CN113231111A - Side chain sulfonated polybenzimidazole composite cation exchange membrane and preparation method and application thereof - Google Patents
Side chain sulfonated polybenzimidazole composite cation exchange membrane and preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
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- B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
Abstract
The invention belongs to the technical field of preparation of cation exchange membranes in electrodialysis, and particularly relates to a side chain sulfonated polybenzimidazole composite cation exchange membrane and a preparation method and application thereof. The preparation method of the side chain sulfonated polybenzimidazole composite cation exchange membrane comprises the following steps: synthesizing side chain sulfonated polybenzimidazole; preparing a composite membrane casting solution; preparing the composite cation exchange membrane. The composite cation exchange membrane has excellent ionic conductivity, pollution resistance and mechanical stability; the preparation method is simple, efficient, high in yield and artificially controllable in membrane structure and characteristics; the membrane product is beneficial to promoting the large-scale application of electrodialysis in water treatment processes of food, chemical industry, seawater desalination and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of cation exchange membranes in electrodialysis, and particularly relates to a side chain sulfonated polybenzimidazole composite cation exchange membrane and a preparation method and application thereof.
Background
The electrodialysis technology (ED) has the advantages of high separation efficiency, artificially controllable desalination rate, simple system, low energy consumption, no environmental pollution and the like, and has wide application prospects in the fields of brackish water and seawater desalination, chemical separation, food and medical product desalination and the like. In particular, ED plays a significant role in the production of complex proteins, the stabilization of wine, the desalination of sugars and fermentation wastewater, etc. in the food industry. Cation Exchange Membranes (CEMs) allow only cations to permeate are the core components of ED systems. An ideal Ion Exchange Membrane (IEM) needs to have excellent permselectivity, hydrophilicity, electrochemical properties, physicochemical stability, and anti-fouling properties. In the process of desalting food products by electrodialysis, because the treated solution contains a large amount of organic matters, inorganic salts, colloidal particles, microorganisms and biological macromolecules thereof, the complex components and ionic membranes are adsorbed or deposited on the surfaces or in membrane pores through physical and chemical actions to form serious membrane pollution. Membrane fouling is a "bottleneck" problem limiting the large-scale application of ED in the food industry. Ion exchange membrane fouling causes a series of problems such as increased membrane resistance, decreased permselectivity and ionic conductivity, decreased limiting current density, and decreased membrane life, and membrane cleaning or membrane replacement significantly affects the operating efficiency of electrodialysis and increases its cost.
The preparation of the anti-pollution cation exchange membrane by modifying the membrane material is the most effective way for solving the problem of membrane pollution. Polybenzimidazole (PBI) has good mechanical strength, chemical stability and heat resistance, and proton exchange membranes, reverse osmosis membranes, forward osmosis membranes and the like are successfully prepared. However, PBI ion conductivity is too low to be used directly in electrodialysis. The ion conductivity of the membrane can be improved by introducing sulfonic acid groups into PBI to obtain sulfonated polybenzimidazole (S-PBI). At present, post-sulfonated S-PBI, S-PBI directly polymerized by sulfonated monomers and side chain S-PBI grafted by alkyl sulfonate or aryl sulfonate have been reported. Although the main chain type S-PBI has high ion conductivity, its decomposition temperature and chemical stability are significantly reduced. Alkyl sulfonate and aryl sulfonate grafted side chain S-PBI can improve the ion conductivity of the membrane without sacrificing the physicochemical stability of the membrane. Therefore, in order to synthesize a side chain S-PBI suitable for ED systems with good ionic conductivity, anti-pollution capability and physicochemical stability, a new PBI modification method still needs to be developed. Although numerous researchers have demonstrated that the addition of inorganic nanomaterials to organic polymers can exploit the properties of both materials and improve the physicochemical stability of composite films. However, direct or improper addition of these inorganic materials causes problems such as decrease in ion conductivity and decrease in mechanical strength of the composite membrane.
Based on the above, a new approach for effectively solving the problems that the cation exchange membrane required by the existing ED system cannot have high ion conductivity, strong anti-pollution capability, excellent physicochemical stability and the like is needed, and no relevant report is found in the technology for preparing the high-performance cation exchange membrane by using the novel methods of ozone pre-activation-free radical-initiated polymer bulk graft modification and sulfonated organic substance-sulfonated inorganic substance blending.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a side chain sulfonated polybenzimidazole composite cation exchange membrane which has excellent anti-pollution capacity, ion conductivity and physical stability.
The invention also provides a preparation method and application of the composite cation exchange membrane.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a side chain sulfonated polybenzimidazole composite cation exchange membrane comprises the following steps:
(1) synthesis of side chain sulfonated polybenzimidazole: dissolving polybenzimidazole in a solvent, stirring for 6-24 h at 20-60 ℃, and filtering to obtain a polybenzimidazole solution; ozone is led into the polybenzimidazole solution for preactivation, N is led into the polybenzimidazole solution after cooling2Removing oxygen and ozone; then, heating to 80-100 ℃, adding benzoyl peroxide, adding 5-20% by mass of sodium p-styrene sulfonate solution, and reacting for 2-6 h under the protection of inert gas; after the reaction is finished, the reactant is precipitated by methanol solution, and then the side chain sulfonated polybenzene is obtained after washing and dryingImidazole;
(2) preparing a composite membrane casting solution: adding the side chain sulfonated polybenzimidazole obtained in the step (1) into a solvent, and stirring for 6-12 h at the temperature of 20-70 ℃ to obtain an S-PBI solution; adding sulfonated inorganic substance into organic solvent to obtain sulfonated inorganic substance dispersion liquid; then adding the sulfonated inorganic substance dispersion liquid into the S-PBI solution, and uniformly mixing to obtain a composite membrane casting solution;
(3) preparing a composite cation exchange membrane: and (3) pouring the composite membrane casting solution obtained in the step (2) into a grinding tool, casting to form a membrane, and drying at the temperature of 60-80 ℃ for 24-48 h to obtain the composite membrane.
Preferably, N is introduced2Removing oxygen and ozone, and introducing nitrogen for 20-40 min.
Preferably, the mass ratio of the polybenzimidazole to the sodium p-styrene sulfonate in the step (1) is 1 (1-8).
Preferably, the addition amount of the sulfonated inorganic substance in the step (2) is 0.5-10% of the mass of the side chain sulfonated polybenzimidazole.
Preferably, the sulfonated inorganic substance in the step (2) is one or more of sulfonated silicon dioxide, sulfonated titanium dioxide, sulfonated graphene oxide and sulfonated zirconium oxide.
Preferably, the ozone concentration in the step (1) is 2-6g/h, and the ozone treatment time is 15-45 min.
Preferably, the amount of benzoyl peroxide used in step (1) is 0.1-0.5% by mass of polybenzimidazole.
Preferably, the solvent in step (1) and step (2) is one or more of dimethylacetamide, dimethylformamide, dimethyl sulfoxide, nitrogen methyl pyrrolidone, tetrahydrofuran and acetone.
Preferably, the mass fraction of solid matters in the composite membrane casting solution in the step (2) is 5-10%.
Specifically, the polybenzimidazole is poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) synthesized in a laboratory (the synthesis method is shown in Kyungho Hwang, Jun-Hyun Kim, Sung-Yul Kim, Hongsik Byun, Preparation of polybenzimidazole-based membranes and the ir potential applications in the fuel cell system [ J ]. Energies, 2014, 7(3): 1721-1732), and is obtained by monomer polymerization of 3,3 '-diaminobenzidine and 4,4' -dicarboxydiphenyl ether in an Eton reagent at 140 ℃ for 4 h.
Specifically, the preparation method of the sulfonated inorganic substance comprises the following steps: adding an inorganic substance into a mixed solution of 0.5 mol/L sulfuric acid and methanol, performing ultrasonic dispersion for 1-2 h, and performing vacuum drying on the obtained solution at the temperature of 105-120 ℃ until the obtained solution is dried to obtain the sulfonated inorganic substance, wherein the inorganic substance is silicon dioxide, titanium dioxide, graphene oxide or zirconium oxide. (see: Chen Li, Yuefei Song, Xudong Wang, Quan Zhang. Synthesis, chromatography and application of S-TiO for preparation method2/PVDF-g-PSSA composite membrane for improved performance in MFCs[J]. Fuel, 2020, 264:116847）。
Specifically, the inert gas in the step (1) is nitrogen.
The side chain sulfonated polybenzimidazole composite cation exchange membrane prepared by the method is adopted.
Preferably, the thickness of the composite cation exchange membrane is 60-120 μm.
The composite cation exchange membrane is applied to electrodialysis treatment, and is particularly used for treating domestic sewage, seawater and brackish water, and food and chemical product processing water.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts the ozone pre-activation-free radical initiated body grafting technology to synthesize the novel sulfonated polybenzimidazole membrane material with a side chain structure in one step, thereby realizing the improvement of the ion conductivity of the membrane material without sacrificing the physical stability of the membrane material;
2. the scientific control of the structure and the grafting rate of the lateral chain polybenzimidazole can be realized by regulating and controlling the synthesis ratio and the reaction conditions of the two grafting monomers;
3. optimizing the hybridization modification process of the sulfonated inorganic substance to the side chain sulfonated polybenzimidazole membrane can scientifically regulate and control the membrane key parameters of the composite cation exchange membrane such as pollution resistance, ion conductivity, ion selective permeability, mechanical strength and the like, thereby realizing the multiple purposes of synchronously improving the ion conductivity, pollution resistance and physical stability of the cation exchange membrane and obtaining the cation exchange membrane suitable for electrodialysis treatment of industrial water of food, chemical industry, medicine and the like;
4. the preparation method is simple in preparation process, simple and quick in used device, easy to operate, low in cost and suitable for large-scale industrial production.
Detailed Description
The invention is further illustrated, but is not intended to be limited, by the following examples. The sulfonated inorganics and poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) used in the examples described below were synthesized by themselves in the laboratory, the synthetic methods being described above.
Specifically, the method comprises the following steps: the sulfonated inorganic substance used in the following examples was obtained by adding 5g of the inorganic substance to a mixed solution (wherein the volumes of sulfuric acid and methanol were 75ml and 25ml, respectively), ultrasonically dispersing for 2 hours, and then drying at 120 ℃.
Example 1
(1) Synthesis of side chain sulfonated polybenzimidazole: dissolving 1 g of poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) (O-PBI) in 19 g of dimethyl sulfoxide, stirring at 20 ℃ for 6 hours, and filtering insoluble substances to obtain an O-PBI solution; introducing ozone into O-PBI solution for 30 min (ozone generation concentration of ozone generator is 4 g/h), pretreating with ozone for 30 min, cooling the reaction solution with ice bath, and introducing 20 min N2Removing oxygen and ozone in the solution; then, gradually heating the solution to 80 ℃, adding 0.001 g of benzoyl peroxide, dropwise adding a sodium p-styrene sulfonate graft monomer solution (specifically, 1 g of sodium p-styrene sulfonate is dissolved in 15 g of dimethyl sulfoxide), and stirring to continuously react for 2 hours under the protection of nitrogen; after the reaction was completed, the reaction product was precipitated with 150 ml of methanol, and then the precipitate was repeatedly washed 3 times with 200 ml of deionized water and 100 ml of methanol in this order, and finally, the precipitate was dried to obtain a side chain sulfonated polybenzimidazole (S-PBI) homopolymer.
(2) Preparing a composite membrane casting solution: weighing 0.5 g of S-PBI synthesized in the step (1), adding the S-PBI into 5g of dimethyl sulfoxide, and stirring at 40 ℃ for 6 hours to obtain an S-PBI solution; adding 0.005 g of sulfonated graphene oxide into 4.5 g of dimethyl sulfoxide, and performing ultrasonic dispersion for 1 h to obtain a sulfonated graphene oxide dispersion liquid; and adding the sulfonated graphene oxide dispersion liquid into the S-PBI solution, and continuously stirring for 1 h to obtain the composite membrane casting solution.
(3) Preparing a composite cation exchange membrane: and (3) pouring the composite membrane casting solution obtained in the step (2) into a self-made glass mold in a laboratory, casting to form a membrane, then placing the glass mold in a vacuum drying oven, and drying at 60 ℃ for 36 hours until the solvent is completely volatilized to obtain the side chain sulfonated polybenzimidazole hybrid modified membrane, wherein the membrane thickness is 80 microns.
Through detection, the composite cation exchange membrane prepared by the embodiment has the water content of 30%, the swelling rate of 7.3%, the hydrophilic contact angle of 62.5 degrees, the ion exchange capacity of 1.8 meq/g and the breaking strength of 20 MPa.
When the composite cation exchange membrane is used for electrodialysis for L-tryptophan desalination recovery, the composite membrane can realize high-efficiency separation of amino acid and cations, the yield of L-tryptophan can reach 85%, the experiment process runs for 10 desalination periods, and only few pollutants appear on the membrane surface. In addition, the fracture strength of the composite membrane after operation is 18 MPa, and good physical stability (also called mechanical stability) is shown.
It should be noted that: high breaking strength indicates good physical stability.
Example 2
(1) Synthesis of side chain sulfonated polybenzimidazole: dissolving 1 g of poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) (O-PBI) in 19 g of dimethylformamide, stirring at 60 ℃ for 18 h, and filtering insoluble substances to obtain an O-PBI solution; introducing ozone into the solution for 45 min (ozone generation concentration of ozone generator is 4 g/h), pretreating with ozone for 45 min, cooling the reaction solution with ice bath, and introducing 40 min N2Removing oxygen and ozone in the solution; then, gradually heating the solution to 100 ℃, adding 0.005 g of benzoyl peroxide, dropwise adding a sodium p-styrene sulfonate graft monomer solution (specifically, 8 g of sodium p-styrene sulfonate is dissolved in 30 g of dimethyl sulfoxide),stirring and continuously reacting for 6 hours under the protection of nitrogen; after the reaction is finished, precipitating the reaction product by using 300 ml of methanol, and then repeatedly washing the precipitate for 4 times by using 200 ml of deionized water and 150 ml of methanol in sequence; finally, the precipitate was dried to obtain a side chain sulfonated polybenzimidazole (S-PBI) homopolymer.
(2) Preparing a composite membrane casting solution: weighing 0.8 g of S-PBI synthesized in the step (1), adding the S-PBI into 5g of dimethyl sulfoxide, and stirring at 70 ℃ for 12 hours to obtain an S-PBI solution; adding 0.04 g of sulfonated titanium dioxide into 5g of dimethyl sulfoxide, and performing ultrasonic dispersion for 2 hours to obtain a sulfonated titanium dioxide dispersion liquid; and adding the sulfonated titanium dioxide dispersion liquid into the S-PBI solution, and continuously stirring for 2 hours to obtain the composite membrane casting solution.
(3) Preparing a composite cation exchange membrane: and (3) pouring the composite membrane casting solution obtained in the step (2) into a self-made glass mold in a laboratory, casting to form a membrane, then placing the glass mold in a vacuum drying oven, and drying at 70 ℃ for 24 times until the solvent is completely volatilized to obtain the side chain sulfonated polybenzimidazole hybrid modified membrane, wherein the membrane thickness is 100 microns.
Through detection, the composite cation exchange membrane prepared by the embodiment has the water content of 38%, the swelling rate of 9.5%, the hydrophilic contact angle of 48.4 degrees, the ion exchange capacity of 2.9 meq/g and the breaking strength of 35 MPa.
The composite cation exchange membrane is used for electrodialysis to separate gamma-aminobutyric acid from glutamic acid, the fermentation liquor of the gamma-aminobutyric acid is used as raw material liquor, the recovery rate of the gamma-aminobutyric acid can reach 90% through an electrodialysis test, and the electrodialysis separation test is carried out for 15 cycles, and only few organic pollutants appear on the membrane surface. In addition, the fracture strength of the composite membrane after operation is 30 MPa, and good physical stability is shown.
Example 3
(1) Synthesis of side chain sulfonated polybenzimidazole: dissolving 1 g of poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) (O-PBI) in 19 g of dimethylacetamide, stirring at 40 ℃ for 12 h, and filtering insoluble substances to obtain an O-PBI solution; introducing ozone into the solution for 30 min (ozone generation concentration of ozone generator is 4 g/h), pretreating with ozone for 30 min, and allowingThe reaction solution was cooled in an ice bath and N was added for 30 min2Removing oxygen and ozone in the solution; then, gradually heating the solution to 90 ℃, adding 0.002 g of benzoyl peroxide, dropwise adding a sodium p-styrene sulfonate graft monomer solution (specifically, 5g of sodium p-styrene sulfonate is dissolved in 25 g of dimethyl sulfoxide), and stirring for continuous reaction for 5 hours under the protection of nitrogen; after the reaction was completed, the reaction product was precipitated with methanol (200 ml), and then the precipitate was repeatedly washed 3 times with deionized water (200 ml) and methanol (100 ml) in this order, and finally, the precipitate was dried to obtain a side chain sulfonated polybenzimidazole (S-PBI) homopolymer.
(2) Preparing a casting solution: weighing 0.8 g of S-PBI synthesized in the step (1), adding the S-PBI into 5g of dimethyl sulfoxide, and stirring at 60 ℃ for 12 hours to obtain an S-PBI solution; adding 0.08 g of sulfonated silicon dioxide into 10 g of dimethyl sulfoxide, and performing ultrasonic dispersion for 2 hours to obtain sulfonated silicon dioxide dispersion liquid; and adding the sulfonated silicon dioxide dispersion liquid into the S-PBI solution, and continuously stirring for 2 hours to obtain the composite membrane casting solution.
(3) Preparing a composite cation exchange membrane: and (3) pouring the composite membrane casting solution obtained in the step (2) into a self-made glass mold in a laboratory, casting to form a membrane, then placing the glass mold in a vacuum drying oven, and drying at 80 ℃ for 24 hours until the solvent is completely volatilized to obtain the side chain sulfonated polybenzimidazole hybrid modified membrane, wherein the membrane thickness is 120 microns.
Through detection, the composite cation exchange membrane prepared by the embodiment has the water content of 32%, the swelling rate of 8.6%, the hydrophilic contact angle of 50.8 degrees, the ion exchange capacity of 2.7 meq/g and the breaking strength of 31 MPa.
Example 4
(1) Synthesis of side chain sulfonated polybenzimidazole: dissolving 1 g of poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) (O-PBI) in 19 g of azomethylpyrrolidone, stirring at 40 ℃ for 8 h, and filtering insoluble substances to obtain an O-PBI solution; introducing ozone into the solution for 30 min (ozone generation concentration of ozone generator is 4 g/h), pretreating with ozone for 30 min, cooling the reaction solution with ice bath, and introducing 30 min N2Removing oxygen and ozone in the solution; then, will beGradually heating the solution to 100 ℃, adding 0.003 g of benzoyl peroxide, dropwise adding a sodium p-styrene sulfonate grafted monomer solution (specifically, 4 g of sodium p-styrene sulfonate is dissolved in 25 g of dimethyl sulfoxide), and stirring for continuous reaction for 4 hours under the protection of nitrogen; after the reaction is finished, precipitating a reaction product by using methanol (200 ml), and then repeatedly washing the precipitate for 3 times by using deionized water (200 ml) and methanol (100 ml) in sequence; finally, the precipitate was dried to obtain a side chain sulfonated polybenzimidazole (S-PBI) homopolymer.
(2) Preparing a composite membrane casting solution: weighing 0.7 g of S-PBI synthesized in the step (1), adding the S-PBI into 5g of dimethyl sulfoxide, and stirring at 20 ℃ for 10 hours to obtain an S-PBI solution; adding 0.0525 g of sulfonated zirconia into 8 g of dimethyl sulfoxide, and performing ultrasonic dispersion for 1.5 h to obtain a sulfonated zirconia dispersion liquid; and adding the sulfonated zirconia dispersion liquid into the S-PBI solution, and continuously stirring for 2 hours to obtain the composite membrane casting solution.
(3) Preparing a composite cation exchange membrane: and (3) pouring the composite membrane casting solution obtained in the step (2) into a self-made glass mold in a laboratory, casting to form a membrane, then placing the glass mold in a vacuum drying oven, and drying at 60 ℃ for 48 hours until the solvent is completely volatilized to obtain the side chain sulfonated polybenzimidazole hybrid modified membrane, wherein the membrane thickness is 60 microns.
Through detection, the composite cation exchange membrane prepared in the embodiment has the water content of 35%, the swelling rate of 7.9%, the hydrophilic contact angle of 53.2 degrees, the ion exchange capacity of 2.4 meq/g and the breaking strength of 26 MPa.
Example 5
(1) Synthesis of side chain sulfonated polybenzimidazole: dissolving 1 g of poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) (O-PBI) in 19 g of tetrahydrofuran, stirring at 40 ℃ for 12 hours, and filtering insoluble substances to obtain an O-PBI solution; introducing ozone for 30 min (ozone generation concentration of ozone generator is 4 g/h), pretreating with ozone for 30 min, cooling the reaction solution with ice bath, and introducing 30 min N2Removing oxygen and ozone in the solution; then, the solution is gradually heated to 100 ℃, 0.005 g of benzoyl peroxide is added, and sodium p-styrene sulfonate graft monomer solution is dropwise added(specifically, 6g of sodium styrene sulfonate is dissolved in 25 g of dimethyl sulfoxide), and the mixture is stirred and continuously reacted for 5 hours under the protection of nitrogen; after the reaction was completed, the reaction product was precipitated with 250 ml of methanol, and then the precipitate was repeatedly washed 4 times with 200 ml of deionized water and 150 ml of methanol in this order, and finally, the precipitate was dried to obtain a side chain sulfonated polybenzimidazole (S-PBI) homopolymer.
(2) Preparing a composite membrane casting solution: weighing 0.6 g of S-PBI synthesized in the step (1), adding the S-PBI into 5g of dimethyl sulfoxide, and stirring at 60 ℃ for 12 hours to obtain an S-PBI solution; adding 0.012 g of sulfonated titanium dioxide into 5g of dimethyl sulfoxide, and performing ultrasonic dispersion for 2 hours to obtain sulfonated titanium dioxide dispersion liquid; and adding the sulfonated titanium dioxide dispersion liquid into the S-PBI solution, and continuously stirring for 2 hours to obtain the composite membrane casting solution.
(3) Preparing a composite cation exchange membrane: and (3) pouring the composite membrane casting solution obtained in the step (2) into a self-made glass mold in a laboratory, casting to form a membrane, then placing the glass mold in a vacuum drying oven, and drying at 80 ℃ for 24 hours until the solvent is completely volatilized to obtain the side chain sulfonated polybenzimidazole hybrid modified membrane, wherein the membrane thickness is 80 microns.
Through detection, the composite cation exchange membrane prepared in the embodiment has the water content of 34%, the swelling rate of 8.2%, the hydrophilic contact angle of 56.6 degrees, the ion exchange capacity of 2.5 meq/g and the breaking strength of 28 MPa.
Example 6
(1) Synthesis of side chain sulfonated polybenzimidazole: dissolving 1 g of poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) (O-PBI) in a mixed solvent of 19 g of dimethyl sulfoxide and acetone (the mass is 15 g and 4 g respectively), stirring at 60 ℃ for 24 hours, and filtering insoluble substances to obtain an O-PBI solution; introducing ozone for 30 min (ozone generation concentration of ozone generator is 4 g/h), pretreating with ozone for 30 min, cooling the reaction solution with ice bath, and introducing 20 min N2Removing oxygen and ozone in the solution; then, the solution was gradually warmed up to 80 ℃, 0.002 g of benzoyl peroxide was added, and a sodium styrenesulfonate graft monomer solution (specifically, 3 g of sodium styrenesulfonate was dissolved in 20 g of dimethyl sulfoxide) was added dropwise under nitrogenStirring and continuously reacting for 4 hours under the protection of gas; after the reaction, the reaction product was precipitated with 150 ml of methanol, and then the precipitate was repeatedly washed 3 times with 200 ml of deionized water and 100 ml of methanol in this order, and finally, the precipitate was dried to obtain a side chain sulfonated polybenzimidazole (S-PBI) homopolymer.
(2) Preparing a composite membrane casting solution: weighing 0.8 g of S-PBI synthesized in the step (1), adding the S-PBI into 5g of N-methyl pyrrolidone, and stirring at 60 ℃ for 12 h to obtain an S-PBI solution; adding 0.032 g of sulfonated silicon dioxide into 8 g of dimethyl sulfoxide, and performing ultrasonic dispersion for 2 hours to obtain sulfonated silicon dioxide dispersion liquid; and adding the sulfonated silicon dioxide dispersion liquid into the S-PBI solution, and continuously stirring for 2 hours to obtain the composite membrane casting solution.
(3) Preparing a composite cation exchange membrane: and (3) pouring the composite membrane casting solution obtained in the step (2) into a self-made glass mold in a laboratory, casting to form a membrane, then placing the glass mold in a vacuum drying oven, and drying at 80 ℃ for 24 hours until the solvent is completely volatilized to obtain the side chain sulfonated polybenzimidazole hybrid modified membrane, wherein the membrane thickness is 90 microns.
Through detection, the composite cation exchange membrane prepared in the embodiment has the water content of 32%, the swelling rate of 7.8%, the hydrophilic contact angle of 59 degrees, the ion exchange capacity of 2.1 meq/g and the breaking strength of 22 MPa.
Example 7
(1) Synthesis of side chain sulfonated polybenzimidazole: dissolving 1 g of poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) (O-PBI) in 19 g of mixed solvent of dimethylformamide and dimethyl sulfoxide (the mass is 9 g and 10 g respectively), stirring at 40 ℃ for 12 hours, and filtering insoluble substances to obtain an O-PBI solution; introducing ozone for 45 min (ozone generation concentration of ozone generator is 4 g/h), pretreating with ozone for 45 min, cooling the reaction solution with ice bath, and introducing 30 min N2Removing oxygen and ozone in the solution; then, gradually heating the solution to 100 ℃, adding 0.005 g of benzoyl peroxide, dropwise adding a sodium p-styrene sulfonate graft monomer solution (specifically, 7 g of sodium p-styrene sulfonate is dissolved in 25 g of dimethyl sulfoxide), and continuously reacting for 5 hours under the protection of nitrogen while stirring; after the reaction is finished, methanol is used250 ml of the reaction product was precipitated, and then the precipitate was washed repeatedly 4 times with 200 ml of deionized water and 150 ml of methanol in this order, and finally, the precipitate was dried to obtain a side chain sulfonated polybenzimidazole (S-PBI) homopolymer.
(2) Preparing a composite membrane casting solution: weighing 0.6 g of S-PBI synthesized in the step (1), adding the S-PBI into 5g of dimethyl sulfoxide, and stirring at 60 ℃ for 12 hours to obtain an S-PBI solution; adding 0.03 g of sulfonated graphene oxide into 6g of dimethyl sulfoxide, and performing ultrasonic dispersion for 2 hours to obtain a sulfonated graphene oxide dispersion liquid; and adding the sulfonated graphene oxide dispersion liquid into the S-PBI solution, and continuously stirring for 2 hours to obtain the composite membrane casting solution.
(3) Preparing a composite cation exchange membrane: and (3) pouring the composite membrane casting solution obtained in the step (2) into a self-made glass mold in a laboratory, casting to form a membrane, then placing the glass mold in a vacuum drying oven, and drying at 80 ℃ for 24 hours until the solvent is completely volatilized to obtain the side chain sulfonated polybenzimidazole hybrid modified membrane, wherein the membrane thickness is 70 microns.
Through detection, the composite cation exchange membrane prepared in the embodiment has the water content of 41%, the swelling rate of 9.2%, the hydrophilic contact angle of 45.6 degrees, the ion exchange capacity of 3.2 meq/g and the breaking strength of 37 MPa.
The composite cation exchange membrane is used for electrodialysis treatment of heavy metal-containing chemical wastewater, and Cu in solution in a desalting chamber is treated by electrodialysis2+The removal rate of the ions reaches 98 percent, and most of copper ions can be removed; and the experiment process runs for 20 desalination periods, and only few inorganic pollutants are scaled on the membrane surface. In addition, the fracture strength of the composite membrane after operation is 34 MPa, and good physical stability is shown.
As can be seen from the above examples, the composite cation exchange membrane prepared by the invention has higher anti-pollution capacity, ion conductivity and water content, and lower swelling ratio, the water content of the composite cation exchange membrane is not less than 30%, the swelling ratio is not more than 9.5%, the hydrophilic contact angle is less than 62.5 degrees, the ion exchange capacity is not less than 1.8 meq/g, and the breaking strength is not less than 20 MPa. Therefore, the composite cation exchange membrane prepared by the method has excellent ion conduction capability, anti-pollution performance and mechanical stability; the ozone pre-activation-free radical initiation bulk grafting and sulfonated inorganic matter and organic matter blending composite modification technology is a simple and efficient synthesis technology for preparing the cation exchange membrane suitable for electrodialysis, and the method is simple to operate, convenient to control and low in cost, can realize large-scale industrial production, and is favorable for promoting large-scale practical application of electrodialysis in water treatment in the fields of food, chemical industry, medical treatment, seawater desalination and the like.
Comparative example 1
(1) Synthesis of side chain sulfonated polybenzimidazole: dissolving 1 g of poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) (O-PBI) in 19 g of tetrahydrofuran solvent, stirring at 40 ℃ for 12 h, and filtering insoluble substances to obtain an O-PBI solution; introducing ozone for 30 min (ozone generation concentration of ozone generator is 4 g/h), pretreating with ozone for 30 min, cooling the reaction solution with ice bath, and introducing 30 min N2Removing oxygen and ozone in the solution; then, gradually heating the solution to 100 ℃, adding 0.005 g of benzoyl peroxide, dropwise adding a sodium p-styrene sulfonate graft monomer solution (specifically, 6g of sodium p-styrene sulfonate is dissolved in 25 g of dimethyl sulfoxide), and stirring for continuous reaction for 5 hours under the protection of nitrogen; after the reaction was completed, the reaction product was precipitated using 250 ml of methanol, and then the precipitate was repeatedly washed 4 times with 200 ml of deionized water and 150 ml of methanol in this order, and finally, the precipitate was dried to obtain a side chain sulfonated polybenzimidazole (S-PBI) homopolymer.
(2) Preparing a casting solution: 0.6 g of S-PBI synthesized in the step (1) is weighed and added into 5g of dimethyl sulfoxide, and the mixture is stirred for 12 hours at the temperature of 60 ℃ to obtain membrane casting liquid.
(3) Preparation of cation exchange membrane: pouring the casting solution obtained in the step (2) into a self-made glass mold in a laboratory, casting to form a film, then placing the glass mold in a vacuum drying oven, and drying at 80 ℃ for 24 hours until the solvent is completely volatilized to obtain the side chain sulfonated polybenzimidazole film, wherein the film thickness is 80 microns.
Through detection, the water content of the cation exchange membrane prepared in the comparative example is 28%, the swelling rate is 7.8%, the hydrophilic contact angle is 70.7 degrees, the ion exchange capacity is 1.5 meq/g, and the breaking strength is 16 MPa.
Compared with example 5, the comparative example does not adopt doping modification of sulfonated inorganic substance, and from data, the side chain sulfonated polybenzimidazole membrane of the comparative example has lower ion conductivity and breaking strength and larger hydrophilic contact angle, which shows that the doping of the sulfonated inorganic substance can synchronously improve the anti-pollution capacity, ion conductivity and mechanical strength of the composite cation exchange membrane.
Comparative example 2
(1) Synthesis of side chain sulfonated polybenzimidazole: dissolving 1 g of poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) (O-PBI) in 19 g of tetrahydrofuran, stirring at 40 ℃ for 12 hours, and filtering insoluble substances to obtain an O-PBI solution; then, gradually heating the solution to 100 ℃, adding 0.005 g of benzoyl peroxide, dropwise adding a sodium p-styrenesulfonate grafted monomer solution (specifically, 6g of sodium styrene sulfonate is dissolved in 25 g of dimethyl sulfoxide), and stirring for continuous reaction for 5 hours under the protection of nitrogen; after the reaction, the reaction product was precipitated with 250 ml of methanol, and then the precipitate was repeatedly washed 4 times with 200 ml of deionized water and 150 ml of methanol in this order, and finally, the precipitate was dried to obtain a side chain sulfonated polybenzimidazole (S-PBI) homopolymer.
(2) Preparing a composite membrane casting solution: weighing 0.6 g of S-PBI synthesized in the step (1), adding the S-PBI into 5g of dimethyl sulfoxide, and stirring at 60 ℃ for 12 hours to obtain an S-PBI solution; adding 0.012 g of sulfonated titanium dioxide into 5g of dimethyl sulfoxide, and performing ultrasonic dispersion for 2 hours to obtain sulfonated titanium dioxide dispersion liquid; and adding the sulfonated titanium dioxide dispersion liquid into the S-PBI solution, and continuously stirring for 2 hours to obtain the composite membrane casting solution.
(3) Preparing a composite cation exchange membrane: and (3) pouring the composite membrane casting solution obtained in the step (2) into a self-made glass mold in a laboratory, casting to form a membrane, then placing the glass mold in a vacuum drying oven, and drying at 80 ℃ for 24 hours until the solvent is completely volatilized to obtain the side chain sulfonated polybenzimidazole hybrid modified membrane, wherein the membrane thickness is 80 microns.
Through detection, the composite cation exchange membrane prepared by the comparative example has the water content of 16 percent, the swelling ratio of 6.0 percent, the hydrophilic contact angle of 74 degrees, the ion exchange capacity of 0.2 meq/g and the breaking strength of 16 MPa.
This comparative example is different from example 5 in that: in the synthesis process of the side chain sulfonated polybenzimidazole in the step (1), ozone pretreatment is not adopted, so that sodium p-styrenesulfonate cannot be smoothly grafted onto the main chain of polybenzimidazole, and finally, the ion conductivity and the mechanical strength of the composite cation exchange membrane are low.
Comparative example 3
(1) Synthesis of side chain sulfonated polybenzimidazole: dissolving 1 g of poly (4, 4 '-diphenyl ether-5, 5' -biphenyl imidazole) (O-PBI) in 19 g of tetrahydrofuran, stirring at 40 ℃ for 12 hours, and filtering insoluble substances to obtain an O-PBI solution; then, gradually heating the solution to 100 ℃, adding 0.005 g of benzoyl peroxide, dropwise adding a sodium p-styrenesulfonate grafted monomer solution (specifically, 6g of sodium styrene sulfonate is dissolved in 25 g of dimethyl sulfoxide), and stirring for continuous reaction for 5 hours under the protection of nitrogen; after the reaction, the reaction product was precipitated with 250 ml of methanol, and then the precipitate was repeatedly washed 4 times with 200 ml of deionized water and 150 ml of methanol in this order, and finally, the precipitate was dried to obtain a side chain sulfonated polybenzimidazole (S-PBI) homopolymer.
(2) Preparing a casting solution: 0.6 g of S-PBI synthesized in the step (1) is weighed and added into 5g of dimethyl sulfoxide, and the solution is stirred for 12 hours at 60 ℃ to obtain an S-PBI solution.
(3) Preparation of cation exchange membrane: pouring the casting solution obtained in the step (2) into a self-made glass mold in a laboratory, carrying out casting film forming, then placing the glass mold in a vacuum drying oven, and carrying out drying treatment at 80 ℃ for 24 hours until the solvent is completely volatilized to obtain the side chain sulfonated polybenzimidazole hybrid modified membrane, wherein the membrane thickness is 80 microns.
Through detection, the composite cation exchange membrane prepared by the comparative example has the water content of 10 percent, the swelling ratio of 4.8 percent, the hydrophilic contact angle of 80 degrees, the ion exchange capacity of 0.05 meq/g and the breaking strength of 14 MPa.
This comparative example is different from example 5 in that: ozone pretreatment is not adopted in the step (1); inorganic matter doping modification is not used in the step (2), and finally, the ion conductivity and the mechanical strength of the composite cation exchange membrane are low.
It should be noted that: the method for preparing the sulfonated inorganic substance in the above examples is not limited thereto, and the sulfonated inorganic substance prepared by other process conditions or methods may be used.
Claims (10)
1. A preparation method of a side chain sulfonated polybenzimidazole composite cation exchange membrane is characterized by comprising the following steps:
(1) synthesis of side chain sulfonated polybenzimidazole: dissolving polybenzimidazole in a solvent, stirring for 6-24 h at 20-60 ℃, and filtering to obtain a polybenzimidazole solution; ozone is led into the polybenzimidazole solution for preactivation, N is led into the polybenzimidazole solution after cooling2Removing oxygen and ozone; then, heating to 80-100 ℃, adding benzoyl peroxide, adding sodium p-styrene sulfonate solution, and reacting for 2-6 h under the protection of inert gas; after the reaction is finished, precipitating the reactant by using a methanol solution, and then washing and drying to obtain the side chain sulfonated polybenzimidazole;
(2) preparing a composite membrane casting solution: adding the side chain sulfonated polybenzimidazole obtained in the step (1) into a solvent, and stirring for 6-12 h at the temperature of 20-70 ℃ to obtain an S-PBI solution; adding sulfonated inorganic substance into organic solvent to obtain sulfonated inorganic substance dispersion liquid; then adding the sulfonated inorganic substance dispersion liquid into the S-PBI solution, and uniformly mixing to obtain a composite membrane casting solution;
(3) preparing a composite cation exchange membrane: and (3) pouring the composite membrane casting solution obtained in the step (2) into a grinding tool, casting to form a membrane, and drying at the temperature of 60-80 ℃ for 24-48 h to obtain the composite membrane.
2. The method for preparing the cation exchange membrane with the sulfonated polybenzimidazole having side chains as claimed in claim 1, wherein the mass ratio of polybenzimidazole to sodium p-styrenesulfonate in step (1) is 1 (1-8).
3. The method for preparing the cation exchange membrane with the sulfonated polybenzimidazole having side chains as claimed in claim 1, wherein the addition amount of the sulfonated inorganic substance in the step (2) is 0.5-10% by mass of the sulfonated polybenzimidazole having side chains.
4. The method for preparing the cation exchange membrane with the sulfonated polybenzimidazole having side chains as claimed in claim 1 or 3, wherein the sulfonated inorganic substance in the step (2) is one or more of sulfonated silica, sulfonated titania, sulfonated graphene oxide and sulfonated zirconia.
5. The method for preparing the cation exchange membrane with the sulfonated polybenzimidazole having side chains as claimed in claim 1, wherein the concentration of ozone in step (1) is 2-6g/h, and the ozone treatment time is 15-45 min.
6. The method for preparing the cation exchange membrane with the sulfonated polybenzimidazole having side chains as claimed in claim 1, wherein the amount of benzoyl peroxide used in step (1) is 0.1-0.5% by mass of polybenzimidazole.
7. The method for preparing the cation exchange membrane with the sulfonated polybenzimidazole having side chains as claimed in claim 1, wherein the solvent in the steps (1) and (2) is one or more selected from the group consisting of dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and acetone.
8. The side chain sulfonated polybenzimidazole composite cation exchange membrane prepared by the method of any one of claims 1 to 7.
9. The side chain sulfonated polybenzimidazole composite cation exchange membrane according to claim 8, wherein the thickness of the composite cation exchange membrane is 60 to 120 μm.
10. Use of the composite cation exchange membrane according to claim 8 or 9 in electrodialysis treatment for treating domestic sewage, seawater and brackish water, and food and chemical product process water.
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