CN111978488B - Method for preparing porous polymer material by high internal phase emulsion method - Google Patents
Method for preparing porous polymer material by high internal phase emulsion method Download PDFInfo
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- CN111978488B CN111978488B CN201910422110.XA CN201910422110A CN111978488B CN 111978488 B CN111978488 B CN 111978488B CN 201910422110 A CN201910422110 A CN 201910422110A CN 111978488 B CN111978488 B CN 111978488B
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- 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
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
Abstract
The invention discloses a method for preparing a porous polymer material by a high internal phase emulsion method, which comprises the following steps: dissolving a sulfonated poly (styrene-co-butadiene) block copolymer, an initiator and a methacrylate monomer in a first organic solvent to obtain a first solution; dissolving polyamine in a second organic solvent to obtain a second solution; mixing the first solution and the second solution to form gel under the condition of vigorous stirring; adding water into the gel, and continuously and violently stirring to form gel with expanded volume; and (3) reacting the gel with the expanded volume for 4-6 hours at the temperature of 60-75 ℃, and freeze-drying after the reaction is finished to obtain the porous polymer material. The method adopts block high polymer and polyamine as stabilizers and methacrylate as monomers to prepare high internal phase emulsion, and obtains the porous high polymer material by initiating continuous phase polymerization and removing the internal phase; the obtained high molecular material is suitable for separating oil-water emulsion.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a method for preparing a porous polymer material by a high internal phase emulsion method.
Background
In recent years, along with the rapid development of social economy, the demand of human beings on energy is continuously expanded, in order to improve the oil exploitation rate, most of exploitation wells of various oil fields in China adopt a water injection exploitation mode, the water content in crude oil is very high, the water content of produced liquid of an east oil field reaches 90%, an oil phase and a water phase can be mixed violently in the exploitation and transportation processes, and the oil phase and the water phase exist in the form of emulsion generally, so that an oil-water mixed system is difficult to separate. The oil-water emulsion has the characteristics of small size, high stability and the like, and is a serious difficulty in oil-water separation. The oily wastewater discharged every year in China is up to hundreds of millions of tons, and the direct discharge of untreated oil-water emulsion has fatal influence on the environment and human health and can cause great economic loss and energy consumption. Therefore, the problem of oil-water emulsion disposal has become a subject of intensive research by scientists around the world.
In recent years, many oil-water separation materials are studied at home and abroad, but few materials are used for oil-water emulsion separation. At present, materials for treating oil-containing emulsions are mainly classified into filtration-type and adsorption-type materials. The filtering material mainly comprises a super-hydrophilic-super-oleophobic or super-oleophilic-super-hydrophobic filtering membrane, but the application of the filtering material is limited by the problems of high cost, serious membrane pollution and the like. The adsorption material is mainly a porous polymer material, and has important application in the field of oil-water separation due to the advantages of high specific surface area, high porosity, low density, rich surface functional groups and the like. The high internal phase emulsion template method is one of effective ways for preparing the porous material, and the structure of the porous material can be controlled in advance by changing factors such as monomers, cross-linking agents and the like, so that the high-efficiency separation of the oil-water emulsion is facilitated. At home and abroad, materials for preparing porous high polymer materials by a high internal phase emulsion template method to realize oil-water emulsion separation are rarely reported. Therefore, it is necessary to develop a high internal phase emulsion method to prepare porous polymer for oil-water emulsion separation.
Disclosure of Invention
The invention provides a method for preparing a porous polymer material by a high internal phase emulsion method, aiming at the problem of treatment of the existing oily wastewater. The method adopts block high polymer and polyamine as stabilizers and methacrylate as monomers to prepare high internal phase emulsion, and obtains the porous high polymer material by initiating continuous phase polymerization and removing the internal phase; the obtained high molecular material is suitable for separating oil-water emulsion.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a porous polymer material by a high internal phase emulsion method comprises the following steps:
dissolving a sulfonated poly (styrene-co-butadiene) block copolymer, an initiator and a methacrylate monomer in a first organic solvent to obtain a first solution;
dissolving polyamine in a second organic solvent to obtain a second solution;
mixing the first solution and the second solution to form gel under the condition of vigorous stirring;
adding water into the gel, and continuously and violently stirring to form gel with expanded volume;
and (3) reacting the gel with the expanded volume for 4-6 hours at the temperature of 60-75 ℃, and freeze-drying after the reaction is finished to obtain the porous polymer material.
Wherein, compared with the traditional stabilizer, the sulfonated poly (styrene-co-butadiene) block copolymer has the advantages of low price, small dosage and no need of further purification. The polyamine contains a large amount of amine groups, which can affect the dissolution of the block copolymer, the initiator and the monomer, so that the polyamine is mixed with the first solution to form gel after forming the second solvent.
Preferably, the molar ratio of the sulfonated poly (styrene-co-butadiene) block copolymer, the initiator and the methacrylate monomer is 1 (0.1-0.5): 140-.
Preferably, the molar ratio of the polyamine to the methacrylate monomer is 1 (70-160).
Preferably, the initiator is one or a combination of azodiisobutyronitrile, azodiisoheptonitrile and dibenzoyl peroxide. The initiator selected by the invention is an oil-soluble initiator, the reaction is stable, the reaction is a first-order reaction, no side reaction exists, and the control is better.
Preferably, the methacrylate monomer is one or a combination of methyl methacrylate, butyl methacrylate, isobutyl methacrylate and lauryl methacrylate. The monomer selected by the invention is a lipophilic monomer, which is beneficial to improving the oil-water separation performance of the prepared material, and the invention has the advantages of wide source and low cost.
Preferably, the first organic solvent is one or a combination of n-butane, n-hexane, cyclohexane, n-heptane, isooctane, toluene and xylene. More preferably toluene.
Preferably, the second organic solvent is one or a combination of several of tetrahydrofuran, ethanol, toluene and benzene. More preferably benzene.
Preferably, the polyamine is an organic diamine or an organic triamine.
Preferably, the organic diamine is hexamethylene diamine.
The invention has the beneficial effects that:
(1) the invention develops a method for preparing the porous high polymer material by using a high internal phase emulsion template method, provides a new thought for preparing the porous high polymer material by using the high internal phase emulsion template method, and has important significance for preparing the porous high polymer material.
(2) The high-molecular material for oil-water separation is prepared by adopting a high internal phase emulsion method, water is used as an internal phase in the preparation process, and the specific surface area of the prepared material can be effectively improved and the oil-water separation efficiency is improved by increasing the water addition amount.
(3) The material prepared by the invention is a hydrophobic oleophylic material with a porous structure, and the oil absorption capacity is higher than that of a common porous polymer material. The material has low density and large specific surface area, and can quickly realize the separation of an oil-water mixed system.
Drawings
FIG. 1 is a scanning electron microscope photograph of the porous polymer material prepared in example 1.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
Dissolving 0.15mL of lauryl methacrylate, 0.008g of sulfonated poly (styrene-co-butadiene) block copolymer and 0.0017g of azobisisobutyronitrile in 0.4mL of toluene, and uniformly mixing; adding 50 mu L of hexamethylenediamine dissolved in benzene, and stirring vigorously; adding 2.5mL of deionized water, and mixing for 5 minutes to form gel; and (3) putting the formed gel into a water bath kettle at 70 ℃ for reaction for 4 hours, taking out, and freeze-drying to obtain the porous polymer material.
Fig. 1 is a scanning electron microscope photograph of the prepared porous polymer material, and the microstructure shows that the material has a multi-stage porous structure, which is beneficial to efficiently adsorbing various oil molecules. The specific surface area of the porous material was 5.61m2The oil-water separation efficiency reaches 99.2 percent.
Example 2
Dissolving 0.15mL of methyl methacrylate, 0.008g of sulfonated poly (styrene-co-butadiene) block copolymer and 0.0017g of azobisisobutyronitrile in 0.4mL of toluene, and uniformly mixing; adding 50 mu L of hexamethylenediamine dissolved in benzene, and stirring vigorously; adding 3.0mL of deionized water, and mixing for 5 minutes to form gel; and (3) putting the formed gel into a water bath kettle at 60 ℃ for reaction for 4 hours, taking out, and freeze-drying to obtain the porous polymer material.
Example 3
Dissolving 0.15mL of butyl methacrylate, 0.008g of sulfonated poly (styrene-co-butadiene) block copolymer and 0.0017g of azobisisobutyronitrile in 0.4mL of toluene, and uniformly mixing; adding 50 mu L of hexamethylenediamine dissolved in benzene, and stirring vigorously; adding 3.0mL of deionized water, and mixing for 5 minutes to form gel; and (3) placing the formed gel into a 65 ℃ water bath kettle for reaction for 5 hours, taking out, and freeze-drying to obtain the porous polymer material.
Example 4
Dissolving 0.15mL of lauryl methacrylate, 0.008g of sulfonated poly (styrene-co-butadiene) block copolymer and 0.0017g of dibenzoyl peroxide in 0.4mL of toluene, and uniformly mixing; adding 50 mu L of hexamethylenediamine dissolved in benzene, and stirring vigorously; adding 3.0mL of deionized water, and mixing for 5 minutes to form gel; and (3) placing the formed gel into a 70 ℃ water bath kettle for reaction for 6 hours, taking out, and freeze-drying to obtain the porous polymer material.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A method for preparing a porous polymer material by a high internal phase emulsion method is characterized by comprising the following steps:
dissolving a sulfonated poly (styrene-co-butadiene) block copolymer, an initiator and a methacrylate monomer in a first organic solvent to obtain a first solution;
dissolving polyamine in a second organic solvent to obtain a second solution;
mixing the first solution and the second solution to form gel under the condition of vigorous stirring;
adding water into the gel, and continuously and violently stirring to form gel with expanded volume;
and (3) reacting the gel with the expanded volume for 4-6 hours at the temperature of 60-75 ℃, and freeze-drying after the reaction is finished to obtain the porous polymer material.
2. The method as claimed in claim 1, wherein the molar ratio of the sulfonated poly (styrene-co-butadiene) block copolymer, the initiator and the methacrylate monomer is 1 (0.1-0.5): 140-190.
3. The method of claim 1, wherein the molar ratio of the polyamine to the methacrylate monomer is 1 (70-160).
4. The method of claim 1, wherein the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, and dibenzoyl peroxide.
5. The method according to claim 1, wherein the methacrylate monomer is one or more of methyl methacrylate, butyl methacrylate, isobutyl methacrylate and lauryl methacrylate.
6. The method according to claim 1, wherein the first organic solvent is one or more selected from the group consisting of n-butane, n-hexane, cyclohexane, n-heptane, isooctane, toluene, and xylene.
7. The method of claim 1, wherein the first organic solvent is toluene.
8. The method according to claim 1, wherein the second organic solvent is one or more of tetrahydrofuran, ethanol, toluene and benzene.
9. The method of claim 1, wherein the polyamine is an organic diamine or an organic triamine.
10. The method of claim 9, wherein the organic diamine is hexamethylene diamine.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238784A (en) * | 1996-11-25 | 1999-12-15 | 巴斯福股份公司 | Method for preparation of polymer dispersion by radical aqueous emulsion polymerization with continuously prepared aqueous monomer emulsion |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7820729B2 (en) * | 2006-04-13 | 2010-10-26 | University of Newcastle Upon Tyne, c/o School of Chemical Engineering and Advanced Materials | Process for preparing a functionalised polyHIPE polymer |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238784A (en) * | 1996-11-25 | 1999-12-15 | 巴斯福股份公司 | Method for preparation of polymer dispersion by radical aqueous emulsion polymerization with continuously prepared aqueous monomer emulsion |
Non-Patent Citations (2)
| Title |
|---|
| High internal phase emulsion (HIPE) xerogels for enhanced oil spill recovery;Yuanpeng Wu等;《Journal of Materials Chemistry A》;20141216;第3卷(第5期);1906-1909 * |
| Hybrid high internal phase emulsion (HIPE) organogels with oil separation properties;Tao Zhang等;《Chemical Communications》;20140909;第50卷(第89期);13821-13824 * |
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