CN101314111B - Organic/inorganic hybridisation strong alkalinity anion exchange membrane and preparation method thereof - Google Patents

Abstract

An organic-inorganic hybrid strongly basic anion-exchange membrane and a preparation method thereof relate to an ion-exchange membrane and a preparation method thereof. It solves the problems of environmental pollution, unsafe operation process and poor product performance in the preparation of anion exchange membranes in the prior art. The organic-inorganic hybrid strongly basic anion exchange membrane of the present invention is composed of polyvinylidene fluoride, polyetheretherketone, divinylbenzene, ethylstyrene, dimethyl phthalate, organic solvents, nano-aluminum oxide particles, Made with Glycidyl Methacrylate and Benzoyl Peroxide. Method: 1. Weigh the required ingredients according to weight percentage; 2. Ultrasonic mixing of nano-alumina particles and organic solvent; 3. Add other ingredients to prepare casting solution; 4. Casting solution to form a film; After dipping and rinsing, put it into HCl solution for dipping, and then wash to get the organic-inorganic hybrid strongly basic anion exchange membrane. The invention does not pollute the environment, has safe operation process and good product performance.

Description

Organic-inorganic hybrid strongly basic anion exchange membrane and preparation method thereof

technical field

The present invention relates to an ion exchange membrane and its preparation method.

Background technique

The ion exchange membrane is a key component of the electrodialyzer. Since the anion exchange membrane is more complicated and difficult to prepare than the cation, and it is most likely to be contaminated by precipitation corrosion and organic substances during the electrodialysis process, it directly affects the life of the desalinator. Therefore, it is of special and important significance to carry out the development of anion exchange membranes.

At present, the preparation of anion exchange membranes adopts the process of "polymerization first - chloromethylation - reamination", but it has the following shortcomings that are difficult to overcome: (1) in the chloromethylation reaction, a large amount of methylene The secondary crosslinking of the bridge is generated, resulting in poor product performance, such as ion selective transmission coefficient of only 0.82 to 0.89, high membrane resistance, poor mechanical properties, and poor anti-pollution ability; (2) chloromethylated mother liquor contains easily Toxic substances such as volatilized chloromethyl ether, formaldehyde and hydrogen chloride seriously pollute the environment; (3) chloromethyl ether (especially dichloromethyl ether) is serious carcinogen, harmful to health, unsafe operation process, and harmful to the production of anion exchange resin And membrane development and production have brought a great impact.

Contents of the invention

The purpose of the present invention is to solve the problems of environmental pollution, unsafe operation process and poor product performance in the preparation of anion exchange membranes in the prior art, and provide an organic-inorganic hybrid strongly basic anion exchange membrane and a preparation method thereof.

The organic-inorganic hybrid strongly basic anion exchange membrane of the present invention consists of 5.0% to 30% of polyvinylidene fluoride, 1% to 20% of polyether ether ketone, 0.5% to 20% of divinylbenzene, and 1% by weight. ～20% ethyl styrene, 1%～10% dimethyl phthalate, 20%～80% organic solvent, 0.01%～4.0% nano-alumina particles, 1.0%～45% Glycidyl methacrylate and 0.05% to 2.0% benzoyl peroxide; the organic solvent is N, N-dimethylacetamide, N, N-dimethylformamide or dimethyl sulfoxide .

The method for preparing an organic-inorganic hybrid strongly basic anion exchange membrane is realized according to the following steps: 1. Weigh 5.0% to 30% of polyvinylidene fluoride, 1% to 20% of polyether ether ketone, 0.5% to 20% divinylbenzene, 1%~20% ethyl styrene, 1%~10% dimethyl phthalate, 20%~80% organic solvent, 0.01%~4.0% nano trioxide Dialuminum particles, 1.0% to 45% of glycidyl methacrylate and 0.05% to 2.0% of benzoyl peroxide; 2. Under the condition of ultrasonic vibration, add the weighed nanometer aluminum oxide particles into the weighing In the organic solvent that gets; Three, add glycidyl methacrylate, divinylbenzene, ethyl styrene, dimethyl phthalate, benzoyl peroxide that take by weighing in the organic solvent and evenly mix, Stand still for defoaming to obtain the casting solution; 4. Make a film from the casting solution on a glass plate at 20-30°C, dry it at 60-70°C for 2-3 hours, and then put it in 100- React at 110°C for 2 to 3 hours. After cooling at room temperature, soak in deionized water until the film falls off the glass plate, and then air dry the film naturally; Immerse in ~33.3% trimethylamine solution for 2~4 days, then rinse with deionized water, then put the membrane in 0.1mol/L HCl solution for 22~26 hours, then wash with deionized water to obtain organic and inorganic Hybrid strongly basic anion exchange membrane; wherein the organic solvent in step 1 is N, N-dimethylacetamide, N, N-dimethylformamide or dimethyl sulfoxide.

In the present invention, the use of volatile toxic substances is avoided, the environment is not polluted, and the carcinogenic substance chloromethyl ether is not used. The operation process is safe, the film forming process is simple, and it is easy to industrialize; the addition of nano-alumina particles improves the mechanical properties of the film. performance, the anti-pollution ability of the membrane is improved, the ion exchange capacity is increased by 8%, the membrane resistance is reduced by 11%, and the ion selective transmission coefficient is as high as 0.92-0.96. In the present invention, membranes with different properties are obtained by adjusting the ratio of various raw materials, and the obtained organic-inorganic hybrid strongly basic anion exchange membrane has wider application prospects.

Detailed ways

Specific implementation mode 1: In this embodiment, the organic-inorganic hybrid strongly basic anion exchange membrane consists of 5.0% to 30% polyvinylidene fluoride, 1% to 20% polyetheretherketone, 0.5% to 20% polyvinylidene fluoride, and 0.5% to 20% Divinylbenzene, 1%-20% ethyl styrene, 1%-10% dimethyl phthalate, 20%-80% organic solvent, 0.01%-4.0% nano-alumina particles , 1.0%~45% glycidyl methacrylate and 0.05%~2.0% benzoyl peroxide; the organic solvents are N,N-dimethylacetamide, N,N-dimethylformamide amide or dimethyl sulfoxide.

Embodiment 2: The difference between this embodiment and Embodiment 1 is that the organic-inorganic hybrid strongly basic anion exchange membrane consists of 10% polyvinylidene fluoride, 8% polyether ether ketone, and 9% di Vinyl benzene, 9% ethyl styrene, 4% dimethyl phthalate, 32% organic solvent, 2.0% nano aluminum oxide particles, 25% glycidyl methacrylate and 1.0% Made from benzoyl peroxide; wherein the organic solvent is N, N-dimethylacetamide, N, N-dimethylformamide or dimethyl sulfoxide. Others are the same as in the first embodiment.

In this embodiment, the molecular weight of the polyvinylidene fluoride is 350,000 to 500,000 Daltons.

Embodiment 3: This embodiment differs from Embodiment 1 or Embodiment 2 in that the average particle diameter of the nano-alumina particles is 5 nm to 100 nm. Others are the same as in the first or second embodiment.

Specific embodiment four: the method for preparing organic-inorganic hybrid strongly basic anion exchange membrane in this embodiment is realized by the following steps: 1. Weigh 5.0% to 30% polyvinylidene fluoride, 1% to 20% polyvinylidene fluoride by weight percentage Polyether ether ketone, 0.5%~20% divinylbenzene, 1%~20% ethyl styrene, 1%~10% dimethyl phthalate, 20%~80% organic solvent, 0.01 %~4.0% of nano-alumina particles, 1.0%~45% of glycidyl methacrylate and 0.05%~2.0% of benzoyl peroxide; 2. Under the condition of ultrasonic vibration, the weighed nano Al2O3 particles are added to the weighed organic solvent; 3. Add the weighed glycidyl methacrylate, divinylbenzene, ethyl styrene, dimethyl phthalate, After the benzoyl oxide is evenly mixed, let it stand for defoaming to obtain a casting solution; 4. Form a film from the casting solution on a glass plate at a temperature of 20 to 30°C, and dry it at a temperature of 60 to 70°C for 2 ～3h, then put it into the reaction at 100～110℃ for 2～3h, after cooling at room temperature, soak it in deionized water until the film falls off the glass plate automatically, and then air dry the film naturally; The membrane is immersed in a trimethylamine solution with a mass concentration of 5% to 33.3% for 2 to 4 days, then rinsed with deionized water, and then immersed in a HCl solution with a concentration of 0.1mol/L for 22 to 26 hours before use. Washing with ionic water to obtain an organic-inorganic hybrid strongly basic anion exchange membrane; wherein the organic solvent in step 1 is N,N-dimethylacetamide, N,N-dimethylformamide or dimethyl sulfoxide.

Embodiment 5: The difference between this embodiment and Embodiment 4 is that in step 1, 10% of polyvinylidene fluoride, 8% of polyetheretherketone, 9% of divinylbenzene, and 9% of Ethyl styrene, 4% dimethyl phthalate, 32% organic solvent, 2.0% nano-alumina particles, 25% glycidyl methacrylate and 1.0% benzoyl peroxide . Other steps and parameters are the same as those in Embodiment 4.

Embodiment 6: The difference between this embodiment and Embodiment 4 is that in Step 4, the casting solution is formed into a film on a glass plate at 25°C, dried at 65°C for 2.5h, and then placed in The reaction was carried out at 105°C for 2.5h. Other steps and parameters are the same as those in Embodiment 4.

Embodiment 7: The difference between this embodiment and Embodiment 4 is that in step 4, at room temperature, the membrane is immersed in a trimethylamine solution with a mass concentration of 30% for 3 days, then rinsed with deionized water, and then the membrane is placed Immerse in 0.1mol/L HCl solution for 24h and wash with deionized water. Other steps and parameters are the same as those in Embodiment 4.

Embodiment 8: The method for preparing an organic-inorganic hybrid strongly basic anion exchange membrane in this embodiment is realized by the following steps: 1. Weigh 10% polyvinylidene fluoride, 8% polyether ether ketone, 9% by weight percentage % of divinylbenzene, 9% of ethyl styrene, 4% of dimethyl phthalate, 32% of N,N-dimethylacetamide, 2.0% of aluminum oxide particles, 25% of Glycidyl methacrylate and 1.0% benzoyl peroxide; 2. Under the condition of ultrasonic vibration, the weighed nano-alumina particles are added to the weighed N,N-dimethylacetamide; 3. Add the weighed glycidyl methacrylate, divinylbenzene, ethylstyrene, dimethyl phthalate, and benzoyl peroxide to N,N-dimethylacetamide and mix evenly , standing for defoaming to obtain the casting solution; 4. Form the casting solution on a glass plate at 25°C to form a film, dry at 65°C for 2.5 hours, and then put it into the reaction at 105°C 2.5h, after cooling at room temperature, soak in deionized water until the film falls off the glass plate, and then air dry the film naturally; 5. Immerse the film in a trimethylamine solution with a mass concentration of 30% at room temperature for 3 days , and then rinsed with deionized water, and then immersed the membrane in a HCl solution with a concentration of 0.1mol/L for 24 hours, and then washed with deionized water to obtain an organic-inorganic hybrid strongly basic anion exchange membrane.

The organic-inorganic hybrid strongly basic anion exchange membrane obtained in this embodiment has been tested, and the ion selective transmission coefficient is as high as 0.95.

Claims (7)

1. Organic-inorganic hybrid strongly basic anion exchange membrane, characterized in that the organic-inorganic hybrid strongly basic anion-exchange membrane consists of 5.0% to 30% polyvinylidene fluoride and 1% to 20% polyether ether by weight percentage Ketone, 0.5%~20% divinylbenzene, 1%~20% ethyl styrene, 1%~10% dimethyl phthalate, 20%~80% organic solvent, 0.01%~4.0 % of nano-alumina particles, 1.0% to 45% of glycidyl methacrylate and 0.05% to 2.0% of benzoyl peroxide; the preparation method: 1. Weigh the above raw materials by weight percentage; 2. 1. Under the condition of ultrasonic vibration, add the weighed nano-alumina particles into the weighed organic solvent; 3. Add the weighed glycidyl methacrylate, divinylbenzene, ethyl Styrene, dimethyl phthalate, and benzoyl peroxide are evenly mixed, and left to defoam to obtain a casting solution; 4. Prepare the casting solution on a glass plate under the condition of 20-30°C The film is dried at 60-70°C for 2-3 hours, then placed in 100-110°C for 2-3 hours, cooled at room temperature, soaked in deionized water until the film falls off the glass plate automatically, Then the membrane is air-dried naturally; 5. At room temperature, the membrane is immersed in a trimethylamine solution with a mass concentration of 5% to 33.3% for 2 to 4 days, then rinsed with deionized water, and then the membrane is placed in a concentration of 0.1mol/ Immerse in HCl solution of L for 22-26 hours and wash with deionized water to obtain an organic-inorganic hybrid strong basic anion exchange membrane; the organic solvents are N, N-dimethylacetamide, N, N-dimethyl formamide or dimethylsulfoxide. 2. The organic-inorganic hybrid strongly basic anion-exchange membrane according to claim 1 is characterized in that the organic-inorganic hybrid strongly basic anion-exchange membrane consists of 10% polyvinylidene fluoride, 8% polyether by weight percentage Ether ketone, 9% divinylbenzene, 9% ethyl styrene, 4% dimethyl phthalate, 32% organic solvent, 2.0% nano-alumina particles, 25% methyl Glycidyl acrylate and 1.0% benzoyl peroxide; wherein the organic solvent is N, N-dimethylacetamide, N, N-dimethylformamide or dimethyl sulfoxide. 3. The organic-inorganic hybrid strongly basic anion exchange membrane according to claim 1 or 2, characterized in that the average particle diameter of the nano-alumina particles is 5nm-100nm. 4. prepare the method for organic-inorganic hybrid strongly basic anion-exchange membrane as claimed in claim 1, it is characterized in that the method for preparing organic-inorganic hybrid strongly basic anion-exchange membrane realizes by the following steps: one, by weight percent Take 5.0%~30% polyvinylidene fluoride, 1%~20% polyether ether ketone, 0.5%~20% divinylbenzene, 1%~20% ethyl styrene, 1%~10% Dimethyl phthalate, 20%-80% organic solvent, 0.01%-4.0% nano-alumina particles, 1.0%-45% glycidyl methacrylate and 0.05%-2.0% super Benzoyl oxidation; 2. Under the condition of ultrasonic vibration, add the weighed nano-aluminum oxide particles into the weighed organic solvent; 3. Add the weighed glycidyl methacrylate, Divinylbenzene, ethyl styrene, dimethyl phthalate, and benzoyl peroxide are evenly mixed, and left to stand for defoaming to obtain a casting solution; 4. Under the condition of 20-30°C, the casting solution Make a film on a glass plate, dry it at 60-70°C for 2-3 hours, then put it in a temperature of 100-110°C for 2-3 hours, cool it at room temperature, soak it in deionized water until the film The glass plate falls off automatically, and then the membrane is air-dried naturally; 5. At room temperature, the membrane is immersed in a trimethylamine solution with a mass concentration of 5% to 33.3% for 2 to 4 days, then rinsed with deionized water, and then placed on the membrane. immerse in HCl solution with a concentration of 0.1mol/L for 22 to 26 hours, and then wash with deionized water to obtain an organic-inorganic hybrid strong basic anion exchange membrane; wherein the organic solvent in step 1 is N,N-dimethylethane amide, N,N-dimethylformamide or dimethyl sulfoxide. 5. the method for preparing organic-inorganic hybrid strongly basic anion exchange membrane according to claim 4 is characterized in that in step 1, take by weight 10% polyvinylidene fluoride, 8% polyether ether ketone, 9% divinylbenzene, 9% ethyl styrene, 4% dimethyl phthalate, 32% organic solvent, 2.0% nano aluminum oxide particles, 25% glycidyl methacrylate Esters and 1.0% Benzoyl Peroxide. 6. The method for preparing an organic-inorganic hybrid strongly basic anion-exchange membrane according to claim 4, characterized in that in step 4, the casting solution is formed into a film on a glass plate under the condition of 25° C., at 65 It was dried under the condition of ℃ for 2.5h, and then placed in the condition of 105℃ for 2.5h to react. 7. The method for preparing organic-inorganic hybrid strongly basic anion-exchange membrane according to claim 4, characterized in that in step 5, at room temperature, the membrane is put into a trimethylamine solution with a mass concentration of 30% and immersed for 3d, Then rinse with deionized water, and then put the membrane into the HCl solution with a concentration of 0.1mol/L and soak it for 24h, and then wash it with deionized water.