CN113045795A - Emulsion separation material, hydrophobic emulsion separation material and preparation method thereof - Google Patents
Emulsion separation material, hydrophobic emulsion separation material and preparation method thereof Download PDFInfo
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- B01D17/02—Separation of non-miscible liquids
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C08J2329/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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Abstract
The invention provides an emulsion separation material, which is a polyvinyl alcohol-based foam material obtained by secondary crosslinking of a polyvinyl acetal porous material; the secondary crosslinking is carried out with an aldehyde crosslinking agent; the pore diameter of the polyvinyl alcohol-based foam material is 20-30 microns. The invention also provides a hydrophobic emulsion separation material. The emulsion separation material and the hydrophobic emulsion separation material provided by the invention have specific structures and apertures, the average aperture of the original polyvinyl acetal porous material is greatly reduced while the specific pore structure of the porous material is kept, and then a large amount of hydrophobic alkyl chain groups are introduced through grafting reaction to endow the foam material with excellent hydrophobic performance.
Description
Technical Field
The invention belongs to the technical field of emulsion separation materials, and particularly relates to an emulsion separation material, a hydrophobic emulsion separation material and a preparation method thereof.
Background
With the development of industry, especially the development of petrochemical industry, the discharge amount of oily wastewater is increasing day by day, and if the oily wastewater is discharged randomly without being effectively treated, not only the ecological environment is seriously damaged, but also the health of human is threatened. Currently, the separation of oil/water in oily wastewater, particularly the separation of emulsified oil/water mixtures, has become a focus of attention. Unlike conventional oil-water mixtures, oily wastewater contains a large amount of surfactant, which forms a stable film on the surface of oil droplets and water droplets, resulting in non-demixing of oil and water to present an opaque emulsion, which can be classified into oil-in-water (oil-in-water) emulsion and water-in-oil (water-in-oil) emulsion, depending on the dispersion system. Generally, the emulsified oil has extremely small particle size (< 20 μm), can be stably and uniformly dispersed in a water body, and is difficult to remove. Therefore, the removal of emulsified oil is a key and difficult point in the treatment of oily wastewater.
At present, The treatment technology of emulsified oil mainly includes three methods, i.e., a Chemical method, a biological method and a physical method, wherein The Chemical method and The biological method utilize a demulsifier (Journal of Hazardous materials, 2007,147, 991-. Two Materials are commonly used in the physical method, one is that a membrane material (desalinization, 2011,268, 266-; secondly, the emulsion separation in the water body is realized by using foam Materials modified by hydrophobic (Nanoscale,2020,12, 17812-. In the traditional emulsified oil treatment technologies, the chemical demulsification effect is good, but the problems of secondary pollution and the like can be caused; the biological method has good demulsification effect, does not generate secondary pollution, but has higher requirement on the environment; the physical method has good membrane separation technical effect, but has high cost and low water flux, and is not suitable for directly treating industrial oily wastewater, which limits the wide application of the industrial oily wastewater to a certain extent.
Therefore, how to find a more suitable way for separating the emulsion, and better separating the emulsion, has become one of the focuses of great attention of many researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an emulsion separation material, a hydrophobic emulsion separation material and a preparation method thereof. The hydrophobic emulsion separation material provided by the invention is a hydrophobic polyvinyl acetal base porous foam material, has the characteristics of good emulsion separation performance, large separation flux and the like, and meanwhile, the preparation method of the whole material has the characteristics of mild reaction conditions, simple and easy method, low cost and short preparation period, so that the preparation method is easy to amplify.
The invention provides an emulsion separation material, which is a polyvinyl alcohol-based foam material obtained by secondary crosslinking of a polyvinyl acetal porous material;
the secondary crosslinking is carried out with an aldehyde crosslinking agent;
the pore diameter of the polyvinyl alcohol-based foam material is 20-30 microns.
Preferably, the pore diameter of the polyvinyl acetal porous material is 70-90 μm;
the aldehyde-based cross-linking agent comprises one or more of formaldehyde, glutaraldehyde and paraformaldehyde;
the polyvinyl alcohol-based foam material has an interpenetrating polymer network structure further formed on the basis of a polyvinyl acetal porous material;
the density of the polyvinyl alcohol-based foam material is 0.10-0.20 g-cm-3;
The porosity of the polyvinyl alcohol-based foam material is 70-90%;
the molecular weight of the polyvinyl alcohol-based foam material is 50000-150000.
The invention provides a hydrophobic emulsion separation material, which comprises a polyvinyl alcohol-based foam material and a micromolecule group which is grafted on the polyvinyl alcohol-based foam material and contains an octadecyl group;
the polyvinyl alcohol-based foam material comprises the polyvinyl alcohol-based foam material in any one of the technical schemes.
Preferably, the grafting comprises grafting through hydroxyl groups on the molecular chains of the polyvinyl alcohol-based foam polymer;
the compound used for grafting the octadecyl-containing small molecular group comprises one or more of stearic acid, stearoyl chloride, methyl stearate and ethyl stearate;
the molar ratio of the small molecular group containing the octadecyl group to the polyvinyl alcohol-based foam material is (1-5): 1.
preferably, the molecular weight of the hydrophobic emulsion separation material is 50000-150000;
the porosity of the hydrophobic emulsion separation material is 70-90%;
the density of the hydrophobic emulsion separation material is 0.10-0.20 g-cm-3。
The invention also provides a preparation method of the hydrophobic emulsion separation material, which comprises the following steps:
1) stirring and mixing a polyvinyl alcohol source solution, a surfactant, an acid solution and an aldehyde-based crosslinking agent to obtain a mixed solution;
the polyvinyl alcohol source solution comprises one or more of a polyvinyl alcohol aqueous solution, a carboxyl group-containing polyvinyl alcohol aqueous solution and a sulfonic group-containing polyvinyl alcohol aqueous solution;
2) adopting a polyvinyl acetal porous material to absorb the mixed solution obtained in the step, and carrying out curing and crosslinking to obtain a polyvinyl alcohol-based foam material;
3) mixing a polyvinyl alcohol-based foam material, a catalyst, a micromolecule compound containing an octadecyl micromolecule group and a solvent, and then carrying out grafting reaction to obtain the hydrophobic emulsion separation material.
Preferably, the mass concentration of the polyvinyl alcohol source solution is 5-20%;
the polymerization degree of the polyvinyl alcohol is 1700-3000;
the alcoholysis degree of the polyvinyl alcohol is 88.0-99.0%;
the content of carboxyl in the polyvinyl alcohol containing carboxyl is 10.5 wt% -21.0 wt%;
the polymerization degree of the polyvinyl alcohol containing carboxyl is 1700-3000;
the alcoholysis degree of the polyvinyl alcohol containing carboxyl is 88.0-99.0%.
Preferably, the content of the sulfonic acid group in the polyvinyl alcohol containing the sulfonic acid group is 4.0 wt% to 5.0 wt%;
the polymerization degree of the polyvinyl alcohol containing sulfonic groups is 1700-3000;
the alcoholysis degree of the polyvinyl alcohol containing sulfonic groups is 88.0-99.0%;
the surfactant comprises one or more of sodium dodecyl sulfate, sodium dibutyl naphthalene sulfonate, polyethylene glycol octyl phenyl ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate and sorbitan monooleate;
the acid solution comprises one or more of a sulfuric acid solution, a phosphoric acid solution and a hydrochloric acid solution;
the mass concentration of the acid solution is 12-32%.
Preferably, the aldehyde-based cross-linking agent comprises one or more of formaldehyde, glutaraldehyde and paraformaldehyde;
the mass-volume ratio of the polyvinyl alcohol source to the acid solution is (1-2) g: (10-20) mL;
the mass ratio of the polyvinyl alcohol source to the surfactant is (60-120): (7-12);
the mass ratio of the polyvinyl alcohol source to the aldehyde-based crosslinking agent is (60-120): (27-38);
the mass ratio of the polyvinyl alcohol source to the polyvinyl acetal porous material is (3-6): (2-4);
the temperature of the curing and crosslinking is 30-75 ℃;
the curing and crosslinking time is 4-48 h.
Preferably, the catalyst comprises pyridine, one or more of sodium hydroxide, sodium carbonate, hydrochloric acid and sulfuric acid;
the molar ratio of the catalyst to the polyvinyl alcohol-based foam material is (0.01-1): 1;
the small molecular compound containing the octadecyl small molecular group comprises one or more of stearic acid, stearoyl chloride, methyl stearate and ethyl stearate;
the molar ratio of the small molecular compound containing the octadecyl small molecular group to the polyvinyl alcohol-based foam material is (1-5): 1;
the solvent comprises acetonitrile;
the grafting reaction time is 6-72 h;
the temperature of the grafting reaction is 0-80 ℃.
The invention provides an emulsion separation material, which is a polyvinyl alcohol-based foam material obtained by secondary crosslinking of a polyvinyl acetal porous material; the secondary crosslinking is carried out with an aldehyde crosslinking agent; the pore diameter of the polyvinyl alcohol-based foam material is 20-30 microns. The invention also provides a hydrophobic emulsion separation material. Compared with the prior art, the invention aims at the problems that the chemical method has good demulsification effect but can cause secondary pollution and the like in the existing three methods of treating the emulsified oil by the chemical method, the biological method and the physical method; the biological demulsification method has the defects of good demulsification effect, no secondary pollution, high requirement on the environment and the like. The invention particularly adopts a physical method for research, has better effect based on a membrane separation technology, but has the limitations of higher cost, lower water flux and unsuitability for directly treating industrial oily wastewater. The invention is based on the research that the traditional polyvinyl alcohol-based porous material can be used as a cleaning material or a medical dressing, and the preparation method of the traditional polyvinyl alcohol-based porous material has been reported at home and abroad (such as British patent GB 573966(A), US patent US2664366, US3034999, US2636013, Chinese patent CN101507826, CN1095387 and CN1557872), but the traditional polyvinyl alcohol-based porous material has no corresponding application in the direction of emulsion separation.
The invention adopts polyvinyl acetal foam material as a precursor to prepare the emulsion separation material, and further obtains the hydrophobic emulsion separation material which can rapidly and efficiently separate the emulsion. The emulsion separation material and the hydrophobic emulsion separation material provided by the invention have specific structures and pore diameters, the average pore diameter of the foam material is adjusted through secondary curing and crosslinking after the precursor base material is physically filled and absorbs the polyvinyl alcohol solution, the polyvinyl alcohol-based emulsion separation material is obtained, and the hydrophobic foam material capable of quickly and efficiently performing emulsion separation is obtained through a method of introducing alkyl chain groups to hydrophobically modify the foam material through a grafting reaction.
The invention firstly utilizes macroporous polyvinyl acetal porous foam material to absorb polyvinyl alcohol under acidic condition, then obtains polyvinyl alcohol-based foam material with adjustable average pore diameter through curing and crosslinking, and introduces alkyl chain group through grafting reaction to modify the foam material in a hydrophobic way. On one hand, after the polyvinyl acetal porous material absorbs polyvinyl alcohol, the average pore size of the polyvinyl acetal porous material is greatly reduced through secondary curing and crosslinking (the original average pore size of the polyvinyl acetal porous material is 70-90 μm, and after the polyvinyl alcohol is absorbed for secondary curing and crosslinking, the average pore size of the material is reduced to 20-30 μm); on the other hand, a large number of alkyl chain groups are creatively introduced through the grafting reaction, so that the foam material is endowed with excellent hydrophobic property.
The secondary curing cross-linked polyvinyl alcohol-based foam material provided by the invention maintains the specific pore structure of the porous material, greatly reduces the average pore diameter of the original polyvinyl acetal porous material, and introduces a large amount of hydrophobic alkyl chain groups through grafting reaction, thereby endowing the foam material with excellent hydrophobic performance. Compared with other three-dimensional foam materials, the hydrophobic polyvinyl acetal-based porous foam material prepared by the invention has the characteristics of good emulsion separation performance, large separation flux and the like, and meanwhile, compared with other foam materials, the preparation method of the whole material has the characteristics of mild reaction conditions, simple and easy method, low cost and short preparation period, so that the preparation method is easy to amplify.
Experimental results show that the hydrophobic polyvinyl acetal base porous foam material prepared by the invention has good emulsion separation performance, the emulsion separation efficiency reaches more than 95%, and the separation flux is large.
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 the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs a purity which is conventional in the field of analytical purification or preparation of emulsion separation materials.
All the raw materials of the invention have the same trade marks as the conventional trade marks in the field, each trade mark is clear and definite in the field of related application, and the raw materials can be purchased from the market by the technicians in the field according to the trade marks and the corresponding application.
The invention provides an emulsion separation material, which is a polyvinyl alcohol-based foam material obtained by secondary crosslinking of a polyvinyl acetal porous material;
the secondary crosslinking is carried out with an aldehyde crosslinking agent;
the pore diameter of the polyvinyl alcohol-based foam material is 20-30 microns.
In the invention, the pore diameter of the polyvinyl acetal porous material is preferably 70-90 μm, more preferably 72-88 μm, more preferably 75-85 μm, and more preferably 77-83 μm.
The invention is not particularly limited to the selection of the polyvinyl acetal porous material in principle, and the person skilled in the art can select and adjust the porous material according to the actual situation, the application situation and the quality requirement, and in order to better ensure the structure, the pore size and the micro-morphology of the emulsion separation material and better improve the emulsion separation effect, the polyvinyl acetal porous material preferably comprises a polyvinyl acetal-based foam material, and more preferably a polyvinyl acetal-based foam material with higher open-cell rate and fast and efficient liquid absorption performance. In particular to a polyvinyl alcohol-based foam material prepared by the patent CN101507826, namely a polyvinyl acetal-based foam material.
In the present invention, the aldehyde-based crosslinking agent preferably includes one or more of formaldehyde, glutaraldehyde and paraformaldehyde, and more preferably formaldehyde, glutaraldehyde or paraformaldehyde.
In the present invention, the polyvinyl alcohol-based foam material preferably has an interpenetrating polymer network structure further formed on the basis of a polyvinyl acetal porous material.
In the invention, the density of the polyvinyl alcohol-based foam material is preferably 0.10-0.20 g-cm-3More preferably 0.12 to 0.18 g/cm-3More preferably 0.14 to 0.16 g/cm-3。
In the present invention, the porosity of the polyvinyl alcohol-based foam material is preferably 70% to 90%, more preferably 72% to 88%, more preferably 75% to 85%, and more preferably 77% to 83%.
In the invention, the molecular weight of the polyvinyl alcohol-based foam material is preferably 50000-150000, more preferably 70000-130000, and more preferably 90000-110000.
The invention also provides a hydrophobic emulsion separation material, which comprises a polyvinyl alcohol-based foam material and a micromolecule group which is grafted on the polyvinyl alcohol-based foam material and contains an octadecyl group;
the polyvinyl alcohol-based foam material comprises the polyvinyl alcohol-based foam material in any one of the technical schemes.
In the present invention, the grafting preferably includes grafting through hydroxyl groups on the molecular chains of the polyvinyl alcohol-based foam polymer.
In the present invention, the compound used for grafting the small molecular group containing an octadecyl group is preferably a small molecular compound, i.e., a non-polymeric compound, more preferably includes one or more of stearic acid, stearoyl chloride, methyl stearate, and ethyl stearate, and more preferably stearic acid, stearoyl chloride, methyl stearate, or ethyl stearate.
In the invention, the molar ratio of the small molecular group containing the octadecyl group to the polyvinyl alcohol-based foam material is preferably (1-5): 1, more preferably (1.5 to 4.5): 1, more preferably (2-4): 1, more preferably (2.5 to 3.5): 1.
in the invention, the molecular weight of the hydrophobic emulsion separation material is preferably 50000-150000, more preferably 70000-130000, and more preferably 90000-110000.
In the present invention, the porosity of the hydrophobic emulsion-separating material is preferably 70% to 90%, more preferably 72% to 88%, more preferably 75% to 85%, and more preferably 78% to 83%.
In the present invention, the density of the hydrophobic emulsion separation material is preferably 0.10 to 0.20 g-cm-3More preferably 0.12 to 0.18 g/cm-3More preferably 0.14 to 0.16 g/cm-3。
The invention also provides a preparation method of the hydrophobic emulsion separation material, which comprises the following steps:
1) stirring and mixing a polyvinyl alcohol source solution, a surfactant, an acid solution and an aldehyde-based crosslinking agent to obtain a mixed solution;
the polyvinyl alcohol source solution comprises one or more of a polyvinyl alcohol aqueous solution, a carboxyl group-containing polyvinyl alcohol aqueous solution and a sulfonic group-containing polyvinyl alcohol aqueous solution;
2) adopting a polyvinyl acetal porous material to absorb the mixed solution obtained in the step, and carrying out curing and crosslinking to obtain a polyvinyl alcohol-based foam material;
3) mixing a polyvinyl alcohol-based foam material, a catalyst, a micromolecule compound containing an octadecyl micromolecule group and a solvent, and then carrying out grafting reaction to obtain the hydrophobic emulsion separation material.
Firstly, stirring and mixing a polyvinyl alcohol source solution, a surfactant, an acid solution and an aldehyde crosslinking agent to obtain a mixed solution.
Among them, the polyvinyl alcohol source solution preferably includes one or more of an aqueous solution of polyvinyl alcohol, an aqueous solution of polyvinyl alcohol containing a carboxyl group, and an aqueous solution of polyvinyl alcohol containing a sulfonic acid group, and more preferably an aqueous solution of polyvinyl alcohol, an aqueous solution of polyvinyl alcohol containing a carboxyl group, or an aqueous solution of polyvinyl alcohol containing a sulfonic acid group.
In the present invention, the mass concentration of the polyvinyl alcohol source solution is preferably 5% to 20%, more preferably 7% to 18%, and still more preferably 10% to 15%.
In the invention, the polymerization degree of the polyvinyl alcohol is preferably 1700 to 3000, more preferably 2000 to 2800, and more preferably 2200 to 2600.
In the present invention, the alcoholysis degree of the polyvinyl alcohol is preferably 88.0% to 99.0%, more preferably 90.0% to 97.0%, and still more preferably 92.0% to 95.0%.
In the present invention, the content of carboxyl groups in the carboxyl group-containing polyvinyl alcohol is preferably 10.5 to 21.0 wt%, more preferably 12.5 to 19.0 wt%, and still more preferably 14.5 to 17.0 wt%.
In the present invention, the polymerization degree of the carboxyl group-containing polyvinyl alcohol is preferably 1700 to 3000, more preferably 2000 to 2800, and still more preferably 2200 to 2600.
In the present invention, the alcoholysis degree of the carboxyl group-containing polyvinyl alcohol is preferably 88.0% to 99.0%, more preferably 90.0% to 97.0%, and still more preferably 92.0% to 95.0%.
In the present invention, the sulfonic acid group content in the sulfonic acid group-containing polyvinyl alcohol is preferably 4.0 wt% to 5.0 wt%, more preferably 4.2 wt% to 4.8 wt%, and still more preferably 4.6 wt% to 4.6 wt%.
In the present invention, the polymerization degree of the polyvinyl alcohol containing sulfonic acid groups is preferably 1700 to 3000, more preferably 2000 to 2800, and still more preferably 2200 to 2600.
In the present invention, the alcoholysis degree of the polyvinyl alcohol containing sulfonic acid groups is preferably 88.0% to 99.0%, more preferably 90.0% to 97.0%, and still more preferably 92.0% to 95.0%.
In the present invention, the surfactant preferably includes one or more of sodium dodecyl sulfate, sodium dibutylnaphthalene sulfonate, polyethylene glycol octylphenyl ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monooleate, and more preferably sodium dodecyl sulfate, sodium dibutylnaphthalene sulfonate, polyethylene glycol octylphenyl ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, or sorbitan monooleate.
In the present invention, the acid solution preferably includes one or more of a sulfuric acid solution, a phosphoric acid solution, and a hydrochloric acid solution, and more preferably a sulfuric acid solution, a phosphoric acid solution, or a hydrochloric acid solution.
In the present invention, the mass concentration of the acid solution is preferably 12% to 32%, more preferably 16% to 28%, and still more preferably 20% to 24%.
In the present invention, the aldehyde-based crosslinking agent preferably includes one or more of formaldehyde, glutaraldehyde and paraformaldehyde, and more preferably formaldehyde, glutaraldehyde or paraformaldehyde.
In the invention, the mass-to-volume ratio of the polyvinyl alcohol source to the acid solution is preferably (1-2) g: (10-20) mL, more preferably (1-2) g: (12-18) mL, more preferably (1-2) g: (14-16) mL. Wherein 1-2 g may be 1.2-1.8 g, or 1.4-1.6 g.
In the invention, the mass ratio of the polyvinyl alcohol source to the surfactant is preferably (60-120): (7-12), more preferably (60-120): (8-11), more preferably (60-120): (9-10). Wherein, 60 to 120 can be 70 to 110, or 80 to 100.
In the invention, the mass ratio of the polyvinyl alcohol source to the aldehyde-based crosslinking agent is preferably (60-120): (27-38), more preferably (60-120): (29-36), more preferably (60-120): (31-34). Wherein, 60 to 120 can be 70 to 110, or 80 to 100.
In the invention, the mass ratio of the polyvinyl alcohol source to the polyvinyl acetal porous material is preferably (3-6): (2-4), more preferably (3-6): (2.4-3.6), more preferably (3-6): (2.8-3.2). Wherein 3 to 6 may be 4 to 5.
And then, adopting a polyvinyl acetal porous material to absorb the mixed solution obtained in the step, and carrying out curing and crosslinking to obtain the polyvinyl alcohol-based foam material.
The invention is not particularly limited to the selection of the polyvinyl acetal porous material in principle, and the person skilled in the art can select and adjust the porous material according to the actual situation, the application situation and the quality requirement, and in order to better ensure the structure, the pore size and the micro-morphology of the emulsion separation material and better improve the emulsion separation effect, the polyvinyl acetal porous material preferably comprises a polyvinyl acetal-based foam material, and more preferably a polyvinyl acetal-based foam material with higher open-cell rate and fast and efficient liquid absorption performance. In particular to a polyvinyl alcohol-based foam material prepared by the patent CN101507826, namely a polyvinyl acetal-based foam material.
The invention takes polyvinyl acetal foam material as a precursor, adjusts the average pore diameter of the foam material through secondary curing and crosslinking after physical filling, and then introduces alkyl chain groups through grafting reaction to modify the hydrophobicity of the foam material, thereby obtaining the hydrophobic foam material which can rapidly and efficiently carry out emulsion separation.
In the present invention, the degree of absorption is preferably such that the mixed liquid is absorbed to saturation.
In the invention, the temperature of the curing and crosslinking is preferably 30-75 ℃, more preferably 40-65 ℃, and more preferably 50-55 ℃.
In the invention, the curing and crosslinking time is preferably 4-48 h, more preferably 14-38 h, and more preferably 24-28 h.
In the present invention, a foaming agent is not required in the preparation method.
Finally, mixing the polyvinyl alcohol-based foam material, a catalyst, a micromolecule compound containing an octadecyl micromolecule group and a solvent, and then carrying out grafting reaction to obtain the hydrophobic emulsion separation material.
In the present invention, the catalyst preferably comprises pyridine, one or more of sodium hydroxide, sodium carbonate, hydrochloric acid and sulfuric acid, more preferably pyridine, sodium hydroxide, sodium carbonate, hydrochloric acid or sulfuric acid.
In the present invention, the molar ratio of the catalyst to the polyvinyl alcohol-based foam material is preferably (0.01 to 1): 1, more preferably (0.05 to 0.8): 1, more preferably (0.1 to 0.5): 1.
in the present invention, the small molecule compound containing an octadecyl small molecule group preferably includes one or more of stearic acid, stearoyl chloride, methyl stearate, and ethyl stearate, and more preferably stearic acid, stearoyl chloride, methyl stearate, or ethyl stearate.
In the invention, the molar ratio of the small molecular compound containing the octadecyl small molecular group to the polyvinyl alcohol-based foam material is preferably (1-5): 1, more preferably (1.5 to 4.5): 1, more preferably (2-4): 1, more preferably (2.5 to 3.5): 1.
in the present invention, the solvent preferably includes acetonitrile.
In the invention, the time of the grafting reaction is preferably 6-72 h, more preferably 16-62 h, more preferably 26-52 h, and more preferably 36-42 h.
In the invention, the temperature of the grafting reaction is preferably 0-80 ℃, more preferably 10-70 ℃, more preferably 20-60 ℃, and more preferably 30-50 ℃.
The invention has the advantages of integrating and refining the whole technical scheme, better ensuring the structure, the appearance and the parameters of the hydrophobic emulsion separation material, and improving the emulsion separation effect, and the preparation method of the hydrophobic emulsion separation material can specifically comprise the following steps:
a preparation method of an emulsion separation foam material with rapid, efficient and hydrophobic properties comprises the following steps:
under an acidic condition, absorbing a polyvinyl alcohol solution by using a polyvinyl alcohol-based foam material (polyvinyl acetal porous material), and carrying out curing and crosslinking reaction with a crosslinking agent in the presence of a surfactant to obtain a secondary curing and crosslinking polyvinyl alcohol-based foam material;
grafting a small molecular compound containing an octadecyl group to the surface of the secondary curing cross-linked polyvinyl alcohol-based foam material in an acetonitrile solution in the presence of a catalyst.
The invention firstly utilizes macroporous polyvinyl acetal porous foam material to absorb polyvinyl alcohol under acidic condition, then obtains polyvinyl alcohol-based foam material with adjustable average pore diameter through curing and crosslinking, and introduces alkyl chain group through grafting reaction to modify the foam material in a hydrophobic way. On one hand, after the polyvinyl acetal porous material absorbs polyvinyl alcohol, the average pore size of the polyvinyl acetal porous material is greatly reduced through secondary curing and crosslinking (the original average pore size of the polyvinyl acetal porous material is 70-90 μm, and after the polyvinyl alcohol is absorbed for secondary curing and crosslinking, the average pore size of the material is reduced to 20-30 μm); on the other hand, a large number of alkyl chain groups are creatively introduced through the grafting reaction, so that the foam material is endowed with excellent hydrophobic property.
The invention provides an emulsion separation material, a hydrophobic emulsion separation material and a preparation method thereof. The invention takes polyvinyl acetal foam material with higher aperture ratio and fast and efficient liquid absorption performance as a precursor to prepare the emulsion separation material, and further obtains the hydrophobic emulsion separation material which can carry out emulsion separation fast and efficiently. The emulsion separation material and the hydrophobic emulsion separation material provided by the invention have specific structures and pore sizes, the average pore size of the foam material is adjusted by secondary curing and crosslinking after the precursor base material is physically filled and absorbs the polyvinyl alcohol solution, the polyvinyl alcohol-based emulsion separation material is obtained, and the hydrophobic foam material capable of quickly and efficiently carrying out emulsion separation is obtained by introducing alkyl chain groups through a grafting reaction to carry out hydrophobic modification on the foam material.
The invention firstly makes polyvinyl alcohol and macroporous polyvinyl acetal porous material generate curing crosslinking reaction under the action of surfactant and crosslinking agent under the acidic condition to obtain the secondary curing crosslinked polyvinyl alcohol-based foam material, the obtained material keeps the specific pore structure of the porous material, simultaneously greatly reduces the average pore diameter of the original polyvinyl acetal porous material, and then introduces a large amount of hydrophobic alkyl chain groups through grafting reaction to endow the foam material with excellent hydrophobic property. Compared with other three-dimensional foam materials, the hydrophobic polyvinyl acetal-based porous foam material prepared by the invention has the characteristics of good emulsion separation performance, large separation flux and the like, and meanwhile, compared with other foam materials, the preparation method of the whole material has the characteristics of mild reaction conditions, simple and easy method, low cost and short preparation period, so that the preparation method is easy to amplify.
Experimental results show that the hydrophobic polyvinyl acetal base porous foam material prepared by the invention has good emulsion separation performance, the emulsion separation efficiency reaches more than 95%, and the separation flux is large.
For further illustration of the present invention, a polylactic acid foaming material and a preparation method thereof provided by the present invention are described in detail below with reference to examples, but it should be understood that the examples are carried out on the premise of the technical scheme of the present invention, and detailed embodiments and specific 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
Mixing 1000g of a 10% polyvinyl alcohol aqueous solution, 10g of sodium dodecyl sulfate and 1000mL of a 30% sulfuric acid aqueous solution by mass, stirring for 30min, adding 35g of a formaldehyde aqueous solution, mixing and stirring for 30min, taking 60g of a polyvinyl alcohol-based foam material to absorb the foam system, curing and crosslinking for 12h in a 60 ℃ drying oven after the foam material is saturated, and washing and drying a sample to constant weight to obtain a secondary cured and crosslinked polyvinyl alcohol-based foam material;
adding 1500mL of acetonitrile, 0.5mol of sodium hydroxide, 50g of secondary curing crosslinked polyvinyl alcohol-based foam material and 1mol of stearoyl chloride into a 2500mL two-neck flask, sealing, reacting at 0 ℃ for 72h, taking out a sample, washing with ethanol, and drying in a vacuum oven to constant weight to obtain the hydrophobically modified polyvinyl alcohol-based foam material.
The hydrophobically modified polyvinyl alcohol-based foam material prepared in example 1 of the present invention was subjected to performance testing.
And (3) testing the separation performance of the emulsion:
accurately weighing a certain amount of the obtained foam material, cutting into pieces with the size of 5cm multiplied by 2cm, detecting the emulsion separation performance and the separation flux by adopting a self-made emulsion separation testing device, wherein the emulsion for detection is a toluene aqueous solution (V) containing a surfactantWater (W)/VToluene1/99), and the surfactant is tween-20. This process was repeated three times, and the average value of the measurements was taken as the emulsion separation efficiency.
Placing the cut polyvinyl alcohol-based foam material in an emulsion separation testing device, pouring the prepared emulsion into the device, collecting the effluent, measuring the toluene content in the effluent by a gas chromatography headspace method, wherein the emulsion separation efficiency of the foam material is not less than 95%, and the highest separation flux can reach 2.40 multiplied by 104L/m2h。
Example 2
Mixing 1000g of a polyvinyl alcohol aqueous solution with the mass percent of 12%, 12g of sodium dodecyl sulfate and 1000mL of a sulfuric acid aqueous solution with the mass percent of 25%, stirring for 30min, adding 28g of a glutaraldehyde aqueous solution, mixing and stirring for 30min, taking 80g of a polyvinyl alcohol-based foam material to absorb the foam system, curing and crosslinking for 12h in a 60 ℃ drying oven after the foam material is saturated, and washing and drying a sample to constant weight to obtain the polyvinyl alcohol-based foam material subjected to secondary curing and crosslinking.
Adding 1500mL of acetonitrile, 0.1mol of sodium hydroxide and 0.5mol of pyridine mixture, 50g of secondary curing crosslinked polyvinyl alcohol-based foam material and 1mol of methyl stearate into a 2500mL two-neck flask, sealing, reacting at 80 ℃ for 6h, taking out a sample, cleaning with ethanol, and drying in a vacuum oven to constant weight to obtain the hydrophobically modified polyvinyl alcohol-based foam material.
The hydrophobically modified polyvinyl alcohol-based foam material prepared in example 2 of the present invention was subjected to performance testing.
And (3) testing the separation performance of the emulsion:
accurately weighing a certain amount of the obtained foam material, cutting into pieces with the size of 5cm multiplied by 2cm, detecting the emulsion separation performance and the separation flux by adopting a self-made emulsion separation testing device, wherein the emulsion for detection is a toluene aqueous solution (V) containing a surfactantWater (W)/VToluene1/99), and the surfactant is tween-20. This process was repeated three times, and the average value of the measurements was taken as the emulsion separation efficiency.
Placing the cut polyvinyl alcohol-based foam material in an emulsion separation testing device, pouring the prepared emulsion into the device, collecting the effluent, measuring the toluene content in the effluent by a gas chromatography headspace method, wherein the emulsion separation efficiency of the foam material is not less than 97%, and the highest separation flux can reach 2.50 multiplied by 104L/m2h。
Example 3
Mixing 1000g of 8 mass percent polyvinyl alcohol aqueous solution containing sulfonic groups, 8g of sodium dodecyl sulfate and 1000mL of 20 mass percent phosphoric acid aqueous solution, stirring for 30min, adding 28g of formaldehyde aqueous solution, mixing and stirring for 30min, taking 60g of polyvinyl alcohol-based foam material to absorb the foam system, curing and crosslinking for 12h in a 60 ℃ oven after the foam material is saturated, and washing and drying a sample to constant weight to obtain the polyvinyl alcohol-based foam material subjected to secondary curing and crosslinking.
Adding 1500mL of acetonitrile, 0.5mol of hydrochloric acid, 80g of secondary curing crosslinked polyvinyl alcohol-based foam material and 3mol of stearoyl chloride into a 2500mL two-neck flask, sealing, reacting at 80 ℃ for 6h, taking out a sample, washing with ethanol, and drying in a vacuum oven to constant weight to obtain the hydrophobically modified polyvinyl alcohol-based foam material.
The hydrophobically modified polyvinyl alcohol-based foam material prepared in example 3 of the present invention was subjected to performance testing.
And (3) testing the separation performance of the emulsion: accurately weighing a certain amount of the obtained foam material, cutting into pieces with the size of 5cm multiplied by 2cm, detecting the emulsion separation performance and the separation flux by adopting a self-made emulsion separation testing device, wherein the emulsion for detection is a toluene aqueous solution (V) containing a surfactantWater (W)/VToluene1/99), and the surfactant is tween-20. This process was repeated three times, and the average value of the measurements was taken as the emulsion separation efficiency.
Placing the cut polyvinyl alcohol-based foam material in an emulsion separation testing device, pouring the prepared emulsion into the device, collecting the effluent, measuring the toluene content in the effluent by a gas chromatography headspace method, wherein the emulsion separation efficiency of the foam material is not less than 96%, and the highest separation flux can reach 2.45 multiplied by 104L/m2h。
Example 4
Mixing 500g of 20 mass percent aqueous solution of polyvinyl alcohol containing carboxyl, 12g of sodium dodecyl sulfate and 800mL of 32 mass percent aqueous solution of hydrochloric acid, stirring for 30min, adding 30g of aqueous solution of paraformaldehyde, mixing and stirring for 30min, taking 40g of polyvinyl alcohol-based foam material to absorb the foam system, curing and crosslinking for 48h in a 30 ℃ oven after the foam material is saturated, and washing and drying a sample to constant weight to obtain the polyvinyl alcohol-based foam material subjected to secondary curing and crosslinking.
Adding 1500mL of acetonitrile, a mixture of 0.01mol of sodium hydroxide and 0.01mol of sodium carbonate, 30g of secondary curing crosslinked polyvinyl alcohol-based foam material and 1mol of stearic acid into a 2500mL two-neck flask, sealing, reacting at 50 ℃ for 48h, taking out a sample, cleaning with ethanol, and drying in a vacuum oven to constant weight to obtain the hydrophobically modified polyvinyl alcohol-based foam material.
The hydrophobically modified polyvinyl alcohol-based foam material prepared in example 4 of the present invention was subjected to performance testing.
And (3) testing the separation performance of the emulsion: accurately weighing a certain amount of the obtained foam material, cutting into pieces of 5cm × 5cm × 2cm, and detecting the separation performance and separation flux of the emulsion by using a self-made emulsion separation testing device, wherein the emulsion for detection containsAqueous toluene solution with surfactant (V)Water (W)/VToluene1/99), and the surfactant is tween-20. This process was repeated three times, and the average value of the measurements was taken as the emulsion separation efficiency.
Placing the cut polyvinyl alcohol-based foam material in an emulsion separation testing device, pouring the prepared emulsion into the device, collecting the effluent, measuring the toluene content in the effluent by a gas chromatography headspace method, wherein the emulsion separation efficiency of the foam material is not less than 98%, and the highest separation flux can reach 2.25 multiplied by 104L/m2h。
Example 5
Mixing 500g of 20 mass percent polyvinyl alcohol aqueous solution, 10g of polyethylene glycol octyl phenyl ether (Triton X-100) and 600mL of 30 mass percent hydrochloric acid aqueous solution, stirring for 30min, adding 30g of glutaraldehyde aqueous solution, mixing and stirring for 30min, taking 50g of polyvinyl alcohol-based foam material to absorb the foam system, curing and crosslinking the foam material in a 30 ℃ oven for 48h after the foam material is saturated, washing and drying a sample to constant weight, and obtaining the secondary cured and crosslinked polyvinyl alcohol-based foam material.
Adding 1500mL of acetonitrile, 1mol of pyridine, 60g of secondary curing crosslinked polyvinyl alcohol-based foam material and 3mol of ethyl stearate into a 2500mL two-neck flask, sealing, reacting at 80 ℃ for 6h, taking out a sample, washing with ethanol, and drying in a vacuum oven to constant weight to obtain the hydrophobically modified polyvinyl alcohol-based foam material.
The hydrophobically modified polyvinyl alcohol-based foam material prepared in example 5 of the present invention was subjected to performance testing.
And (3) testing the separation performance of the emulsion: accurately weighing a certain amount of the obtained foam material, cutting into pieces with the size of 5cm multiplied by 2cm, detecting the emulsion separation performance and the separation flux by adopting a self-made emulsion separation testing device, wherein the emulsion for detection is a toluene aqueous solution (V) containing a surfactantWater (W)/VToluene1/99), and the surfactant is tween-20. This process was repeated three times, and the average value of the measurements was taken as the emulsion separation efficiency.
Taking the cut polyvinyl alcohol-based foam material, placing the cut polyvinyl alcohol-based foam material in an emulsion separation testing device,pouring the prepared emulsion into a device, collecting effluent, measuring the toluene content in the effluent by a gas chromatography headspace method, wherein the emulsion separation efficiency of the foam material is more than or equal to 99 percent, and the separation flux can reach 2.65 multiplied by 10 to the maximum4L/m2h。
Example 6
Mixing 800g of a 10 mass percent aqueous solution of polyvinyl alcohol containing carboxyl, 10g of sorbitan monolaurate (Span-20) and 800mL of a 30 mass percent aqueous solution of phosphoric acid, stirring for 30min, adding 30g of an aqueous solution of glutaraldehyde, mixing and stirring for 30min, absorbing the foam system by 80g of a polyvinyl alcohol-based foam material, curing and crosslinking for 24h in a 50 ℃ oven after the foam material is saturated, washing and drying a sample to constant weight, and obtaining the polyvinyl alcohol-based foam material subjected to secondary curing and crosslinking.
Adding 1500mL of acetonitrile, 0.5mol of sulfuric acid, 30g of secondary curing crosslinked polyvinyl alcohol-based foam material and 2mol of stearic acid into a 2500mL two-neck flask, sealing, reacting at 30 ℃ for 60 hours, taking out a sample, washing with ethanol, and drying in a vacuum oven to constant weight to obtain the hydrophobically modified polyvinyl alcohol-based foam material.
The hydrophobically modified polyvinyl alcohol-based foam material prepared in example 6 of the present invention was subjected to performance testing.
And (3) testing the separation performance of the emulsion: accurately weighing a certain amount of the obtained foam material, cutting into pieces with the size of 5cm multiplied by 2cm, detecting the emulsion separation performance and the separation flux by adopting a self-made emulsion separation testing device, wherein the emulsion for detection is a toluene aqueous solution (V) containing a surfactantWater (W)/VToluene1/99), and the surfactant is tween-20. This process was repeated three times, and the average value of the measurements was taken as the emulsion separation efficiency.
Placing the cut polyvinyl alcohol-based foam material in an emulsion separation testing device, pouring the prepared emulsion into the device, collecting the effluent, measuring the toluene content in the effluent by a gas chromatography headspace method, wherein the emulsion separation efficiency of the foam material is not less than 95%, and the highest separation flux can reach 2.50 multiplied by 104L/m2h。
Example 7
Mixing 800g of a 10 mass percent aqueous solution of polyvinyl alcohol containing carboxyl, 8g of sorbitan monopalmitate (Span-40) and 800mL of a 30 mass percent aqueous solution of sulfuric acid, stirring for 30min, adding 30g of an aqueous solution of glutaraldehyde, mixing and stirring for 30min, absorbing the foam system by 40g of a polyvinyl alcohol-based foam material, curing and crosslinking for 24h in a 50 ℃ oven after the foam material is saturated, and washing and drying a sample to constant weight to obtain the polyvinyl alcohol-based foam material subjected to secondary curing and crosslinking.
Adding 1500mL of acetonitrile, 0.5mol of pyridine, 50g of secondary curing crosslinked polyvinyl alcohol-based foam material and a mixture of 1mol of methyl stearate and 1mol of stearic acid into a 2500mL two-neck flask, sealing, reacting at 50 ℃ for 48 hours, taking out a sample, cleaning with ethanol, and drying in a vacuum oven to constant weight to obtain the hydrophobically modified polyvinyl alcohol-based foam material.
The hydrophobically modified polyvinyl alcohol based foam material prepared in example 7 of the present invention was subjected to performance testing.
And (3) testing the separation performance of the emulsion: accurately weighing a certain amount of the obtained foam material, cutting into pieces with the size of 5cm multiplied by 2cm, detecting the emulsion separation performance and the separation flux by adopting a self-made emulsion separation testing device, wherein the emulsion for detection is a toluene aqueous solution (V) containing a surfactantWater (W)/VToluene1/99), and the surfactant is tween-20. This process was repeated three times, and the average value of the measurements was taken as the emulsion separation efficiency.
Placing the cut polyvinyl alcohol-based foam material in an emulsion separation testing device, pouring the prepared emulsion into the device, collecting the effluent, measuring the toluene content in the effluent by a gas chromatography headspace method, wherein the emulsion separation efficiency of the foam material is not less than 98%, and the highest separation flux can reach 2.40 multiplied by 104L/m2h。
Example 8
Mixing 800g of a 10 mass percent aqueous solution of polyvinyl alcohol containing carboxyl, 8g of sorbitan monostearate (Span-60) and 1000mL of a 30 mass percent aqueous solution of sulfuric acid, stirring for 30min, adding 30g of an aqueous solution of paraformaldehyde, mixing and stirring for 30min, absorbing the foam system by 50g of a polyvinyl alcohol-based foam material, solidifying and crosslinking for 4h in a 75 ℃ drying oven after the foam material is absorbed to saturation, washing and drying a sample to constant weight to obtain the polyvinyl alcohol-based foam material subjected to secondary solidification and crosslinking.
Adding 1500mL of acetonitrile, 0.5mol of hydrochloric acid, 80g of secondary curing crosslinked polyvinyl alcohol-based foam material and a mixture of 1mol of stearoyl chloride and 1mol of stearic acid into a 2500mL two-neck flask, sealing, reacting at 80 ℃ for 6h, taking out a sample, washing with ethanol, and drying in a vacuum oven to constant weight to obtain the hydrophobically modified polyvinyl alcohol-based foam material.
The hydrophobically modified polyvinyl alcohol-based foam material prepared in example 8 of the present invention was subjected to performance testing.
And (3) testing the separation performance of the emulsion: accurately weighing a certain amount of the obtained foam material, cutting into pieces with the size of 5cm multiplied by 2cm, detecting the emulsion separation performance and the separation flux by adopting a self-made emulsion separation testing device, wherein the emulsion for detection is a toluene aqueous solution (V) containing a surfactantWater (W)/VToluene1/99), and the surfactant is tween-20. This process was repeated three times, and the average value of the measurements was taken as the emulsion separation efficiency.
Placing the cut polyvinyl alcohol-based foam material in an emulsion separation testing device, pouring the prepared emulsion into the device, collecting the effluent, measuring the toluene content in the effluent by a gas chromatography headspace method, wherein the emulsion separation efficiency of the foam material is not less than 97%, and the highest separation flux can reach 2.30 multiplied by 104L/m2h。
The present invention provides an emulsion separation material, a hydrophobic emulsion separation material and a method for preparing the same, which are described in detail above, and the principles and embodiments of the present invention are explained herein using specific examples, which are provided only to help understand the method of the present invention and its core ideas, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any devices or systems and performing any combination of methods. 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. An emulsion separation material is characterized in that the emulsion separation material is a polyvinyl alcohol-based foam material obtained by secondary crosslinking of a polyvinyl acetal porous material;
the secondary crosslinking is carried out with an aldehyde crosslinking agent;
the pore diameter of the polyvinyl alcohol-based foam material is 20-30 microns.
2. An emulsion separation material according to claim 1, wherein the pore diameter of the porous polyvinyl acetal material is 70 to 90 μm;
the aldehyde-based cross-linking agent comprises one or more of formaldehyde, glutaraldehyde and paraformaldehyde;
the polyvinyl alcohol-based foam material has an interpenetrating polymer network structure further formed on the basis of a polyvinyl acetal porous material;
the density of the polyvinyl alcohol-based foam material is 0.10-0.20 g-cm-3;
The porosity of the polyvinyl alcohol-based foam material is 70-90%;
the molecular weight of the polyvinyl alcohol-based foam material is 50000-150000.
3. A hydrophobic emulsion separation material is characterized by comprising a polyvinyl alcohol-based foam material and a micromolecular group which is grafted on the polyvinyl alcohol-based foam material and contains an octadecyl group;
the polyvinyl alcohol-based foam material comprises the polyvinyl alcohol-based foam material according to any one of claims 1 to 2.
4. A hydrophobic emulsion separating material according to claim 3, wherein the grafting comprises grafting through hydroxyl groups on the polymer molecular chains of the polyvinyl alcohol-based foam material;
the compound used for grafting the octadecyl-containing small molecular group comprises one or more of stearic acid, stearoyl chloride, methyl stearate and ethyl stearate;
the molar ratio of the small molecular group containing the octadecyl group to the polyvinyl alcohol-based foam material is (1-5): 1.
5. the hydrophobic emulsion separation material according to claim 3, wherein the molecular weight of the hydrophobic emulsion separation material is 50000 to 150000;
the porosity of the hydrophobic emulsion separation material is 70-90%;
the density of the hydrophobic emulsion separation material is 0.10-0.20 g-cm-3。
6. A preparation method of a hydrophobic emulsion separation material is characterized by comprising the following steps:
1) stirring and mixing a polyvinyl alcohol source solution, a surfactant, an acid solution and an aldehyde-based crosslinking agent to obtain a mixed solution;
the polyvinyl alcohol source solution comprises one or more of a polyvinyl alcohol aqueous solution, a carboxyl group-containing polyvinyl alcohol aqueous solution and a sulfonic group-containing polyvinyl alcohol aqueous solution;
2) adopting a polyvinyl acetal porous material to absorb the mixed solution obtained in the step, and carrying out curing and crosslinking to obtain a polyvinyl alcohol-based foam material;
3) mixing a polyvinyl alcohol-based foam material, a catalyst, a micromolecule compound containing an octadecyl micromolecule group and a solvent, and then carrying out grafting reaction to obtain the hydrophobic emulsion separation material.
7. The preparation method according to claim 6, wherein the mass concentration of the polyvinyl alcohol source solution is 5-20%;
the polymerization degree of the polyvinyl alcohol is 1700-3000;
the alcoholysis degree of the polyvinyl alcohol is 88.0-99.0%;
the content of carboxyl in the polyvinyl alcohol containing carboxyl is 10.5 wt% -21.0 wt%;
the polymerization degree of the polyvinyl alcohol containing carboxyl is 1700-3000;
the alcoholysis degree of the polyvinyl alcohol containing carboxyl is 88.0-99.0%.
8. The production method according to claim 6, wherein the sulfonic acid group-containing polyvinyl alcohol has a sulfonic acid group content of 4.0 to 5.0 wt%;
the polymerization degree of the polyvinyl alcohol containing sulfonic groups is 1700-3000;
the alcoholysis degree of the polyvinyl alcohol containing sulfonic groups is 88.0-99.0%;
the surfactant comprises one or more of sodium dodecyl sulfate, sodium dibutyl naphthalene sulfonate, polyethylene glycol octyl phenyl ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate and sorbitan monooleate;
the acid solution comprises one or more of a sulfuric acid solution, a phosphoric acid solution and a hydrochloric acid solution;
the mass concentration of the acid solution is 12-32%.
9. The preparation method according to claim 6, wherein the aldehyde-based cross-linking agent comprises one or more of formaldehyde, glutaraldehyde and paraformaldehyde;
the mass-volume ratio of the polyvinyl alcohol source to the acid solution is (1-2) g: (10-20) mL;
the mass ratio of the polyvinyl alcohol source to the surfactant is (60-120): (7-12);
the mass ratio of the polyvinyl alcohol source to the aldehyde-based crosslinking agent is (60-120): (27-38);
the mass ratio of the polyvinyl alcohol source to the polyvinyl acetal porous material is (3-6): (2-4);
the temperature of the curing and crosslinking is 30-75 ℃;
the curing and crosslinking time is 4-48 h.
10. The method of claim 6, wherein the catalyst comprises one or more of pyridine, sodium hydroxide, sodium carbonate, hydrochloric acid, and sulfuric acid;
the molar ratio of the catalyst to the polyvinyl alcohol-based foam material is (0.01-1): 1;
the small molecular compound containing the octadecyl small molecular group comprises one or more of stearic acid, stearoyl chloride, methyl stearate and ethyl stearate;
the molar ratio of the small molecular compound containing the octadecyl small molecular group to the polyvinyl alcohol-based foam material is (1-5): 1;
the solvent comprises acetonitrile;
the grafting reaction time is 6-72 h;
the temperature of the grafting reaction is 0-80 ℃.
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