CN112830998B - Preparation method and application of core-shell fluorine-containing polymer nano emulsion - Google Patents
Preparation method and application of core-shell fluorine-containing polymer nano emulsion Download PDFInfo
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08F2/16—Aqueous medium
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- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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Abstract
The invention relates to a preparation method and application of a shell-core type fluorine-containing polymer nano emulsion. The method comprises the steps of pre-polymerizing acrylic monomers in water in the presence of an emulsifier and an initiator to prepare a polymer core nano emulsion; then, dissolving the fluorine-containing monomer in an organic solvent, adding the dissolved fluorine-containing monomer into the polymer core nano emulsion, and carrying out secondary polymerization to obtain the fluorine-containing polymer nano emulsion with the core-shell structure. The application of the core-shell fluoropolymer nano-emulsion in changing the reservoir wettability changes the reservoir wettability from hydrophilicity to super-hydrophobicity.
Description
Technical Field
The invention relates to a preparation method and application of a shell-core type fluorine-containing polymer nano emulsion, belonging to the technical field of oilfield chemistry and colloid and interface chemistry.
Background
The composite material with the core-shell structure has high specific surface area, larger pore volume, abundant mesoporous structure and the like, and simultaneously has the excellent properties of the inner core and the outer shell, so the composite material has wide application prospects in the aspects of cosmetics, coating materials, water treatment, catalytic load and the like. In the preparation process of the ultraphobic surface, reducing the free energy of the interface is the core problem of changing the wettability of the interface. Because the carbon-fluorine bond has extremely low free energy, the fluorine-containing compound is introduced into the material structure, and the free energy of the material can be obviously reduced. Therefore, the fluorine-containing material is prepared into a core-shell structure, so that the fluorine-containing material has the advantages of the core-shell material and the fluorine-containing material, and the wettability of a solid-liquid interface is changed, so that the effect of hydrophobicity or super hydrophobicity is achieved.
In the oil and gas exploitation process, aiming at the serious water lock problem existing in the exploitation process of low-permeability or ultra-low-permeability stratum, the wettability modification of a reservoir plays a crucial role in the exploitation of oil and gas and the back drainage of working fluid. The common method is to use a surfactant to inject a large amount of surfactant into a stratum so as to improve the wettability of a reservoir stratum, but the introduction of the large amount of surfactant can generate strong emulsification in produced and flowback liquid, and can increase the use cost and the post-treatment difficulty. Fluoropolymer materials have also been used as a wetting reversal material to alter the wettability of the reservoir. The contact angle of the core treated by the fluorine-containing polymer material prepared in the patent document CN110982009A and water can reach about 130 degrees. However, for more complex hydrophilic formations, changing their wettability to superhydrophobicity would be more beneficial for the recovery of hydrocarbon resources.
Disclosure of Invention
Aiming at the problem of reservoir wettability, particularly complex hydrophilic stratum, the invention provides a core-shell type fluorine-containing polymer nano emulsion capable of remarkably changing the reservoir wettability and a preparation method thereof.
The fluorine-containing polymer emulsion prepared by the invention has a core-shell structure, is stable in property, simple and easy to operate in a preparation process, can remarkably change the wettability of a reservoir, and can change the wettability from hydrophilicity to hydrophobicity, even super-hydrophobicity.
The invention also provides application of the core-shell type fluorine-containing polymer nano emulsion.
The technical scheme of the invention is as follows:
a method for preparing core-shell fluorine-containing polymer nano-emulsion comprises the steps of adopting an emulsion polymerization method, pre-polymerizing acrylic monomers in water in the presence of an emulsifier and an initiator to prepare polymer core nano-emulsion; then, dissolving the fluorine-containing monomer in an organic solvent, adding the dissolved fluorine-containing monomer into the polymer core nano emulsion, and carrying out secondary polymerization to obtain the fluorine-containing polymer nano emulsion with the core-shell structure.
The fluorine-containing monomer is methacrylic acid dodecafluoroheptyl ester, 2- (perfluorohexyl) ethyl methacrylate and heptadecafluorodecyl methacrylate.
The core-shell type fluorine-containing polymer nano emulsion prepared by the invention has the performance of changing the wettability of a reservoir from hydrophilicity to hydrophobicity and even super hydrophobicity.
According to the invention, the acrylic monomer is preferably one of methacrylic acid, methyl methacrylate, ethyl methacrylate and butyl methacrylate.
The emulsifier is one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, dodecyl trimethyl ammonium bromide, perfluoro caprylic acid and perfluoro nonene oxy benzene sulfonate. Further preferably, the emulsifier is sodium perfluorononenoxybenzene sulfonate.
The initiator is one of ammonium persulfate, benzoyl peroxide and azobisisobutyronitrile. Further preferably, the initiator is azobisisobutyronitrile.
The organic solvent is selected from ethanol, N-Dimethylformamide (DMF), tetrahydrofuran or dichloromethane. Further preferably, the organic solvent is DMF.
Preferably, according to the invention, the molar ratio of the acrylic monomer to the fluorine-containing monomer is 1:1 to 4. More preferably, the molar ratio of the acrylic monomer to the fluorine-containing monomer is 1: 1.5-2. It has been unexpectedly discovered that the acrylic monomer molar amount must not exceed the fluoromonomer otherwise the emulsion particle size increases due to the increased particle size of the core polymer. The proportion of the fluorine-containing monomer and the acrylic monomer cannot be too large, otherwise, the shell layer is too thick, so that the particle size of the emulsion is increased; too much amount of the fluorine-containing monomer is not favorable for the emulsification and polymerization of the monomer.
Preferably, according to the invention, the ratio of the total number of moles of acrylic and fluorinated monomers to the total volume of organic solvent and water is between 0.020 and 0.035mol/100 mL. Particularly preferably 0.020 to 0.025mol/100 mL. The invention unexpectedly discovers that when the two monomers are used in a small amount, a stable core-shell structure cannot be formed, and the obtained product is rod-shaped and has poor performance.
The dosage of the organic solvent is the dissolving amount. Preferably, the volume ratio of the organic solvent to the water is 1 (0.5-4). Further preferably, the volume ratio of the organic solvent to water is 1:1. Preferably, the water is distilled water.
The addition amount of the emulsifier is 0.1-2g/100mL based on the total volume of the organic solvent and the water, and more preferably, the addition amount of the emulsifier is 1g/100 mL.
The addition amount of the initiator is 0.1-2g/100mL based on the total volume of the organic solvent and the water, and more preferably, the addition amount of the initiator is 0.5g/100 mL.
According to the present invention, it is preferable that the emulsion, the initiator and the acrylic monomer are ultrasonically emulsified in water at normal temperature before the prepolymerization. The ultrasonic emulsification time is 20-40 min.
According to the present invention, it is preferable that the temperature of the prepolymerization is 60 to 90 ℃ and it is further preferable that the temperature of the prepolymerization is 80 ℃. The prepolymerization time is 2-6h, and the prepolymerization time is more preferably 3-5 h. For the prepolymerization reaction, the acrylic monomer can not completely react due to too short reaction time, a linear polymer is easily formed with the fluorine-containing monomer after secondary polymerization, the obtained product is mainly of a rod-shaped structure, and the performance of the product is poor; the polymerization of the polymer emulsion occurs due to the long reaction time, and the formed core is large, which is not beneficial to forming the small-particle-size nano emulsion.
According to the present invention, the secondary polymerization temperature is preferably 60 to 90 ℃, and more preferably 80 ℃. The secondary polymerization reaction time is 2 to 6 hours, and the secondary polymerization reaction time is more preferably 3 to 5 hours. For the secondary polymerization reaction, the fluorine-containing monomer with too short reaction time can not be completely reacted, the utilization rate of the monomer is reduced, and the stability of the product is poor. The reaction time is too long, the monomers are fully reacted, and the energy consumption is increased while the performance of the product is not greatly influenced by the increase of the reaction time.
The fluorine-containing polymer emulsion prepared by the invention has a core-shell structure and small emulsion particle size, and the emulsion particle size is distributed at 100-300 nm; the particle size of the emulsion is preferably 150-250 nm; the most preferred emulsion particle size is around 200 nm. The acrylic monomer is polymerized to be used as a core, and the fluorine-containing monomer is coated on the basis of the core to form a shell layer. Factors influencing the particle size of the emulsion are complex, such as the molar ratio of the acrylic monomer to the fluorine-containing monomer, the amount of the emulsifier, the ratio of the organic solvent to water, the reaction temperature and the reaction time, and the like. The shell-core type fluorine-containing polymer nano-emulsion with better performance can be obtained by adopting the specific reaction condition of the invention.
According to the invention, a preferred embodiment is as follows:
a preparation method of a shell-core type fluorine-containing polymer nano emulsion comprises the following steps:
respectively adding 50mL of distilled water and 1.0g of emulsifier into a reaction container with a reflux device and electromagnetic stirring, after the solid is completely dissolved, dissolving 0.01mol of acrylic monomer and 0.5g of initiator into 50mL of organic solvent, then adding the above distilled water, ultrasonically emulsifying at normal temperature for 30min, and heating to 80 ℃ for reaction for 4h to obtain prepolymer emulsion; and cooling to normal temperature, adding 0.015mol of fluorine-containing monomer into the prepolymer emulsion, ultrasonically emulsifying at normal temperature for 30min, and heating to 80 ℃ for reaction for 4h to obtain a white emulsion product. Thus obtaining the core-shell type fluorine-containing polymer nano emulsion.
The core-shell type fluorine-containing polymer nano emulsion prepared by the invention is applied to changing the wettability of a reservoir. According to the application, preferably, at the use concentration of 1.0 wt.%, the contact angle of the formation and water can be maximally more than 150 degrees, the wettability of the reservoir is changed from hydrophilicity to superhydrophobicity (see table 1), the wettability of the formation is remarkably improved, and the oil and gas recovery rate is improved.
The invention also provides a stability experiment of the core-shell type fluorine-containing polymer nano emulsion. The core-shell type fluorine-containing polymer nano emulsion prepared by the invention can be stably dispersed in a water-based system.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Firstly, emulsifying and dispersing an acrylate monomer into nano emulsion, and performing prepolymerization to form a polymer core; and then the fluorine-containing monomer is coated on the polymer core to form a shell layer after secondary polymerization. The core of the invention is to change the interfacial energy of the reservoir by using the fluorine-containing polymer, thereby changing the wettability. The fluorine-containing material is used as a shell layer, the characteristic of high specific surface area of the nano material is utilized, the fluorine-containing material in the raw material can be fully utilized, the product prepared by CN110982009A in the prior art does not have a shell-core structure and a nano size, and a large amount of fluorine-containing monomers are wrapped in the block copolymer and cannot play a role in reducing the interfacial energy, so that the performance of the product in the comparative example 4 is not as good as that of the product in the embodiment of the invention.
The invention has the technical characteristics and excellent effects that:
1. the fluorine-containing polymer emulsion prepared by the invention has a core-shell structure, the particle size of the emulsion is small, and the particle size distribution of latex particles in the emulsion is about 100-300 nm.
2. The shell-core type fluorine-containing polymer nano emulsion prepared by the invention enables the contact angle of a stratum and water to be more than 150 degrees at the use concentration of 1.0 wt.%, and enables the wettability of a reservoir to be changed from hydrophilicity to super hydrophobicity.
3. The core-shell type fluorine-containing polymer nano emulsion prepared by the invention has stable property, can be stably dispersed in a water-based system, and can be stably stored for more than two months at normal temperature and normal pressure.
4. The preparation method of the core-shell fluorine-containing polymer nano emulsion has the advantages of industrial production of the used raw materials, easily obtained raw materials, simple reaction process, mild preparation conditions, easily controlled reaction conditions and safe reaction process, and can be used for completing the preparation under common chemical conditions.
5. The core-shell type fluorine-containing polymer nano emulsion prepared by the invention has good compatibility with other water-based systems, and can be directly put into use without purification.
6. The core-shell type fluorine-containing polymer nano emulsion prepared by the invention has stronger wetting reversal capability, is used for oil and gas resource reservoir transformation, and can effectively solve the problems of water lock and the like caused by reservoir wettability in the oil and gas resource development process.
Drawings
FIG. 1 is an infrared spectrum of a core-shell fluoropolymer prepared in example 4.
FIG. 2 is a transmission electron micrograph of a core-shell fluoropolymer emulsion prepared according to example 4.
FIG. 3 is a graph showing the contact angle of the core with water before and after the treatment of the shell-core type fluoropolymer emulsion prepared in example 4 in the experimental examples. Wherein a is the contact angle between the rock core of the blank control group and water; b is the contact angle of the treated core of the product of example 4 with water.
FIG. 4 is a photograph of a stability test and turbidity of the product prepared in example 4 of Experimental example 2.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, without limiting the scope of the invention thereto.
Example 1
50mL of distilled water and 1.0g of sodium perfluorononenoxybenzenesulfonate are respectively added into a 250mL three-neck flask with a reflux device and electromagnetic stirring, after the solid is completely dissolved, 1.0g (0.01mol) of methyl methacrylate (acrylic monomer) and 0.5g of initiator Azobisisobutyronitrile (AIBN) are dissolved in 50mL of N, N-Dimethylformamide (DMF) and added into water, ultrasonic emulsification is carried out at normal temperature for 30min, and then the temperature is raised to 80 ℃ for reaction for 4h, so as to obtain prepolymer emulsion. After cooling to normal temperature, 6.0g (0.015mol) of dodecafluoroheptyl methacrylate (fluorine-containing monomer) is added into the prepolymer emulsion, ultrasonic emulsification is carried out at normal temperature for 30min, and then the temperature is raised to 80 ℃ for reaction for 4h, so as to obtain a white emulsion product. The particle size distribution of the emulsion is 150-250 nm; the materials are not separated after being placed for 60 days at normal temperature and normal pressure.
Example 2
The preparation was carried out as described in example 1, except that the acrylic monomer was 1.4g (0.01mol) of butyl methacrylate. The particle size distribution of the obtained product emulsion is 200-250 nm; the materials are not separated after being placed for 60 days at normal temperature and normal pressure.
Example 3
The process is as in example 1, except that the fluoromonomer is 6.5g (0.015mol) of 2- (perfluorohexyl) ethyl methacrylate. The particle size distribution of the obtained product emulsion is 150-250 nm; the materials are not separated after being placed for 60 days at normal temperature and normal pressure.
Example 4
The process is as in example 1, except that the fluoromonomer is 8.0g (0.015mol) of heptadecafluorodecyl methacrylate. The particle size of the obtained product emulsion is about 200 nm; the materials are not separated after being placed for 60 days at normal temperature and normal pressure.
The IR spectrum of the core-shell fluoropolymer prepared in this example is shown in FIG. 1. The wave number in the figure is 1750cm-1The carbon-oxygen telescopic absorption peak at the position of ester group is 1350--1A fluorocarbon telescopic absorption peak of fluorine substituted alkyl and a fingerprint area of 650-400cm-1The absorption peaks indicate the successful synthesis of the product.
The transmission electron micrograph of the core-shell fluoropolymer emulsion prepared in this example is shown in FIG. 2. As can be seen from FIG. 2, the polymer particles have a distinct shell-core structure, and the particle size distribution is around 200nm, indicating that the prepared fluorine-containing polymer is a shell-core type nano-emulsion.
The photographs of the contact angle of the core with water before and after the treatment of the core-shell fluoropolymer emulsion prepared in this example are shown in fig. 3. Wherein a is the contact angle between the rock core of the blank control group and water; b is the contact angle of the treated core of the product of example 4 with water. As can be seen from fig. 3, the natural core before treatment was hydrophilic, and the contact angle between the treated core and water was over 150 °, and the wettability was changed to superhydrophobic.
The experimental photograph and turbidity of the product prepared in this example are shown in FIG. 4. From FIG. 4, it can be seen that the turbidity of the emulsion slowly increased with time, from the initial 502.3NTU to 535.8NTU after 60 days, and the change rate of the opacity was only 6.7%. The results show that the product retains good stability after long-term storage.
Example 5.
Respectively adding 70mL of distilled water and 2g of sodium dodecyl benzene sulfonate into a 250mL three-neck flask with a reflux device and electromagnetic stirring, after the solid is completely dissolved, dissolving 0.01mol of propyl methacrylate (acrylic monomer) and 1g of initiator Azobisisobutyronitrile (AIBN) into 30mL of N, N-Dimethylformamide (DMF), adding into water, ultrasonically emulsifying at normal temperature for 35min, and heating to 75 ℃ for reacting for 4.5h to obtain prepolymer emulsion. And cooling to normal temperature, adding 0.02mol of fluorine-containing monomer into the prepolymer emulsion, ultrasonically emulsifying at normal temperature for 35min, and heating to 75 ℃ for reaction for 5h to obtain a white emulsion product. The particle size distribution of the emulsion is 200-300 nm; the materials are not separated after being placed for 60 days at normal temperature and normal pressure.
Example 6.
40mL of distilled water and 1.5g of perfluorononenoxybenzene sodium sulfonate are respectively added into a 250mL three-neck flask with a reflux device and electromagnetic stirring, after the solid is completely dissolved, 0.012mol of methyl methacrylate (acrylic monomer) and 1.2g of initiator Azobisisobutyronitrile (AIBN) are dissolved in 60mL of N, N-Dimethylformamide (DMF) and added into water, ultrasonic emulsification is carried out at normal temperature for 35min, and then the temperature is raised to 85 ℃ for reaction for 3.5h, so as to obtain prepolymer emulsion. And cooling to normal temperature, adding 0.028mol of fluorine-containing monomer into the prepolymer emulsion, ultrasonically emulsifying at normal temperature for 35min, and heating to 85 ℃ for reaction for 4h to obtain a white emulsion product. The particle size distribution of the emulsion is 200-300 nm; the materials are not separated after being placed for 60 days at normal temperature and normal pressure.
Example 7. the procedure as described in example 1, except that 0.5g of the initiator Azobisisobutyronitrile (AIBN) was replaced by 0.5g of initiator ammonium persulfate.
Comparative example 1
The preparation was carried out as described in example 1, except that the acrylic monomer was 2.5g (0.01mol) of dodecyl methacrylate. The obtained product is emulsion with particle size distribution of 1-2 μm.
Comparative example 2
The preparation was carried out as described in example 4, except that the prepolymerization time was 2 h. The obtained product is a rod-shaped polymer, and the particle size distribution of the emulsion is 2-5 mu m.
Comparative example 3
The process as described in example 4, except that the acrylic monomer is 0.005mol of methyl methacrylate and the fluorine-containing monomer is 0.01mol of dodecafluoroheptyl methacrylate. The obtained product is mostly rod-shaped polymer, and the particle size distribution of the emulsion is 1-2 μm. The total amount of monomers and the contents of organic solvents and water are too small to form a stable core-shell structure.
Comparative example 4
The fluoropolymer microemulsion prepared in example 1 of patent document CN110982009a wets the inverter.
Experimental example 1: contact angle experiments.
The products synthesized in the examples and comparative examples of the present invention were prepared into 1.0 wt.% of emulsion by adding water, respectively, and the natural core slices were immersed in the emulsion, kept at room temperature and pressure for 12 hours, taken out, dried at 60 ℃ for 4 hours, and measured for their contact angle with water using distilled water as a blank control, and the experimental results are shown in table 1.
TABLE 1 contact angle and interfacial free energy of core surface after Redox treatment
Note: the data for comparative example 4 is derived from CN110982009 a.
The data in table 1 show that the selected core is a natural hydrophilic core, the contact angles between the surface of the core and water after treatment are all larger than 140 degrees, and particularly, the contact angle between the surface of the core and water after the product treatment in example 4 is larger than 150 degrees (see b in fig. 3), so that the super-hydrophobic effect is achieved.
In comparative examples 1 and 2, the contact angle of the core and water after product treatment gradually increases with the increase of the alkyl substituted chain segment in the acrylic monomer in the polymer core, and in comparative examples 1, 3 and 4, the contact angle of the core and water after product treatment gradually increases with the increase of the fluorine content of the fluorine-containing monomer in the shell.
Comparing example 1 with comparative example 1, at the same molar mass, the increase of the monomer molecular weight in the prepolymerization makes the emulsion particles of the product larger, and the contact angle of the core and water after the product treatment is reduced. Comparing example 4 with comparative example 2, decreasing the time for the prepolymerization resulted in incomplete reaction of the acrylic monomer in the prepolymer, thereby forming a linear polymer with the fluorine-containing monomer in the second polymerization and failing to maintain the spherical shape of the product.
The contact angles of the interfaces with water in the examples are all larger than those in the comparative example, wherein the comparative example 3 is a fluoropolymer emulsion, and the synthesized product has better wetting reversion capability than the same type of product reported in the literature.
Therefore, the core-shell type fluorine-containing polymer nano emulsion prepared by the invention has stronger wetting reversal capability and can effectively improve the problems caused by reservoir wettability problems in the development process of oil and gas resources.
Experimental example 2: stability test
50mL of the product of example 4 was taken and stored at room temperature while sealed, and the turbidity of the emulsion was measured at various times over a period of 60 days and photographs were taken to obtain the data in FIG. 4. As can be seen from the figure, the turbidity of the emulsion increased from the initial 502.3NTU to 535.8NTU after 2 months storage, with a change of only 6.7%, indicating that the product remained stable over long periods of storage.
Claims (11)
1. A method for preparing core-shell fluorine-containing polymer nano-emulsion comprises the steps of adopting an emulsion polymerization method, in the presence of an emulsifier and an initiator, pre-polymerizing an acrylic monomer in a mixed solution of water and an organic solvent to prepare polymer core nano-emulsion; then, adding the fluorine-containing monomer into the polymer core nano emulsion for secondary polymerization to obtain the fluorine-containing polymer nano emulsion with a core-shell structure; the particle size distribution of the core-shell type fluorine-containing polymer nano-emulsion is 100-300 nm;
the fluorine-containing monomer is methacrylic acid dodecafluoroheptyl ester, 2- (perfluorohexyl) ethyl methacrylate or methacrylic acid heptadecafluorodecyl ester; the acrylic monomer is methyl methacrylate, propyl methacrylate or butyl methacrylate; the molar ratio of the acrylic monomer to the fluorine-containing monomer is 1: 1-4;
the emulsifier is perfluorooctanoic acid or perfluorononene oxy benzene sodium sulfonate; the initiator is azobisisobutyronitrile;
the volume ratio of the organic solvent to the water is 1 (0.5-4);
the addition amount of the emulsifier is 0.1-2g/100mL based on the total volume of the organic solvent and the water;
the ratio of the total mole number of the acrylic monomer and the fluorine-containing monomer to the total volume of the organic solvent and the water is 0.020-0.035mol/100 mL;
before prepolymerization, emulsifying emulsifier, initiator and acrylic monomer in the mixture of water and organic solvent by ultrasonic emulsification at normal temperature;
the temperature of the prepolymerization reaction is 60-90 ℃; the prepolymerization reaction time is 3-5 h;
the temperature of the secondary polymerization reaction is 60-90 ℃; the secondary polymerization reaction time is 2-6 h;
the fluoropolymer nanoemulsion changes reservoir wettability from hydrophilic to superhydrophobic.
2. The method of claim 1, wherein the organic solvent is selected from the group consisting of ethanol, N-dimethylformamide, tetrahydrofuran, and dichloromethane.
3. The method of preparing the core-shell fluoropolymer nanoemulsion of claim 1, wherein the molar ratio of the acrylic monomer to the fluoromonomer is 1: 1.5-2.
4. The method of preparing the core-shell fluoropolymer nanoemulsion of claim 1, wherein the ratio of the total moles of acrylic monomer and fluoromonomer to the total volume of organic solvent and water is 0.020 to 0.025mol/100 mL.
5. The method of preparing a core-shell fluoropolymer nanoemulsion of claim 1, wherein the reaction conditions include one or more of the following:
a. the volume ratio of the organic solvent to the water is 1: 1;
b. the addition amount of the initiator is 0.1-2g/100mL based on the total volume of the organic solvent and the water.
6. The method of preparing the core-shell fluoropolymer nanoemulsion of claim 1, wherein the emulsifier is added in an amount of 1g/100mL, based on the total volume of the organic solvent and water; the initiator was added in an amount of 0.5g/100mL based on the total volume of the organic solvent and water.
7. The method of preparing the core-shell fluoropolymer nanoemulsion of claim 1, wherein the prepolymerization temperature is 80 ℃.
8. The method of preparing the core-shell fluoropolymer nanoemulsion of claim 1, wherein the secondary polymerization temperature is 80 ℃; the secondary polymerization reaction time is 3-5 h.
9. The method for preparing the core-shell type fluoropolymer nano-emulsion according to claim 1, wherein the particle size distribution of the core-shell type fluoropolymer nano-emulsion is 150-250 nm.
10. The method of preparing the core-shell fluoropolymer nanoemulsion of claim 1, comprising the steps of: respectively adding 50mL of distilled water and 1.0g of emulsifier into a reaction container with a reflux device and electromagnetic stirring, after the solid is completely dissolved, dissolving 0.01mol of acrylic monomer and 0.5g of initiator into 50mL of organic solvent, then adding the above distilled water, ultrasonically emulsifying at normal temperature for 30min, and heating to 80 ℃ for reaction for 4h to obtain prepolymer emulsion; and cooling to normal temperature, adding 0.015mol of fluorine-containing monomer into the prepolymer emulsion, ultrasonically emulsifying at normal temperature for 30min, and heating to 80 ℃ for reaction for 4h to obtain a white emulsion product.
11. Use of the core-shell fluoropolymer nanoemulsion prepared by the preparation method of any one of claims 1-10 to change the reservoir wettability from hydrophilic to superhydrophobic.
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