CN113828173A - Preparation method and application of fluorine-containing hydrophobic copolymer oil-water separation film - Google Patents

Preparation method and application of fluorine-containing hydrophobic copolymer oil-water separation film Download PDF

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CN113828173A
CN113828173A CN202111220091.6A CN202111220091A CN113828173A CN 113828173 A CN113828173 A CN 113828173A CN 202111220091 A CN202111220091 A CN 202111220091A CN 113828173 A CN113828173 A CN 113828173A
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oil
fluorine
water
copolymer
water separation
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马鹏程
吕重江
艾克热木·牙生
郝斌
岳秀
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
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    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/39—Electrospinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2325/38—Hydrophobic membranes

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Abstract

The invention discloses a preparation method of a fluorine-containing hydrophobic copolymer oil-water separation film, which adopts a homogeneous solution free radical polymerization method to copolymerize a main chain monomer and a fluorine-containing monomer under the action of an oil-soluble initiator, and obtains fluorine-containing hydrophobic copolymer powder after precipitation in water and vacuum drying. Dissolving the nano-oil-water separation membrane in an organic solvent to prepare a spinning solution with a certain concentration, and preparing the nano-oil-water separation membrane with super-hydrophobic/super-lipophilic performance by an electrostatic spinning method. The fluorine-containing hydrophobic copolymer oil-water separation film obtained by the method has the characteristics of adjustable pore diameter, fiber diameter, thickness and the like, can realize high-efficiency separation of various oil/water mixtures and water-in-oil (W/O) emulsions under the action of gravity, is simple to operate, and has a certain industrial application prospect.

Description

Preparation method and application of fluorine-containing hydrophobic copolymer oil-water separation film
Technical Field
The invention relates to a preparation method of a fluorine-containing hydrophobic copolymer oil-water separation film, belonging to the technical field of environmental pollution treatment and engineering.
Background
The management of environmental pollution is receiving wide attention all over the world, and oil pollution is one of the most serious problems and always threatens human health and ecological balance. In recent years, accidents of crude oil leakage and discharge of oily wastewater occur frequently in daily life and industrial development, and how to effectively treat the oily wastewater is urgent. The traditional oil-water treatment methods comprise oil skimming, air flotation, coagulation-flocculation, centrifugation, deep filtration and the like, but the methods inevitably produce secondary pollution, and have high cost and complex operation. The film material is used as a novel separation material and has the advantages of low cost, simple method, high separation efficiency and the like. In particular, a functional separation membrane having a specific wettability is more advantageous for separation of emulsified oil according to its selective permeability to water or oil. Among the various film preparation methods, electrospinning is considered as the most effective and commonly used method for reasonably regulating and controlling the chemical structure, porosity, micro-nano structure and fiber diameter of a film so as to achieve the purpose of separating an oil-water mixture with high permeability and low energy consumption. The existing polymer electrostatic spinning oil-water separation membrane is prepared by preparing a polymer into a membrane, and then modifying low-surface-energy substances such as fluorosilane, long-chain alkane, polysiloxane and the like on the surface of the membrane by methods such as dipping, spraying, coating and the like. CN 104014259A discloses a method for preparing a hydrophobic separation membrane, which comprises dissolving a hydrophobic monomer and a conventional polymer membrane-forming material in a solvent, irradiating with gamma rays to initiate a grafting reaction, dissolving or dispersing in an organic solvent, and coating and spraying the surface of a porous base membrane to form the hydrophobic separation membrane. The application publication No. CN 105749770A, a preparation method of a novel super-oleophylic and super-hydrophobic separation membrane, refers to that one or more hydrophobic monomers are polymerized to generate a hydrophobic modified polymer, and then the solution is dipped and coated on the surface of the separation membrane. The application publication No. CN112516807A, namely separation membrane, preparation method, and aviation kerosene water removal and purification method and application, mentions that a hydrophobic polymer membrane forming material and a fluorine-containing water drawing agent are dissolved in an organic solvent, and then the porous membrane is prepared by electrostatic spinning, and can be used for effectively separating aviation kerosene with high emulsifying degree. Although the method has a high-efficiency oil-water separation effect, the method has multiple experimental steps and complex operation, and the low-surface-energy substance and the film are only in a physical combination mode, so that the hydrophobicity and the durability are not strong. Perfluoropolymers such as Polytetrafluoroethylene (PTFE), perfluoroethylene propylene copolymer (FEP), while having very low surface energy, are not feasible for solution spinning. Therefore, the fluorine-containing copolymer with high spinnability and low surface energy can be formed by the copolymerization of the fluorine-containing monomer and the main chain monomer, and the application prospect of the fluorine-containing copolymer is expanded.
Disclosure of Invention
The invention aims to provide a preparation method of a fluorine-containing hydrophobic copolymer oil-water separation film, which adopts a homogeneous solution free radical polymerization method to copolymerize a main chain monomer and a fluorine-containing monomer under the action of an oil-soluble initiator, and obtains fluorine-containing hydrophobic copolymer powder after water precipitation and vacuum drying. Dissolving the nano-oil-water separation membrane in an organic solvent to prepare a spinning solution with a certain concentration, and preparing the nano-oil-water separation membrane with super-hydrophobic/super-lipophilic performance by an electrostatic spinning method. The fluorine-containing hydrophobic copolymer oil-water separation film obtained by the method has the characteristics of adjustable pore diameter, fiber diameter, thickness and the like, can realize high-efficiency separation of various oil/water mixtures and water-in-oil (W/O) emulsions under the action of gravity, is simple to operate, has high oil-water separation efficiency, and is easy for industrial production. Has certain industrial application prospect.
The preparation method of the fluorine-containing hydrophobic copolymer oil-water separation film comprises the following steps:
preparation of fluorine-containing hydrophobic copolymer:
a. adding a main chain monomer, a fluorine-containing monomer and an oil-soluble initiator accounting for 0.5wt.% of the total monomer mass into an organic solvent according to a molar ratio of 99:1-60:40, continuously stirring and reacting at 50-70 ℃ for 12-48h under the protection of inert gas to obtain a polymer solution, precipitating with water, and drying in a vacuum drying oven at 70 ℃ to obtain polymer powder; wherein the main chain monomer is acrylonitrile, styrene, methyl methacrylate or ethyl methacrylate; the fluorine-containing monomer has 6-14 carbon atoms and 9-21 fluorine atoms, and comprises hexafluorobutyl acrylate, perfluorobutyl ethylene, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, perfluorodecyl ethylene, perfluorobutyl ethyl acrylate, perfluorobutyl ethyl methacrylate, perfluorooctyl acrylate or perfluorooctyl ethyl acrylate; the oil-soluble initiator is azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide; the organic solvent is trifluoroacetic acid, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, sulfolane or ethylene nitrate;
preparing an electrostatic spinning solution:
b. b, dissolving the copolymer powder obtained in the step a in an organic solvent, wherein the mass fraction of the copolymer is 5% -30%, stirring for 4-6h under the heating condition of 50-80 ℃, and then standing for 0.5-2 h for defoaming to obtain a copolymer solution; wherein the organic solvent is trifluoroacetic acid, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, sulfolane or ethylene nitrate;
spinning an oil-water separation film by an electrostatic spinning method:
c. b, absorbing the copolymer solution in the step b in an injector, selecting a needle head with the number of 18-24, installing the injector in an injection pump of electrostatic spinning equipment, setting the injection speed to be 0.3-3ml/h, the translation distance to be 5-15cm and the spinning distance to be 8-20cm, taking a roller as a receiver, setting the rotation speed to be 40-300rpm, the spinning voltage to be 10-25kV and the spinning time to be 0.5-6h, and after spinning is finished, placing a sample in an oven with the temperature of 60-80 ℃ for drying for 2-4h to obtain the fluorine-containing hydrophobic copolymer oil-water separation film.
The fluorine-containing hydrophobic copolymer oil-water separation film obtained by the method is used for preparing a separation oil-water mixture or a water-in-oil emulsion.
Compared with the prior art, the preparation method of the fluorine-containing hydrophobic copolymer oil-water separation membrane has the following innovations:
the invention adopts an in-situ synthesis modification method to directly synthesize fluorine-containing hydrophobic copolymer, and then obtains the film with high-efficiency oil-water separation performance by an electrostatic spinning method. Which is different from the traditional multi-polymer hybrid spinning method. The method has simple preparation process and is easy for industrial production.
Drawings
FIG. 1 is a contact angle diagram of static water and static oil and a scanning electron micrograph of a film prepared according to example 1 of the present invention, wherein a) wettability and optical image of water droplet on the surface of the electrospun film; b) wettability and optical images of oil drops on the surface of the electrostatic spinning film; c) scanning electron microscopy of electrospun film;
FIG. 2 is a diagram of the oil-water separation and water-in-oil emulsion separation process in all examples of the invention, a) oil-water mixture separation process; b) in the process of separating the water-in-oil emulsion;
FIG. 3 is an optical microscope image of a water-in-oil (water/n-hexane) emulsion before and after separation a) and b) before and after separation of a prepared membrane emulsion according to example 5 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but is not limited to the following examples.
Example 1
Preparation of fluorine-containing hydrophobic copolymer:
a. adding 30g of acrylonitrile and perfluorodecyl ethylene monomer and 0.15g of azobisisobutyronitrile into an N, N-dimethylformamide solvent according to a molar ratio of 99:1, continuously stirring at 50 ℃ for reaction for 15h to obtain a polymer solution, precipitating with water, and drying in a vacuum drying oven at 70 ℃ to obtain a copolymer;
preparing an electrostatic spinning solution:
b. b, dissolving the copolymer obtained in the step a in N, N-dimethylformamide, wherein the mass fraction of the copolymer is 20%, stirring for 4 hours under the heating condition of 60 ℃, and then standing for 1 hour to defoam the copolymer to obtain a copolymer solution;
spinning an oil-water separation film by an electrostatic spinning method:
c. b, absorbing the copolymer solution in the step b in an injector, selecting a 19-gauge needle, installing the injector in an injection pump of electrostatic spinning equipment, setting the injection speed to be 0.5ml/h, the translation distance to be 6cm and the spinning distance to be 10cm, using a roller as a receiver, setting the rotation speed to be 60rpm, the spinning voltage to be 12kV and the spinning time to be 2h, and after spinning is finished, placing a sample in an oven at the temperature of 70 ℃ for drying for 2h to obtain the fluorine-containing hydrophobic copolymer oil-water separation film.
The obtained fluorine-containing hydrophobic copolymer oil-water separation membrane was sandwiched between oil-water separation devices (as shown in FIG. 2), and the oil-water mixture and the water-in-oil emulsion were separated, with a final separation efficiency of 95.3%.
Example 2
Preparation of fluorine-containing hydrophobic copolymer:
a. adding 20g of styrene and perfluorooctanol acrylate monomer and 0.1g of benzoyl peroxide into N-methyl pyrrolidone according to a molar ratio of 80:20, stirring and reacting at 55 ℃ for 30h to obtain a polymer solution, precipitating with water, and drying in a vacuum drying oven at 70 ℃ to obtain a copolymer;
preparing an electrostatic spinning solution:
b. b, dissolving the copolymer obtained in the step a in a dimethyl sulfoxide solvent, wherein the mass fraction of the copolymer is 15%, stirring for 5 hours under the heating condition of 50 ℃, standing for 2 hours, defoaming, and obtaining a copolymer solution;
spinning an oil-water separation film by an electrostatic spinning method:
c. b, absorbing the copolymer solution in the step b in an injector, selecting a No. 21 needle, installing the injector in an injection pump of electrostatic spinning equipment, setting the injection speed to be 1ml/h, setting the translation distance to be 12cm, setting the spinning distance to be 15cm, using a roller as a receiver, setting the rotation speed to be 100rpm, the spinning voltage to be 20kV, setting the spinning time to be 3h, and after the spinning is finished, placing the sample in an oven at the temperature of 80 ℃ for drying for 4h to obtain the fluorine-containing hydrophobic copolymer oil-water separation film.
The obtained fluorine-containing hydrophobic copolymer oil-water separation membrane is clamped in an oil-water separation device (as shown in figure 2), and an oil-water mixture and a water-in-oil emulsion are separated, wherein the final separation efficiency is 98.2%.
Example 3
Preparation of fluorine-containing hydrophobic copolymer:
a. adding 25g of methyl methacrylate and dodecafluoroheptyl methacrylate and 0.125g of azobisisoheptonitrile into sulfolane according to a molar ratio of 75:25, continuously stirring and reacting at 70 ℃ for 16h to obtain a polymer solution, precipitating with water, and drying in a vacuum drying oven at 70 ℃ to obtain a copolymer;
preparing an electrostatic spinning solution:
b. b, dissolving the copolymer obtained in the step a in sulfolane, wherein the mass fraction of the copolymer is 8%, stirring for 4.5 hours under a heating condition at the temperature of 65 ℃, standing for 1.5 hours, and defoaming to obtain a copolymer solution;
spinning an oil-water separation film by an electrostatic spinning method:
c. b, absorbing the copolymer solution in the step b in an injector, selecting a No. 24 needle, installing the injector in an injection pump of electrostatic spinning equipment, setting the injection speed to be 3ml/h, setting the translation distance to be 12cm, setting the spinning distance to be 20cm, using a roller as a receiver, setting the rotation speed to be 250rpm, the spinning voltage to be 18kV, setting the spinning time to be 3h, and after the spinning is finished, placing the sample in an oven at the temperature of 80 ℃ for drying for 3h to obtain the fluorine-containing hydrophobic copolymer oil-water separation film.
The obtained fluorine-containing hydrophobic copolymer oil-water separation membrane was sandwiched between oil-water separation devices (as shown in FIG. 2), and the oil-water mixture and the water-in-oil emulsion were separated, with a final separation efficiency of 98.7%.
Example 4
Preparation of fluorine-containing hydrophobic copolymer:
a. adding 30g of ethyl methacrylate and perfluorobutylethyl methacrylate monomer and 0.15g of methyl ethyl ketone peroxide into trifluoroacetic acid according to a molar ratio of 60:40, continuously stirring and reacting at 70 ℃ for 42h to obtain a polymer solution, precipitating with water, and drying in a vacuum drying oven at 70 ℃ to obtain a copolymer;
preparing an electrostatic spinning solution:
b. b, dissolving the copolymer obtained in the step a in N, N-dimethylacetamide at the mass fraction of 25%, stirring for 5 hours under the heating condition at the temperature of 65 ℃, and standing for 1.5 hours to defoam to obtain a copolymer solution;
spinning an oil-water separation film by an electrostatic spinning method:
c. b, absorbing the copolymer solution in the step b in an injector, selecting a No. 18 needle, installing the injector in an injection pump of electrostatic spinning equipment, setting the injection speed to be 1.5ml/h, the translation distance to be 12cm and the spinning distance to be 10cm, using a roller as a receiver, setting the rotation speed to be 250rpm, the spinning voltage to be 25kV and the spinning time to be 2h, and after the spinning is finished, placing the sample in an oven at the temperature of 65 ℃ for drying for 3h to obtain the fluorine-containing hydrophobic copolymer oil-water separation film.
The obtained fluorine-containing hydrophobic copolymer oil-water separation membrane was sandwiched between oil-water separation devices (as shown in FIG. 2), and the oil-water mixture and the water-in-oil emulsion were separated, with a final separation efficiency of 95%.
Example 5
Preparation of fluorine-containing hydrophobic copolymer:
a. adding 18g of ethyl methacrylate and hexafluorobutyl acrylate monomer and 0.09g of azodiisovaleronitrile into N, N-dimethylformamide according to a molar ratio of 95:5, continuously stirring and reacting at 50 ℃ for 36 hours to obtain a polymer solution, precipitating with water, and drying in a vacuum drying oven at 70 ℃ to obtain a copolymer;
preparing an electrostatic spinning solution:
b. b, dissolving the copolymer obtained in the step a in N, N-dimethylacetamide at the mass fraction of 25%, stirring for 5 hours under the heating condition of 70 ℃, and standing for 1 hour to defoam to obtain a copolymer solution;
spinning an oil-water separation film by an electrostatic spinning method:
c. b, absorbing the copolymer solution in the step b in an injector, selecting an 18-gauge needle, installing the injector in an injection pump of electrostatic spinning equipment, setting the injection speed to be 1.2ml/h, the translation distance to be 10cm and the spinning distance to be 12.5cm, taking a roller as a receiver, setting the rotation speed to be 250rpm, the spinning voltage to be 18kV and the spinning time to be 4h, and after spinning is finished, placing a sample in an oven at the temperature of 65 ℃ for drying for 3h to obtain the fluorine-containing hydrophobic copolymer oil-water separation film.
The obtained fluorine-containing hydrophobic copolymer oil-water separation membrane was sandwiched between oil-water separation devices (as shown in FIG. 2), and the oil-water mixture and the water-in-oil emulsion were separated, with a final separation efficiency of 96.3%.
Example 6
Preparation of fluorine-containing hydrophobic copolymer:
a. adding 25g of acrylonitrile and perfluorobutyl ethylene monomer and 0.125g of dimethyl azodiisobutyrate into dimethyl sulfoxide according to a molar ratio of 70:30, continuously stirring and reacting at 55 ℃ for 28h to obtain a polymer solution, precipitating with water, and drying in a vacuum drying oven at 70 ℃ to obtain a copolymer;
preparing an electrostatic spinning solution:
b. b, dissolving the copolymer obtained in the step a in N-methyl pyrrolidone, wherein the mass fraction of the copolymer is 28%, stirring for 4.5 hours under the heating condition of 60 ℃, standing for 2 hours, and defoaming to obtain a copolymer solution;
spinning an oil-water separation film by an electrostatic spinning method:
c. b, absorbing the copolymer solution in the step b in an injector, selecting a No. 21 needle, installing the injector in an injection pump of electrostatic spinning equipment, setting the injection speed to be 1ml/h, setting the translation distance to be 8cm, setting the spinning distance to be 9cm, using a roller as a receiver, setting the rotation speed to be 1250rpm, the spinning voltage to be 17kV, and the spinning time to be 5h, and after the spinning is finished, placing the sample in an oven at the temperature of 60 ℃ for drying for 4h to obtain the fluorine-containing hydrophobic copolymer oil-water separation film.
The obtained fluorine-containing hydrophobic copolymer oil-water separation membrane was sandwiched between oil-water separation devices (as shown in FIG. 2), and the oil-water mixture and the water-in-oil emulsion were separated, with a final separation efficiency of 97.8%.
Example 7
Preparation of fluorine-containing hydrophobic copolymer:
a. adding 20g of styrene and hexafluorobutyl methacrylate monomer and 0.1g of benzoyl peroxide tert-butyl ester into N, N-dimethylacetamide according to a molar ratio of 65:35, continuously stirring and reacting at 70 ℃ for 45 hours to obtain a polymer solution, precipitating with water, and drying in a vacuum drying oven at 70 ℃;
preparing an electrostatic spinning solution:
b. b, dissolving the copolymer obtained in the step a in trifluoroacetic acid, wherein the mass fraction of the copolymer is 20%, stirring for 4 hours under the heating condition of 60 ℃, and standing for 1.5 hours to defoam to obtain a copolymer solution;
spinning an oil-water separation film by an electrostatic spinning method:
c. b, absorbing the copolymer solution in the step b in an injector, selecting a No. 20 needle, installing the injector in an injection pump of electrostatic spinning equipment, setting the injection speed to be 1.5ml/h, the translation distance to be 12cm and the spinning distance to be 12cm, using a roller as a receiver, setting the rotation speed to be 200rpm, the spinning voltage to be 24kV and the spinning time to be 6h, and after spinning is finished, placing a sample in an oven at the temperature of 60 ℃ for drying for 2h to obtain the fluorine-containing hydrophobic copolymer oil-water separation film.
The obtained fluorine-containing hydrophobic copolymer oil-water separation membrane was sandwiched between oil-water separation devices (as shown in FIG. 2), and the oil-water mixture and the water-in-oil emulsion were separated, with a final separation efficiency of 96.9%.
Example 8
Preparation of fluorine-containing hydrophobic copolymer:
a. adding 30g of ethyl methacrylate and perfluorobutyl ethyl acrylate monomer and 0.15g of methyl ethyl ketone peroxide into ethylene nitrate according to a molar ratio of 90:10, continuously stirring and reacting at 70 ℃ for 30h to obtain a polymer solution, precipitating with water, and drying in a vacuum drying oven at 70 ℃ to obtain a copolymer;
preparing an electrostatic spinning solution:
b. b, dissolving the copolymer obtained in the step a in ethylene nitrate, wherein the mass fraction of the copolymer is 20%, stirring for 4 hours under the heating condition of 75 ℃, and then standing for 1 hour to defoam to obtain a copolymer solution;
spinning an oil-water separation film by an electrostatic spinning method:
c. b, absorbing the copolymer solution in the step b in an injector, selecting a No. 18 needle, installing the injector in an injection pump of electrostatic spinning equipment, setting the injection speed to be 0.5ml/h, the translation distance to be 8cm and the spinning distance to be 15cm, using a roller as a receiver, setting the rotation speed to be 80rpm, the spinning voltage to be 13kV and the spinning time to be 3h, and after spinning is finished, placing a sample in an oven at the temperature of 65 ℃ for drying for 2.5h to obtain the fluorine-containing hydrophobic copolymer oil-water separation film.
The obtained fluorine-containing hydrophobic copolymer oil-water separation membrane was sandwiched between oil-water separation devices (as shown in FIG. 2), and the oil-water mixture and the water-in-oil emulsion were separated, with a final separation efficiency of 97.6%.

Claims (2)

1. A preparation method of a fluorine-containing hydrophobic copolymer oil-water separation film is characterized by comprising the following steps:
preparation of fluorine-containing hydrophobic copolymer:
a. adding a main chain monomer, a fluorine-containing monomer and an oil-soluble initiator accounting for 0.5wt.% of the total monomer mass into an organic solvent according to a molar ratio of 99:1-60:40, continuously stirring and reacting at 50-70 ℃ for 12-48h under the protection of inert gas to obtain a polymer solution, precipitating with water, and drying in a vacuum drying oven at 70 ℃ to obtain polymer powder; wherein the main chain monomer is acrylonitrile, styrene, methyl methacrylate or ethyl methacrylate; the fluorine-containing monomer has 6-14 carbon atoms and 9-21 fluorine atoms, and comprises hexafluorobutyl acrylate, perfluorobutyl ethylene, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, perfluorodecyl ethylene, perfluorobutyl ethyl acrylate, perfluorobutyl ethyl methacrylate, perfluorooctyl acrylate or perfluorooctyl ethyl acrylate; the oil-soluble initiator is azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide; the organic solvent is trifluoroacetic acid, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, sulfolane or ethylene nitrate;
preparing an electrostatic spinning solution:
b. b, dissolving the copolymer powder obtained in the step a in an organic solvent, wherein the mass fraction of the copolymer is 5% -30%, stirring for 4-6h under the heating condition of 50-80 ℃, and then standing for 0.5-2 h to defoam to obtain a copolymer solution; wherein the organic solvent is trifluoroacetic acid, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, sulfolane or ethylene nitrate;
preparing an oil-water separation film by an electrostatic spinning method:
c. b, absorbing the copolymer solution in the step b in an injector, selecting a needle head with the number of 18-24, installing the injector in an injection pump of electrostatic spinning equipment, setting the injection speed to be 0.3-3ml/h, the translation distance to be 5-15cm and the spinning distance to be 8-20cm, taking a roller as a receiver, setting the rotation speed to be 40-300rpm, the spinning voltage to be 10-25kV and the spinning time to be 0.5-6h, and after spinning is finished, placing a sample in an oven with the temperature of 60-80 ℃ for drying for 2-4h to obtain the fluorine-containing hydrophobic copolymer oil-water separation film.
2. Use of the fluorine-containing hydrophobic copolymer oil-water separation membrane obtained by the method according to claim 1 for preparing a separated oil-water mixture or a water-in-oil emulsion.
CN202111220091.6A 2021-10-20 2021-10-20 Preparation method and application of fluorine-containing hydrophobic copolymer oil-water separation film Pending CN113828173A (en)

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CN114874675A (en) * 2022-03-10 2022-08-09 中国科学院兰州化学物理研究所 Preparation method of durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite

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CN102886210A (en) * 2012-09-28 2013-01-23 天津大学 Solvent-free preparation method of anti-pollution self-cleaning oil-water separation film
CN105749770A (en) * 2016-03-28 2016-07-13 无锡市绿之星环保有限公司 Preparation method of novel super-oleophylic and super-hydrophobic separation membrane
CN110102085A (en) * 2019-06-14 2019-08-09 四川轻化工大学 The preparation method and oil-water separation method of oil water separator
CN110743201A (en) * 2018-07-23 2020-02-04 中国石油化工股份有限公司 Super-hydrophobic and super-oleophilic porous net film and preparation method and application thereof
CN112516807A (en) * 2020-11-26 2021-03-19 中国船舶工业系统工程研究院 Separation membrane, preparation method, aviation kerosene dewatering and purifying method and application

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Publication number Priority date Publication date Assignee Title
CN102886210A (en) * 2012-09-28 2013-01-23 天津大学 Solvent-free preparation method of anti-pollution self-cleaning oil-water separation film
CN105749770A (en) * 2016-03-28 2016-07-13 无锡市绿之星环保有限公司 Preparation method of novel super-oleophylic and super-hydrophobic separation membrane
CN110743201A (en) * 2018-07-23 2020-02-04 中国石油化工股份有限公司 Super-hydrophobic and super-oleophilic porous net film and preparation method and application thereof
CN110102085A (en) * 2019-06-14 2019-08-09 四川轻化工大学 The preparation method and oil-water separation method of oil water separator
CN112516807A (en) * 2020-11-26 2021-03-19 中国船舶工业系统工程研究院 Separation membrane, preparation method, aviation kerosene dewatering and purifying method and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114874675A (en) * 2022-03-10 2022-08-09 中国科学院兰州化学物理研究所 Preparation method of durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite

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