CN114409953A - Hydrophilic porous structure polymer and preparation method and application thereof - Google Patents
Hydrophilic porous structure polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a polymer material with a porous structure, which is obtained by etching away Pickering particles from a polymer material precursor containing Pickering particles. The polymer material with a specific porous structure prepared by the Pickering emulsion method provided by the invention has an open pore structure and hydrophilicity, and can be used for adsorbing and removing dyes in wastewater. According to the invention, a hydrophilic polymer material with a porous structure is prepared by a Pickering emulsion template method, and then Pickering stabilizer particles in the polymer material are removed by hydrofluoric acid etching, so that the hydrophilic polymer material with the open pore structure is finally prepared. And the production cost is low, the process is simple, the control is easy, and the industrial scale production and application are favorably realized.
Description
Technical Field
The invention belongs to the technical field of porous polymers, relates to a polymer material with a porous structure, and a preparation method and application thereof, and particularly relates to a hydrophilic porous structure polymer, and a preparation method and application thereof.
Background
Due to the unique physical properties of the porous material, such as low density, large specific surface area, high porosity and the like, the material has wide application value in the fields of material transmission, adsorption separation, catalyst carriers and the like. There are many methods for preparing porous materials, such as block copolymer templating, phase separation, emulsion freeze-drying, etching, and the like. Compared to these methods, the high internal phase emulsion templating method has several advantages: 1) the porosity of the polymer can be regulated and controlled; 2) the polymerization is easy to control, and the selectivity of the polymerized monomers and the reaction route is high; 3) the emulsion template is easily removed. Therefore, the high internal phase emulsion template method is widely applied to the preparation of porous polymer materials.
However, conventional high internal phase emulsions require the addition of large amounts of toxic small molecule surfactants, which on the one hand increase the production costs of the materials and on the other hand bring about serious environmental pollution. The Pickering emulsion is stable emulsion with solid particles replacing small molecular surfactants, and the Pickering high internal phase emulsion can also be used for preparing porous polymer materials. However, the polymer prepared by using the Pickering high internal phase emulsion as a template is often in a closed pore structure, so that the application range of the material is limited.
Therefore, how to find a suitable method for preparing a hydrophilic polymer material with an open pore structure to solve the above problems in the prior art has become one of the focuses of many research and development manufacturers and front-line researchers.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polymer material with a porous structure and a preparation method thereof, and particularly to a hydrophilic polymer with a porous structure.
The invention provides a polymer material with a porous structure, which is obtained by etching away Pickering particles from a polymer material precursor containing Pickering particles.
Preferably, the porous structure of the polymeric material comprises an open cell structure;
the pore diameter of the porous structure of the polymer material is 0.5-100 mu m;
the polymer comprises one or more of poly (dimethylaminoethyl methacrylate), polyacrylamide, N-dimethylacrylamide polymer and poly (hydroxyethyl methacrylate).
Preferably, the Pickering particles comprise modified diatomite or modified SiO2；
The particle size of the modified diatomite is less than or equal to 20 mu m;
the modified SiO2The particle size of (A) is 0.2-5 μm;
the water contact angle of the modified diatomite is 10-95 degrees;
the modified SiO2The water contact angle is 10-95 degrees.
Preferably, the polymeric material precursor has a closed cell structure;
the Pickering particles are located on the walls of the pores in the polymer material precursor from pore to pore;
the mass content of the Pickering particles in the polymer material precursor is 1-10%;
the etching manner comprises acid etching.
The invention provides a preparation method of a polymer material with a porous structure, which comprises the following steps:
1) mixing a water-soluble monomer, a cross-linking agent, an initiator and water to obtain a water phase, and dispersing Pickering stabilizer particles in the water phase;
2) emulsifying the organic solvent and the water phase obtained in the step by taking the organic solvent as an oil phase to obtain an oil-in-water Pickering high internal phase emulsion;
3) and taking the Pickering high internal phase emulsion obtained in the step as a template, carrying out polymerization reaction to obtain a polymer material precursor, placing the polymer material precursor in acid, and removing Pickering stabilizer particles to obtain the polymer material with a porous structure.
Preferably, the water-soluble monomer comprises dimethylaminoethyl methacrylate, acrylamide, N-dimethylacrylamide or hydroxyethyl methacrylate;
the cross-linking agent comprises polyethylene glycol diacrylate and/or methylene bisacrylamide;
the initiator comprises ammonium persulfate and/or VA-044;
the Pickering stabilizer particles comprise modified diatomite or modified SiO2。
Preferably, the mass ratio of the cross-linking agent to the water-soluble monomer is (2-10): 100, respectively;
the mass ratio of the initiator to the water-soluble monomer is (1-5): 100, respectively;
the mass concentration of the water-soluble monomer in the water phase is 15-40%;
the mass ratio of the water-soluble monomer to the Pickering stabilizer particles is (1-8): 100.
preferably, the organic solvent comprises one or more of toluene, n-hexane and xylene;
the volume ratio of the oil phase to the water phase is (74-90): (26-10);
the emulsification comprises high speed emulsification;
the rotation speed of the emulsification is 3000-15000 rpm;
the emulsifying time is 1-3 min.
Preferably, the temperature of the polymerization reaction is 35-60 ℃;
the polymerization reaction time is 6-12 hours;
the acid comprises hydrofluoric acid;
the molar concentration of the hydrofluoric acid is 20-40%;
the time for removing Pickering stabilizer particles is 4-18 h.
The invention also provides application of the polymer material with the porous structure in any one of the technical schemes or the polymer material with the porous structure prepared by the preparation method in any one of the technical schemes in dye waste liquid treatment.
The invention provides a polymer material with a porous structure, which is obtained by etching away Pickering particles from a polymer material precursor containing Pickering particles. Compared with the prior art, the invention is based on the problems of high production cost and serious environmental pollution caused by the addition of a large amount of toxic micromolecular surfactant in the high internal phase emulsion adopted for preparing the porous polymer material. The Pickering emulsion method is difficult to prepare porous polymer with open pore structure.
The invention creatively provides a polymer material which is prepared by a Pickering emulsion method and has a specific porous structure, has an open pore structure and hydrophilicity, and can be used for adsorbing and removing dye in wastewater. According to the invention, a hydrophilic polymer material with a porous structure is prepared by a Pickering emulsion template method, and then Pickering stabilizer particles in the polymer material are removed by hydrofluoric acid etching, so that the hydrophilic polymer material with the open pore structure is finally prepared. And the production cost is low, the process is simple, the control is easy, and the industrial scale production and application are favorably realized.
Experimental results show that the porous polymer material prepared by the invention has an open pore structure, and the polymer material can be used for adsorbing and removing pollutants such as dye and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a polymeric material precursor prepared in accordance with the present invention;
FIG. 2 is a scanning electron microscope image of a polymer material with a porous structure prepared by the present invention;
FIG. 3 is an absorption spectrum of the porous polymer material prepared by the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All starting materials according to the invention are not particularly restricted with regard to their purity, and the purity requirements customary in the art of the preparation of analytically pure or porous polymer materials are preferably employed according to the invention.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides a polymer material with a porous structure, which is obtained by etching away Pickering particles from a polymer material precursor containing Pickering particles.
In the present invention, the porous structure of the polymer material is preferably an open-cell structure.
In the invention, the pore diameter of the porous structure of the polymer material is preferably 0.5-100 μm, more preferably 20-80 μm, and more preferably 40-60 μm.
In the present invention, the polymer preferably includes one or more of dimethylaminoethyl methacrylate, polyacrylamide, N-dimethylacrylamide polymer, and polyhydroxyethyl methacrylate, and more preferably dimethylaminoethyl methacrylate, polyacrylamide, N-dimethylacrylamide polymer, or polyhydroxyethyl methacrylate.
In the present invention, the Pickering particles preferably include modified diatomaceous earth or modified SiO2。
In the present invention, the particle diameter of the modified diatomaceous earth is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less.
In the present invention, the modified SiO2The particle size of (A) is preferably 0.2 to 5 μm, more preferably 1 to 4 μm, and still more preferably 2 to 3 μm.
The modification method is not particularly limited in principle, and may be any modification method known to those skilled in the art, such as modified diatomaceous earth or modified SiO2Is, diatomaceous earth or SiO2The surface hydrophilicity and hydrophobicity are regulated.
In the present invention, the modified diatomaceous earth preferably has a water contact angle of from 10 ° to 95 °, more preferably from 20 ° to 85 °, more preferably from 30 ° to 75 °, more preferably from 40 ° to 65 °, and more preferably from 50 ° to 55 °.
In the present invention, the modified SiO2The water contact angle of (d) is preferably 10 ° to 95 °, more preferably 20 ° to 85 °, more preferably 30 ° to 75 °, more preferably 40 ° to 65 °, and more preferably 50 ° to 55 °.
In the present invention, the polymer material precursor preferably has a closed cell structure.
In the present invention, the Pickering particles are preferably located on the pore walls from pore to pore in the polymer material precursor.
In the present invention, the mass content of the Pickering particles in the polymer material precursor is preferably 1% to 10%, more preferably 3% to 8%, and still more preferably 5% to 6%.
In the present invention, the etching manner preferably includes acid etching.
The invention provides a preparation method of a polymer material with a porous structure, which comprises the following steps:
1) mixing a water-soluble monomer, a cross-linking agent, an initiator and water to obtain a water phase, and dispersing Pickering stabilizer particles in the water phase;
2) emulsifying the organic solvent and the water phase obtained in the step by taking the organic solvent as an oil phase to obtain an oil-in-water Pickering high internal phase emulsion;
3) and taking the Pickering high internal phase emulsion obtained in the step as a template, carrying out polymerization reaction to obtain a polymer material precursor, placing the polymer material precursor in acid, and removing Pickering stabilizer particles to obtain the polymer material with a porous structure.
According to the invention, firstly, a water-soluble monomer, a cross-linking agent, an initiator and water are mixed to obtain a water phase, and then Pickering stabilizer particles are dispersed in the water phase.
In the present invention, the water-soluble monomer preferably includes dimethylaminoethyl methacrylate, acrylamide, N-dimethylacrylamide or hydroxyethyl methacrylate.
In the present invention, the crosslinking agent preferably includes polyethylene glycol diacrylate and/or methylene bisacrylamide, and more preferably polyethylene glycol diacrylate or methylene bisacrylamide.
In the present invention, the initiator preferably comprises ammonium persulfate and/or VA-044, more preferably ammonium sulfate or VA-044.
In the present invention, the Pickering stabilizer particles preferably comprise modified diatomaceous earth or modified SiO2。
In the invention, the mass ratio of the cross-linking agent to the water-soluble monomer is preferably (2-10): 100, more preferably (3-9): 100, more preferably (4-8): 100, more preferably (5-7): 100.
in the invention, the mass ratio of the initiator to the water-soluble monomer is preferably (1-5): 100, more preferably (1.5 to 4.5): 100, more preferably (2-4): 100, more preferably (2.5 to 3.5): 100.
in the present invention, the mass concentration of the water-soluble monomer in the aqueous phase is preferably 15% to 40%, more preferably 20% to 35%, and still more preferably 25% to 30%.
In the invention, the mass ratio of the water-soluble monomer to the Pickering stabilizer particles is preferably (1-8): 100, more preferably (2-7): 100, more preferably (3-6): 100, more preferably (4-5): 100.
according to the invention, an organic solvent is used as an oil phase, and the oil-in-water Pickering high internal phase emulsion is obtained after the organic solvent and the water phase obtained in the above step are emulsified.
In the present invention, the organic solvent preferably includes one or more of toluene, n-hexane, and xylene, more preferably toluene, n-hexane, or xylene.
In the present invention, the volume ratio of the oil phase to the aqueous phase is preferably (74 to 90): (26-10), more preferably (77-87): (26-10), more preferably (80-84): (26-10), or (74-90): (23-13), or (74-90): (20-16).
In the present invention, the emulsification preferably includes high-speed emulsification.
In the invention, the rotation speed of emulsification is preferably 3000-15000 rpm, more preferably 5000-13000 rpm, and more preferably 7000-11000 rpm.
In the invention, the emulsifying time is preferably 1-3 min, more preferably 1.4-2.6 min, and more preferably 1.8-2.2 min.
Finally, the Pickering high internal phase emulsion obtained in the steps is used as a template to carry out polymerization reaction to obtain a polymer material precursor, and then the polymer material precursor is placed in acid to remove Pickering stabilizer particles to obtain the polymer material with a porous structure.
In the invention, the polymerization reaction temperature is preferably 35-60 ℃, more preferably 40-55 ℃, and more preferably 45-50 ℃.
In the present invention, the time for the polymerization reaction is preferably 6 to 12 hours, more preferably 7 to 11 hours, and still more preferably 8 to 10 hours.
In the present invention, the acid preferably comprises hydrofluoric acid.
In the present invention, the molar concentration of the hydrofluoric acid is preferably 20% to 40%, more preferably 24% to 36%, and still more preferably 28% to 32%.
In the invention, the time for removing the Pickering stabilizer particles is preferably 4-18 h, more preferably 7-15 h, and more preferably 10-12 h.
The invention is a complete and refined integral preparation process, better ensures the specific structure and composition of the polymer material with the porous structure, and improves the performance of the polymer material, and the preparation method of the polymer material with the porous structure can specifically comprise the following steps:
dissolving water-soluble monomers, a cross-linking agent and an initiator in water to serve as a water phase, and dispersing the Pickering stable particles in the water phase.
Taking an organic solvent as an oil phase, adding the oil phase into a water phase for emulsification to obtain a stable oil-in-water Pickering high internal phase emulsion, and then taking the Pickering high internal phase emulsion as a template to prepare a porous polymer material through free radical polymerization.
And then the polymer material is immersed into hydrofluoric acid to etch and remove Pickering stable particles in the polymer, and the polymer material with the open pore structure is obtained.
The invention also provides application of the polymer material with the porous structure in any one of the technical schemes or the polymer material with the porous structure prepared by the preparation method in any one of the technical schemes in dye waste liquid treatment.
The invention provides a hydrophilic porous structure polymer, a preparation method and application thereof. The polymer material with a specific porous structure prepared by the Pickering emulsion method provided by the invention has an open pore structure and hydrophilicity, and can be used for adsorbing and removing dyes in wastewater. According to the invention, a hydrophilic polymer material with a porous structure is prepared by a Pickering emulsion template method, and then Pickering stabilizer particles in the polymer material are removed by hydrofluoric acid etching, so that the hydrophilic polymer material with the open pore structure is finally prepared. And the production cost is low, the process is simple, the control is easy, and the industrial scale production and application are favorably realized.
Experimental results show that the porous polymer material prepared by the invention has an open pore structure, and the polymer material can be used for adsorbing and removing pollutants such as dye and the like.
For further illustration of the present invention, the following will describe in detail a polymer material with porous structure and its preparation method and application in conjunction with the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given, only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
24g of toluene is used as an oil phase, 3g of dimethylaminoethyl methacrylate, 1.5g N, N-dimethylacrylamide, 0.4g of methylene bisacrylamide and 0.02g of ammonium persulfate are dissolved in 7.5g of deionized water to be used as a water phase, 0.6g of modified diatomite is used as a Pickering stabilizer and is dispersed in the water phase, then the oil-water mixture is emulsified at a high speed of 8000rpm to form a stable oil-in-water Pickering high internal phase emulsion, and the Pickering emulsion is used as a template to carry out polymerization reaction for 10 hours at 40 ℃ to obtain the polymer material precursor containing Pickering particles with a closed pore structure.
The polymeric material precursor prepared in example 1 of the present invention was characterized.
Referring to fig. 1, fig. 1 is a scanning electron microscope image of a polymer material precursor prepared according to the present invention.
And (3) immersing the polymer material precursor prepared in the step into a hydrofluoric acid aqueous solution with the concentration of 40%, and immersing for 24 hours to etch and remove diatomite particles in the hydrofluoric acid aqueous solution to prepare the porous polymer material with the open pore structure.
The polymeric material having a porous structure prepared in example 1 of the present invention was characterized.
Referring to fig. 2, fig. 2 is a scanning electron microscope image of the polymer material with porous structure prepared by the present invention.
Example 2
24g of toluene is taken as an oil phase, 2g of dimethylaminoethyl methacrylate, 2.5g of hydroxyethyl methacrylate, 0.4g of methylene bisacrylamide and 0.02g of ammonium persulfate are dissolved in 7.5g of deionized water to be taken as a water phase, 0.8g of modified diatomite is taken as a Pickering stabilizer and dispersed in the water phase, then the oil-water mixture is emulsified at a high speed of 8000rpm to form a stable oil-in-water Pickering high internal phase emulsion, the Pickering emulsion is taken as a template, and a polymerization reaction is carried out for 12 hours at a temperature of 45 ℃ to obtain a polymer material precursor containing Pickering particles with a closed pore structure, and the polymer material precursor is immersed in a 28% hydrofluoric acid water solution for 20 hours to obtain the porous polymer material with an open pore structure.
The porous polymer material prepared in example 2 of the present invention was subjected to performance testing.
0.1g of the polymer material obtained in example 2 was used for adsorption of sunset yellow, the concentration of the sunset yellow solution was 10ppm, and after 1 hour of adsorption, the concentration of sunset yellow was 0.02ppm and the adsorption rate was 99.8% by ultraviolet spectrophotometer analysis.
Referring to fig. 3, fig. 3 is an adsorption spectrum of the porous polymer material prepared according to the present invention.
Example 3
24g of toluene is used as an oil phase, 2g of dimethylaminoethyl methacrylate, 1.5g of hydroxyethyl methacrylate, 1.0g N, N-dimethylacrylamide, 0.4g of methylene bisacrylamide and 0.02g of ammonium persulfate are dissolved in 7.5g of deionized water to serve as a water phase, 0.8g of modified diatomite is a Pickering stabilizer and is dispersed in the water phase, then the oil-water mixture is emulsified at a high speed of 8000rpm to form a stable oil-in-water Pickering high internal phase emulsion, the Pickering emulsion is used as a template, and a polymerization reaction is carried out at a temperature of 50 ℃ for 14 hours to obtain a polymer material precursor with a closed pore structure and containing Pickering particles, and the closed pore polymer material precursor is immersed in a 28% hydrofluoric acid aqueous solution for 24 hours to obtain the porous polymer material with an open pore structure.
The porous polymer material prepared in example 3 of the present invention was examined.
The result shows that the specific surface area of the porous polymer material with the open-pore structure reaches 243m2/g。
Example 4
24g of toluene is used as an oil phase, 2g of dimethylaminoethyl methacrylate, 1.5g of hydroxyethyl methacrylate, 1.0g of acrylamide, 0.4g of methylene bisacrylamide and 0.02g of ammonium persulfate are dissolved in 7.5g of deionized water to be used as a water phase, 1.0g of modified diatomite is a Pickering stabilizer and is dispersed in the water phase, then the oil-water mixture is emulsified at a high speed of 10000rpm to form a stable oil-in-water Pickering high internal phase emulsion, the Pickering emulsion is used as a template, and a polymerization reaction is carried out at 55 ℃ for 18 hours to obtain a polymer material precursor containing Pickering particles with a closed-cell structure, and the closed-cell polymer material precursor is immersed in 25% hydrofluoric acid water solution for 30 hours to obtain the porous polymer material with an open-cell structure.
The porous polymer material prepared in example 4 of the present invention was examined.
The result shows that the specific surface area of the porous polymer material with the open pore structure reaches 256m2/g。
While the present invention has been described in detail with respect to the preferred embodiments and applications thereof, it is to be understood that the present invention is not limited to the details of the particular embodiments and applications, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A polymer material having a porous structure, wherein the polymer material is obtained by etching away Pickering particles from a polymer material precursor containing Pickering particles.
2. The polymeric material of claim 1, wherein the porous structure of the polymeric material comprises an open-cell structure;
the pore diameter of the porous structure of the polymer material is 0.5-100 mu m;
the polymer comprises one or more of poly (dimethylaminoethyl methacrylate), polyacrylamide, N-dimethylacrylamide polymer and poly (hydroxyethyl methacrylate).
3. The polymeric material of claim 1, wherein the Pickering particles comprise modified diatomaceous earth or modified SiO2；
The particle size of the modified diatomite is less than or equal to 20 mu m;
the modified SiO2The particle size of (A) is 0.2-5 μm;
the water contact angle of the modified diatomite is 10-95 degrees;
the modified SiO2The water contact angle is 10-95 degrees.
4. The polymeric material of claim 1, wherein the polymeric material precursor has a closed cell structure;
the Pickering particles are located on the walls of the pores in the polymer material precursor from pore to pore;
the mass content of the Pickering particles in the polymer material precursor is 1-10%;
the etching manner comprises acid etching.
5. A method for preparing a polymeric material having a porous structure, comprising the steps of:
1) mixing a water-soluble monomer, a cross-linking agent, an initiator and water to obtain a water phase, and dispersing Pickering stabilizer particles in the water phase;
2) emulsifying the organic solvent and the water phase obtained in the step by taking the organic solvent as an oil phase to obtain an oil-in-water Pickering high internal phase emulsion;
3) and taking the Pickering high internal phase emulsion obtained in the step as a template, carrying out polymerization reaction to obtain a polymer material precursor, placing the polymer material precursor in acid, and removing Pickering stabilizer particles to obtain the polymer material with a porous structure.
6. The method according to claim 5, wherein the water-soluble monomer comprises dimethylaminoethyl methacrylate, acrylamide, N-dimethylacrylamide or hydroxyethyl methacrylate;
the cross-linking agent comprises polyethylene glycol diacrylate and/or methylene bisacrylamide;
the initiator comprises ammonium persulfate and/or VA-044;
the Pickering stabilizer particles comprise modified diatomite or modified SiO2。
7. The preparation method according to claim 5, wherein the mass ratio of the cross-linking agent to the water-soluble monomer is (2-10): 100, respectively;
the mass ratio of the initiator to the water-soluble monomer is (1-5): 100, respectively;
the mass concentration of the water-soluble monomer in the water phase is 15-40%;
the mass ratio of the water-soluble monomer to the Pickering stabilizer particles is (1-8): 100.
8. the method of claim 1, wherein the organic solvent comprises one or more of toluene, n-hexane, and xylene;
the volume ratio of the oil phase to the water phase is (74-90): (26-10);
the emulsification comprises high speed emulsification;
the rotation speed of the emulsification is 3000-15000 rpm;
the emulsifying time is 1-3 min.
9. The method according to claim 1, wherein the polymerization reaction temperature is 35 to 60 ℃;
the polymerization reaction time is 6-12 hours;
the acid comprises hydrofluoric acid;
the molar concentration of the hydrofluoric acid is 20-40%;
the time for removing Pickering stabilizer particles is 4-18 h.
10. Use of the polymer material with a porous structure according to any one of claims 1 to 4 or the polymer material with a porous structure prepared by the preparation method according to any one of claims 5 to 9 in dye waste liquid treatment.
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