CN111763291B - Hydrophilic oleophobic three-dimensional porous polymer material and preparation method thereof - Google Patents
Hydrophilic oleophobic three-dimensional porous polymer material and preparation method thereof Download PDFInfo
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- CN111763291B CN111763291B CN202010676374.0A CN202010676374A CN111763291B CN 111763291 B CN111763291 B CN 111763291B CN 202010676374 A CN202010676374 A CN 202010676374A CN 111763291 B CN111763291 B CN 111763291B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
Abstract
The invention relates to a hydrophilic oleophobic three-dimensional porous polymer material and a preparation method thereof, wherein the preparation method comprises the following steps: uniformly mixing a functional monomer and a cross-linking agent in an organic solvent to form a mixed solution; the functional monomer comprises a hydrophilic monomer containing a carbon-carbon double bond, a fluoroalkyl oleophobic monomer and a mercapto monomer or a fluoroalkyl oleophobic monomer and a mercapto monomer; the monomer containing the sulfydryl at least contains two sulfydryl; and carrying out catalytic reaction on the mixed solution under the action of a catalyst, and removing the catalyst after the reaction is completed to obtain the hydrophilic and oleophobic three-dimensional porous polymer material, wherein the catalyst comprises ammonia water. The porous material has hydrophilic and oleophobic properties, and can realize an efficient oil-water separation function.
Description
Technical Field
The invention relates to the technical field of oil-water separation material preparation, in particular to a hydrophilic oleophobic three-dimensional porous polymer material and a preparation method thereof.
Background
In recent years, with the development of industry, the discharge of oily wastewater poses great harm to the environment and human health. Particularly, the frequent occurrence of oil leakage at sea leads to the death of a large number of fishes and other marine organisms, and the ecological balance is seriously damaged. Achieving rapid and efficient separation of oil-water mixtures has become a global challenge. At present, materials commonly used for oil-water separation include filter membranes, particles, three-dimensional porous materials and the like with different wetting properties, wherein the three-dimensional porous materials realize the function of efficiently absorbing oil/water from an oil-water mixture due to the high porosity and the hydrophilic or oleophilic properties of the materials, and are effective methods for solving the problem of oil pollution.
At present, the three-dimensional porous material commonly used for oil-water separation is generally a hydrophobic oleophilic material, the material can absorb oil from oil-water mixed liquid, and water cannot enter the material, so that the effect of oil-water separation is achieved.
The patent with the application number of 2015100766477 discloses a three-dimensional oil-water separation preparation method based on an electrostatic spinning technology: preparing a nanofiber solution by adopting an electrostatic spinning technology, removing redundant liquid by freeze drying to obtain three-dimensional nanofibers, pre-oxidizing, carbonizing and activating to form three-dimensional carbon nanofibers, and finally coating a layer of oleophylic hydrophobic membrane on the surface to obtain the three-dimensional oil-water separation material.
The invention with application number of 201810532122.3 discloses a preparation method of a multi-scale organic/inorganic composite porous material for oil-water separation, which comprises the following steps: calcining tetraethyl orthosilicate/phosphoric acid-soluble/polyvinyl alcohol nanofiber membrane prepared by electrostatic spinning to obtain SiO2Breaking up the nanofiber membrane in water to obtain SiO2Soaking the porous material in the nanofiber suspension, cross-linking the porous material in glutaraldehyde steam after freeze drying, soaking the cross-linked porous material in an aqueous solution containing divalent metal salt, trivalent metal salt and alkaline substances, and carrying out hydrothermal reaction to finally obtain the multi-scale organic/inorganic composite porous material. The maximum oil-water separation efficiency of the material can reach 99.5%.
Although the hydrophobic oleophylic three-dimensional porous material shows high-efficiency oil absorption performance in the aspect of oil-water separation, the material cannot be completely removed after oil absorption due to the hydrophobicity of the material, and the adsorption efficiency and the recyclable performance of the material are seriously influenced. Recently, some hydrophilic and oleophobic materials are reported successively by reasonably regulating and controlling the surface energy and the morphology of the materials. The hydrophilic-oleophobic material can realize oil-water separation without being wetted in advance, can realize the function of removing water in oil, has high separation efficiency and can be recycled for multiple times. The preparation of the hydrophilic and oleophobic material is generally realized by surface modification or the doping of an oleophobic and hydrophilic component at present. At present, few reports on hydrophilic and oleophobic three-dimensional porous polymer materials exist.
The invention with the application number of 201910446326.X discloses a hydrophilic and oleophobic porous polymer and a preparation method thereof: by using an emulsion template method, under the stirring condition, adding an organic solution of a perfluoro (methyl) acrylate monomer containing 4-12 carbon atoms as an oil phase into a water phase containing a water-soluble emulsifier, a water-soluble monomer, a water-soluble cross-linking agent, a water-soluble initiator and water, uniformly mixing, heating, and carrying out interfacial polymerization reaction on the emulsion to finally obtain the porous material with the hydrophilic and oleophobic functions. However, the hydrophilic and oleophobic performance of the material is realized by the doping distribution of the oleophobic oil phase polymer and the hydrophilic water phase polymer, so the requirements on the oil phase and water phase distribution are strict, and meanwhile, the preparation process of the material is long in time consumption and complex in operation.
Therefore, a three-dimensional porous material directly composed of hydrophilic oleophobic polymer is developed, the material can rapidly absorb water from oil-water mixture, meanwhile, the oleophobic property is strong enough, the material can be prevented from being polluted, and the preparation method is simple, short in time consumption, very necessary and has practical value.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a hydrophilic and oleophobic three-dimensional porous polymer material and a preparation method thereof.
The invention discloses a preparation method of a hydrophilic oleophobic three-dimensional porous polymer material, which comprises the following steps:
(1) uniformly mixing a functional monomer and a cross-linking agent in an organic solvent to form a mixed solution; the functional monomer comprises a hydrophilic monomer containing a carbon-carbon double bond, a fluoroalkyl oleophobic monomer and a mercapto monomer or a fluoroalkyl oleophobic monomer and a mercapto monomer; the monomer containing the sulfydryl at least contains two sulfydryl; the organic solvent has stronger affinity to water than NH3Affinity to water;
(2) and (3) carrying out catalytic reaction on the mixed solution at 10-60 ℃ under the action of a catalyst, and removing the catalyst after the reaction is completed to obtain the hydrophilic and oleophobic three-dimensional porous polymer material, wherein the catalyst comprises ammonia water.
Further, in the step (1), the hydrophilic monomer containing a carbon-carbon double bond includes any one or more of acrylic acid, methacrylic acid, acrylamide, methacrylamide or methacryloyl ethyl sulfobetaine. Preferably, the hydrophilic monomer containing a carbon-carbon double bond is methacrylic acid. The hydrophilic monomer containing carbon-carbon double bonds functions to provide hydrophilicity to the porous polymer. According to the invention, the hydrophilic monomer containing the carbon-carbon double bond can be selectively added, and when the hydrophilic monomer containing the carbon-carbon double bond is not used, the hydrophilic oleophobic porous material can still be prepared, only the wettability of the material to water and oil is slightly different.
Further, in step (1), the fluoroalkyl monomer is selected from compounds of the following general structural formula:
wherein R is hydrogen or methyl, m is any integer of 1-5, and n is any integer of 3-9. Preferably, m is 2 and n is 5 or 7. The fluoroalkyl monomer is an oleophobic monomer, and endows the porous material with oleophobic property.
Further, in the step (1), the cross-linking agent is selected from any one or more of polyethylene glycol diacrylate, N-carboxyethyl acrylamide, 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, dipentaerythritol penta-/hexa-acrylic acid and pentaerythritol triacrylate. Preferably, the crosslinker is polyethylene glycol diacrylate. The two ends of the cross-linking agent both contain carbon-carbon double bonds, and the function of the cross-linking agent is to connect fluorine monomers and mercapto monomers together to form a net structure, so that the excellent strength and elasticity of the high-molecular porous material are provided. Because the polyethylene glycol diacrylate contains polyethylene glycol flexible units, the porous material prepared by the cross-linking agent has good elasticity, and the porous material with poor elasticity is formed by adopting other cross-linking agents.
Further, in the step (1), the mercapto group-containing monomer is an acrylate monomer containing two or more mercapto groups. Preferably, the mercapto group-containing monomer is pentaerythritol tetramercaptoacetate. The mercapto group in the mercapto group-containing monomer reacts with electron-deficient olefin through Michael addition, the mercapto group is deprotonated under the action of ammonia water to generate mercaptan anion and ammonia cation, and then the mercaptan anion is a strong nucleophilic reagent and is added to an activated carbon-carbon double bond to form an anion intermediate product which is a strong alkali. This anion randomly acquires either the proton of the thiol group or the proton of the ammonium cation to form a thiol-ene addition product. The invention utilizes the advantage that the thiol-ene photopolymerization is not inhibited by oxygen and can be carried out under the environmental condition, and the multifunctional thiol is introduced into the reaction to form the uniform cross-linked network polymer.
The reaction between mercapto group and electron-deficient olefin through Michael addition generally uses organic base as catalyst, such as organic amine, organic phosphide, etc., but usually obtains non-porous material. The invention takes ammonia water as a catalyst and takes an organic solvent with strong affinity with water, such as acetone as a solvent, when the ammonia water carries out catalytic reaction, partial water molecules in the ammonia water are captured by the acetone, and ammonia gas is released in a gas form to form a porous structure.
Further, in the step (1), the mole ratio of the hydrophilic monomer containing carbon-carbon double bond, the fluoroalkyl oleophobic monomer, the cross-linking agent and the mercapto group-containing monomer is as follows: 0-0.8: 0.1-0.6: 1.2-1.8: 0.9 to 1.1. When the amount of the hydrophilic monomer containing a carbon-carbon double bond is 0, the functional monomer only contains the fluoroalkyl oleophobic monomer and the sulfhydryl-containing monomer.
Further, in the step (1), the volume ratio of the organic solvent to the functional monomer is 1: 2-5. Preferably, the volume ratio is 1: 3.
Further, in the step (1), the organic solvent includes any one or more of acetone, tetrahydrofuran, ethanol and N, N' -dimethylformamide. Preferably, the organic solvent is acetone. In the invention, the selected organic solvent has good affinity with water, when the ammonia water carries out catalytic reaction, part of water molecules in the ammonia water are captured by the organic solvent, and the ammonia gas is released in a gas form to form a porous structure. Porous materials cannot be obtained by using organic solvents having poor affinity for water.
Further, in the step (2), the volume ratio of the ammonia water to the mixed solution is 2: 1; the concentration of the ammonia water is 5wt% -30 wt%. Preferably, the ammonia concentration is 25 wt%.
Further, in the step (2), a three-dimensional porous material is obtained after the completion of the catalytic reaction, and then is soaked in water to remove ammonia.
Further, in the step (2), a step of freeze-drying at-10 ℃ to-80 ℃ is included after the catalyst is removed. The purpose of freeze-drying is to remove the solvent from the porous material and to keep the original volume and structure of the porous material unchanged.
The invention also claims a hydrophilic oleophobic three-dimensional porous polymer material prepared by the preparation method, which has a plurality of three-dimensional holes, the aperture is 1-600 μm, and the porosity is 40% -90%.
Preferably, the hydrophilic oleophobic three-dimensional porous polymer material has hydrophilic oleophobic performance, the surface of the hydrophilic oleophobic three-dimensional porous polymer material can realize a contact angle of 0 degree to water within 8s, and the contact angle to hexadecane liquid drops can be kept to be about 125 degrees.
By the scheme, the invention at least has the following advantages:
the invention provides a preparation method of a hydrophilic oleophobic three-dimensional porous polymer material, which is simple and short in time consumption.
The hydrophilic oleophobic three-dimensional porous polymer material prepared by the method has hydrophilic oleophobic performance, can quickly absorb water from an oil-water mixture, and simultaneously has strong oleophobic performance enough to prevent the material from being polluted.
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 SEM low-power image of a hydrophilic oleophobic porous material of the invention;
FIG. 2 is a SEM high magnification image of a hydrophilic oleophobic porous material of the invention;
FIG. 3 is a result of a water contact angle test performed on a hydrophilic oleophobic porous material using a contact angle meter;
FIG. 4 is the results of a hexadecane contact angle test performed on a hydrophilic oleophobic porous material using a contact angle meter;
FIG. 5 is an elasticity evaluation of a hydrophilic oleophobic porous material.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1:
a preparation method of a hydrophilic oleophobic porous polymer material comprises the following specific steps:
(1) and stirring the acetone solution of the fluoroalkyl monomer perfluorohexyl ethyl methacrylate, the cross-linking agent polyethylene glycol diacrylate and pentaerythritol tetramercaptoacetate at room temperature for 20min to obtain the porous material precursor solution. Wherein the mol ratio of the perfluorohexyl ethyl methacrylate to the polyethylene glycol diacrylate to the pentaerythritol tetramercaptoacetate is 0.2:1.9: 1. The volume ratio of acetone to functional monomer is 1: 3. Functional monomers refer to fluoroalkyl monomers and pentaerythritol tetramercaptoacetate.
(2) Adding 6mL of 25 wt% ammonia water into 3mL of precursor solution to obtain a reaction solution, and fully reacting at room temperature to obtain the porous material.
(3) And soaking the obtained porous material in deionized water to remove redundant ammonia water, and then placing the porous material in a freeze drying box at the temperature of minus 80 ℃ for drying to obtain the hydrophilic oleophobic porous polymer material. The contact angle of hexadecane on the surface of the obtained hydrophilic and oleophobic three-dimensional porous polymer material is about 130 degrees, and the wetting time of water is about 15 s.
Example 2:
a preparation method of a hydrophilic oleophobic porous polymer material comprises the following specific steps:
(1) and stirring the acetone solution of a hydrophilic monomer methacrylic acid, a fluoroalkyl monomer perfluorohexyl ethyl methacrylate, a cross-linking agent polyethylene glycol diacrylate and pentaerythritol tetrasulfamoyl acetate at room temperature for 20min to obtain a porous material precursor solution. Wherein the molar ratio of the methacrylic acid, the perfluorohexylethyl methacrylate, the polyethylene glycol diacrylate and the pentaerythritol tetramercaptoacetate is 0.2:0.4:1.7: 1. The volume ratio of acetone to functional monomer is 1: 3. The functional monomers refer to hydrophilic monomers, fluoroalkyl monomers, and pentaerythritol tetramercaptoacetate.
(2) Adding 6mL of 25 wt% ammonia water into 2mL of precursor solution to obtain a reaction solution, and fully reacting at room temperature to obtain the porous material.
(3) And soaking the obtained porous material in deionized water to remove redundant ammonia water, and then placing the porous material in a freeze drying box at the temperature of minus 80 ℃ for drying to obtain the hydrophilic oleophobic porous polymer material. The contact angle of hexadecane on the surface of the obtained hydrophilic and oleophobic three-dimensional porous polymer material is about 125 degrees, and the wetting time of water is about 8 s.
Example 3:
a preparation method of a hydrophilic oleophobic porous polymer material comprises the following specific steps:
(1) and stirring the acetone solution of a hydrophilic monomer methacrylic acid, a fluoroalkyl monomer perfluorohexyl ethyl methacrylate, a cross-linking agent polyethylene glycol diacrylate and pentaerythritol tetrasulfamoyl acetate at room temperature for 20min to obtain a porous material precursor solution. Wherein the molar ratio of the methacrylic acid, the perfluorohexylethyl methacrylate, the polyethylene glycol diacrylate and the pentaerythritol tetramercaptoacetate is 0.4:0.2:1.7: 1. The volume ratio of acetone to functional monomer is 1: 3. The functional monomers refer to hydrophilic monomers, fluoroalkyl monomers, and pentaerythritol tetramercaptoacetate.
(2) Adding 6mL of 25 wt% ammonia water into 3mL of precursor solution to obtain a reaction solution, and fully reacting at room temperature to obtain the porous material.
(3) And soaking the obtained porous material in deionized water to remove redundant ammonia water, and then placing the porous material in a freeze drying box at the temperature of minus 80 ℃ for drying to obtain the hydrophilic oleophobic porous polymer material. The contact angle of hexadecane on the surface of the obtained hydrophilic and oleophobic three-dimensional porous polymer material is about 95 degrees, and the wetting time of water is about 5 s.
Example 4:
a preparation method of a hydrophilic oleophobic porous polymer material comprises the following specific steps:
(1) and stirring the acetone solution of a hydrophilic monomer methacrylic acid, a fluoroalkyl monomer perfluorohexyl ethyl methacrylate, a cross-linking agent polyethylene glycol diacrylate and pentaerythritol tetrasulfamoyl acetate at room temperature for 20min to obtain a porous material precursor solution. Wherein the molar ratio of the methacrylic acid, the perfluorohexylethyl methacrylate, the polyethylene glycol diacrylate and the pentaerythritol tetramercaptoacetate is 0.2:0.8:1.5: 1. The volume ratio of acetone to functional monomer is 1: 3. The functional monomers refer to hydrophilic monomers, fluoroalkyl monomers, and pentaerythritol tetramercaptoacetate.
(2) Adding 6mL of 25 wt% ammonia water into 3mL of precursor solution to obtain a reaction solution, and fully reacting at room temperature to obtain the porous material.
(3) And soaking the obtained porous material in deionized water to remove redundant ammonia water, and then placing the porous material in a freeze drying box at the temperature of minus 80 ℃ for drying to obtain the hydrophilic oleophobic porous polymer material. The contact angle of hexadecane on the surface of the obtained hydrophilic and oleophobic three-dimensional porous polymer material is about 133 degrees, and the wetting time of water is about 240 seconds.
Example 5:
a preparation method of a hydrophilic oleophobic porous polymer material comprises the following specific steps:
(1) and stirring the acetone solution of a hydrophilic monomer methacrylic acid, a fluoroalkyl monomer perfluorohexyl ethyl methacrylate, a cross-linking agent polyethylene glycol diacrylate and pentaerythritol tetrasulfamoyl acetate at room temperature for 20min to obtain a porous material precursor solution. Wherein the molar ratio of the methacrylic acid, the perfluorohexylethyl methacrylate, the polyethylene glycol diacrylate and the pentaerythritol tetramercaptoacetate is 0.2:0.4:1.7: 1. The volume ratio of acetone to functional monomer is 1: 2. The functional monomers refer to hydrophilic monomers, fluoroalkyl monomers, and pentaerythritol tetramercaptoacetate.
(2) Adding 6mL of 25 wt% ammonia water into 3mL of precursor solution to obtain a reaction solution, and fully reacting at room temperature to obtain the porous material.
(3) And soaking the obtained porous material in deionized water to remove redundant ammonia water, and then placing the porous material in a freeze drying box at the temperature of minus 80 ℃ for drying to obtain the hydrophilic oleophobic porous polymer material. The contact angle of hexadecane on the surface of the obtained hydrophilic and oleophobic three-dimensional porous polymer material is about 118 degrees, and the wetting time of water is about 25 s.
FIGS. 1-2 are SEM images of hydrophilic oleophobic porous materials prepared in example 2 of the invention; as can be seen from the figure, porous structures are uniformly distributed on the surface and inside of the material, and micro-nano convex structures are arranged on the hole walls.
FIG. 3 is the result of a water contact angle test using a contact angle meter on the hydrophilic and oleophobic porous material prepared in example 2, the contact angle of a water drop at 8s on the porous material; it can be seen from the figure that at 8s the water droplets spread out evenly over the surface of the material, indicating that the material has good and rapid hydrophilicity.
Fig. 4 is the result of a hexadecane contact angle test performed on the hydrophilic oleophobic porous material prepared in example 2 using a contact angle meter.
The elasticity and recoverability of the porous material of example 2 were simply tested by pressing the porous material with hands, and it was found that the porous material was restored to its original shape and height (fig. 5c) after being crushed (fig. 5b), indicating that the porous material had excellent elasticity and recoverability.
Example 6:
a preparation method of a hydrophilic oleophobic porous polymer material comprises the following specific steps:
(1) and stirring the acetone solution of a hydrophilic monomer methacrylic acid, a fluoroalkyl monomer perfluorohexyl ethyl methacrylate, a cross-linking agent pentaerythritol triacrylate and pentaerythritol tetramercaptoacetate at room temperature for 20min to obtain a porous material precursor solution. Wherein the molar ratio of the methacrylic acid, the perfluorohexylethyl methacrylate, the polyethylene glycol diacrylate and the pentaerythritol tetramercaptoacetate is 0.2:0.4:1.7: 1. The volume ratio of acetone to functional monomer is 1: 3. The functional monomers refer to hydrophilic monomers, fluoroalkyl monomers, and pentaerythritol tetramercaptoacetate.
(2) Adding 6mL of 25 wt% ammonia water into 2mL of precursor solution to obtain a reaction solution, and fully reacting at room temperature to obtain the porous material.
(3) And soaking the obtained porous material in deionized water to remove redundant ammonia water, and then placing the porous material in a freeze drying box at the temperature of minus 80 ℃ for drying to obtain the hydrophilic oleophobic porous polymer material. The contact angle of hexadecane on the surface of the obtained hydrophilic and oleophobic three-dimensional porous polymer material is about 120 degrees, and the wetting time of water is about 14 s.
Pentaerythritol triacrylate is used as a cross-linking agent, and the obtained porous material has a loose structure and poor elasticity, and is crushed after being extruded by hands.
Example 7:
a preparation method of a hydrophilic oleophobic porous polymer material comprises the following specific steps:
(1) and stirring the acetone solution of hydrophilic monomer methacrylic acid, fluoroalkyl monomer perfluorohexyl ethyl methacrylate, cross-linking agent poly dipentaerythritol pentaacrylate and pentaerythritol tetramercaptoacetate for 20min at room temperature to obtain the porous material precursor solution. Wherein the molar ratio of the methacrylic acid, the perfluorohexylethyl methacrylate, the polyethylene glycol diacrylate and the pentaerythritol tetramercaptoacetate is 0.2:0.4:1.7: 1. The volume ratio of acetone to functional monomer is 1: 3. The functional monomers refer to hydrophilic monomers, fluoroalkyl monomers, and pentaerythritol tetramercaptoacetate.
(2) Adding 6mL of 25 wt% ammonia water into 2mL of precursor solution to obtain a reaction solution, and fully reacting at room temperature to obtain the porous material.
(3) And soaking the obtained porous material in deionized water to remove redundant ammonia water, and then placing the porous material in a freeze drying box at the temperature of minus 80 ℃ for drying to obtain the hydrophilic oleophobic porous polymer material. The contact angle of hexadecane on the surface of the obtained hydrophilic and oleophobic three-dimensional porous polymer material is about 115 degrees, and the wetting time of water is about 11 s.
The polydipentaerythritol pentaacrylate is used as a cross-linking agent, the obtained porous material has a loose structure and poor elasticity, and the material is cracked after being squeezed by hands.
Comparative example 1:
in order to verify the performance of the material prepared by other catalysts, triethylamine is used as a catalyst to prepare the polymer material, and the method comprises the following specific steps:
(1) and stirring the acetone solution of a hydrophilic monomer methacrylic acid, a fluoroalkyl monomer perfluorohexyl ethyl methacrylate, a cross-linking agent polyethylene glycol diacrylate and pentaerythritol tetramercapto acetate for 20min at room temperature to obtain a precursor solution. Wherein the molar ratio of the methacrylic acid, the perfluorohexylethyl methacrylate, the polyethylene glycol diacrylate and the pentaerythritol tetramercaptoacetate is 0.2:0.4:1.7: 1. The volume ratio of acetone to functional monomer is 1: 3. The functional monomers refer to hydrophilic monomers, fluoroalkyl monomers, and pentaerythritol tetramercaptoacetate. (2) And adding 6mL of 25 wt% triethylamine into 2mL of precursor solution to obtain a reaction solution, and fully reacting at room temperature to obtain the polymer material.
(3) And soaking the obtained material in deionized water to remove redundant triethylamine, and then placing the material in a freeze drying oven at the temperature of minus 80 ℃ for drying to obtain the hydrophilic oleophobic polymer material. The porous structure could not be prepared by other catalysts, and the material obtained in this example is a non-porous transparent bulk material, the contact angle of hexadecane on the surface of the material is about 80 °, and the wetting time of water is about 65 s.
Comparative example 2:
in order to verify the performance of the material prepared by other solvents, the polymer material is prepared by adopting ethyl acetate as a solvent, and the method comprises the following specific steps:
(1) and stirring the ethyl acetate solution of a hydrophilic monomer methacrylic acid, a fluoroalkyl monomer perfluorohexyl ethyl methacrylate, a cross-linking agent polyethylene glycol diacrylate and pentaerythritol tetramercapto acetate at room temperature for 20min to obtain a precursor solution. Wherein the molar ratio of the methacrylic acid, the perfluorohexylethyl methacrylate, the polyethylene glycol diacrylate and the pentaerythritol tetramercaptoacetate is 0.2:0.4:1.7: 1. The volume ratio of the ethyl acetate to the functional monomer is 1: 3. The functional monomers refer to hydrophilic monomers, fluoroalkyl monomers, and pentaerythritol tetramercaptoacetate.
(2) And adding 6mL of 25 wt% triethylamine into 2mL of precursor solution to obtain a reaction solution, and fully reacting at room temperature to obtain the polymer material.
(3) And soaking the obtained material in deionized water to remove redundant triethylamine, and then placing the material in a freeze drying oven at the temperature of minus 80 ℃ for drying to obtain the hydrophilic oleophobic polymer material. The porous structure cannot be prepared by using a solvent with poor affinity with water, the material obtained in the embodiment is a non-porous transparent bulk material, the contact angle of hexadecane on the surface of the material is about 73 degrees, and the wetting time of water is about 80 s.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a hydrophilic and oleophobic three-dimensional porous polymer material is characterized by comprising the following steps:
(1) uniformly mixing a functional monomer and a cross-linking agent in an organic solvent to form a mixed solution; the functional monomer comprises a fluoroalkyl oleophobic monomer, a sulfhydryl-containing monomer and an optional hydrophilic monomer containing a carbon-carbon double bond; the monomer containing the sulfydryl at least contains two sulfydryl; the organic solvent has a stronger affinity for water than NH3Affinity to water;
(2) and carrying out catalytic reaction on the mixed solution at 10-60 ℃ under the action of a catalyst, and removing the catalyst after the reaction is completed to obtain the hydrophilic and oleophobic three-dimensional porous polymer material, wherein the catalyst comprises ammonia water.
2. The method of claim 1, wherein: in the step (1), the hydrophilic monomer containing a carbon-carbon double bond comprises any one or more of acrylic acid, methacrylic acid, acrylamide, methacrylamide or methacryloyl ethyl sulfobetaine.
3. The method of claim 1, wherein: in step (1), the fluoroalkyl oleophobic monomer is selected from the compounds of the following general structural formula:
wherein R is hydrogen or methyl, m is any integer of 1-5, and n is any integer of 3-9.
4. The method of claim 1, wherein: in the step (1), the cross-linking agent is selected from any one or more of polyethylene glycol diacrylate, N-carboxyethyl acrylamide, 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, dipentaerythritol penta-/hexa-acrylic acid and pentaerythritol triacrylate.
5. The method of claim 1, wherein: in the step (1), the mercapto group-containing monomer is selected from acrylate monomers containing two or more mercapto groups.
6. The method of claim 1, wherein: in the step (1), the molar ratio of the hydrophilic monomer containing carbon-carbon double bonds, the fluoroalkyl oleophobic monomer, the cross-linking agent and the mercapto monomer is 0-0.8: 0.1-0.6: 1.2-1.95: 0.9 to 1.1.
7. The method of claim 1, wherein: in the step (1), the volume ratio of the organic solvent to the functional monomer is 1: 1-1: 5.
8. The method of claim 1, wherein: in the step (2), the volume ratio of the ammonia water to the mixed solution is 2: 1; the concentration of the ammonia water is 5wt% -30 wt%.
9. The method of claim 1, wherein: in the step (2), the step of freeze-drying at-10 ℃ to-80 ℃ is further included after the catalyst is removed.
10. A hydrophilic oleophobic three-dimensional porous polymeric material prepared by the preparation method of any one of claims 1-9, characterized in that: it has a plurality of three-dimensional holes, the aperture is 1-600 μm, and the porosity is 40% -90%.
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| US20150299412A1 (en) * | 2012-11-02 | 2015-10-22 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Thiol Acrylate Nanocomposite Foams |
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| CN104474930A (en) * | 2014-11-25 | 2015-04-01 | 天津工业大学 | Anti-pollution oil-water separation film and preparation method thereof |
| CN110172123A (en) * | 2019-05-27 | 2019-08-27 | 苏州大学 | Hydrophilic and oleophobic property porous polymer and preparation method thereof |
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