Preparation method of bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane

Abstract

The present invention relates to a preparation method of a bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane, wherein a sulfonated polyaryletherketonesulfone (Am-SPAEKS) containing an amino group is prepared by affinity polycondensation reaction as a proton exchange membrane, and a cross-linked membrane is obtained by using bromoethoxy column [5] aromatic hydrocarbon as a cross-linking agent, wherein the mass ratio of aminosulfonated polyaryletherketonesulfone (Am-SPAEKS) to bromoethoxy column [5] aromatic hydrocarbon is 1:0.03-0.15. The cross-linked membrane prepared by the present invention has high thermal stability, oxidative stability and mechanical properties, and reduces the problem of easy cracking of proton exchange membrane in fuel cell operation. It provides a good application prospect for being used as a proton exchange membrane material in a fuel cell.

Description

Technical Field

[0001] The present invention relates to the field of proton exchange membrane fuel cells and supramolecular macrocycles, and specifically relates to a method for preparing a bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane. Technical Background

[0002] Fuel cells are now widely used in transportation, energy and factories. As a new generation of power generation technology, fuel cells are devices that convert chemical energy into electrical energy. They have the advantages of less pollution to the environment and high power generation efficiency.

[0003] Proton exchange membrane fuel cells are one of the most widely studied fuel cells. As an important core component of fuel cells, the performance of proton exchange membranes affects the efficiency and life of fuel cells. As the temperature rises during the operation of the fuel cell, the membrane will degrade at high temperatures. At the same time, high temperatures will reduce the water content in the membrane, causing cracks in the membrane. During the operation of the fuel cell, free radicals are generated, which will attack the proton exchange membrane, resulting in reduced mechanical properties and thermal stability of the membrane, thereby shortening the service life of the fuel cell. Therefore, the proton exchange membrane should have a high H + Electrical conductivity, excellent oxidation stability, thermal stability and mechanical properties.

[0004] Aromatic polymers have excellent thermodynamic stability, mechanical properties, and chemical stability, strong oxidation resistance, and low cost. 3 H can improve the proton transfer efficiency. Therefore, sulfonated aromatic polymers are considered as a substitute for proton exchange membranes in fuel cells.

[0005] Proton exchange membrane fuel cells can operate at 30℃-80℃. Compared with inorganic modification, the cross-linked network formation of the cross-linked membrane helps to improve the mechanical properties, thermal stability, oxidation stability and other advantages of the proton exchange membrane. As the core component of proton exchange membrane fuel cells, proton exchange membrane has received more and more attention. Summary of the invention

[0006] The present invention provides a method for preparing a bromoethoxy-column[5]arene / aminosulfonated polyaryletherketonesulfone cross-linked membrane and application thereof in a fuel cell. The prepared bromoethoxy-column[5]arene / aminosulfonated polyaryletherketonesulfone cross-linked membrane has high thermal stability, oxidation stability and mechanical properties, and has good application prospects for use as a proton exchange membrane material in a fuel cell.

[0007] The present invention comprises the following steps:

[0008] (1) The preparation method of aminosulfonated polyaryletherketonesulfone (Am-SPAEKS) is as follows: under nitrogen protection, a mol of bisphenol A is fully mixed with b mol of 2,2-bis(3-amino-4-hydroxyphenyl)propane, c mol of 4,4'-difluorobenzophenone (DFB), and d mol of 3,3'-disulfonated-4,4'-dichlorodiphenylsulfone. A quantitative amount of solvent, water-carrying agent, and salt-forming agent are added. Then, condensation reflux and mechanical stirring are turned on, and the temperature is raised to 130-140°C to start carrying water. The water-carrying agent is released after condensation reflux for 4-5 hours, and then the temperature is raised to 170-180°C, and the reaction is continued for 3-6 hours. Then, the generated viscous liquid is poured into 2 mol H 2 SO 4 Finally, the polymer was chopped, boiled and dried to obtain aminosulfonated poly(aryletherketonesulfone) (Am-SPAEKS), where a+b=c+d;

[0009] (2) Synthesis of bromoethoxy-column [5] aromatic hydrocarbons is as follows: Under nitrogen protection, 10.0 g of hydroquinone dihydroxyethyl ether and 31.5 g of triphenylphosphine are added to a round-bottom flask, and 250 mL of acetonitrile is added and stirred at 0°C. 39.8 g of carbon tetrabromide is dissolved in 20 mL of acetonitrile solution and added to the above solution, stirred for 4 h, and 200 mL of deionized water is added and stirred for 20 min to quench the reaction. The reaction product is then washed with methanol: water (3:2) and filtered to obtain the synthesized monomer 1,4-bis(2-bromoethoxy)benzene. 3 g of 1,4-bis(2-bromoethoxy)benzene and 842.3 mg of polyformaldehyde are added to a round-bottom flask, and 200 mL of dichloromethane is added and stirred at 0°C. 3 mL of boron trifluoride etherate was added, and the solution turned dark green. TCL spot plate detection was performed. The reaction was continued for 30 min. 200 mL of water and 5 g of NaOH were added and stirred for 4 h to quench the reaction. The bromoethoxy column [5] aromatic hydrocarbon was synthesized by ring formation. The crude product was extracted with dichloromethane, and the obtained organic layer was washed with MgSO 4 The mixture was dried, concentrated by rotary evaporation, and further purified by silica gel column chromatography (dichloromethane 100%) to obtain a white powder of bromoethoxy column [5] aromatic hydrocarbon (BrP [5]) (yield 20%);

[0010] (3) A method for preparing a bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane, comprising the following steps: first, preparing a solution containing aminosulfonated polyaryletherketonesulfone; second, preparing bromoethoxy-column [5] aromatic hydrocarbon; third, adding the solution of the first step dropwise into the solution of the second step, cross-linking at 30°C for 24 hours to obtain a casting solution; and fourth, laying a membrane using the casting solution obtained in the third step.

[0011] (4) Casting the casting solution on a clean glass plate of 8 cm×8 cm, drying in an oven at 60-80°C for 48-72 h, removing the membrane with deionized water, and then soaking in trimethylamine for 72 h, then soaking in 1 mol KOH for 48 h, and then acidifying with sulfuric acid for 24-48 h, and then washing with deionized water until the acid on the membrane surface is completely removed, thereby obtaining a bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked proton exchange membrane for fuel cells;

[0012] As a preferred embodiment, the method for preparing a bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane is characterized in that the solvent in the preferred step (1) is one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO);

[0013] As a preferred embodiment, the preparation method of a bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane is characterized in that the preparation method of the amino-containing sulfonated polyaryletherketonesulfone solution is: adding the amino-containing sulfonated polyaryletherketonesulfone into a solvent, stirring for 24-48 hours, and obtaining a uniform solution of the amino-containing sulfonated polyaryletherketonesulfone. The mass of the polymer in the amino-containing sulfonated polyaryletherketonesulfone solution is 0.3-0.6g. Preferably, the solvent is the solvent N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or cyclopentanesulfone.

[0014] As a preferred embodiment, the method for preparing a bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated poly(aryletherketonesulfone) cross-linked membrane is characterized in that the water-carrying agent in the preferred step (1) is benzene, xylene, petroleum ether or toluene.

[0015] As a preferred embodiment, the method for preparing a bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated poly(aryletherketonesulfone) cross-linked membrane is characterized in that the salt-forming agent in the preferred step (1) is potassium carbonate. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The sol-gel content of the bromoethoxy-column [5]arene / aminosulfonated poly(aryletherketonesulfone) cross-linked membrane is shown;

[0017] Figure 2 The oxidative stability of the bromoethoxy-column[5]arene / aminosulfonated poly(aryletherketonesulfone) cross-linked membrane is shown;

[0018] Figure 3 Shown are the mechanical properties of bromoethoxy-column[5]arene / aminosulfonated poly(aryletherketonesulfone) cross-linked membranes;

[0019] Figure 4Shown are the proton conductivity and activation energy of the bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated poly (aryletherketonesulfone) cross-linked membrane;

[0020] The following is a clear and complete description of the technical solution of the present invention, providing a detailed implementation method and a specific operation process. It must be pointed out that for researchers in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the scope of protection of the present invention.

[0021] Embodiment 1 comprises the following steps:

[0022] 1. Under nitrogen protection, 0.9 mol of bisphenol A, 0.1 mol of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 0.8 mol of 4,4'-difluorobenzophenone (DFB), and 0.2 mol of 3,3'-disulfonated-4,4'-dichlorodiphenyl sulfone were fully mixed. A certain amount of solvent, water-carrying agent, and salt-forming agent were added. Then, condensation reflux and mechanical stirring were turned on, and the temperature was raised to 130-140°C to start carrying water. The water-carrying agent was released after condensation reflux for 4-5 hours, and then the temperature was raised to 170-180°C, and the reaction was continued for 3-6 hours. Then, the generated viscous liquid was poured into 2 mol H 2 SO 4 Finally, the polymer was chopped, boiled and dried to obtain aminosulfonated poly(aryletherketonesulfone) (Am-SPAEKS);

[0023] 2. Under nitrogen protection, 10.0g of hydroquinone dihydroxyethyl ether and 31.5g of triphenylphosphine were added to a round-bottom flask, and 250mL of acetonitrile was added, and stirred at 0°C. 39.8g of carbon tetrabromide was dissolved in 20mL of acetonitrile solution, added to the above solution, stirred for 4h, and 200mL of deionized water was added, stirred for 20min, and the reaction was quenched. Then, the reaction product was washed with methanol: water (3:2), and the synthesized monomer 1,4-bis(2-bromoethoxy)benzene was filtered. 3g of 1,4-bis(2-bromoethoxy)benzene and 842.3mg of polyformaldehyde were added to a round-bottom flask, and 200mL of dichloromethane was added, and stirred at 0°C. 3 mL of boron trifluoride etherate was added, and the solution turned dark green. TCL spot plate detection was performed. The reaction was continued for 30 min. 200 mL of water and 5 g of NaOH were added and stirred for 4 h to quench the reaction. The bromoethoxy column [5] aromatic hydrocarbon was synthesized by ring formation. The crude product was extracted with dichloromethane, and the obtained organic layer was washed with MgSO 4 The mixture was dried, concentrated by rotary evaporation, and further purified by silica gel column chromatography (dichloromethane 100%) to obtain a white powder of bromoethoxy column [5] aromatic hydrocarbon (BrP [5]) (yield 20%);

[0024] 3. Weigh 0.3-0.6 g of aminosulfonated polyaryletherketonesulfone into a beaker, add 10 mL of N,N-dimethylformamide (DMF), and stir at room temperature for 24 hours to obtain a uniform solution. The preferred solvent includes but is not limited to N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO), dichloromethane (DCM).

[0025] 4. Weigh 9-45 mg of bromoethoxy column [5] aromatic hydrocarbon (BrP[5]) into a beaker, add 2 mL of N,N-dimethylformamide (DMF), and dissolve by ultrasonication. Add the solution in step 3 dropwise into step 4, and crosslink at 30°C for 24 hours to obtain a casting solution. The preferred solvent includes but is not limited to N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO), dichloromethane (DCM).

[0026] 5. Cast the casting liquid on a clean glass plate of 8 cm × 8 cm, dry it in an oven at 60-80°C for 48-72 hours, remove the membrane with deionized water, and then soak it in trimethylamine for 72 hours, then soak it in 1 mol KOH for 48 hours, and then acidify it with sulfuric acid for 24-48 hours, and then wash it with deionized water until the acid on the membrane surface is completely removed, to obtain a bromoethoxy-coated [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked proton exchange membrane for fuel cells. The obtained bromoethoxy-coated [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane was tested at 80°C. By comparison, the conductivity of the cross-linked membrane was 0.039-0.088S cm -1 The film thickness is 35 μm and the conductivity is 0.017-0.039 S cm-1 at 30 °C. -1 .

[0027] Specific Example 1 The sol-gel content of the prepared bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated poly (aryl ether ketone sulfone) cross-linked membrane is as follows: Figure 1 As shown in the figure, it can be seen that with the addition of bromoethoxy [5] aromatic hydrocarbon crosslinking agent, the gel content of the crosslinked membrane increases, proving that bromoethoxy [5] aromatic hydrocarbon / aminosulfonated poly (aryletherketonesulfone) crosslinked membrane has been prepared.

[0028] Specific Example 1 The oxidative stability of the prepared bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated poly (aryletherketonesulfone) cross-linked membrane is as follows Figure 2 As shown in the figure, it can be seen that with the extension of time, the oxidation stability of the cross-linked membrane is stronger than that of the pure membrane, which indicates that the addition of the cross-linking agent significantly improves the oxidation stability of the proton exchange membrane.

[0029] The mechanical properties of the prepared bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated poly (aryletherketonesulfone) cross-linked membrane are as follows: Figure 3 As shown in the figure, it can be seen that with the increase of cross-linking agent content, the stress and strain of the cross-linked membrane are stronger than those of the pure membrane, which indicates that the addition of cross-linking agent can significantly improve the mechanical properties of the proton exchange membrane.

[0030] Specific Example 1 The proton conduction and activation energy of the prepared bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated poly (aryl ether ketone sulfone) cross-linked membrane are as follows Figure 4 As shown, Figure 4 a is the proton conduction of the cross-linked membrane, Figure 4 b is the activation energy of the cross-linked membrane. The results show that with the increase of the cross-linking agent content, the proton conductivity of the cross-linked membrane will decrease. This is because the increase of the cross-linking agent content makes the cross-linked network more compact, the proton transmission channel is reduced, and the proton conductivity is reduced. When the cross-linking agent content is 7%, the conductivity of the cross-linked membrane reaches the highest, and the maximum conductivity is 0.088S cm -1 , the minimum activation energy is 11.91KJ / mol.

Claims

1. A method for preparing a bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane, characterized in that: The method comprises the following steps:

1. The preparation method of aminosulfonated polyaryletherketonesulfone (Am-SPAEKS) is as follows: under nitrogen protection, a mol of bisphenol A is fully mixed with b mol of 2,2-bis(3-amino-4-hydroxyphenyl)propane, c mol of 4,4'-difluorobenzophenone (DFB), and d mol of 3,3'-disulfonated-4,4'-dichlorodiphenylsulfone; a quantitative amount of solvent, water-carrying agent and salt-forming agent are added, and then condensation reflux and mechanical stirring are turned on, the temperature rises to 130-140°C to start carrying water, and the water-carrying agent is released during condensation reflux for 4-5h, and then the temperature is raised to 170-180°C, and the reaction is continued for 3-6h, and then the generated viscous liquid is poured into a 2molH2SO4 solution; finally, the polymer is cut into pieces, boiled and dried to obtain aminosulfonated polyaryletherketonesulfone (Am-SPAEKS), wherein a+b=c+d; 2. Synthesis of bromoethoxy-column [5] aromatic hydrocarbons is as follows: under nitrogen protection, 10.0 g of hydroquinone dihydroxyethyl ether and 31.5 g of triphenylphosphine are added to a round-bottom flask, and 250 mL of acetonitrile is added and stirred at 0°C; 39.8 g of carbon tetrabromide is dissolved in 20 mL of acetonitrile solution and added to the above solution, stirred for 4 h, 200 mL of deionized water is added, stirred for 20 min, the reaction is quenched, and then the reaction product is washed with methanol: water (3:2), and the synthesized monomer 1,4-bis(2-bromoethoxy)benzene is filtered off; 3 g of 1,4-bis(2-bromoethoxy)benzene, 842.3 mg Add the polyformaldehyde into a round-bottom flask, add 200 mL of dichloromethane, and stir at 0°C; add 3 mL of boron trifluoride etherate, the solution turns dark green, TCL spot plate detection, react for 30 minutes, add 200 mL of water and 5 g of NaOH, stir for 4 hours to quench the reaction, and form a ring to synthesize bromoethoxy column [5] aromatic hydrocarbons. Extract the crude product with dichloromethane, dry the obtained organic layer with MgSO4, and then concentrate it by rotary evaporation. Further purify it by silica gel column chromatography (dichloromethane 100%) to obtain bromoethoxy column [5] aromatic hydrocarbons (BrP[5]) as a white powder (yield 20%); 3. A method for preparing a bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane, comprising the following steps: first, preparing a solution containing aminosulfonated polyaryletherketonesulfone; second, preparing a bromoethoxy-column [5] aromatic hydrocarbon solution; third, adding the solution of the first step dropwise into the solution of the second step, cross-linking at 30°C for 24 hours to obtain a casting solution; and fourth, laying a membrane using the casting solution obtained in the third step to obtain a bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane.

2. The method for preparing the bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane according to claim 1, characterized in that: The raw materials of the aminosulfonated polyaryletherketonesulfone preparation method are 2.0546g of bisphenol A, 0.2583g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1.7456g of 4,4'-difluorobenzophenone (DFB) and 0.982g of 3,3'-disulfonated-4,4'-dichlorodiphenyl sulfone.

3. The method for preparing the bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane according to claim 2, characterized in that: The solvent in the preparation method of aminosulfonated polyaryletherketonesulfone includes N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or cyclopentane sulfone, the salt-forming agent is anhydrous potassium carbonate, and the water-carrying agent is benzene, xylene, petroleum ether or toluene.

4. The method for preparing the bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane according to claim 1, characterized in that: In the preparation method of the bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane, the concentration of the aminosulfonated polyaryletherketonesulfone solution is 0.3-0.6 g / 10 mL, the concentration of the bromoethoxy column [5] aromatic hydrocarbon solution is 9-45 mg / 2 mL, and the preparation solvent of the solution is N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide.

5. The method for preparing the bromoethoxy-column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked membrane according to claim 1, characterized in that: The specific operation steps of the casting liquid membrane are as follows: casting the casting liquid on a clean glass plate of 8cm×8cm, drying in an oven at 60-80°C for 48-72h, removing the membrane with deionized water, and then soaking in trimethylamine for 72h, then soaking in 1mol KOH for 48h, and then acidifying with sulfuric acid for 24-48h, and then washing with deionized water until the acid on the membrane surface is completely removed, thereby obtaining a bromoethoxy column [5] aromatic hydrocarbon / aminosulfonated polyaryletherketonesulfone cross-linked proton exchange membrane for fuel cells.

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