CN110655607A - Porous polymer with oleophobic property and pH responsiveness, preparation and application thereof - Google Patents
Porous polymer with oleophobic property and pH responsiveness, preparation and application thereof Download PDFInfo
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- 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
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- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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Abstract
The invention relates to a preparation method of a porous polymer with both hydrophobic and oleophobic properties and pH responsiveness, which comprises the following steps: adding the oil phase into a water phase, and uniformly mixing to obtain an oil-in-water emulsion, wherein the water phase comprises a water-soluble emulsifier, a water-soluble monomer, a pH responsive monomer, a water-soluble cross-linking agent, a water-soluble initiator and water, and the pH responsive monomer comprises amino-containing methacrylate and/or amino-containing acrylate monomers; and carrying out interfacial initiation polymerization reaction on the oil-in-water emulsion at the temperature of 30-80 ℃, and obtaining the porous polymer with hydrophobic and oleophobic properties and pH responsiveness after the reaction is finished. Treating the porous polymer by using a solution with the pH value of 0-4 to obtain a hydrophilic oleophobic porous polymer; and then the hydrophilic oleophobic porous polymer is reversibly converted into the hydrophobic oleophobic porous polymer after being treated by a solution with the pH value of 9-13. The polymer can realize the functions of collecting and removing aqueous solution from oil-aqueous solution mixture with controllable pH.
Description
Technical Field
The invention relates to the field of oil-water separation and the field of heavy metal and pigment removal, in particular to a porous polymer with both oleophobicity and pH responsiveness, and preparation and application thereof.
Background
The oil-water separation material has important significance for solving the world major challenges of water pollution, oil pollution and the like. Through studying nature, people have successfully constructed various materials with special wettability, such as super-hydrophobic-super-oleophilic materials, super-hydrophilic-underwater super-oleophobic materials and the like, and the materials are used for separating oil in water or water in oil. Among them, the super hydrophilic-underwater super oleophobic material is one of the most effective materials for removing water in oil at present. However, due to the potential lipophilicity of the material, the material is easily polluted by oil, so that the oil absorption performance and reusability are reduced. This problem can be solved by constructing the material to have hydrophilic-oleophobic properties in air. This requires that the material have a lower contact angle for water than for oil, which is contrary to conventional theory. Thus, challenges are presented to material design. Recently, some hydrophilic-oleophobic materials have been produced by molecular recombination or molecular defects at the surface of the materials of construction. The hydrophilic-oleophobic material can remove a small amount of water from oil without pre-wetting, such as water from diesel oil, and is very important for protecting an engine; it is becoming increasingly important to remove dyes or heavy metal ions from waste water containing greasy dirt, such as printing and dyeing waste water. Under the conditions, the oleophobic porous material has important advantages, can effectively avoid preferential adsorption of oil stains on the oleophobic porous material, and ensures that effective selective filtration, absorption, adsorption and other modes separate water, dye and heavy metal ions from an oil-water mixture.
Significant advances have been made in hydrophilic oleophobic porous polymers. However, once prepared, the hydrophilic oleophobic porous polymer cannot be altered in its hydrophilicity. For example, Chinese patent application No. 201910446326.X discloses a hydrophilic and oleophobic porous polymer and a preparation method thereof, wherein the porous polymer has no pH responsiveness, and the hydrophilicity of the polymer is fixed after the polymer is prepared. If the material with adjustable surface hydrophilicity can be prepared, the hydrophilicity of the material can be regulated, so that the separation process can be effectively controlled.
Disclosure of Invention
The invention aims to provide a porous polymer material with both oleophobicity and pH responsiveness, and preparation and application thereof.
The first purpose of the invention is to provide a preparation method of a porous polymer with both hydrophobic and oleophobic properties and pH responsiveness, which comprises the following steps:
(1) adding the oil phase into the water phase, and uniformly mixing to obtain an oil-in-water emulsion, wherein the oil phase is an organic solution of a perfluoroacrylate monomer containing 4-12 carbon atoms and/or a perfluoromethacrylate monomer containing 4-12 carbon atoms; the water phase comprises a water-soluble emulsifier, a water-soluble monomer, a pH responsive monomer slightly soluble in water, a water-soluble cross-linking agent, a water-soluble initiator and water, the water-soluble monomer comprises a methacrylamide monomer and/or an acrylamide monomer, the pH responsive monomer comprises an amino-containing methacrylate monomer and/or an amino-containing acrylate monomer, and the water-soluble initiator is an oxidation-reduction or thermal decomposition type initiator; the mass ratio of the water-soluble monomer to the oil phase is 1:50-1: 500;
(2) and carrying out interfacial initiation polymerization reaction on the oil-in-water emulsion at the temperature of 30-80 ℃, and obtaining the porous polymer with hydrophobic and oleophobic properties and pH responsiveness after the reaction is finished. Further, in the step (1), the perfluorinated acrylate monomer or the perfluorinated methacrylate monomer accounts for 1-20% of the total volume of the oil phase; the perfluoroacrylic ester monomer or the perfluoromethacrylic ester monomer contains 4-10 carbon atoms.
Preferably, the perfluoroacrylate-based monomer is perfluorobutyl acrylate, perfluoropentyl acrylate, perfluorohexyl acrylate, perfluoroheptyl acrylate, perfluorooctyl acrylate, perfluorononyl acrylate, perfluorodecyl acrylate, perfluorobutyl ethyl acrylate, perfluoropentyl ethyl acrylate, perfluorohexyl ethyl acrylate, perfluoroheptyl ethyl acrylate, perfluorooctyl ethyl acrylate, perfluorononyl ethyl acrylate, perfluorodecyl ethyl acrylate, or the like. The perfluoromethacrylate-based monomer is perfluorobutyl- (meth) acrylate, perfluoropentyl- (meth) acrylate, perfluorohexyl- (meth) acrylate, perfluoroheptyl- (meth) acrylate, perfluorooctyl- (meth) acrylate, perfluorononyl- (meth) acrylate, perfluorodecyl- (meth) acrylate, perfluorobutylethyl- (meth) acrylate, perfluoropentylethyl- (meth) acrylate, perfluorohexylethyl- (meth) acrylate, perfluoroheptylethyl- (meth) acrylate, perfluorooctylethyl- (meth) acrylate, perfluorononylethyl- (meth) acrylate, perfluorodecylethyl- (meth) acrylate, or the like.
Further, in the step (1), the water-soluble emulsifier accounts for 2-25% of the total weight of the water phase; the water-soluble emulsifier is poloxamer and/or alkylphenol polyoxyethylene.
Further, in the step (1), the water-soluble monomer accounts for 5-20% of the total weight of the water phase; the water-soluble monomer is one or more of acrylamide, methacrylamide, hydroxyethyl acrylate and hydroxyethyl methacrylate.
Further, in the step (1), the pH responsive monomer accounts for 5-20% of the total weight of the water phase; the pH responsive monomer is one or more of dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
Further, in the step (1), the water-soluble cross-linking agent accounts for 0.01-10% of the total weight of the water phase; the water-soluble cross-linking agent is methylene bisacrylamide, polyethylene glycol diacrylate or polyethylene glycol dimethacrylate.
Further, in the step (1), the water-soluble initiator accounts for 0.01-0.1% of the total weight of the water phase; the water-soluble initiator is ammonium persulfate, potassium persulfate or hydrogen peroxide.
Further, in the step (1), the volume ratio of the oil phase to the water phase is 1: 4-20: 1. Further, in the step (1), the solvent in the organic solution is toluene, xylene, or the like.
Further, before the step (2), a step of adding a catalyst into the emulsion is also included, wherein the catalyst is tetramethylethylenediamine, triethylamine and the like, and the mass ratio of the catalyst to the water-soluble monomer is 0-0.1%.
Further, in step (2), the reaction is completed, and then the steps of removing the solvent and unreacted monomers in the water phase and the oil phase and drying are included.
Further, in the step (2), the reaction time is 1-24 h. Preferably, the reaction time is 1-5 h.
The invention also discloses a porous polymer with hydrophobic and oleophobic properties and pH responsiveness prepared by the preparation method, which comprises a hydrophilic part, a hydrophobic part and an oleophobic part which are connected by covalent bonds, wherein the hydrophilic part is a polymer of a water-soluble monomer, the hydrophobic part is a polymer of a pH responsive monomer, and the oleophobic part is a polymer of a perfluoroacrylate monomer and/or a perfluoromethacrylate monomer; the water contact angle of the porous polymer is 80-150 degrees.
The reaction principle of the porous polymer with the water and oil repellency and the pH responsiveness is as follows:
the invention uses emulsifier, monomer, cross-linking agent, initiator and water to form the continuous phase of the emulsion, uses oil solution of perfluoroacrylate monomer as the disperse phase, forms cross-linked polymer in the continuous phase through polymerization, and solidifies the microstructure of the emulsion; the dispersed phase of the emulsion is removed at a later stage, thereby forming pores. During the polymerization, the interconnected pores may occur due to the brittleness of the interface of the continuous phase and the dispersed phase and the non-uniformity of the polymerization. In the polymerization process, the perfluoro (methyl) acrylate monomer in the dispersed phase is initiated through an interface, and bonds are crosslinked on the surfaces of the water-soluble monomer and the pH responsive monomer, so that the porous polymer is endowed with oleophobicity. The polymer formed by the pH-responsive monomer imparts a certain hydrophobicity to the porous polymer, thereby rendering the porous polymer hydrophobic and oleophobic as a whole. In an acidic solution environment, a polymer formed by pH-responsive monomers is protonated and can be converted into hydrophilicity, so that the porous material has hydrophilic and oleophobic properties; in an alkaline environment, the protonated pH-responsive polymer reversibly converts to hydrophobic through deprotonation. Thereby enabling the porous material to have a reversible change from hydrophobic-oleophobic to hydrophilic-oleophobic with pH control.
The third purpose of the invention is to protect the application of the porous polymer with hydrophobic and oleophobic properties and pH responsiveness as a pH responsiveness hydrophobic and oleophobic-hydrophilic and oleophobic reversible conversion material.
Further, the preparation method of the pH-responsive hydrophobic oleophobic-hydrophilic oleophobic reversible transition material comprises the following steps:
soaking the porous polymer with the hydrophobic and oleophobic properties and pH responsiveness in an acid solution for reaction to obtain a hydrophilic and oleophobic porous polymer after the reaction is completed; water can be quickly spread on the hydrophilic oleophobic porous polymer, the contact angle of the water is 0 degree, and the oil contact angle is 80-150 degrees;
and then soaking the hydrophilic oleophobic porous polymer in an alkaline solution for reaction, and recovering to the original hydrophobic oleophobic porous polymer after the reaction is completed.
Further, the pH value of the acidic solution is 0 to 4; the solute of the acidic solution is an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or an organic acid such as formic acid, acetic acid, or sulfonic acid.
Further, the pH value of the alkaline solution is between 9 and 13; the solute of the alkaline solution is triethylamine, diethylamine, ammonia water, sodium hydroxide or potassium hydroxide.
The porous polymer with the hydrophobic and oleophobic property and the pH responsiveness is acidified, and the hydrophobic and oleophobic property is converted into the hydrophilic and oleophobic property, because the polymer formed by the pH responsiveness monomer realizes protonation, so that the polymer is converted into the hydrophilic property from the hydrophobic property. And reacting the acidified hydrophilic oleophobic porous polymer with alkali again to realize deprotonation of the pH-responsive polymer, so that the polymer is changed from hydrophilicity to hydrophobicity. The pH is adjusted by an acid-base solution, so that the conversion between the hydrophobic and oleophobic properties and the hydrophilic and oleophobic properties of the porous polymer is realized.
In the invention, the reaction raw material contains water-soluble monomer and oil phase, in the product, the polymer of the water-soluble monomer and the oil phase plays a role in hydrophilic-hydrophobic balance, and if the reaction raw material does not contain hydrophilic monomer, the porous polymer with hydrophobic and oleophobic properties and pH responsiveness does not have hydrophilicity even after protonation. And the water-soluble monomer and the oil phase are controlled in mass ratio to make the product hydrophobic and oleophobic.
By the scheme, the invention at least has the following advantages:
the preparation of the hydrophobic and oleophobic porous polymer and the conversion from hydrophobic and oleophobic property to hydrophilic and oleophobic property are respectively realized through two steps, so that the porous polymer with different oleophobic properties and pH responsiveness is obtained.
According to the invention, the hydrophobic and oleophobic porous polymer is firstly prepared by an emulsion polymerization method, the porous polymer has pH responsiveness, the hydrophobic and oleophobic properties and the hydrophilic and oleophobic properties of the porous polymer are converted by controlling the change of pH, and the pH responsiveness hydrophobic and oleophobic-hydrophilic and oleophobic reversible conversion material can be prepared by utilizing the properties.
The hydrophilic oleophobic porous polymer can be used for absorbing/permeating water from an oil-water mixture to achieve the purpose of oil-water separation; can also be used for adsorbing pigment or metal ions from an oil-water mixture to achieve the aim of removing the pigment and the metal ions. The interconversion of the hydrophobic oleophobic property and the hydrophilic oleophobic property can realize the effective control of the separation process and avoid the influence of the existence of oil on the separation.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is an electronic energy spectrum of a hydrophobic and oleophobic porous material of example 1 and a hydrophilic and oleophobic porous material of example 2 in the invention;
FIG. 2 is a test chart of the contact angle of the hydrophobic and oleophobic porous material of example 1 of the invention to water and octadecane according to the time;
FIG. 3 is a graph showing the change of contact angle of water drops on the surface of a hydrophilic oleophobic porous material in example 2 of the invention;
FIG. 4 is a scanning electron micrograph of example 1 hydrophobic and oleophobic and example 2 hydrophilic and oleophobic porous materials of the invention;
FIG. 5 is a photograph showing the morphology of oil droplets and water droplets on the surface of the hydrophobic and oleophobic porous material of example 1 of the present invention after acid and alkali treatment.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The embodiment provides a preparation method of a hydrophobic and oleophobic porous material, which comprises the following steps:
(1) 2.8g of acrylamide, 0.5g N', N-methylenebisacrylamide and 8g of
F-127 and 1.8mL of diethylaminoethyl methacrylate are dissolved in 16.9g of water to prepare an aqueous solution; 6.9mL of 2- (perfluorooctyl) ethyl methacrylate was dissolved in 69.3mL of toluene, the toluene solution was added to the above aqueous solution with stirring at 400rpm to form an emulsion, and then 0.3g of ammonium persulfate and 0.16mL of N, N, N, N-tetramethylethylenediamine were added to the emulsion.
(2) And (3) polymerizing the emulsion for 1 hour at the temperature of 40 ℃, removing water, toluene and the like after polymerization, and drying to obtain the hydrophobic and oleophobic porous material.
Example 2
This example provides a method for converting the hydrophobic and oleophobic porous material of example 1 into a hydrophilic and oleophobic porous material by changing the pH,
and (2) soaking the hydrophobic and oleophobic porous material prepared in the example 1 in a 1 wt% HCl water and ethanol solution for 1 hour, extracting with ethanol, and drying to obtain the hydrophilic and oleophobic porous material.
Example 3
This example provides a method for converting the hydrophilic oleophobic porous material of example 2 to the hydrophobic oleophobic porous material of example 1 by changing the pH.
And (3) soaking the hydrophilic oleophobic porous material prepared in the example 2 in a water and ethanol solution of 1 wt% triethylamine for 1 hour, and extracting and drying the soaked material by ethanol to obtain the hydrophobic oleophobic porous material.
The curves of fig. 1a and b are the electron energy spectra of the hydrophobic oleophobic property in example 1 and the hydrophilic oleophobic property in example 2 respectively. FIG. 2 is a test chart of the change of contact angles of water and octadecane of the hydrophobic and oleophobic porous material of example 1 with time, and it can be seen from the chart that the hydrophobic and oleophobic porous material has stable oleophobic property, and the contact angle of hexadecane on the surface of the hydrophobic and oleophobic porous material is as high as 130 degrees, and the contact angle does not change with time; the contact angle of water on the porous material is slightly reduced with time, but can still be kept above 100 degrees.
3a-d are contact angle change graphs of 0s, 10s, 20s and 30s of the hydrophilic and oleophobic porous material surface of the water drop in the sequence of example 2, and it can be seen that within 30s, the water drop is infiltrated on the material surface, which indicates that the material has hydrophilicity.
Fig. 4a and b are scanning electron microscope images of the hydrophobic and oleophobic porous material in example 1 and the hydrophilic and oleophobic porous material in example 2, respectively, and it can be seen that the materials have a communicated macroporous structure, and the macroporous structure is beneficial to absorption and transmission of liquid.
Fig. 5 is a photograph of the oil droplets and water droplets on the surface of the hydrophobic and oleophobic porous material (fig. 5a) treated by acid and alkali, which are converted into the hydrophilic and oleophobic material after acid treatment, the water droplets wet the surface of the hydrophobic and oleophobic porous material, and the oil droplets return to the original hydrophobic and oleophobic property after alkali treatment (fig. 5 b).
Example 4
This example provides a method for preparing a hydrophobic and oleophobic porous polymer, the reaction steps of which are the same as in example 1, except that the polymerization time is 2 hours, 3 hours or 4 hours, respectively.
Example 5
This example provides a method for preparing a hydrophobic and oleophobic porous polymer, which includes the same reaction steps as in example 1, except that: the aqueous solution was composed of 3.6g of acrylamide, 0.5g N', N-methylenebisacrylamide, 8gF-123, 16.9g of water, 1.0mL of diethylaminoethyl methacrylate.
Example 6
This example provides a method for preparing a hydrophobic and oleophobic porous polymer, which includes the same reaction steps as in example 1, except that: the aqueous phase was composed of 2.0g acrylamide, 0.5g N', N-methylenebisacrylamide, 8g
F-127, 16.9g of water, 2.6mL of diethylaminoethyl methacrylate.
The microstructure and properties of the hydrophobic and oleophobic porous polymers prepared in examples 4-7 above are similar to those in example 1.
Example 7
The embodiment provides a method for realizing controllable water separation by adjusting the pH value of an aqueous solution. Placing the hydrophilic and oleophobic porous material obtained in the example 2 into an oil-water mixture, placing the oil-water mixture into a container, and placing the hydrophilic and oleophobic porous material for 2min to ensure that water in the oil-water mixture is selectively absorbed by the hydrophilic and oleophobic porous material; the continuous separation of water can be realized by connecting the hydrophilic oleophobic porous material to a water pump; adjusting the pH value of the aqueous solution to be alkaline, and stopping water absorption; and the pH value of the aqueous solution is adjusted to be acidic, so that the continuous absorption and separation of water in the solution can be realized.
Example 8
This example provides a pH-responsive oleophobic hydrophilic porous polymer based for pigment removal in aqueous oil-containing solutions. The method comprises the following steps: the porous material obtained in example 2 was placed in an oil-water mixture, and stirred to achieve adsorption and removal of the pigment. The results show an adsorption capacity of 0.1 g/g for methylene blue.
Claims (10)
1. A preparation method of a porous polymer with hydrophobic and oleophobic properties and pH responsiveness is characterized by comprising the following steps:
(1) adding an oil phase into the water phase, and uniformly mixing to obtain an oil-in-water emulsion, wherein the oil phase is an organic solution of a perfluoroacrylate monomer containing 4-12 carbon atoms and/or a perfluoromethacrylate monomer containing 4-12 carbon atoms; the water phase comprises a water-soluble emulsifier, a water-soluble monomer, a slightly water-soluble pH responsive monomer, a water-soluble cross-linking agent, a water-soluble initiator and water, wherein the water-soluble monomer comprises a methacrylamide monomer and/or an acrylamide monomer, the pH responsive monomer comprises an amino-containing methacrylate monomer and/or an amino-containing acrylate monomer, and the water-soluble initiator is an oxidation-reduction or thermal decomposition type initiator; the mass ratio of the water-soluble monomer to the oil phase is 1:50-1: 500;
(2) and carrying out interfacial initiation polymerization reaction on the oil-in-water emulsion at the temperature of 30-80 ℃, and obtaining the porous polymer with hydrophobic and oleophobic properties and pH responsiveness after the reaction is finished.
2. The method of claim 1, wherein: in the step (1), the perfluorinated acrylate monomer or the perfluorinated methacrylate monomer accounts for 1-20% of the total volume of the oil phase; the perfluorinated acrylate monomer or the perfluorinated methacrylate monomer contains 4-10 carbon atoms.
3. The method of claim 1, wherein: in the step (1), the water-soluble emulsifier accounts for 2-25% of the total weight of the water phase; the water-soluble emulsifier is poloxamer and/or alkylphenol polyoxyethylene.
4. The method of claim 1, wherein: in the step (1), the water-soluble monomer accounts for 5-20% of the total weight of the water phase; the water-soluble monomer is one or more of acrylamide, methacrylamide, hydroxyethyl acrylate and hydroxyethyl methacrylate.
5. The method of claim 1, wherein: in the step (1), the pH responsive monomer accounts for 5-20% of the total weight of the water phase; the pH responsive monomer is one or more of dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
6. The method of claim 1, wherein: in the step (1), the water-soluble cross-linking agent accounts for 0.01-10% of the total weight of the water phase; the water-soluble cross-linking agent is methylene bisacrylamide, polyethylene glycol diacrylate or polyethylene glycol dimethacrylate.
7. The method of claim 1, wherein: in the step (1), the volume ratio of the oil phase to the water phase is 1: 4-20: 1.
8. A porous polymer having water and oil repellency and pH responsiveness prepared by the preparation method according to any one of claims 1 to 7, characterized in that: the water-soluble acrylate/oil-repellent acrylate composite material comprises a hydrophilic part, a hydrophobic part and an oleophobic part which are connected by covalent bonds, wherein the hydrophilic part is a polymer of a water-soluble monomer, the hydrophobic part is a polymer of a pH responsive monomer, and the oleophobic part is a polymer of a perfluoroacrylate monomer and/or a perfluoromethacrylate monomer; the water contact angle of the porous polymer is 80-150 degrees.
9. Use of the porous polymer with hydrophobic oleophobic and pH responsive properties according to claim 8 as a pH responsive hydrophobic oleophobic-hydrophilic oleophobic reversible transition material.
10. The use according to claim 9, characterized in that the method for preparing the pH-responsive hydrophobic oleophobic-hydrophilic oleophobic reversible transition material comprises the following steps:
soaking the porous polymer with hydrophobic and oleophobic properties and pH responsiveness of claim 8 in an acidic solution for reaction to obtain a hydrophilic and oleophobic porous polymer after the reaction is completed;
and soaking the hydrophilic oleophobic porous polymer in an alkaline solution for reaction, and obtaining the hydrophobic oleophobic porous polymer after the reaction is completed.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519270A (en) * | 2020-05-18 | 2020-08-11 | 苏州大学 | Porous fiber and preparation method and application thereof |
| CN113788909A (en) * | 2021-09-07 | 2021-12-14 | 上海弗鲁克科技发展有限公司 | pH response type porous adsorption material and preparation method and application thereof |
| CN114196065A (en) * | 2021-12-27 | 2022-03-18 | 苏州大学 | Renewable hydrophilic-oleophobic porous polymer and preparation method thereof |
| CN114344950A (en) * | 2021-12-15 | 2022-04-15 | 北京中石大绿色能源科技有限公司 | Super-hydrophilic-super-oleophobic surface stable in air-water-oil and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080237117A1 (en) * | 2007-03-30 | 2008-10-02 | Vishal Bansal | Coated asymmetric membrane system having oleophobic and hydrophilic properties |
| CN104910338A (en) * | 2015-06-18 | 2015-09-16 | 辽宁大学 | Preparation method of temperature/pH dual-response flexible polymer Janus hollow sphere |
| CN108659241A (en) * | 2018-04-27 | 2018-10-16 | 同济大学 | With temperature-responsive, pH responses, the star-type polymer of photosynthesis-carbon dioxide response, self-healing hydrogel and preparation method |
| CN110172123A (en) * | 2019-05-27 | 2019-08-27 | 苏州大学 | Hydrophilic and oleophobic property porous polymer and preparation method thereof |
-
2019
- 2019-11-01 CN CN201911060122.9A patent/CN110655607B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080237117A1 (en) * | 2007-03-30 | 2008-10-02 | Vishal Bansal | Coated asymmetric membrane system having oleophobic and hydrophilic properties |
| CN104910338A (en) * | 2015-06-18 | 2015-09-16 | 辽宁大学 | Preparation method of temperature/pH dual-response flexible polymer Janus hollow sphere |
| CN108659241A (en) * | 2018-04-27 | 2018-10-16 | 同济大学 | With temperature-responsive, pH responses, the star-type polymer of photosynthesis-carbon dioxide response, self-healing hydrogel and preparation method |
| CN110172123A (en) * | 2019-05-27 | 2019-08-27 | 苏州大学 | Hydrophilic and oleophobic property porous polymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 任芳等: ""聚(甲基丙烯酸N，N-二甲氨基乙酯)的温度和pH敏感性及其对乳液稳定性的影响"", 《高分子学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519270A (en) * | 2020-05-18 | 2020-08-11 | 苏州大学 | Porous fiber and preparation method and application thereof |
| CN111519270B (en) * | 2020-05-18 | 2022-01-18 | 苏州大学 | Porous fiber and preparation method and application thereof |
| CN113788909A (en) * | 2021-09-07 | 2021-12-14 | 上海弗鲁克科技发展有限公司 | pH response type porous adsorption material and preparation method and application thereof |
| CN114344950A (en) * | 2021-12-15 | 2022-04-15 | 北京中石大绿色能源科技有限公司 | Super-hydrophilic-super-oleophobic surface stable in air-water-oil and preparation method and application thereof |
| CN114196065A (en) * | 2021-12-27 | 2022-03-18 | 苏州大学 | Renewable hydrophilic-oleophobic porous polymer and preparation method thereof |
| CN114196065B (en) * | 2021-12-27 | 2022-11-18 | 苏州大学 | Renewable hydrophilic-oleophobic porous polymer and preparation method thereof |
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