 hours to fully react to obtain a product; continuously stirring the product at constant temperature for 0.5h, adding 3 parts of aminopropyltriethoxysilane, adding 2 parts of polyethylene glycol, and fully reacting for 1h to obtain a fluorine-containing polyurethane product; adding 6 parts of deionized water into the product, and stirring to obtain emulsion; removing the organic solvent from the mixture by using a rotary evaporator to obtain a fluorine-containing polyurethane emulsion;
(2) diluting the fluorine-containing polyurethane polymer and ultrapure water according to a mass ratio of 10% and a 90% ratio to obtain a coating solution;
(3) respectively coating the fluorine-containing polyurethane coating solution on a glass sheet and a cellulose fiber filter medium, wherein the pore diameter of the cellulose fiber filter medium is 8 mu m, and curing the coated glass sheet and the cellulose fiber filter medium in a drying oven at 140 ℃ for 1h to obtain the glass sheet with the fluorocarbon coating and the cellulose fiber filter medium.
The coating on the glass sheet is only used for testing the contact angle of the fluorinated polyurethane coating with water and oil, the contact angle of the obtained fluorocarbon coating glass sheet with water is 100 degrees, the contact angle with oil is 50 degrees, and the contact angle of a water drop under oil is reduced from 120 degrees to 70 degrees within 2 minutes. For diesel oil emulsions containing 50ppm, 100ppm, 200ppm of high purity trimer acid, the oil-water separation efficiency using uncoated cellulose fiber filter media was 93.8%, 92.2%, 88.1%, and the oil-water separation efficiency using this fluorinated polyurethane coated cellulose fiber filter media was 93.5%, 92.4%, 91.9%. For diesel fuel containing 50ppm, 100ppm, 200ppm glycerol monooleate, the oil-water separation efficiency was 91.5%, 49.4%, 41.3% using uncoated cellulose fiber filter media, and the oil-water separation efficiency was 95.2%, 93.2%, 91.4% using this fluorinated polyurethane coated cellulose fiber filter media.
Example 6
An emulsified water coalescence material, which comprises a nylon nano-fiber filter medium with the pore diameter of 10 mu m and a fluorine-containing polyurethane coating coated on the surface of the nylon nano-fiber filter medium, wherein-C in the fluorine-containing polyurethane coating5F11-and-CH2CH2The molar ratio of O-is 6: 1.
The preparation steps are as follows:
(1) preparing a fluorine-containing polyurethane emulsion: under the nitrogen atmosphere, at the constant temperature of 45 ℃, in parts by weight, adding 6 parts of fluorine-containing alcohol (fluorine-containing alcohol structure: X-Y-N (R) -R 'OH, wherein the carbon atom number of a fluorine-containing alkyl chain X is 5, a transition group Y is a sulfoxy group, R and R' are respectively alkyl chains with the carbon atom numbers of 2 and 4), 4-methyl-2-pentanone and dibutyltin dilaurate into a reaction container, fully mixing, adding 8 parts of HDI, stirring at the constant temperature of 45 ℃ for 2 hours, and fully reacting to obtain a product; continuously stirring the product at constant temperature for 1h, adding 5 parts of aminopropyl trimethoxy silane and 4 parts of polyethylene glycol, and fully reacting for 2h to obtain a fluorine-containing polyurethane product; adding 7 parts of deionized water into the product, and stirring to obtain emulsion; removing the organic solvent from the mixture by using a rotary evaporator to obtain a fluorine-containing polyurethane emulsion;
(2) diluting fluorine-containing polyurethane polymer, acetone and ultrapure water according to the mass ratio of 10%, 10% and 80% to obtain coating liquid;
(3) respectively coating the fluorine-containing polyurethane coating solution on a glass sheet and a nylon nano-fiber filter medium, wherein the aperture of the nylon nano-fiber filter medium is 10 mu m, and curing the coated glass sheet and the nylon nano-fiber filter medium in a muffle furnace at 110 ℃ for 4h to obtain the glass sheet with the fluorocarbon coating and the nylon nano-fiber filter medium.
The coating on the glass sheet was used only to test the contact angle of the fluorinated polyurethane coating with water and oil, the resulting fluorinated polyurethane coating had a contact angle with water of 120 ° with oil of 80 °, and the contact angle of a drop of water under oil dropped within 2min dropped from 150 ° to 70 °. For diesel containing 50ppm, 100ppm and 200ppm of high-purity trimer acid, the oil-water separation efficiency of the uncoated nylon nanofiber filter medium is 96.7%, 95.2% and 87.1%, and the oil-water separation efficiency of the nylon nanofiber filter medium using the fluorinated polyurethane coating is 95.6%, 93.5% and 94.3%. For diesel emulsions containing 50ppm, 100ppm, 200ppm glycerol monooleate, the oil-water separation efficiency using uncoated nylon nanofiber filter media was 94.9%, 50.7%, 37.0%, and the oil-water separation efficiency using this fluorinated polyurethane coated nylon nanofiber filter media was 93.3%, 92.5%, 91.8%.
Comparative example 1
The only difference from example 1 is: the fluorinated polyurethane coating was omitted.
An SEM image of the uncoated stainless steel felt is shown in fig. 2.
Comparative example 2
The only difference from example 1 is: a Polytetrafluoroethylene (PTFE) coating is used in place of the fluorinated polyurethane coating.
Comparative example 3
An emulsified water coalescing material comprising a stainless steel felt having a pore size of 8 μm and a PTFE coating applied to the surface of the stainless steel felt.
The preparation method comprises the following steps:
(1) diluting a PTFE polymer and ultrapure water according to the mass ratio of 30% to 70% to obtain a coating solution;
(2) respectively coating the PTFE coating solution on a glass sheet and a stainless steel felt with the average pore diameter of 8 mu m, and curing the coated glass sheet and the stainless steel felt in a 330 ℃ muffle furnace for 15min to obtain the glass sheet with the fluorocarbon coating and the stainless steel felt.
The coating on the glass sheet was used only to test the contact angle of the coating with water and oil, the resulting PTFE coating had a contact angle with water of 120 °, a contact angle with oil of 30 °, and a contact angle of a drop of water under oil of 160 °. The oil-water separation efficiency of uncoated stainless steel felt was 94.1%, 93.8%, 84.4% for diesel oil emulsion containing 50ppm, 100ppm, 200ppm of high purity trimer acid, and the separation efficiency of PTFE coated stainless steel felt was 81.3%, 57.5%, 47.4%, and the separation efficiency of uncoated stainless steel felt was 93.5%, 40.8%, 35.0% for diesel oil emulsion containing 50ppm, 100ppm, 200ppm of glycerol monooleate, and the separation efficiency of stainless steel felt using this PTFE coating was 85.2%, 23.1%, 23.8%, respectively. It can be seen that in both cases the coating worsens the separation.
Comparative example 4
The only difference from example 1 is: the fluorine-containing polyurethane coating was replaced by a PVDF coating.
Comparative example 5
An emulsified water coalescing material comprising a stainless steel felt having a pore size of 10 μm and a fluorinated ethylene propylene copolymer (FEP) coating applied to the surface of the stainless steel felt.
The preparation method comprises the following steps:
(1) diluting FEP, isopropanol and ultrapure water according to the mass ratio of 15%, 15% and 70% to obtain a coating liquid;
(2) respectively coating the FEP coating solution on a glass sheet and a stainless steel felt, wherein the aperture of the stainless steel felt is 10 mu m, and curing the coated glass sheet and the coated stainless steel felt in a 180 ℃ muffle furnace for 30min to obtain the glass sheet with the fluorocarbon coating and the stainless steel felt.
The coating on the glass sheet was used only to test the contact angle of the coating with water, oil, the resulting FEP coating had a contact angle with water of 110 °, a contact angle with oil of 80 °, and a contact angle of a drop of water under oil of 160 °. For diesel oil emulsion containing 50ppm, 100ppm and 200ppm high purity trimer acid, the oil-water separation efficiency of uncoated stainless steel felt is 93.2%, 92.6% and 80.1%, and the oil-water separation efficiency of the stainless steel felt coated with FEP is 88.7%, 75.7% and 45.2%. For diesel emulsions containing 50ppm, 100ppm and 200ppm of glycerol monooleate, the oil-water separation efficiency of uncoated stainless steel felts was 92.7%, 43.5% and 29.3%, and that of FEP-coated stainless steel felts was 81.4%, 25.7% and 28.8%. It can be seen that in both cases the coating worsens the separation.
Comparative example 6
An emulsified water coalescing material comprising a stainless steel felt having a pore size of 12 μm and a PVDF coating layer coated on the surface of the stainless steel felt.
The preparation method comprises the following steps:
(1) diluting a PVDF polymer and N-methyl pyrrolidone according to the mass ratio of 20% to 80% to obtain a coating liquid;
(2) and respectively coating the PVDF coating solution on a glass sheet and a stainless steel felt, selecting the stainless steel felt with the aperture of 12 mu m, and putting the coated glass sheet and the stainless steel felt into a drying oven at 80 ℃ for curing for 3h to obtain the glass sheet with the PVDF coating and the stainless steel felt.
The coating on the glass sheet is only used for testing the contact angle of the coating with water and oil, the contact angle of the obtained fluorocarbon coated glass sheet with water is 100 degrees, the contact angle with oil is 10 degrees, and the contact angle of a water drop under oil is 160 degrees. For diesel oil emulsion containing 50ppm, 100ppm and 200ppm high purity trimer acid, the oil-water separation efficiency of uncoated stainless steel felt is 92.0%, 86.7% and 76.4%, and the oil-water separation efficiency of the stainless steel felt coated with PVDF is 89.0%, 83.2% and 75.5%. For diesel emulsions containing 50ppm, 100ppm, and 200ppm glycerol monooleate, the oil-water separation efficiency was 90.7%, 44.6%, and 32.5% for uncoated stainless steel felts, and 94.7%, 41.5%, and 27.8% for PVDF-coated stainless steel felts. In both cases, it can be seen that at high surfactant concentrations, the coating worsens separation.
Comparative example 7
An emulsified water coalescing material comprising a stainless steel felt having a pore size of 14 μm and a polyfluoroethylene coating applied to the surface of the stainless steel felt.
The preparation method comprises the following steps:
(1) diluting a polyvinyl fluoride polymer and N, N-dimethylformamide according to the mass ratio of 25% to 75% to obtain a coating liquid;
(2) respectively coating the polyfluortetraethylene coating solution on a glass sheet and a stainless steel felt, selecting the stainless steel felt with the aperture of 14 mu m, and curing the coated glass sheet and the coated stainless steel felt in a muffle furnace at 170 ℃ for 20min to obtain the glass sheet with the fluorocarbon coating and the stainless steel felt.
The coating on the glass sheet was used only to test the contact angles of the coating with water and oil, the resulting polyfluoroethylene coating had a contact angle with water of 96 °, a contact angle with oil of 8 °, and a contact angle with a drop of water under oil of 150 °. The contact angle of the obtained fluorocarbon-coated glass sheet with water is 96 degrees, the contact angle with oil is 8 degrees, and the contact angle of a water drop under the oil is 150 degrees. For diesel oil emulsion containing 50ppm, 100ppm and 200ppm high purity trimer acid, the oil-water separation efficiency of uncoated stainless steel felt is 89.7%, 83.4% and 79.6%, and the oil-water separation efficiency of the polyfluoroethylene coated stainless steel felt is 88.3%, 80.7% and 70.4%. For diesel emulsions containing 50ppm, 100ppm and 200ppm of glycerol monooleate, the oil-water separation efficiency of uncoated stainless steel felts was 90.5%, 41.5% and 33.2%, and the oil-water separation efficiency of the polyfluoroethylene-coated stainless steel felts was 89.3%, 38.8% and 25.1%. It can be seen that in both cases the coating worsens the separation.
Fig. 6 is a graph showing contact angle change curves of emulsified water drops in diesel oil containing 200ppm of glycerol monooleate on the surfaces of example 1 (fluorinated polyurethane coating), comparative example 2(PTFE coating), and comparative example 4(PVDF coating), and it can be seen that the contact angle of the water drop under oil is reduced from 120 ° to 70 ° within 2min for the fluorinated polyurethane coating of example 1, while the contact angle of the surfaces of comparative example 2(PTFE coating) and comparative example 4(PVDF coating) is not changed.
FIG. 7 is a graph of the separation efficiency of the emulsion water coalescent material of example 1 (coating layer is a fluorinated polyurethane coating layer), comparative example 1 (no coating layer), comparative example 2 (coating layer is a PTFE coating layer), and comparative example 4 (coating layer is a PVDF coating layer) of the present invention versus the separation efficiency of the emulsion water in the ultra low sulfur diesel containing different concentrations of high purity trimer acid. FIG. 8 is a graph showing the separation efficiency of the emulsified water coalescent material of example 1 (the coating layer is a fluorinated polyurethane coating layer), comparative example 1 (no coating layer), comparative example 2 (the coating layer is a PTFE coating layer), and comparative example 4 (the coating layer is a PVDF coating layer) according to the present invention with respect to the emulsified water in the ultra low sulfur diesel fuel containing different concentrations of high glycerol monooleate. As can be seen from fig. 7 and 8, in the water-oil emulsion containing the surfactant, the separation effect is deteriorated by both the PTFE coating and the PVDF coating as compared with that in the case of not containing the coating, and the surfactant concentration is particularly remarkable at higher concentrations, so that neither the PTFE coating nor the PVDF coating can improve the emulsion-water separation efficiency. Compared with other fluorocarbon materials in the prior art, the fluorine-containing polyurethane coating has an obviously better coalescence and separation effect on emulsified water, and the separation efficiency of the fluorine-containing polyurethane coating is hardly influenced by the concentration and the type of the surfactant and still reaches 91-98% when the fluorine-containing polyurethane coating contains 200ppm of the surfactant.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. An emulsified water coalescing material comprising a substrate and a coating layer of a fluorine-containing polyurethane coated on a surface of the substrate.
2. The emulsified water coalescing material according to claim 1, wherein the substrate comprises a filter material;
preferably, the filter material is selected from any one or a combination of at least two of stainless steel felt, cellulose fiber, glass microfiber, glass wool, melt-blown polymer fiber, nylon nanofiber and polyvinylidene fluoride fiber;
preferably, the aperture of the base material is 0.5-20 μm;
preferably, the thickness of the base material is 0.05-100 mm.
3. The emulsified water coalescing material according to claim 1 or 2, wherein-C in the fluorinated polyurethane coating layerxF2x+1-and-CH2CH2The molar ratio of O < - > is (2-8) to 1, preferably (4-5) to 1;
preferably, x is 2-6.
Preferably, the contact angle of the fluorine-containing polyurethane coating and a water drop is 100-120 degrees.
4. A method of preparing an emulsified water coalescing material according to any one of claims 1 to 3, comprising the steps of:
(1) preparing a fluorine-containing polyurethane emulsion: mixing fluorine-containing alcohol, an organic solvent and a catalyst, adding polyisocyanate, prepolymerizing to obtain a prepolymer, adding a coupling agent and a hydrophilic polymer, continuing to react to obtain a pre-emulsion, adding water to dilute, and removing the organic solvent to obtain a fluorine-containing polyurethane emulsion;
(2) adding a solvent into the fluorinated polyurethane emulsion obtained in the step (1) for dilution to obtain a coating liquid;
(3) and (3) coating the coating liquid obtained in the step (2) on the surface of a base material, and curing to obtain the emulsified water coalescence material.
5. The method of preparing an emulsified water coalescing material according to claim 4, wherein the fluorinated alcohol of step (1) has a formula of X-Y-n (R) -R' OH;
wherein X is a fluoroalkyl chain with 3-10 carbon atoms; y is selected from any one or a combination of at least two of alkylene, alkyleneoxy, sulfenyl or sulfoxy; r and R' are alkyl chains with 1-10 carbon atoms respectively and independently;
preferably, the number of carbon atoms of X is 3-5;
preferably, Y is a sulfoxy group.
6. The method of producing an emulsified water coalescing material according to claim 4 or 5, wherein the organic solvent in step (1) comprises any one of acetone, butanone, cyclohexanone, or 4-methyl-2-pentanone, or a combination of at least two thereof;
preferably, the catalyst of step (1) comprises a tin-containing catalyst, preferably dibutyltin dilaurate and/or dibutyltin diacetate;
preferably, the polyisocyanate of step (1) comprises any one of or a combination of at least two of diphenylmethane diisocyanate, toluene-2, 4-diisocyanate or hexamethylene diisocyanate;
preferably, the prepolymerization conditions in step (1) are as follows: reacting for 1-2 h at 40-80 ℃, preferably for 1-2 h at 50-70 ℃;
preferably, the mass ratio of the fluorine-containing alcohol to the polyisocyanate in the step (1) is (1-6) to (2-8);
preferably, the coupling agent in step (1) comprises a silane coupling agent, preferably any one or a combination of at least two of aminopropyltriethoxysilane, aminoethyltriethoxysilane or aminopropyltrimethoxysilane;
preferably, the hydrophilic polymer in step (1) comprises a polyoxyethylene alcohol hydrophilic polymer, preferably polyethylene glycol or a derivative thereof, further preferably polyethylene glycol monomethyl ether and/or polyethylene glycol dimethyl ether;
preferably, the conditions for continuing the reaction in step (1) are as follows: reacting for 0.5-1 h at 60-80 ℃;
preferably, the mass ratio of the fluorine-containing alcohol to the coupling agent to the hydrophilic polymer in the step (1) is (1-6) to (1-5) to (2-6);
preferably, the water of step (1) comprises deionized water;
preferably, the mass ratio of the fluorine-containing alcohol to the water in the step (1) is (1-6) to (5-8);
preferably, the method for removing the organic solvent in the step (1) comprises rotary evaporation.
7. The method of preparing an emulsified water coalescing material according to any one of claims 4 to 6, wherein the solvent in step (2) comprises an organic solvent and/or water;
preferably, the organic solvent comprises any one of isopropanol, N-dimethylformamide, N-methylpyrrolidone or acetone or a combination of at least two thereof;
preferably, the content of the fluorinated polyurethane emulsion in the coating liquid in the step (2) is 5-30 wt%;
preferably, when the solvent in the step (2) is a mixture of an organic solvent and water, the mass ratio of the organic solvent to the water is 1 (10-17).
8. The method for producing an emulsified water-coalescing material according to any one of claims 4 to 7, wherein the curing in the step (3) is carried out under the following conditions: curing at 60-350 ℃ for 5 min-4 h;
preferably, the curing of step (3) is performed in a drying oven or a muffle furnace.
9. Use of the emulsified water coalescing material according to any one of claims 1 to 3, wherein the emulsified water coalescing material is used for oil-water separation of a diesel emulsion.
10. Use of an emulsified water coalescing material according to claim 9 wherein the diesel emulsion comprises a surfactant, preferably a fat soluble surfactant, further preferably a trimer acid and/or glycerol monooleate;
preferably, the concentration of the surfactant in the diesel oil emulsion is 0-400 ppm;
preferably, the diesel emulsion comprises a diesel emulsion in a diesel engine.
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