CN114031803A - Method for preparing polyamide-amine gel composite membrane based on click chemistry and application - Google Patents
Method for preparing polyamide-amine gel composite membrane based on click chemistry and application Download PDFInfo
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 27
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- -1 tetra (3-mercaptopropionic acid) pentaerythritol ester Chemical class 0.000 claims abstract description 3
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- 239000000463 material Substances 0.000 claims description 6
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- 230000035484 reaction time Effects 0.000 claims description 2
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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- C08J2327/00—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 a halogen; Derivatives of such polymers
- C08J2327/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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Abstract
The invention relates to a method for preparing a polyamide-amine gel composite membrane based on click chemistry and application thereof, belonging to the technical field of preparation of environment functional materials. The preparation method adopts a polyvinylidene fluoride (PVDF) membrane as a substrate, introduces unsaturated bonds on the surface of the membrane through alkali treatment, and utilizes a click chemistry method to cross-link 3-generation polyamide-amine with double bonds and the PVDF membrane with tetra (3-mercaptopropionic acid) pentaerythritol ester containing sulfydryl, so that the polyamide-amine gel composite membrane prepared based on click chemistry is prepared through a one-pot method, and high flux of the membrane and high-efficiency separation of various oil-water emulsions are realized. The invention adopts a membrane separation technology, has simple preparation method, easy operation, low energy consumption and no secondary pollution, conforms to the green chemical concept and has wide application prospect.
Description
Technical Field
The invention relates to a preparation method of a polyamide-amine gel composite membrane based on click chemistry preparation, and belongs to the technical field of preparation of environment functional materials.
Background
At present, most of oil fields in China adopt a water injection development mode to generate a large amount of oily wastewater. Most of the sewage exists in the form of emulsified oil, which can not meet the requirements of water quality discharge standard and water reinjection, and the environment is greatly harmed by random discharge. As the oil field enters the later stage of high water content, the amount of the oil extraction wastewater of part of the oil field is greatly increased, and the produced water is seriously emulsified, so that great difficulty and pressure are brought to the treatment of the oil-containing wastewater. Therefore, the development of effective treatment technology for the emulsified oil wastewater in the oil field has very important significance for the long-term development of the petroleum industry in China.
The traditional methods such as gravity separation and adsorption can remove unstable free oil drops and floating oil in a water body to a certain extent, but the stable emulsified oil drops are difficult to effectively remove. Although the methods such as chemical flocculation, high-voltage electric demulsification and the like can realize the demulsification effect, the problems of secondary pollution, high energy consumption and the like still exist, and the method is difficult to be applied to the field of oily sewage treatment in a large scale. The membrane separation method can achieve a good separation effect with a small energy input because it utilizes affinity properties of materials. However, the traditional separation membrane is easy to generate membrane pollution in the oil-water separation process, so that the membrane flux and the separation efficiency are reduced, and the traditional separation membrane and the combination interface of the functional material have the problem of poor stability, so that the application of the traditional separation membrane in the separation field is limited. Therefore, the problems of the conventional separation membrane such as pollution, low flux and poor interface binding stability are urgently solved.
The polymer hydrogel is a gel material taking water as a dispersion medium, and the water is bound in the three-dimensional cross-linked polymer network in the polymer hydrogel under the action of hydrogen bonds with the water, so that the water loses fluidity and is converted into a quasi-solid soft substance, and the polymer hydrogel is widely applied to construction of an underwater super-oleophobic surface due to unique hydrophilicity. Polyamide-amine (PAMAM) is a dendritic macromolecule, has a polar but hydrophobic internal structure, and abundant amino functional groups of the PAMAM can rapidly dissolve or adsorb demulsification of an original interface substance experimental emulsion, and can endow a base membrane with super-hydrophilic and super-oleophobic properties, so that the problem of membrane pollution is solved, and the membrane flux and the separation efficiency are improved. The technology of combining the high molecular polyamide-amine hydrogel with the PVDF membrane has not been reported at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to overcome the technical defects in the prior art, introduces polyamide-amine containing double bonds and utilizes click chemistry to crosslink the whole generation of polyamide-amine containing double bonds on a PVDF membrane with double bonds to form a layer of polymer gel, thereby improving the flux of the membrane, solving the problems of pollution, low flux, poor interface bonding stability and the like of the traditional separation membrane, and leading the prepared polyamide-amine gel composite membrane prepared based on click chemistry to be capable of separating various oil-water emulsions and greatly improving the separation efficiency.
The technical scheme adopted by the invention is as follows, and the invention is completed by four steps of reaction:
(1) preparation of double-bond PVDF base membrane:
soaking a commercial hydrophobic PVDF membrane in NaOH solution to obtain a double-bond modified PVDF base membrane;
(2) synthesis of 3-generation polyamidoamines: adopting a divergent synthesis method and taking ethylenediamine as a reaction core, firstly carrying out Michael addition with methyl acrylate, then carrying out amidation reaction on the obtained product and the ethylenediamine diluted by anhydrous methanol to obtain first-generation polyamide-amine, and repeating the two steps of reaction to alternately carry out to finally obtain 3-generation polyamide-amine;
(3) synthesis of Polyamide-amine containing double bonds: dissolving 3-generation polyamide-amine and allyl glycidyl ether in ethanol, placing the mixture in a three-neck flask, and refluxing the mixture in a nitrogen atmosphere to obtain polyamide-amine containing double bonds;
(4) and (2) putting the double-bond modified PVDF base membrane obtained in the step (1) and the step (3) and 3-generation polyamide-amine with double bonds into a flask, sequentially adding pentaerythritol tetrakis (3-mercaptopropionate) and a photoinitiator I-907 into the flask, adding a certain amount of ethanol into the flask, and stirring under ultraviolet irradiation to crosslink the materials mutually to obtain the polyamide-amine gel modified PVDF composite membrane.
Wherein in the step (1), the concentration of the NaOH solution is 2 mol.L-1The soaking time is 12 h.
Wherein, in the step (2), all the solvents are new distilled solvents; the molar ratio of the methyl acrylate to the ethylenediamine is 1: 8-1: 10; the molar ratio of the ethylenediamine to the product obtained by the reaction is 1: 12-1: 16; the reaction condition is that the reaction is carried out for 48 hours at the temperature of 25-30 ℃.
Wherein, in the step (3), the mol ratio of the allyl glycidyl ether to the amino group in the 3-generation polyamide-amine is 1:2, and the reflux temperature is 78 ℃. The reflux time was 10 h.
Wherein, in the step (4), the molar ratio of the 3 generation polyamide-amine containing double bonds to the pentaerythritol tetrakis (3-mercaptopropionate) is 1: 6.
wherein in the step (4), the mass of the photoinitiator I-907 is 0.5 percent of the total mass of the double-bond-containing 3-generation polyamide-amine and the tetra (3-mercaptopropionic acid) pentaerythritol ester; the wavelength of ultraviolet light is 365nm, and the illumination reaction time is 2 hours.
The polyamide-amine gel modified PVDF membrane is applied to oil-water separation experiments:
the volume ratio of water to oil in the oil-water emulsion used in the experiment is 99:1, 10mg of ionic surfactant is added, the mixture is stirred for 12 hours to form stable emulsion, and then the oil-water separation experiment is carried out by a suction filtration device. Concentration C before separation by emulsion0Concentration of the emulsion after separation is CpThe separation efficiency R is calculated.
The invention has the beneficial effects that:
(1) the PVDF is used as the base film, so that the material is low in price, good in mechanical property, environment-friendly and good in recycling performance.
(2) The polyamide-amine gel is simply and efficiently grafted on the surface of the PVDF membrane by a click chemistry method.
(3) The polyamide-amine gel obtained by the one-pot method enables the PVDF membrane to obtain high flux super-hydrophilicity and super-oleophobicity under water.
(4) The preparation method disclosed by the invention is simple, convenient to operate, low in energy consumption, easy to treat, free of secondary pollution, in line with green chemical concepts, and has a good application prospect in the field of oil-water separation.
Drawings
FIG. 1 is a scanning electron micrograph of a hydrophobic PVDF-based film.
FIG. 2 is a scanning electron microscope image of the prepared polyamide-amine gel modified PVDF composite membrane.
Fig. 3 is a photograph of a water contact angle of the prepared polyamidoamine gel-modified PVDF composite membrane.
Fig. 4 is a photograph of an underwater oil contact angle of the prepared polyamidoamine gel-modified PVDF composite membrane.
FIG. 5 is a graph showing the separation efficiency of the prepared PVDF composite membrane modified by polyamide-amine gel after treatment in acid, alkali and salt environments for different types of oil-water emulsions.
FIG. 6 is a diagram of a cyclic separation experiment of the prepared polyamide-amine gel modified PVDF composite membrane.
Detailed description of the preferred embodiment
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and a detailed operation flow and specific reaction conditions are given, but the scope of the present invention is not limited to the following examples.
Example 1
1. Preparation of double-bond PVDF base membrane: soaking a commercially available hydrophobic PVDF membrane in 2 mol.L-1And obtaining the double-bond modified PVDF basal membrane in the NaOH solution.
FIG. 1 shows that the surface of the hydrophobic PVDF-based membrane is relatively smooth and the pore size is sparse.
2. Synthesis of different generations of polyamidoamines: 7.25mL of freshly distilled methyl acrylate was dissolved in 9mL of anhydrous methanol in the flask, and the flask was placed in an ice-water bath for 30 minutes, followed by vacuum evacuation and nitrogen purge three times. Dissolving 0.668mL of freshly distilled ethylenediamine and 1mL of methanol in a centrifuge tube, dropwise adding the mixed solution into a flask, removing an ice water bath after dropwise adding, keeping the reaction temperature at 25 ℃, magnetically stirring for 24 hours, and removing excessive methanol and methyl acrylate by rotary evaporation after the reaction is finished to obtain the 0.5-substituted polyamide-amine. Dissolving 3.77g of the 0.5-generation polyamidoamine obtained by the reaction in 8mL of anhydrous methanol, mixing 6.21mL of freshly distilled ethylenediamine and 7mL of anhydrous methanol, dropwise adding the mixture into a flask system to react with the 0.5-generation polyamidoamine at the reaction temperature of 30 ℃, magnetically stirring for 48 hours, and removing excessive methanol and ethylenediamine by rotary evaporation after the reaction is finished to obtain the 1-generation polyamidoamine. The 2-and 3-generation polyamidoamine synthesis steps are similar to the 1-generation, and are divided into two steps of Michael addition reaction and amidation reaction.
3. Synthesis of Polyamide-amine containing double bonds: 3g of 3-substituted polyamidoamine and 0.8428g of allyl glycidyl ether are respectively dissolved in ethanol, the mixture is placed in a three-neck flask and refluxed for 10 hours at 78 ℃ in nitrogen atmosphere, after the reaction is finished, the excessive ethanol is removed by rotary evaporation, and then the mixture is precipitated in n-hexane for three times and dried in vacuum to obtain the polyamidoamine containing double bonds.
4. Taking 0.15g of the synthesized PVDF membrane containing double bond polyamide-amine and double bond modification, adding 0.1g of pentaerythritol tetrakis (3-mercaptopropionate) and 0.001g of photoinitiator I-907 into a flask, dispersing in 13mL of ethanol, sealing the flask by using a rubber plug, vacuumizing, introducing nitrogen repeatedly for three times, stirring for 2 hours under the irradiation of 365nm ultraviolet light, fully washing the obtained product by using ethanol, and drying to obtain the PVDF composite membrane modified by polyamide-amine gel.
Fig. 2 shows that the PVDF membrane surface modified by the polyamide-amine gel becomes rough and has reduced pore size compared to the PVDF base membrane, indicating that the polyamide-amine gel is successfully crosslinked on the PVDF membrane surface.
FIG. 3 shows that the PVDF composite membrane modified by polyamide-amine gel has super-hydrophilic performance.
FIG. 4 shows that the PVDF composite membrane modified by polyamide-amine gel has super oleophobic performance under water.
Fig. 5 shows that the separation efficiency of the PVDF composite membrane modified by polyamide-amine gel to different types of oil-water emulsions can reach more than 99% after the composite membrane is treated by acid, alkali and salt environments.
FIG. 6 shows that the PVDF composite membrane modified by polyamide-amine gel still maintains good separation efficiency and emulsion flux after 10 times of oil-water emulsion cycle separation.
Example 2:
1. preparation of double-bond PVDF base membrane: soaking a commercially available hydrophobic PVDF membrane in 2 mol.L-1And obtaining the double-bond modified PVDF basal membrane in the NaOH solution.
2. Synthesis of different generations of polyamidoamines: 3.1mL of freshly distilled methyl acrylate was dissolved in 4mL of anhydrous methanol in a flask, and the flask was placed in an ice-water bath for 30 minutes, followed by vacuum evacuation and nitrogen purge three times. Dissolving 0.297mL of freshly distilled ethylenediamine and 0.5mL of methanol in a centrifuge tube, dropwise adding the mixed solution into a flask, removing an ice water bath after dropwise adding, keeping the reaction temperature at 25 ℃, magnetically stirring for 24 hours, and removing excessive methanol and methyl acrylate by rotary evaporation after the reaction is finished to obtain the 0.5-substituted polyamide-amine. Dissolving 1.22g of the 0.5-generation polyamidoamine obtained by the reaction in 4mL of anhydrous methanol, mixing 2.51mL of freshly distilled ethylenediamine and 3mL of anhydrous methanol, dropwise adding the mixture into a flask system to react with the 0.5-generation polyamidoamine at the reaction temperature of 30 ℃, magnetically stirring for 48 hours, and removing excessive methanol and ethylenediamine by rotary evaporation after the reaction is finished to obtain the 1-generation polyamidoamine. The 2-and 3-generation polyamidoamine synthesis steps are similar to the 1-generation, and are divided into two steps of Michael addition reaction and amidation reaction.
3. Synthesis of Polyamide-amine containing double bonds: respectively dissolving 1g and 0.2809g of 3-substituted polyamidoamine in ethanol, placing in a three-neck flask, refluxing for 10h at 78 ℃ in a nitrogen atmosphere, removing excessive ethanol by rotary evaporation after the reaction is finished, precipitating in n-hexane for three times, and drying in vacuum to obtain the polyamidoamine containing double bonds.
4. Taking 0.2g of the synthesized PVDF membrane containing double bond polyamide-amine and double bond modification, adding 0.13g of pentaerythritol tetrakis (3-mercaptopropionate) and 0.0015g of photoinitiator I-907, dispersing in 16mL of ethanol, sealing the flask by using a rubber plug, vacuumizing, introducing nitrogen repeatedly for three times, stirring for 2 hours under the irradiation of 365nm ultraviolet light, fully washing the obtained product by using ethanol, and drying to obtain the PVDF composite membrane modified by polyamide-amine gel.
Example 3:
1. preparation of double-bond PVDF base membrane: soaking a commercially available hydrophobic PVDF membrane in 2 mol.L-1And obtaining the double-bond modified PVDF basal membrane in the NaOH solution.
2. Synthesis of different generations of polyamidoamines: 9mL of freshly distilled methyl acrylate was dissolved in 12mL of anhydrous methanol in a flask, and the flask was placed in an ice-water bath for 30 minutes, followed by vacuum evacuation and nitrogen purging three times. Dissolving 0.736mL of freshly distilled ethylenediamine and 1.2mL of methanol in a centrifuge tube, dropwise adding the mixed solution into a flask, removing an ice water bath after dropwise adding, keeping the reaction temperature at 25 ℃, magnetically stirring for 24 hours, and removing excessive methanol and methyl acrylate by rotary evaporation after the reaction is finished to obtain the 0.5-substituted polyamide-amine. Dissolving 4.3g of the 0.5-generation polyamidoamine obtained by the reaction in 10mL of anhydrous methanol, mixing 6.91mL of freshly distilled ethylenediamine and 7.5mL of anhydrous methanol, dropwise adding the mixture into a flask system to react with the 0.5-generation polyamidoamine, wherein the reaction temperature is 30 ℃, magnetically stirring for 48 hours, and removing excessive methanol and ethylenediamine by rotary evaporation after the reaction is finished to obtain the 1-generation polyamidoamine. The 2-and 3-generation polyamidoamine synthesis steps are similar to the 1-generation, and are divided into two steps of Michael addition reaction and amidation reaction.
3. Synthesis of Polyamide-amine containing double bonds: respectively dissolving 2g and 0.5619g of 3-substituted polyamidoamine in ethanol, placing in a three-neck flask, refluxing for 10h at 78 ℃ in a nitrogen atmosphere, removing excessive ethanol by rotary evaporation after the reaction is finished, precipitating in n-hexane for three times, and drying in vacuum to obtain the polyamidoamine containing double bonds.
4. Taking 0.13g of the synthesized PVDF membrane containing double bond polyamide-amine and double bond modification, adding 0.097g of pentaerythritol tetrakis (3-mercaptopropionate) and 0.001g of photoinitiator I-907, dispersing in 12mL of ethanol, sealing the flask by using a rubber plug, vacuumizing, introducing nitrogen repeatedly for three times, stirring for 2 hours under 365nm ultraviolet illumination, fully washing the obtained product by using ethanol, and drying to obtain the PVDF composite membrane modified by polyamide-amine gel.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (7)
1. A method for preparing a polyamide-amine gel composite membrane based on click chemistry is characterized by comprising the following steps:
(1) obtaining a double-bond modified PVDF (polyvinylidene fluoride) base membrane through alkali treatment;
(2) respectively dissolving 3 generation polyamide-amine PAMAM and allyl glycidyl ether AGE taking ethylenediamine as a core in a solvent, placing in a three-neck flask, and refluxing in a nitrogen atmosphere to obtain 3 generation polyamide-amine PAMAM-AGE containing double bonds;
(3) and (3) putting the double-bond modified PVDF base membrane obtained in the step (1) and the step (2) and 3-generation polyamide-amine PAMAM-AGE with double bonds into a flask, sequentially adding tetra (3-mercaptopropionic acid) pentaerythritol ester (PTMP) and a photoinitiator I-907 into the flask, adding a certain amount of ethanol into the flask, and stirring under ultraviolet irradiation to obtain the polyamide-amine gel modified PVDF composite membrane.
2. The method for preparing a polyamide-amine gel composite membrane based on click chemistry of claim 1, wherein the alkali solution used to treat the base membrane in the step (1) is 2 mol-L-1The soaking time of the NaOH solution is 12 hours.
3. The method for preparing a polyamide-amine gel composite membrane based on click chemistry of claim 1, wherein in the step (2), the molar ratio of allyl glycidyl ether to amino groups in the 3 rd generation polyamide-amine is 1: 2; the reflux temperature is 78 ℃, and the reflux time is 10 hours; the solvent is ethanol.
4. The method for preparing a polyamide-amine gel composite membrane based on click chemistry of claim 1, wherein in the step (3), the ratio of the amounts of the PAMAM-AGE and the PTMP material is 1: 6.
5. the method for preparing a polyamide-amine gel composite membrane based on click chemistry of claim 1, wherein in the step (3), the mass of the photoinitiator I-907 is 0.5% of the total mass of the 3 generation polyamide-amine containing double bonds and pentaerythritol tetrakis (3-mercaptopropionate).
6. The method for preparing a polyamide-amine gel composite membrane based on click chemistry of claim 1, wherein in the step (3), the wavelength of the ultraviolet light is 365nm, and the light irradiation reaction time is 2 h.
7. Use of the polyamide-amine gel composite membrane prepared by the method of any one of claims 1 to 6 for the separation of a plurality of oil and water emulsions.
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