CN107903416B - Polyaryletherketone zwitter-ion exchange membrane containing phthalazinone structure and preparation method thereof - Google Patents
Polyaryletherketone zwitter-ion exchange membrane containing phthalazinone structure and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
Abstract
The invention belongs to the technical field of ion exchange membranes, and discloses a polyaryletherketone amphoteric ion exchange membrane containing a phthalazinone structure and a preparation method thereof. The polyaryletherketone zwitter ion exchange membrane containing the phthalazinone structure is prepared by mixing polyaryletherketone containing a halogenated methyl phthalazinone structure with sulfonated polyaryletherketone containing a phthalazinone structure, dissolving the mixture in a solvent to prepare a casting membrane solution, scraping the casting membrane to form a membrane, obtaining a blended base membrane, soaking the blended base membrane in polyamine or pyridine solution to carry out amination treatment on halomethyl, and obtaining the polyaryletherketone zwitter ion exchange membrane containing the phthalazinone structure, wherein the polyaryletherketone zwitter ion exchange membrane contains sulfonic acid groups and quaternary ammonium groups or pyridine groups. Because the molecular chain of the polymer contains the full aromatic ring twisted non-coplanar phthalazinone biphenyl structure, the polymer has good chemical stability in strong acid strong oxidizing solution, high ion selectivity and conductivity, and has good application prospect in the field of full vanadium flow batteries.
Description
Technical Field
The invention belongs to the technical field of ion exchange membranes, and particularly relates to a polyaryletherketone amphoteric ion exchange membrane containing a phthalazinone structure and a preparation method thereof.
Background
An ion exchange membrane is a high molecular functional membrane with ion selective permeability, and has been widely applied in the technical fields of electrodialysis, diffusion dialysis, electrolysis, proton exchange membrane fuel cells, flow batteries, sensors and the like. With the continuous widening of the application field of the ion exchange membrane, the demand for the function diversification of the ion exchange membrane is increasing. The function of the ion exchange membrane is mainly determined by the kind of the ion exchange groups fixed on the membrane, the electric property of the charged charges and the distribution of the charged charges in the membrane. Based on the difference in membrane function, ion exchange membranes can be classified into cation exchange membranes, anion exchange membranes, bipolar membranes, amphoteric ion exchange membranes, and the like. Because the amphoteric ion exchange membrane contains both cation exchange groups and anion exchange groups, the amphoteric ion exchange membrane has the characteristics of both the cation exchange membrane and the anion exchange membrane, and has attracted extensive attention in recent years.
Xi et al [ Journal of Materials Chemistry,2008,18(11),1232-1238] adopting electrolyte self-assembly technology to alternately adsorb polydiallyl dimethyl ammonium chloride (PDDA) and sodium polystyrene sulfonate (PSS) solution on the surface of a Nafion membrane to prepare the Nafion- [ PDDA-PSS ] n multilayer amphoteric ion exchange membrane, having lower vanadium ion permeability, higher coulombic efficiency and energy efficiency (compared with the Nafion membrane); qiu et al [ Journal of Membrane Science,2009,334(1-2),9-15, Journal of Membrane Science,2009,342(1-2),215-219] respectively modify PVDF Membrane and ETFE by using styrene and dimethylaminoethyl methacrylate as grafting monomers by adopting radiation grafting technology to prepare the zwitter-ion exchange Membrane for the all-vanadium flow battery, wherein the zwitter-ion exchange Membrane has higher conductivity and lower vanadium ion permeability, and the coulombic efficiency and the energy efficiency of the assembled all-vanadium flow battery are higher than those of a Nafion Membrane; however, the existing amphoteric ion exchange membrane still has the defects that the preparation process is difficult to industrialize or the stability of the membrane is poor and the like.
With the continuous expansion of the application field of ion exchange membranes, the ion exchange membrane material is also expanded from the initial styrene-divinylbenzene polymer to isoprene-styrene block copolymer, styrene-butadiene copolymer and fluorine-containing polymer, and aromatic polymers such as polysulfone, polyethersulfone and polyphenylene oxide. But still can not meet the requirements of the industrial field on the ion exchange membrane, and the development of the novel ion exchange membrane is still a hot spot of domestic and foreign research. The polyaryletherketone containing the phthalazinone structure is novel polyaryletherresin, and the phthalazinone biphenyl structure with the distortion of the full aromatic ring and non-coplanar is introduced into the main chain of the polymer, so that the novel polyaryletherketone is high-temperature resistant, soluble and excellent in chemical stability. The anion exchange membrane prepared by introducing positively charged groups or negatively charged groups into polyaryletherketone containing a phthalazinone structure shows better selective permeability and chemical stability. Has very wide application prospect in the field of ion exchange membranes.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyaryletherketone zwitter-ion exchange membrane containing a phthalazinone structure and a preparation method thereof, and the polyaryletherketone zwitter-ion exchange membrane containing the phthalazinone structure, which is high in stability, high in ion selectivity and low in resistance, is prepared.
The technical scheme of the invention is as follows:
a polyaryletherketone zwitter ion exchange membrane containing a phthalazinone structure is mainly prepared by performing blending, membrane preparation, inorganic salt solution soaking, amination and acidification on halomethylated polyaryletherketone containing the phthalazinone structure and sulfonated polyaryletherketone containing the phthalazinone structure;
the structural formula of the halomethylated polyaryletherketone containing the phthalazinone structure is as follows:
wherein: x is Cl or Br;
R1is H, CH3Or CH2X；
Ar is
The halomethyl content of the halomethylated polyaryletherketone containing the phthalazinone structure is between 0.2 and 2.0 mmol/g;
the sulfonated polyaryletherketone containing a phthalazinone structure has the following structural formula:
wherein: r2And R3Are respectively H and SO3H, H and
and
ar is
The content of sulfonic acid groups of the sulfonated polyaryletherketone containing a phthalazinone structure is between 0.2 and 2.0 mmol/g.
A preparation method of polyaryletherketone zwitter ion exchange membrane containing phthalazinone structure comprises the following steps:
1) mixing and dissolving halomethylated polyaryletherketone containing a phthalazinone structure and sulfonated polyaryletherketone containing a phthalazinone structure in a solvent to prepare a membrane casting solution, filtering and defoaming the membrane casting solution, scraping the membrane casting solution to form a membrane, heating the membrane casting solution to evaporate the solvent, and then soaking the membrane casting solution into a precipitator to obtain a blended basement membrane; wherein the mass ratio of the halomethylated polyaryletherketone containing a phthalazinone structure to the sulfonated polyaryletherketone containing a phthalazinone structure is 1: 99-99: 1, and the total concentration of the halomethylated polyaryletherketone containing a phthalazinone structure and the sulfonated polyaryletherketone containing a phthalazinone structure in the casting solution is 3-30 wt%;
2) soaking the blended base membrane in an inorganic salt solution to convert a sulfonic acid hydrogen type group in the blended base membrane into a sulfonic acid salt type group; wherein, the concentration of the inorganic salt solution is 0.1-3.0mol/L, the soaking time is 1-48 hours, and the soaking temperature is 10-50 ℃;
3) soaking a sulfonate base membrane in a polyamine solution or a pyridine solution to cause an amination reaction of a halomethyl; wherein, the concentration of the polyamine solution or the pyridine solution is 5 to 50 weight percent, the amination temperature is 5 to 80 ℃, and the amination time is 1 to 72 hours;
4) soaking the aminated membrane in an acid solution, neutralizing unreacted polyamine or pyridine, simultaneously converting a sulfonate type into a hydrogen sulfonate type group, and washing with deionized water to obtain a polyaryletherketone zwitterion exchange membrane containing a phthalazinone structure; the concentration of the acid solution is 0.1-3.0mol/L, the acidification temperature is 10-60 ℃, and the acidification time is 1-36 hours.
The solvent of the casting solution is one or a mixed solution of more than two of chloroform, dichloromethane, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone; the precipitant is one or more of water, methanol, ethanol, propanol, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate.
The inorganic salt solution comprises one or more than two mixed solutions of sodium chloride, sodium sulfate, sodium carbonate, potassium chloride, potassium sulfate, potassium carbonate, magnesium chloride and magnesium sulfate, the concentration of the inorganic salt solution is 0.5-2.5mol/L, the soaking time is 12-36 hours, and the soaking temperature is 20-40 ℃.
The solvent evaporation conditions are as follows: the temperature is 20-150 ℃ and the time is 0.5-30 hours.
The polyamine is one or a mixture of more than two of ethylenediamine, trimethylamine, triethylamine, tripropylamine, tributylamine and 1,1,2, 2-tetramethyl ethylenediamine, the amination temperature is 10-50 ℃, and the amination time is 5-60 hours.
The acid solution comprises one or more mixed aqueous solution of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, the concentration of the acid solution is 0.5-2.5mol/L, and the acidification time is 6-24 hours.
The solvent evaporation conditions are as follows: the temperature is 30-90 ℃ and the time is 0.5-12 hours.
The invention has the beneficial effects that:
1) the polymer molecule chain segment used by the invention contains a full aromatic ring twisted non-coplanar phthalazinone biphenyl structure, has good chemical stability in strong acid strong oxidizing solution,
2) the amphoteric ion exchange membrane disclosed by the invention contains both cation exchange groups and anion exchange groups, the cation exchange groups are favorable for promoting the conduction of hydrogen ions, and the anion exchange groups are favorable for preventing the penetration of vanadium ions, so that the amphoteric ion exchange membrane has high ion selectivity and high ion conductivity, and has a very good application prospect in the field of all-vanadium redox flow batteries.
3) The modified polyaryletherketone membrane material containing the phthalazinone structure has similar main chain structure and good compatibility; meanwhile, the solution blending method is used for preparing the membrane, the preparation process is simple and convenient, and the industrial production is easy to carry out.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. The examples, which are given for the purpose of illustration only and do not limit the scope of the invention, set forth the preparation process and properties of a portion of the zwitterionic exchange membrane.
Example 1
Blending bromomethyl-containing heteronaphthalene biphenyl polyaryletherketone (BPPEK-80, the bromomethyl content is 1.76mmol/g) and sulfonated heteronaphthalene biphenyl polyaryletherketone (SPPEK, the sulfonic group content is 1.37mmol/g) to prepare a zwitterionic exchange membrane: BPPEK-80 and SPPEK (IEC 1.37mmol/g) were mixed at a mass ratio of 9/1, 7/3 and 5/5, and dissolved in N-methylpyrrolidone (NMP) to prepare 13 wt.% of a casting solution. Then filtering and defoaming, scraping the mixture on a glass plate at 60 ℃ to form a film, and immersing the film in water after 4 hours to obtain the blended basement membrane BPPEK-80/SPPEK. Soaking the blended basement membrane in 1mol/L NaCl solution (25 ℃), taking out and soaking the basement membrane in 33 percent trimethylamine solution after 24 hours, and carrying out amination reaction for 48 hours at 40 ℃. And after the reaction is finished, putting the membrane into 0.5mol/L hydrochloric acid to remove redundant trimethylamine, converting the sodium sulfonate type group into a hydrogen sulfonate type group, and then washing with deionized water to remove residual hydrochloric acid to obtain the amphoteric ion exchange membrane. The zwitterionic ion-exchange membranes made from BPPEK-80/SPPEK (IEC ═ 1.37mmol/g) with mass ratios of 9/1, 7/3 and 5/5 were respectively named QB80/S137-10, QB80/S137-30 and QB 80/S137-50. And testing the ion exchange capacity of each component of the blend membrane by an acid-base titration method to obtain the quaternary ammonium group component and the sulfonic acid group component IEC of the QB80/S137 membrane close to the theoretical values thereof. The water absorption rates of the QB80/S137-10, QB80/S137-30 and QB80/S137-50 films were 32.0%, 27.2% and 22.4%, respectively. The membrane surface resistances of QB80/S137-10, QB80/S137-30 and QB80/S137-50 are respectively 0.89 omega cm2、0.90Ωcm2And 1.33. omega. cm2(ii) a The permeability coefficients of vanadium are respectively 4.31 multiplied by 10-5cm/min、1.75×10-5cm/min and 0.25X 10-5cm/min. Current density 40mA/cm2The performance of the single vanadium battery assembled by the QB80/S137 zwitterionic ion exchange membrane is tested, and the Coulombic Efficiency (CE), the Voltage Efficiency (VE) and the Energy Efficiency (EE) of the vanadium battery are shown in the table 1.
TABLE 1 QB80/S137 Membrane vanadium cell Performance (40 mA/cm)2)
IECa-M、IECa-TRespectively is an ion exchange capacity test value and a theoretical value of the quaternary ammonium group; IECc-M、IECc-TThe ion exchange capacity test value and the theoretical value of the sulfonic acid group are respectively shown.
Example 2
Blending bromomethyl-containing heteronaphthalene biphenyl polyaryletherketone (BPPEK-90, the bromomethyl content is 1.80mmol/g) with sulfonated polymer SPPEK with IEC being 0.7mmol/g to prepare the amphoteric ion exchange membrane: BPPEK-90 and SPPEK (IEC 0.7mmol/g) were mixed in a mass ratio of 9/1 and 7/3, and dissolved in N-methylpyrrolidone to prepare 13 wt.% of casting solution. Then filtering and defoaming, scraping the mixture on a glass plate at 90 ℃ to form a membrane, and obtaining the blended basement membrane BPPEK-90/SPPEK after 4 hours. Soaking the blended base membrane in 1mol/L NaCl solution (25 ℃), taking out and soaking in 33% trimethylamine solution after 24 hours, and carrying out amination reaction for 48 hours at 40 ℃. And after the reaction is finished, putting the membrane into 0.5mol/L hydrochloric acid to remove redundant trimethylamine, converting the sodium sulfonate type group into a hydrogen sulfonate type group, and then washing with deionized water to remove residual hydrochloric acid to obtain the zwitter-ion exchange membrane. The amphoteric ion-exchange membranes prepared from BPPEK-90/SPPEK (IEC ═ 0.7mmol/g) with mass ratios of 9/1 and 7/3 are named as QB90/S07-10 and QB90/S07-30, respectively. The quaternary ammonium group component and the sulfonic acid group component IEC of the QB90/S07 membrane are close to their theoretical values. The water absorption rates of the QB90/S07-10 and QB90/S07-30 films were 30.9% and 23.0%, respectively, and the sheet resistances were 0.78. omega. cm2And 1.38. omega. cm2The permeability coefficients of vanadium are respectively 1.70 multiplied by 10-5cm/min and 0.85X 10-5cm/min。
TABLE 2 QB90/S07 film vanadium cell performanceEnergy (40 mA/cm)2)
IECa-M、IECa-TRespectively is an ion exchange capacity test value and a theoretical value of the quaternary ammonium group; IECc-M、IECc-TThe ion exchange capacity test value and the theoretical value of the sulfonic acid group are respectively shown.
Example 3
Blending bromomethyl-containing heteronaphthalene biphenyl polyaryletherketone (BPPEK-70, the bromomethyl content of which is 1.45mmol/g) with sulfonated polymer SPPEK with IEC being 0.7mmol/g to prepare the amphoteric ion exchange membrane: BPPEK-70 and SPPEK (IEC 0.7mmol/g) were mixed in a mass ratio of 9/1, 7/3 and 5/5, and dissolved in N-methylpyrrolidone to prepare 13 wt.% of casting solution. Then filtering and defoaming, scraping the mixture on a glass plate at 70 ℃ to form a membrane, and obtaining the blended basement membrane BPPEK-70/SPPEK after 4 hours. The blended basement membrane is soaked in 1mol/L NaCl solution (25 ℃) for 24 hours, then taken out and soaked in 33 percent trimethylamine solution, and aminated for 48 hours at 40 ℃. After the reaction is finished, the membrane is put into 0.5mol/L hydrochloric acid to remove excessive trimethylamine, and then the membrane is washed by deionized water to remove residual hydrochloric acid, so that the QBPPEK-70/SPPEK (IEC ═ 0.7mmol/g) zwitter ion exchange membrane is obtained. The zwitterionic ion-exchange membranes prepared from BPPEK-70/SPPEK (IEC ═ 0.7mmol/g) with mass ratios of 9/1 and 7/3 were named QB70/S07-10 and QB70/S07-30, respectively. The quaternary ammonium group component and the sulfonic acid group component IEC of the QB70/S07 membrane are close to their theoretical values. The water absorption rates of the QB70/S07-10 and QB70/S07-30 films are 20.8% and 16.9% respectively, and the film surface resistances are 1.00 omega cm2And 2.30. omega. cm2The permeability coefficients of vanadium are respectively 0.85 multiplied by 10-5cm/min and 0.17X 10-5cm/min. Current density 40mA/cm2The single cell performance of the QB70/S07 zwitterionic ion exchange membrane assembled vanadium battery is tested, and the battery efficiency of the vanadium battery is shown in Table 3.
TABLE 3 QB70/S07 Membrane vanadium cell Performance (40 mA/cm)2)
IECa-M、IECa-TRespectively is an ion exchange capacity test value and a theoretical value of the quaternary ammonium group; IECc-M、IECc-TThe ion exchange capacity test value and the theoretical value of the sulfonic acid group are respectively shown.
Example 4
1.0mmol/g of chloromethyl-containing heteronaphthalene biphenyl polyaryletherketone (CMPPEK) and 1.37mmol/g of IEC sulfonated polymer SPPEK are blended to prepare the amphoteric ion exchange membrane: CMPPEK and SPPEK (IEC 1.37mmol/g) were mixed in a mass ratio of 9/1, 5/5, and 1/9, and dissolved in N-methylpyrrolidone (NMP) to prepare 13 wt.% of a casting solution. Then filtering and defoaming, scraping the mixture on a glass plate at 70 ℃ to form a film, and obtaining the blended basement membrane CMPPEK/SPPEK after 4 hours. The blended basement membrane is soaked in 1mol/L NaCl solution (25 ℃) for 24 hours, then taken out and soaked in 33 percent trimethylamine solution, and aminated for 48 hours at 40 ℃. After the reaction, the membrane was placed in 0.5mol/L hydrochloric acid to remove excess trimethylamine, and then washed with deionized water to remove residual hydrochloric acid, thereby obtaining QAPEK/SPPEK (IEC ═ 1.37mmol/g) membrane. Ion exchange membranes made from CMPPEK/SPPEK (IEC ═ 1.37mmol/g) with mass ratios of 9/1, 7/3, and 5/5, respectively, were named QA/S137-10, QA/S137-50, and QA/S137-90. The water absorption of QA/S137-10, QA/S137-50, and QA/S137-90 films was 26.9%, 26.0%, and 27.7%, respectively. The film surface resistances of QA/S137-10, QA/S137-50 and QA/S137-90 are respectively 3.89 omega cm2、2.50Ωcm2And 1.79. omega. cm2. Current density 40mA/cm2The unit cell performance of the QAPPEK/SPPEK (IEC ═ 1.37mmol/g) zwitterionic exchange membrane assembled vanadium cell was tested, and the cell efficiency of the vanadium cell is shown in table 4.
TABLE 4 QAPEK/SPPEK (IEC ═ 1.37mmol/g) membrane vanadium cell performance (40 mA/cm)2)
IECa-M、IECa-TRespectively is an ion exchange capacity test value and a theoretical value of the quaternary ammonium group; IECc-M、IECc-TThe ion exchange capacity test value and the theoretical value of the sulfonic acid group are respectively shown.
Example 5
1.0mmol/g of chloromethyl-containing phthalazinone polyaryletherketone (CMPPEK) was mixed with SPPEK having IEC of 1.37mmol/g, 1.70mmol/g and 1.90mmol/g, respectively, in a mass ratio of 5/5, and dissolved in N-methylpyrrolidone (NMP) to prepare 13 wt.% of a casting solution. Then filtering and defoaming, scraping the mixture on a glass plate at 70 ℃ to form a film, and obtaining the blended basement membrane CMPPEK/SPPEK after 4 hours. The blended basement membrane is soaked in 1mol/L NaCl solution (25 ℃) for 24 hours, then taken out and soaked in 33 percent trimethylamine solution, and aminated for 48 hours at 40 ℃. And after the reaction is finished, putting the membrane into 0.5mol/L HCl to remove redundant trimethylamine, and washing with deionized water to remove residual hydrochloric acid to obtain the zwitter-ion exchange membrane. The amphoteric ion exchange membrane QAPEK/SPPEK membranes prepared by SPPEK respectively named with IEC of 1.37mmol/g, 1.70mmol/g and 1.90mmol/g are QA/S137-50, QA/S170-50 and QA/S190-50. The water absorption rates of the QA/S137-50, QA/S170-50 and QA/S190-50 films are respectively 26.0%, 30.1 and 33.1%, and the film surface resistances are respectively 3.89 omega cm2、1.96Ωcm2And 1.81. omega. cm2. Current density 40mA/cm2The performance of a single battery of the vanadium battery assembled by the QAPPEK/SPPEK zwitterionic exchange membrane is tested, and the coulombic efficiency, the voltage efficiency and the energy efficiency of the vanadium battery are shown in Table 5.
TABLE 5 QAPEK/SPPEK film vanadium cell Performance (40 mA/cm)2)
IECa-M、IECa-TRespectively is an ion exchange capacity test value and a theoretical value of the quaternary ammonium group; IECc-M、IECc-TThe ion exchange capacity test value and the theoretical value of the sulfonic acid group are respectively shown.
Under the same test condition, the coulombic efficiency of the vanadium battery assembled by the polyaryletherketone zwitter-ion exchange membrane containing the phthalazinone structure is greater than the value (95.7%) of a Nafion117 membrane; the energy efficiency is close to or exceeds the value (85.7%) of Nafion117 under the same condition, which indicates that the polyaryletherketone zwitter-ion exchange membrane containing the phthalazinone structure has better application prospect in the aspect of vanadium batteries.
Claims (8)
1. A polyaryletherketone zwitter ion exchange membrane containing a phthalazinone structure is characterized in that the polyaryletherketone zwitter ion exchange membrane containing the phthalazinone structure is mainly prepared by mixing halomethylated polyaryletherketone containing the phthalazinone structure and sulfonated polyaryletherketone containing the phthalazinone structure, preparing a membrane, soaking in an inorganic salt solution, aminating and acidifying;
the structural formula of the halomethylated polyaryletherketone containing the phthalazinone structure is as follows:
wherein: x is Cl or Br;
R1is H, CH3Or CH2X；
Ar is
The halomethyl content of the halomethylated polyaryletherketone containing the phthalazinone structure is between 0.2 and 2.0 mmol/g;
the sulfonated polyaryletherketone containing a phthalazinone structure has the following structural formula:
wherein: r2And R3Are respectively H and SO3H, H and
ar is
The content of sulfonic acid groups of the sulfonated polyaryletherketone containing a phthalazinone structure is between 0.2 and 2.0 mmol/g.
2. A preparation method of polyaryletherketone zwitter ion exchange membrane containing phthalazinone structure is characterized by comprising the following steps:
1) mixing and dissolving halomethylated polyaryletherketone containing a phthalazinone structure and sulfonated polyaryletherketone containing a phthalazinone structure in a solvent to prepare a membrane casting solution, filtering and defoaming the membrane casting solution, scraping the membrane casting solution to form a membrane, heating the membrane casting solution to evaporate the solvent, and then soaking the membrane casting solution into a precipitator to obtain a blended basement membrane; wherein the mass ratio of the halomethylated polyaryletherketone containing a phthalazinone structure to the sulfonated polyaryletherketone containing a phthalazinone structure is 1: 99-99: 1, and the total concentration of the halomethylated polyaryletherketone containing a phthalazinone structure and the sulfonated polyaryletherketone containing a phthalazinone structure in the casting solution is 3-30 wt%;
2) soaking the blended base membrane in an inorganic salt solution to convert a sulfonic acid hydrogen type group in the blended base membrane into a sulfonic acid salt type group; wherein, the concentration of the inorganic salt solution is 0.1-3.0mol/L, the soaking time is 1-48 hours, and the soaking temperature is 10-50 ℃;
3) soaking a sulfonate base membrane in a polyamine solution or a pyridine solution to cause an amination reaction of a halomethyl; wherein, the concentration of the polyamine solution or the pyridine solution is 5 to 50 weight percent, the amination temperature is 5 to 80 ℃, and the amination time is 1 to 72 hours;
4) soaking the aminated membrane in an acid solution, neutralizing unreacted polyamine or pyridine, simultaneously converting a sulfonate type into a hydrogen sulfonate type group, and washing with deionized water to obtain a polyaryletherketone zwitterion exchange membrane containing a phthalazinone structure; the concentration of the acid solution is 0.1-3.0mol/L, the acidification temperature is 10-60 ℃, and the acidification time is 1-36 hours.
3. The preparation method according to claim 2, characterized in that the solvent of the casting solution is one or a mixed solution of two or more of chloroform, dichloromethane, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone; the precipitant is one or more of water, methanol, ethanol, propanol, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate.
4. The preparation method according to claim 2 or 3, characterized in that the inorganic salt solution comprises one or more mixed solution of sodium chloride, sodium sulfate, sodium carbonate, potassium chloride, potassium sulfate, potassium carbonate, magnesium chloride and magnesium sulfate, the concentration of the inorganic salt solution is 0.5-2.5mol/L, the soaking time is 12-36 hours, and the soaking temperature is 20-40 ℃.
5. The process according to claim 4, wherein the solvent is evaporated under the following conditions: the temperature is 20-150 ℃ and the time is 0.5-30 hours.
6. The process according to claim 2, 3 or 5, wherein the polyamine is one or a mixture of two or more of ethylenediamine, trimethylamine, triethylamine, tripropylamine, tributylamine and 1,1,2, 2-tetramethylethylenediamine, and the amination temperature is 10 to 50 ℃ and the amination time is 5 to 60 hours.
7. The method according to claim 6, wherein the acid solution comprises a mixed aqueous solution of one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, the concentration of the acid solution is 0.5 to 2.5mol/L, and the acidification time is 6 to 24 hours.
8. The process according to claim 2, 3, 5 or 7, characterized in that the solvent is evaporated under the following conditions: the temperature is 30-90 ℃ and the time is 0.5-12 hours.
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| Novel amphoteric ion exchange membranes by blending sulfonated poly(ether ether ketone)/quaternized poly(ether imide) for vanadium redox flow battery applications;Shuai Liu,等;《Journal of Materials Chemistry A》;20150626;第3卷;全文 * |
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