CN113067022A - Amino-containing sulfonated polyaryletherketone sulfone blended metal organic framework composite membrane and preparation method thereof - Google Patents
Amino-containing sulfonated polyaryletherketone sulfone blended metal organic framework composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an amino-containing sulfonated polyaryl ether ketone sulfone blended ZIF-67 metal organic framework composite proton exchange membrane, wherein the mass ratio of the amino-containing sulfonated polyaryl ether ketone sulfone to ZIF-67 is 1: 0.05-0.15. The ZIF-67 crystal prepared by a conventional solution method is formed by bridging 2-methylimidazole and cobalt ions and has an SDO type topological structure. Meanwhile, ZIF-67 has an open framework structure and a regular pore structureHas excellent chemical stability and thermal stability. The amino group in the sulfonated polyaryletherketone sulfone containing the amino group and the cobalt ion contained in the ZIF-67 have good coordination effect, so that a compact ZIF-67 hybrid membrane is formed, and the proton transmission capability of the composite membrane can be improved. ZIF-67 may also enhance the thermal, dimensional and chemical stability of the composite membrane. The experimental results show that the hybrid membrane of the invention is 80oProton conductivity at C of 0.044S cm‑1‑0.116 S cm‑1The thickness of the hybrid membrane is 35-65 μm.
Description
Technical Field
The invention belongs to the two fields of proton exchange membrane fuel cells and polymer chemistry, and particularly relates to an amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane and a preparation method thereof.
Background
The pem is the "heart" of a pem fuel cell, and its role in the fuel cell is twofold. Currently, the most commonly used proton exchange membrane is commercial perfluorosulfonic acid resin (Nafion), but the high price and complex process of Nafion also limit the commercialization of Nafion membranes. Therefore, the fluorine-free sulfonated aromatic polymer electrolyte membrane material has become the most potential PEM material due to its excellent thermal stability, chemical stability and mechanical properties. The sulfonated aromatic polymer electrolyte membrane with the sulfonic acid side chain is prepared on the same molecular chain by introducing the flexible side chain segment, has higher proton conductivity and better stability, and the sulfonated polyaryletherketone sulfone has simple preparation method and lower cost, and has the most development prospect as a proton exchange membrane material. Meanwhile, the introduction of long side chains with sulfonic acid groups can form obvious hydrophilic and hydrophobic microphase separation structures, thereby improving the dimensional stability of the membrane. However, sulfonated polyaryletherketone sulfones with increasing degrees of sulfonation lead to excessive swelling on water absorption, so that their dimensional stability is reduced.
In order to overcome the difficulties of mechanical property reduction of proton exchange membranes caused by high sulfonation degree, metal-organic frameworks (MOFs) attract the attention of researchers. The metal-organic framework has the remarkable advantages of tunable pore structure, controllable object molecules and modifiable functional groups, and the ZIF-67 is formed by bridging 2-methylimidazole and diamond ions and has an SOD (super oxide dismutase) type topological structure. Due to excellent chemical stability and thermal stability, the ZIF-67 has a certain application prospect in the field of proton exchange membranes. Particularly, cobalt ions contained in ZIF-67 can have a good coordination effect with amino groups in sulfonated polyaryletherketone sulfone containing amino groups, and a proton exchange hybrid membrane with good compactness is formed. Meanwhile, ZIF-67 has hydrophobicity, can form an obvious hydrophilic-hydrophobic microphase separation structure with sulfonated polyaryletherketone containing amino, and improves the proton conductivity of the hybrid membrane.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention mainly aims to provide a novel sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane containing amino and a preparation method thereof. According to the invention, 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) is grafted to a polymer main chain to form a sulfonated polyaryletherketone sulfone membrane containing alkyl long side chains, so that an obvious hydrophilic-hydrophobic microphase separation structure is formed, the water swelling behavior of the membrane is inhibited, and the membrane has good dimensional stability. ZIF-67 is introduced as a proton carrier, so that the proton conductivity, the dimensional stability and the mechanical property of the composite proton exchange membrane can be effectively improved, and the preparation process is simple; metal-organic frameworks (MOFs) have attracted much attention as a new crystalline porous material due to their significant advantages of adjustable pore structure, controllable guest molecules, abundant active sites and modifiable functional groups. Cobalt ions contained in the ZIF-67 can have a good coordination effect with amino groups in sulfonated polyaryletherketone sulfone containing amino groups, and a compact proton exchange hybrid membrane with good performance is formed. Meanwhile, the introduction of MOFs can also improve the dimensional stability, mechanical property and chemical stability of the composite film. The invention is realized by the following technical scheme:
the invention provides a novel amino-containing functionalized sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane, which is composed of amino-containing sulfonated polyaryletherketone sulfone grafted 2-acrylamide-2-methylpropanesulfonic acid and ZIF-67, wherein the mass ratio of the amino-containing sulfonated polyaryletherketone sulfone to the ZIF-67 is 1: 0.05-0.15.
In the scheme, the thickness of the composite proton exchange membrane is 35-65 μm.
The invention also provides a preparation method of the amino-containing novel functionalized sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane, which comprises the following steps:
the method comprises the following steps: preparing sulfonated polyaryletherketone sulfone containing amino into a sulfonated polyaryletherketone sulfone solution containing amino;
step two: adding a proper amount of ZIF-67 into the sulfonated polyaryletherketone sulfone solution containing amino groups obtained in the step one;
step three: adding 2-acrylamide-2-methylpropanesulfonic acid into the solution;
step four: adding benzoyl peroxide into the solution to obtain a membrane casting solution;
step five: spreading the membrane casting solution obtained in the fourth step to obtain an amino-containing polyaryletherketone sulfone blended ZIF-67 metal organic framework composite proton exchange membrane for the fuel cell;
preferably, the bisphenol monomer is bisphenol A, bisphenol S, hexafluorobisphenol A, phenolphthalein, tetramethylbiphenol or tert-butylhydroquinone.
Preferably, the solvent is one of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) or Dimethylsulfoxide (DMSO);
preferably, the water-carrying agent is toluene;
in the above scheme, the preparation method of the sulfonated polyaryletherketone sulfone solution containing amino groups in the first step comprises:
adding the sulfonated polyaryletherketone sulfone containing amino into a solvent at room temperature, and stirring for 24 hours to obtain a uniform solution of the sulfonated polyaryletherketone sulfone containing amino. The mass volume fraction of the sulfonated polyaryletherketone sulfone solution containing amino is 0.06-0.12 g/mL. Preferably, the solvent is one of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) or Dimethylsulfoxide (DMSO);
in the above scheme, the preparation method of the membrane casting solution in the second step comprises:
adding ZIF-67 into an amino-containing sulfonated polyaryletherketone sulfone solution, carrying out ultrasonic dispersion for 4 hours, and continuously stirring for 1-2 days to obtain a uniformly dispersed solution. Wherein the mass ratio of the sulfonated polyaryletherketone sulfone containing amino to ZIF-67 is 1:0.05 to 0.15;
in the above scheme, the third step specifically comprises:
adding 2-acrylamide-2-methylpropanesulfonic acid into a solution of sulfonated polyaryletherketone sulfone containing amino blended ZIF-67 metal organic framework, and stirring at room temperature in a dark place for 8 hours. The mass ratio of the sulfonated polyaryletherketone sulfone containing amino to the 2-acrylamide-2-methylpropanesulfonic acid is 2:1;
in the above scheme, the fourth step specifically comprises:
adding benzoyl peroxide into a solution of sulfonated polyaryletherketone sulfone blend ZIF-67 metal organic framework containing amino, and stirring for 2 hours at room temperature in a dark place. The mass ratio of 2-acrylamide-2-methylpropanesulfonic acid to benzoyl peroxide is 10:1, and then the casting solution is obtained;
in the above scheme, the fifth step specifically comprises:
casting the membrane solution on a clean glass plate of 8 cm multiplied by 8 cm, and placing the glass plate on a glass plate of 80 cmoDrying in an oven for 48 hours, removing the membrane by using deionized water, then acidizing for 48 hours by using sulfuric acid, and then cleaning by using deionized water until the surface of the membrane is acid-removed, thereby obtaining the novel amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite proton exchange membrane for the fuel cell;
in the scheme, the preparation method of the quaternary sulfonated polyaryletherketone sulfone containing amino comprises the following steps:
under the conditions of nitrogen protection, condensation reflux and mechanical stirring, adding a mol of amino monomer, b mol of 4,4 '-difluorobenzophenone, c mol of 4, 4' -sulfonated dichlorodiphenyl sulfone and d mol of bisphenol monomer into a three-neck flask (100ml), then adding a proper amount of solvent, water-carrying agent and salt-forming agent into the three-neck flask, and raising the temperature to 120-130%oC, carrying out water carrying, discharging the water carrying agent after condensing and refluxing for 4-6 hours, and then raising the temperature to 170-175 DEG CoC, continuing the reactionAnd (4) discharging the solution after 4-5 hours until the solution is viscous in deionized water to obtain the sulfonated polyaryletherketone sulfone containing amino. Wherein a + d = b + c;
preferably, the bisphenol monomer is preferably bisphenol a, bisphenol S, hexafluorobisphenol a, phenolphthalein, tetramethylbiphenol or tert-butylhydroquinone, more preferably bisphenol S, the amino monomer is 4-aminophenylhydroquinone, the solvent is sulfolane, the salt forming agent is anhydrous potassium carbonate, and the water-carrying agent is toluene;
in the scheme, the preparation method of the ZIF-67 metal organic framework comprises the following steps:
dissolving cobalt nitrate hexahydrate in a proper amount of deionized water; meanwhile, 2-methylimidazole is dissolved in an appropriate amount of deionized water. The cobalt nitrate hexahydrate solution was slowly added dropwise to the 2-methylimidazole solution with stirring, and the mixture was magnetically stirred at room temperature for 6 hours. Finally, the solution was washed centrifugally, three times with water and three times with methanol. At 80 oCThe vacuum oven is placed for 24 hours for drying, and a ZIF-67 product is obtained;
preferably, the molar ratio of cobalt nitrate hexahydrate to deionized water in ZIF-67 is 1.55:3, and the molar ratio of 2-methylimidazole to deionized water is 67:20;
compared with the prior art, the invention has the following beneficial effects:
the invention firstly provides an amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite proton exchange membrane for a fuel cell. Wherein the mass ratio of the sulfonated polyaryletherketone sulfone containing amino to ZIF-67 is 1: 0.05-0.15. 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) is grafted to a polymer main chain to prepare the sulfonated polyaryletherketone sulfone membrane containing alkyl long side chains, so that an obvious hydrophilic-hydrophobic microphase separation structure is formed, the water swelling behavior of the membrane is inhibited, and the good dimensional stability of the membrane is ensured. The ZIF-67 crystal prepared by a conventional solution method is formed by bridging 2-methylimidazole and cobalt ions and has an SDO type topological structure. ZIF-67 has open skeleton structure and regular pore structure, has excellent chemical stability and thermal stability. The amino group in the sulfonated polyaryletherketone containing the amino group and the cobalt ion contained in the ZIF-67 have better coordination effectThereby forming a compact ZIF-67 hybrid membrane and improving the proton transmission capability of the composite membrane. Meanwhile, ZIF-67 can also enhance the thermal stability, dimensional stability and chemical stability of the composite membrane. The experimental results show that the hybrid membrane of the invention is 80oProton conductivity at C of 0.044S cm-1-0.116 S cm-1The thickness of the hybrid membrane is 35-65 μm.
Drawings
FIG. 1 is a graph showing the proton conductivity of pure novel sulfonated polyaryletherketone sulfones with amino groups, hybrid membranes prepared in example 1, example 2 and example 3;
FIG. 2 is a graph showing the change in thermal stability of ZIF-67 in the present invention;
FIG. 3 is a graph showing the variation of thermal stability of pure novel sulfonated polyaryletherketone sulfones with amino groups, hybrid membranes prepared in example 1, example 2 and example 3.
Detailed description of the invention
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a novel sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite proton exchange membrane containing amino groups for a fuel cell comprises the following specific steps:
(1) adding 0.2 mol of amino-containing bisphenol monomer, 0.8 mol of 4,4 '-difluorobenzophenone, 0.8 mol of bisphenol monomer and 0.2 mol of 4, 4' -sulfonated dichlorodiphenyl sulfone into a 100ml three-neck flask, uniformly mixing, adding anhydrous potassium carbonate, toluene and sulfolane into the three-neck flask, and carrying out 120-130 times of condensation reflux and mechanical stirring under the protection of nitrogenoC, carrying out water carrying for 4-6 hours, discharging the water carrying agent, and raising the temperature to 175-180 DEG CoAnd C, continuously reacting for 4-6 hours until the reaction solution becomes viscous, and discharging the reaction solution into deionized water to obtain the sulfonated polyaryletherketone sulfone containing amino, wherein the bisphenol monomer containing amino is 4-aminophenyl hydroquinone. The bisphenol monomer is preferably bisphenol A, bisphenol S, hexafluorobisphenol A, phenolphthalein, tetramethylbiphenol or tert-butylhydroquinone, and is more preferably allyl bisphenol S. The water-carrying agent is toluene;
(2) weighing 450 mg of cobalt nitrate hexahydrate and dissolving the cobalt nitrate hexahydrate in 3 ml of deionized water; meanwhile, 5.5 g of 2-methylimidazole was weighed out and dissolved in 20 ml of deionized water. The cobalt nitrate hexahydrate solution was slowly added dropwise to the 2-methylimidazole solution with stirring, and the mixture was magnetically stirred at room temperature for 6 hours. Finally, the solution was washed centrifugally, three times with water and three times with methanol. At 80oC, placing the mixture in a vacuum oven for 24 hours for drying to obtain a ZIF-67 product;
(3) 0.3 g of sulfonated polyaryletherketone sulfone containing amino groups is weighed into a beaker, 8 ml of N-methyl-2-pyrrolidone (NMP) solvent is added, and the mixture is stirred at room temperature for 24 hours to obtain a uniform solution. The solvent preferably has a boiling point of 150oC or higher, including but not limited to N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), or Dimethylsulfoxide (DMSO);
(4) 0.015 g of ZIF-67 was weighed and added to the homogeneous solution of step (3). Ultrasonically dispersing for 4 hours, and then continuing to magnetically stir for 48 hours, wherein the mass ratio of ZIF-67 to sulfonated polyaryletherketone sulfone containing amino in the mixed solution is 0.05:1;
(5) 0.15 g of 2-acrylamido-2-methylpropanesulfonic acid was weighed out and added to the homogeneous solution of step (4), protected from light and magnetically stirred for 8 hours. Wherein the mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the sulfonated polyaryletherketone sulfone containing amino in the mixed solution is 1:2;
(6) 0.015 g of benzoyl peroxide was weighed into the homogeneous solution of step (5) and magnetic stirring was continued for 2 hours in the dark. Wherein the mass ratio of the benzoyl peroxide to the 2-acrylamide-2-methylpropanesulfonic acid in the mixed solution is 1:10;
casting the casting solution obtained in the step (6) onto a clean glass plate of 8 cm multiplied by 8 cm, and placing the glass plate into a casting mold of 80 cmoDrying in an oven for 48 hours, naturally cooling to room temperature, then demoulding in deionized water, acidizing with 2 mol/L sulfuric acid for 48 hours, and then repeatedly washing in deionized water to remove residual sulfuric acid, thus obtaining the amino-containing polyaryletherketone sulfone blended ZIF-67 composite proton exchange membrane;
will getThe obtained sulfonated polyaryletherketone sulfone containing amino is blended with ZIF-67 composite proton exchange membrane at 80oThe conductivity of the proton exchange composite membrane is 0.103S cm when tested under C-1Film thickness 35 μm at 30oThe conductivity of the product is 0.066S cm when tested under C-1。
Example 2
(1) Adding 0.2 mol of amino-containing bisphenol monomer, 0.8 mol of 4,4 '-difluorobenzophenone, 0.8 mol of bisphenol monomer and 0.2 mol of 4, 4' -sulfonated dichlorodiphenyl sulfone into a 100ml three-neck flask, uniformly mixing, adding anhydrous potassium carbonate, toluene and sulfolane into the three-neck flask, and stirring under the conditions of nitrogen protection, condensation reflux and mechanical stirring for 110-130%oC, carrying out water carrying for 4-6 hours, discharging the water carrying agent, and raising the temperature to 170-175 DEG CoAnd C, continuously reacting for 4-6 hours until the reaction solution becomes viscous, and discharging the reaction solution into deionized water to obtain the sulfonated polyaryletherketone sulfone containing amino, wherein the bisphenol monomer containing amino is 4-aminophenyl hydroquinone. The bisphenol monomer is preferably bisphenol A, bisphenol S, hexafluorobisphenol A, phenolphthalein, tetramethylbiphenol or tert-butylhydroquinone, and is more preferably allyl bisphenol S. The water-carrying agent is toluene;
(2) weighing 450 mg of cobalt nitrate hexahydrate and dissolving the cobalt nitrate hexahydrate in 3 ml of deionized water; meanwhile, 5.5 g of 2-methylimidazole was weighed out and dissolved in 20 ml of deionized water. The cobalt nitrate hexahydrate solution was slowly added dropwise to the 2-methylimidazole solution with stirring, and the mixture was magnetically stirred at room temperature for 6 hours. Finally, the solution was washed centrifugally, three times with water and three times with methanol. Placing the mixture in a vacuum oven at the temperature of 80 ℃ for 24 hours for drying to obtain a ZIF-67 product;
(3) 0.3 g of sulfonated polyaryletherketone sulfone containing amino groups is weighed into a beaker, 8 ml of N-methyl-2-pyrrolidone (NMP) solvent is added, and the mixture is stirred at room temperature for 24 hours to obtain a uniform solution. The solvent preferably has a boiling point of 150oC or higher, including but not limited to N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), or Dimethylsulfoxide (DMSO);
(4) 0.03 g of ZIF-67 was weighed and added to the homogeneous solution of step (3). Ultrasonic dispersion was carried out for 4 hours, and then magnetic stirring was continued for 48 hours. Wherein the mass ratio of ZIF-67 to sulfonated polyaryletherketone sulfone containing amino in the mixed solution is 0.1:1;
(5) 0.15 g of 2-acrylamido-2-methylpropanesulfonic acid was weighed out and added to the homogeneous solution of step (4), protected from light and magnetically stirred for 8 hours. Wherein the mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the sulfonated polyaryletherketone sulfone containing amino in the mixed solution is 1:2;
(6) 0.015 g of benzoyl peroxide was weighed into the homogeneous solution of step (5) and magnetic stirring was continued for 2 hours in the dark. Wherein the mass ratio of the benzoyl peroxide to the 2-acrylamide-2-methylpropanesulfonic acid in the mixed solution is 1:10;
casting the casting solution obtained in the step (6) onto a clean glass plate of 8 cm multiplied by 8 cm, and placing the glass plate into a casting mold of 80 cmoDrying in an oven for 48 hours, naturally cooling to room temperature, then demoulding in deionized water, acidizing with 2 mol/L sulfuric acid for 48 hours, and then repeatedly washing in deionized water to remove residual sulfuric acid, thus obtaining the sulfonated polyaryletherketone sulfone blended ZIF-67 composite proton exchange membrane containing amino;
the obtained sulfonated polyaryletherketone sulfone containing amino and a loaded ZIF-67 composite proton exchange membrane are mixed at 80oThe conductivity of the proton exchange composite membrane is 0.115S cm when tested under C-1Film thickness 35 μm at 30oThe conductivity of the product is 0.069S cm when tested under C-1。
Example 3
(1) Adding 0.2 mol of amino-containing bisphenol monomer, 0.8 mol of 4,4 '-difluorobenzophenone, 0.8 mol of bisphenol monomer and 0.2 mol of 4, 4' -sulfonated dichlorodiphenyl sulfone into a 100ml three-neck flask, uniformly mixing, adding anhydrous potassium carbonate, toluene and sulfolane into the three-neck flask, and stirring under the conditions of nitrogen protection, condensation reflux and mechanical stirring for 110-130%oC, carrying out water carrying for 4-6 hours, discharging the water carrying agent, and raising the temperature to 170-175 DEG CoAnd C, continuously reacting for 4-6 hours until the reaction solution becomes viscous, and discharging the reaction solution into deionized water to obtain the sulfonated polyaryletherketone sulfone containing amino, wherein the bisphenol monomer containing amino is 4-aminophenyl hydroquinone.The bisphenol monomer is preferably bisphenol A, bisphenol S, hexafluorobisphenol A, phenolphthalein, tetramethylbiphenol or tert-butylhydroquinone, and is more preferably allyl bisphenol S. The water-carrying agent is toluene;
(2) weighing 450 mg of cobalt nitrate hexahydrate and dissolving the cobalt nitrate hexahydrate in 3 ml of deionized water; meanwhile, 5.5 g of 2-methylimidazole was weighed out and dissolved in 20 ml of deionized water. The cobalt nitrate hexahydrate solution was slowly added dropwise to the 2-methylimidazole solution with stirring, and the mixture was magnetically stirred at room temperature for 6 hours. Finally, the solution was washed centrifugally, three times with water and three times with methanol. At 80oC, placing the mixture in a vacuum oven for 24 hours for drying to obtain a ZIF-67 product;
(3) 0.3 g of sulfonated polyaryletherketone sulfone containing amino groups is weighed into a beaker, 8 ml of N-methyl-2-pyrrolidone (NMP) solvent is added, and the mixture is stirred at room temperature for 24 hours to obtain a uniform solution. The solvent preferably has a boiling point of 150oC or higher, including but not limited to N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), or Dimethylsulfoxide (DMSO);
(4) 0.045 g of ZIF-67 was weighed and added to the homogeneous solution of step (3). Ultrasonic dispersion was carried out for 4 hours, and then magnetic stirring was continued for 48 hours. Wherein the mass ratio of ZIF-67 to sulfonated polyaryletherketone sulfone containing amino in the mixed solution is 0.15:1;
(5) 0.15 g of 2-acrylamido-2-methylpropanesulfonic acid was weighed out and added to the homogeneous solution of step (4), protected from light and magnetically stirred for 8 hours. Wherein the mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the sulfonated polyaryletherketone sulfone containing amino in the mixed solution is 1:2;
(6) 0.015 g of benzoyl peroxide was weighed into the homogeneous solution of step (5) and magnetic stirring was continued for 2 hours in the dark. Wherein the mass ratio of the benzoyl peroxide to the 2-acrylamide-2-methylpropanesulfonic acid in the mixed solution is 1:10;
casting the casting solution obtained in the step (6) onto a clean glass plate of 8 cm multiplied by 8 cm, and placing the glass plate into a casting mold of 80 cmoDrying in an oven for 48 hours, naturally cooling to room temperature, removing the film in deionized water, and adding 2 mol/L sulfuric acidRepeatedly washing in deionized water after acidizing for 48 hours to remove residual sulfuric acid, thus obtaining the sulfonated polyaryletherketone sulfone blended ZIF-67 composite proton exchange membrane containing amino;
blending the obtained sulfonated polyaryletherketone sulfone containing amino with ZIF-67 composite proton exchange membrane at 80oThe conductivity of the proton exchange composite membrane is 0.078S cm when tested under C-1Film thickness 35 μm at 30oThe conductivity of the conductive material is 0.044S cm when the conductive material is tested under C-1。
FIG. 1 is a graph of proton conductivity as a function of temperature for pure amino group-containing sulfonated polyaryletherketone sulfones of the present invention, and for hybrid membranes prepared in example 1, example 2, and example 3. All hybrid membranes showed higher proton conductivity than pure Am-SPAEKS-DBS. Among them, the hybrid membrane prepared in example 2 has the highest proton conductivity;
FIG. 2 is a ZIF-67 thermogravimetric plot of the present invention. There are two decomposition stages in the TGA curve for ZIF-67. 150oC ~200 oC is the first stage, mainly due to the decomposition of impurities of ZIF-67. Second stage at 500oC ~600 oInterval C, crystal skeleton 500oC begins to decompose, which shows that the ZIF-67 material has good thermal stability;
FIG. 3 is a graph of the thermogravimetric curves of pure amino-containing sulfonated polyaryletherketone sulfones (Am-SPAEKS-DBS), hybrid membranes prepared in example 1, example 2 and example 3 in the present invention. The thermal stability of the hybrid membrane was greatly affected by incorporation of ZIF-67 in the membrane. There are three decomposition stages in the TGA curve of the hybrid membrane. Therein 30oC ~200 oC is the first stage, which is attributed to the absorption of water by the proton exchange membrane, the temperature increase leading to evaporation of residual solvent and bound water in the membrane. Second stage 275oC~500 oInterval C at 275 oCThe sulfonic acid groups, amino groups and side chains in Am-SPAEKS-DBS start to decompose, which leads to significant weight loss of the hybrid membrane. The hybrid membrane incorporating ZIF-67 had a more significant loss during the second weight loss stage and increased with increasing ZIF-67 content due to weight loss from the decomposition of ZIF-67. Finally, Am-SPAEKS-DBS has a backbone structure500 oC or more is destroyed.
The above description of the embodiments is only for the purpose of assisting understanding of the method of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall into the protection scope of the claims of the present invention.
Claims (10)
1. The amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane is mainly characterized in that the proton exchange membrane is mainly composed of amino-containing sulfonated polyaryletherketone sulfone blended metal organic framework ZIF-67, wherein the mass ratio of the amino-containing sulfonated polyaryletherketone sulfone to the ZIF-67 is 1: 0.05-0.15.
2. The amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane according to claim 1, wherein the preparation method of the amino-containing sulfonated polyaryletherketone sulfone comprises the following steps: under the conditions of nitrogen protection, condensation reflux and mechanical stirring, adding a mol of amino monomer, b mol of 4,4 '-difluorobenzophenone, c mol of 4, 4' -sulfonated dichlorodiphenyl sulfone and d mol of bisphenol monomer into a three-neck flask (100ml), then adding a proper amount of solvent, water-carrying agent and salt-forming agent into the three-neck flask, and raising the temperature to 120-130%oC, carrying out water carrying, discharging the water carrying agent after condensing and refluxing for 4-6 hours, and then raising the temperature to 175-180 DEG CoAnd C, continuously reacting for 4-5 hours until the solution is viscous, discharging the solution into deionized water to obtain sulfonated polyaryletherketone sulfone containing amino, wherein a + d = b + C, the bisphenol monomer is preferably bisphenol A, bisphenol S, hexafluorobisphenol A, phenolphthalein, tetramethyl diphenol or tert-butyl hydroquinone, more preferably allyl bisphenol S, the amino monomer is 4-aminophenyl hydroquinone, the solvent is sulfolane, the salt forming agent is anhydrous potassium carbonate, and the water carrying agent is toluene.
3. The novel sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane containing amino groups as claimed in claim 1, wherein the preparation method of the ZIF-67 metal organic framework comprises the following steps: dissolving cobalt nitrate hexahydrate in a proper amount of deionized water; and meanwhile, dissolving 2-methylimidazole in a proper amount of deionized water, slowly dripping cobalt nitrate hexahydrate solution into the 2-methylimidazole solution while stirring, magnetically stirring the mixed solution at room temperature for 6 hours, finally, centrifugally washing the solution, washing with water for three times, washing with methanol for three times, placing the solution in a vacuum oven at the temperature of 80 ℃ for 24 hours, and drying to obtain the ZIF-67 product.
4. The novel functionalized sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane containing amino groups as claimed in claim 3, wherein the molar ratio of the cobalt nitrate hexahydrate to the deionized water is 1.55:3, and the molar ratio of the 2-methylimidazole to the deionized water is 67: 20.
5. The preparation method of the amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane as claimed in claim 1, comprising the following steps:
the method comprises the following steps: preparing sulfonated polyaryletherketone sulfone containing amino into a sulfonated polyaryletherketone sulfone solution containing amino; step two: adding a proper amount of ZIF-67 into the sulfonated polyaryletherketone sulfone solution containing amino groups obtained in the step one; step three: adding 2-acrylamide-2-methylpropanesulfonic acid into the solution; step four: adding benzoyl peroxide into the solution to obtain a membrane casting solution, and spreading the membrane casting solution obtained in the fourth step to obtain the amino-containing sulfonated polyaryletherketone sulfone and ZIF-67 metal organic framework composite proton exchange membrane for the fuel cell.
6. The method for preparing the amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane according to claim 5, wherein the preparation method of the amino-containing sulfonated polyaryletherketone sulfone solution in the first step comprises the following steps:
adding the sulfonated polyaryletherketone sulfone containing amino into a solvent at room temperature, and stirring for 24 hours to obtain a uniform sulfonated polyaryletherketone sulfone solution containing amino, wherein the mass volume fraction of the sulfonated polyaryletherketone sulfone solution containing amino is 0.06-0.12 g/mL.
7. The method for preparing the amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane as claimed in claim 5, wherein the preparation method of the amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework solution in the second step comprises the following steps:
adding ZIF-67 into an amino-containing sulfonated polyaryletherketone sulfone solution, ultrasonically dispersing the solution for 4 hours, and continuously stirring for 1-2 days to obtain a uniformly dispersed solution, wherein the mass ratio of the amino-containing sulfonated polyaryletherketone sulfone to the ZIF-67 is 1:0.05 to 0.15.
8. The method for preparing the amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane as claimed in claim 4, wherein the preparation method of the amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework solution in the third step comprises the following steps:
adding 2-acrylamide-2-methylpropanesulfonic acid into a solution of sulfonated polyaryletherketone sulfone containing amino blended ZIF-67 metal organic framework, and stirring at room temperature in a dark place for 8 hours, wherein the mass ratio of the sulfonated polyaryletherketone sulfone containing amino to the 2-acrylamide-2-methylpropanesulfonic acid is 2: 1.
9. The method for preparing the amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane according to claim 5, wherein the method for preparing the amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework solution in the fourth step comprises the following steps:
adding benzoyl peroxide into a solution of sulfonated polyaryletherketone sulfone blend ZIF-67 metal organic framework containing amino, and stirring at room temperature in a dark place for 2 hours, wherein the mass ratio of 2-acrylamide-2-methylpropanesulfonic acid to benzoyl peroxide is 10:1, so as to obtain a casting solution.
10. The preparation method of the amino-containing sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite membrane as claimed in claim 5, wherein the four specific operation steps are as follows:
casting the membrane solution on a clean glass plate of 8 cm multiplied by 8 cm, and placing the glass plate on a glass plate of 80 cmoAnd C, drying in an oven for 48 hours, removing the membrane by using deionized water, then acidizing by using sulfuric acid for 48 hours, and then cleaning by using deionized water until the surface of the membrane is acid-removed, thereby obtaining the sulfonated polyaryletherketone sulfone blended ZIF-67 metal organic framework composite proton exchange membrane for the fuel cell.
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