CN108923056B - Preparation method of high-conductivity polyphenyl ether anion exchange membrane - Google Patents
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Abstract
The invention belongs to the technical field of fuel cells, and discloses a preparation method of a novel high-conductivity polyphenyl ether anion exchange membrane. The anion exchange membrane prepared by the invention has multiple conduction sites, can maintain higher ionic conductivity, and simultaneously has good alkali resistance and mechanical property.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a preparation method of a high-conductivity polyphenyl ether anion exchange membrane.
Background
The anion exchange membrane fuel cell has the advantages of lower catalyst price, simplified water management, high fuel oxidation rate, low permeability and the like, but compared with a proton exchange membrane, the anion exchange membrane still has the problems of lower ionic conductivity, poorer high-temperature alkali resistance and the like, and cannot meet the commercial application. Therefore, the preparation of the anionic membrane material with high conductivity and good stability is a direction with research prospect.
Research shows that increasing the conductance sites can effectively increase the conductance of the anion exchange membrane by increasing the ion exchange capacity. There are generally two methods of increasing conduction sites: firstly, grafting ionic groups containing a plurality of conduction sites onto a polymer skeleton through graft polymerization; and secondly, directly doping the ionic liquid capable of conducting hydroxide ions into the polymer.
Polyphenylene oxide is a nonpolar high molecular polymer with a linear structure, has the characteristics of high rigidity, high heat resistance, excellent electrical property and the like, has dielectric constant and dielectric loss which are one of the smallest varieties in engineering plastics, is hardly influenced by temperature and humidity, has low price, and is suitable to be used as a base material of an anion exchange membrane. The prior anion exchange membranes based on polyphenyl ether comprise imidazole type, pyridine type, quaternary ammonium type, guanidine type, phosphine type and the like, but the membrane materials can not achieve high conductivity, high alkali resistance and high dimensional stability at the same time, and have a great distance from the practical application of fuel cells, so that the development of a high-performance anion exchange membrane is needed.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide the preparation method of the high-conductivity polyphenyl ether anion exchange membrane, and the high-conductivity polyphenyl ether anion exchange membrane prepared by the method has the advantages of multiple conduction sites, high mechanical strength and good alkali resistance.
In order to solve the technical problems, the invention provides a preparation method of a high-conductivity polyphenyl ether anion exchange membrane, which comprises the steps of brominating and hydroxylating polyphenyl ether to obtain partially hydroxylated brominated polyphenyl ether, reacting the hydroxylated brominated polyphenyl ether with epichlorohydrin to generate ether, reacting the obtained product with a quaternization reagent to introduce conduction sites, and finally generating a cross-linked structure through heat treatment to obtain the high-conductivity polyphenyl ether anion exchange membrane.
Preferably, the preparation method of the high-conductivity polyphenylene ether anion-exchange membrane provided by the invention further comprises part or all of the following technical characteristics:
as an improvement of the technical proposal, the specific preparation method is as follows,
(1) dissolving polyphenyl ether in a solvent, adding a bromination reagent under the condition of introducing nitrogen, carrying out bromination reaction to obtain a bromomethylated polyphenyl ether solution, and precipitating and drying to obtain the bromomethylated polyphenyl ether;
(2) soaking the bromomethylated polyphenylene oxide obtained in the step (1) in a sodium hydroxide solution, then reacting for a period of time at constant temperature to obtain a partially hydroxylated brominated polyphenylene oxide solution, and washing and drying to obtain partially hydroxylated brominated polyphenylene oxide;
(3) dissolving part of the hydroxylated brominated polyphenylene ether obtained in the step (2) in a solvent to obtain a part of hydroxylated brominated polyphenylene ether solution, slowly dropwise adding epoxy chloropropane under the condition of introducing nitrogen to perform ring opening and ether forming reaction, washing by using a saturated sodium bicarbonate solution, and drying to obtain an etherified product;
(4) and (3) dissolving the etherified product obtained in the step (3) in a solvent, adding a quaternization reagent under the condition of introducing nitrogen, carrying out quaternization reaction to obtain a quaternization polyphenyl ether anion exchange membrane solution, then pouring the quaternization polyphenyl ether anion exchange membrane solution into a polytetrafluoroethylene mould disc for heat treatment, cooling and demoulding to obtain the polyphenyl ether anion exchange membrane with high conductivity.
As an improvement of the technical scheme, the molar ratio of the polyphenyl ether to the brominating agent in the step (1) is 1: 1, the brominating reagent is liquid bromine, and the solvent is chlorobenzene.
As an improvement of the technical scheme, in the step (1), the bromination reaction temperature is 135 ℃, and the reaction time is 4-6 h.
As an improvement of the technical scheme, in the step (2), the molar concentration of the sodium hydroxide solution is 2-4 mol/L, the reaction temperature is 70-90 ℃, and the reaction time is 20-30 h.
As an improvement of the above technical scheme, in the step (3), the molar ratio of the partially hydroxylated brominated polyphenylene ether to the epichlorohydrin is 1: 1-2, wherein the solvent is chlorobenzene.
As an improvement of the technical scheme, in the step (3), the ring-opening ether-forming reaction temperature is 45-65 ℃, and the reaction time is 5-7 h.
As an improvement of the above technical scheme, in the step (4), the molar ratio of the etherification product to the quaternizing agent is 1: 1-2, wherein the solvent is N-methylpyrrolidone, and the quaternizing agent is one of trimethylamine, triethylamine and perfluorinated triethylamine.
As an improvement of the technical scheme, in the step (4), the substitution reaction temperature is 20-40 ℃, and the reaction time is 20-24 hours.
As an improvement of the technical scheme, in the step (4), the heat treatment temperature is 150 ℃, and the heat treatment time is 2 hours.
According to the invention, methyl hydrogen atoms on polyphenyl ether are replaced by bromination reaction to obtain bromomethylated polyphenyl ether; soaking the brominated polyphenylene oxide in a sodium hydroxide solution to obtain partially hydroxylated brominated polyphenylene oxide; then reacting the epoxy chloropropane solution with partial hydroxylated polyphenyl ether, and generating ether through ring opening and breaking of an epoxy group; then adding a quaternizing agent for reaction to introduce a conduction site; and finally, performing heat treatment to ensure that the residual unreacted bromomethyl and carbon on another benzene ring are subjected to electrophilic substitution and crosslinking, and preparing the high-conductivity polyphenyl ether anion exchange membrane by a gel-sol process.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. according to the preparation method, ring-opening ether-forming reaction is carried out between partial hydroxylated brominated polyphenylene ether and epoxy chloropropane, a quaternary ammonium group is introduced to form a plurality of conduction sites, and then electrophilic substitution is carried out on the remaining unreacted bromomethyl and carbon on another benzene ring through heat treatment to generate crosslinking, so that the polyphenylene ether anion exchange membrane with high mechanical property and high conductivity is obtained.
2. In the high-conductivity polyphenyl ether anion exchange membrane, the main chain skeleton is hydrophobic brominated polyphenyl ether, and the brominated polyphenyl ether and hydrophilic epichlorohydrin groups are easy to separate to form an ion transmission channel, so that the conductivity of hydroxide ions is improved, and the improvement of the conductivity of anions is further promoted; meanwhile, the problem of size stability reduction caused by conductivity increase can be solved through thermal crosslinking, so that the obtained anion-exchange membrane has high ion exchange capacity (reaching 1.53-1.97 mmol/g), good mechanical property (tensile strength reaching 16.6-23.3 MPa) and alkali resistance (after the anion-exchange membrane is soaked in a KOH solution within the range of 1-5M at normal temperature for 8 days, the conductivity of the membrane is only reduced by 6.43% -11.52%, and after the anion-exchange membrane is soaked in a 3MKOH solution environment at 60 ℃ for 8 days, the conductivity of the membrane still remains 0.024-0.044S/cm;
3. the preparation method has the advantages of simple process, mild conditions, low cost and easy industrial production.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the contents of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
Example 1
FIG. 1 is a flow chart of a preparation method of a high-conductivity polyphenylene ether anion exchange membrane, which comprises the following specific steps:
(1) placing polyphenyl ether (number average molecular weight 30000, 0.02mol, 2.4040 g) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 20mL of chlorobenzene, introducing nitrogen after completely dissolving, heating to 135 ℃, adding liquid bromine (0.02 mol, 1.0246 mL), reacting for 4 hours, pouring the resultant into anhydrous methanol for precipitation, washing with the anhydrous methanol for several times, and drying at 80 ℃ to obtain bromomethylated polyphenyl ether;
(2) placing the bromomethylated polyphenylene oxide (0.001 mol, 2.0050 g) obtained in the step (1) in NaOH solution (2 mol/L), soaking for 24h at 70 ℃, washing for several times by using distilled water, and drying to obtain partially hydroxylated brominated polyphenylene oxide;
(3) under the condition of introducing nitrogen, putting the partially hydroxylated brominated polyphenylene oxide (0.001 mol, 1.9820 g) obtained in the step (2) and a boron trifluoride diethyl etherate complex catalyst (0.0038 mL) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, after complete dissolution, slowly dropwise adding epoxy chloropropane (0.0015 mol, 0.1388 g) under the stirring state, maintaining at 65 ℃ for 6 hours to complete the reaction, then pouring the product into a saturated sodium bicarbonate solution for washing, and obtaining an etherified product after reduced pressure distillation;
(4) and (3) putting the etherified product (0.001 mol, 3.5840 g) obtained in the step (3) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, maintaining the temperature at 20 ℃ after complete dissolution, adding trimethylamine (0.002 mol, 0.3933mL of a commercially available 30wt% trimethylamine ethanol solution) for reaction for 24 hours to obtain a quaternized product, pouring the reaction solution containing the quaternized product into a polytetrafluoroethylene mold, carrying out heat treatment for 2 hours at 150 ℃, cooling and demolding to obtain the high-conductivity polyphenylene ether anion-exchange membrane.
Tests prove that the tensile strength of the anion-exchange membrane prepared in the embodiment is 19.8MPa, the ion exchange capacity is 1.97mmol/g, the conductivity is 0.055S/cm, the conductivity reduction rates of the membrane after the membrane is soaked in lmol/L, 3mol/L and 5mol/LKOH solutions for 8 days at normal temperature are 9.23%, 9.88% and 10.32% respectively, the alkali resistance is good, and the conductivity of the membrane after the membrane is soaked in 3mol/LKOH solutions for 8 days at 60 ℃ is 0.043S/cm.
Example 2
The preparation method of the high-conductivity polyphenyl ether anion exchange membrane comprises the following specific steps:
(1) placing polyphenyl ether (number average molecular weight 30000, 0.02mol, 2.4040 g) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 20mL of chlorobenzene, introducing nitrogen after completely dissolving, heating to 135 ℃, adding liquid bromine (0.02 mol, 1.0246 mL), reacting for 4 hours, pouring the resultant into anhydrous methanol for precipitation, washing with the anhydrous methanol for several times, and drying at 80 ℃ to obtain bromomethylated polyphenyl ether;
(2) placing the bromomethylated polyphenylene oxide (0.001 mol, 2.0050 g) obtained in the step (1) in NaOH solution (2 mol/L), soaking for 24h at 70 ℃, washing for several times by using distilled water, and drying to obtain partially hydroxylated brominated polyphenylene oxide;
(3) under the condition of introducing nitrogen, putting the partially hydroxylated brominated polyphenylene oxide (0.001 mol, 1.9820 g) obtained in the step (2) and a boron trifluoride diethyl etherate complex catalyst (0.0038 mL) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, after complete dissolution, slowly dropwise adding epoxy chloropropane (0.0015 mol, 0.1388 g) under the stirring state, maintaining at 65 ℃ for 6 hours to complete the reaction, then pouring the product into a saturated sodium bicarbonate solution for washing, and obtaining an etherified product after reduced pressure distillation;
(4) and (3) putting the etherified product (0.001 mol, 3.5840 g) obtained in the step (3) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, maintaining the temperature at 20 ℃ after completely dissolving, adding triethylamine (0.002 mol, 0.2780mL, available in the market) to react for 24h to obtain a quaternized product, pouring the reaction solution into a polytetrafluoroethylene mold, carrying out heat treatment at 150 ℃ for 2h, cooling and demolding to obtain the high-conductivity polyphenylene ether anion exchange membrane.
Tests prove that the tensile strength of the anion-exchange membrane prepared in the embodiment is 23.3MPa, the ion exchange capacity is 1.78mmol/g, the conductivity is 0.033S/cm, the conductivity reduction rates of the membrane after the membrane is soaked in lmol/L, 3mol/L and 5mol/LKOH solutions for 8 days at normal temperature are 6.43%, 7.04% and 7.76% respectively, the alkali resistance is good, and the conductivity of the membrane after the membrane is soaked in 3mol/LKOH solutions for 8 days at 60 ℃ is 0.030S/cm.
Example 3
The preparation method of the high-conductivity polyphenyl ether anion exchange membrane comprises the following specific steps:
(1) placing polyphenyl ether (number average molecular weight 30000, 0.02mol, 2.4040 g) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 20mL of chlorobenzene, introducing nitrogen after completely dissolving, heating to 135 ℃, adding liquid bromine (0.02 mol, 1.0246 mL), reacting for 4 hours, pouring the resultant into anhydrous methanol for precipitation, washing with the anhydrous methanol for several times, and drying at 80 ℃ to obtain bromomethylated polyphenyl ether;
(2) placing the bromomethylated polyphenylene oxide (0.001 mol, 2.0050 g) obtained in the step (1) in NaOH solution (2 mol/L), soaking for 24h at 70 ℃, washing for several times by using distilled water, and drying to obtain partially hydroxylated brominated polyphenylene oxide;
(3) under the condition of introducing nitrogen, putting the partially hydroxylated brominated polyphenylene oxide (0.001 mol, 1.9820 g) obtained in the step (2) and a boron trifluoride diethyl etherate complex catalyst (0.0038 mL) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, after complete dissolution, slowly dropwise adding epoxy chloropropane (0.0015 mol, 0.1388 g) under the stirring state, maintaining at 65 ℃ for 6 hours to complete the reaction, then pouring the product into a saturated sodium bicarbonate solution for washing, and obtaining an etherified product after reduced pressure distillation;
(4) and (3) putting the etherified product (0.001 mol, 3.5840 g) obtained in the step (3) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, maintaining the temperature at 20 ℃ after completely dissolving, adding perfluorotriethylamine (0.002 mol, 0.4275mL, available in the market) to react for 24h to obtain a quaternized product, pouring the reaction solution into a polytetrafluoroethylene mold, carrying out heat treatment at 150 ℃ for 2h, cooling and demolding to obtain the high-conductivity polyphenylene ether anion exchange membrane.
Tests prove that the tensile strength of the anion-exchange membrane prepared in the embodiment is 20.6MPa, the ion exchange capacity is 1.85mmol/g, the conductivity is 0.042S/cm, the conductivity reduction rates of the membrane after the membrane is soaked in lmol/L, 3mol/L and 5mol/LKOH solutions for 8 days at normal temperature are 8.23%, 8.85% and 10.08% respectively, the alkali resistance is good, and the conductivity of the membrane after the membrane is soaked in 3mol/LKOH solutions for 8 days at 60 ℃ is 0.038S/cm.
Example 4
The preparation method of the high-conductivity polyphenyl ether anion exchange membrane comprises the following specific steps:
(1) placing polyphenyl ether (number average molecular weight 30000, 0.02mol, 2.4040 g) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 20mL of chlorobenzene, introducing nitrogen after completely dissolving, heating to 135 ℃, adding liquid bromine (0.02 mol, 1.0246 mL), reacting for 4 hours, pouring the resultant into anhydrous methanol for precipitation, washing with the anhydrous methanol for several times, and drying at 80 ℃ to obtain bromomethylated polyphenyl ether;
(2) placing the bromomethylated polyphenylene oxide (0.001 mol, 2.0050 g) obtained in the step (1) in NaOH solution (2 mol/L), soaking for 24h at 70 ℃, washing for several times by using distilled water, and drying to obtain partially hydroxylated brominated polyphenylene oxide;
(3) under the condition of introducing nitrogen, putting the partially hydroxylated brominated polyphenylene oxide (0.001 mol, 1.9820 g) obtained in the step (2) and a boron trifluoride diethyl etherate complex catalyst (0.0038 mL) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, after complete dissolution, slowly dropwise adding epoxy chloropropane (0.0015 mol, 0.1388 g) under the stirring state, maintaining at 65 ℃ for 6 hours to complete the reaction, then pouring the product into a saturated sodium bicarbonate solution for washing, and obtaining an etherified product after reduced pressure distillation;
(4) and (3) putting the etherified product (0.001 mol, 3.5840 g) obtained in the step (3) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, maintaining the temperature at 30 ℃ after completely dissolving, adding trimethylamine (0.002 mol, 0.3933mL of a commercially available 30wt% trimethylamine ethanol solution) for reacting for 24h to obtain a quaternized product, pouring the reaction solution into a polytetrafluoroethylene mold, carrying out heat treatment for 2h at 150 ℃, cooling and demolding to obtain the high-conductivity polyphenylene ether anion-exchange membrane.
Tests prove that the tensile strength of the anion-exchange membrane prepared in the embodiment is 16.6MPa, the ion exchange capacity is 1.92mmol/g, the conductivity is 0.050S/cm, the conductivity reduction rates of the membrane after the membrane is soaked in lmol/L, 3mol/L and 5mol/LKOH solutions for 8 days at normal temperature are 10.35%, 10.82% and 11.52% respectively, the alkali resistance is good, and the conductivity of the membrane after the membrane is soaked in the 3mol/LKOH solution for 8 days at 60 ℃ is 0.044S/cm.
Example 5
The preparation method of the high-conductivity polyphenyl ether anion exchange membrane comprises the following specific steps:
(1) placing polyphenyl ether (number average molecular weight 30000, 0.02mol, 2.4040 g) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 20mL of chlorobenzene, introducing nitrogen after completely dissolving, heating to 135 ℃, adding liquid bromine (0.02 mol, 1.0246 mL), reacting for 4 hours, pouring the resultant into anhydrous methanol for precipitation, washing with the anhydrous methanol for several times, and drying at 80 ℃ to obtain bromomethylated polyphenyl ether;
(2) placing the bromomethylated polyphenylene oxide (0.001 mol, 2.0050 g) obtained in the step (1) in NaOH solution (2 mol/L), soaking for 24h at 70 ℃, washing for several times by using distilled water, and drying to obtain partially hydroxylated brominated polyphenylene oxide;
(3) under the condition of introducing nitrogen, putting the partially hydroxylated brominated polyphenylene oxide (0.001 mol, 1.9820 g) obtained in the step (2) and a boron trifluoride diethyl etherate complex catalyst (0.0038 mL) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, after complete dissolution, slowly dropwise adding epoxy chloropropane (0.0015 mol, 0.1388 g) under the stirring state, maintaining at 65 ℃ for 6 hours to complete the reaction, then pouring the product into a saturated sodium bicarbonate solution for washing, and obtaining an etherified product after reduced pressure distillation;
(4) and (3) putting the etherified product (0.001 mol, 3.5840 g) obtained in the step (3) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, maintaining the temperature at 30 ℃ after completely dissolving, adding triethylamine (0.002 mol, 0.2780mL, available in the market) to react for 24h to obtain a quaternized product, pouring the reaction solution into a polytetrafluoroethylene mold, carrying out heat treatment at 150 ℃ for 2h, cooling and demolding to obtain the high-conductivity polyphenylene ether anion exchange membrane.
Tests prove that the tensile strength of the anion-exchange membrane prepared in the embodiment is 20.3MPa, the ion exchange capacity is 1.81mmol/g, the conductivity is 0.038S/cm, the conductivity reduction rates of the membrane after the membrane is soaked in lmol/L, 3mol/L and 5mol/LKOH solutions for 8 days at normal temperature are 8.36%, 9.27% and 9.86% respectively, the alkali resistance is good, and the conductivity of the membrane after the membrane is soaked in 3mol/LKOH solutions for 8 days at 60 ℃ is 0.035S/cm.
Example 6
The preparation method of the high-conductivity polyphenyl ether anion exchange membrane comprises the following specific steps:
(1) placing polyphenyl ether (number average molecular weight 30000, 0.02mol, 2.4040 g) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 20mL of chlorobenzene, introducing nitrogen after completely dissolving, heating to 135 ℃, adding liquid bromine (0.02 mol, 1.0246 mL), reacting for 4 hours, pouring the resultant into anhydrous methanol for precipitation, washing with the anhydrous methanol for several times, and drying at 80 ℃ to obtain bromomethylated polyphenyl ether;
(2) placing the bromomethylated polyphenylene oxide (0.001 mol, 2.0050 g) obtained in the step (1) in NaOH solution (2 mol/L), soaking for 24h at 70 ℃, washing for several times by using distilled water, and drying to obtain partially hydroxylated brominated polyphenylene oxide;
(3) under the condition of introducing nitrogen, putting the partially hydroxylated brominated polyphenylene oxide (0.001 mol, 1.9820 g) obtained in the step (2) and a boron trifluoride diethyl etherate complex catalyst (0.0038 mL) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, after complete dissolution, slowly dropwise adding epoxy chloropropane (0.0015 mol, 0.1388 g) under the stirring state, maintaining at 65 ℃ for 6 hours to complete the reaction, then pouring the product into a saturated sodium bicarbonate solution for washing, and obtaining an etherified product after reduced pressure distillation;
(4) and (3) putting the etherified product (0.001 mol, 3.5840 g) obtained in the step (3) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, maintaining the temperature at 30 ℃ after completely dissolving, adding perfluorotriethylamine (0.002 mol, 0.4275mL, available in the market) to react for 24h to obtain a quaternized product, pouring the reaction solution into a polytetrafluoroethylene mold, carrying out heat treatment at 150 ℃ for 2h, cooling and demolding to obtain the high-conductivity polyphenylene ether anion exchange membrane.
Tests prove that the tensile strength of the anion-exchange membrane prepared in the embodiment is 21.3MPa, the ion exchange capacity is 1.89mmol/g, the conductivity is 0.046S/cm, the conductivity reduction rates of the membrane after the membrane is soaked in lmol/L, 3mol/L and 5mol/LKOH solutions for 8 days at normal temperature are 7.12%, 7.53% and 8.18% respectively, the alkali resistance is good, and the conductivity of the membrane after the membrane is soaked in 3mol/LKOH solutions for 8 days at 60 ℃ is 0.037S/cm.
Example 7
The preparation method of the high-conductivity polyphenyl ether anion exchange membrane comprises the following specific steps:
(1) placing polyphenyl ether (number average molecular weight 30000, 0.02mol, 2.4040 g) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 20mL of chlorobenzene, introducing nitrogen after completely dissolving, heating to 135 ℃, adding liquid bromine (0.02 mol, 1.0246 mL), reacting for 4 hours, pouring the resultant into anhydrous methanol for precipitation, washing with the anhydrous methanol for several times, and drying at 80 ℃ to obtain bromomethylated polyphenyl ether;
(2) placing the bromomethylated polyphenylene oxide (0.001 mol, 2.0050 g) obtained in the step (1) in NaOH solution (2 mol/L), soaking for 24h at 70 ℃, washing for several times by using distilled water, and drying to obtain partially hydroxylated brominated polyphenylene oxide;
(3) under the condition of introducing nitrogen, putting the partially hydroxylated brominated polyphenylene oxide (0.001 mol, 1.9820 g) obtained in the step (2) and a boron trifluoride diethyl etherate complex catalyst (0.0038 mL) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, after complete dissolution, slowly dropwise adding epoxy chloropropane (0.0015 mol, 0.1388 g) under the stirring state, maintaining at 65 ℃ for 6 hours to complete the reaction, then pouring the product into a saturated sodium bicarbonate solution for washing, and obtaining an etherified product after reduced pressure distillation;
(4) and (3) putting the etherified product (0.001 mol, 3.5840 g) obtained in the step (3) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, maintaining the temperature at 40 ℃ after complete dissolution, adding trimethylamine (0.002 mol, 0.3933mL of a commercially available 30wt% trimethylamine ethanol solution) for reaction for 24 hours to obtain a quaternized product, pouring the reaction solution into a polytetrafluoroethylene mold, carrying out heat treatment for 2 hours at 150 ℃, cooling and demolding to obtain the high-conductivity polyphenylene ether anion-exchange membrane.
Tests prove that the tensile strength of the anion-exchange membrane prepared in the embodiment is 17.8MPa, the ion exchange capacity is 1.53mmol/g, the conductivity is 0.025S/cm, the conductivity reduction rates of the membrane after the membrane is soaked in lmol/L, 3mol/L and 5mol/LKOH solutions for 8 days at normal temperature are 9.75%, 10.23% and 10.98% respectively, the alkali resistance is good, and the conductivity of the membrane after the membrane is soaked in 3mol/LKOH solutions for 8 days at 60 ℃ is 0.024S/cm.
Example 8
The preparation method of the high-conductivity polyphenyl ether anion exchange membrane comprises the following specific steps:
(1) placing polyphenyl ether (number average molecular weight 30000, 0.02mol, 2.4040 g) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 20mL of chlorobenzene, introducing nitrogen after completely dissolving, heating to 135 ℃, adding liquid bromine (0.02 mol, 1.0246 mL), reacting for 4 hours, pouring the resultant into anhydrous methanol for precipitation, washing with the anhydrous methanol for several times, and drying at 80 ℃ to obtain bromomethylated polyphenyl ether;
(2) placing the bromomethylated polyphenylene oxide (0.001 mol, 2.0050 g) obtained in the step (1) in NaOH solution (2 mol/L), soaking for 24h at 70 ℃, washing for several times by using distilled water, and drying to obtain partially hydroxylated brominated polyphenylene oxide;
(3) under the condition of introducing nitrogen, putting the partially hydroxylated brominated polyphenylene oxide (0.001 mol, 1.9820 g) obtained in the step (2) and a boron trifluoride diethyl etherate complex catalyst (0.0038 mL) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, after complete dissolution, slowly dropwise adding epoxy chloropropane (0.0015 mol, 0.1388 g) under the stirring state, maintaining at 65 ℃ for 6 hours to complete the reaction, then pouring the product into a saturated sodium bicarbonate solution for washing, and obtaining an etherified product after reduced pressure distillation;
(4) and (3) putting the etherified product (0.001 mol, 3.5840 g) obtained in the step (3) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, maintaining the temperature at 40 ℃ after completely dissolving, adding triethylamine (0.002 mol, 0.2780mL, available in the market) to react for 24h to obtain a quaternized product, pouring the reaction solution into a polytetrafluoroethylene mold, carrying out heat treatment at 150 ℃ for 2h, cooling and demolding to obtain the high-conductivity polyphenylene ether anion exchange membrane.
Tests prove that the tensile strength of the anion-exchange membrane prepared in the embodiment is 21.5MPa, the ion exchange capacity is 1.90mmol/g, the conductivity is 0.047S/cm, the conductivity reduction rates of the membrane after the membrane is soaked in lmol/L, 3mol/L and 5mol/LKOH solutions for 8 days at normal temperature are 7.41%, 8.23% and 8.98% respectively, the alkali resistance is good, and the conductivity of the membrane after the membrane is soaked in 3mol/LKOH solutions for 8 days at 60 ℃ is 0.043S/cm.
Example 9
The preparation method of the high-conductivity polyphenyl ether anion exchange membrane comprises the following specific steps:
(1) placing polyphenyl ether (number average molecular weight 30000, 0.02mol, 2.4040 g) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 20mL of chlorobenzene, introducing nitrogen after completely dissolving, heating to 135 ℃, adding liquid bromine (0.02 mol, 1.0246 mL), reacting for 4 hours, pouring the resultant into anhydrous methanol for precipitation, washing with the anhydrous methanol for several times, and drying at 80 ℃ to obtain bromomethylated polyphenyl ether;
(2) placing the bromomethylated polyphenylene oxide (0.001 mol, 2.0050 g) obtained in the step (1) in NaOH solution (2 mol/L), soaking for 24h at 70 ℃, washing for several times by using distilled water, and drying to obtain partially hydroxylated brominated polyphenylene oxide;
(3) under the condition of introducing nitrogen, putting the partially hydroxylated brominated polyphenylene oxide (0.001 mol, 1.9820 g) obtained in the step (2) and a boron trifluoride diethyl etherate complex catalyst (0.0038 mL) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, after complete dissolution, slowly dropwise adding epoxy chloropropane (0.0015 mol, 0.1388 g) under the stirring state, maintaining at 65 ℃ for 6 hours to complete the reaction, then pouring the product into a saturated sodium bicarbonate solution for washing, and obtaining an etherified product after reduced pressure distillation;
(4) and (3) putting the etherified product (0.001 mol, 3.5840 g) obtained in the step (3) into a dry four-neck flask provided with a stirrer, a thermometer and a condenser, adding 15mL of N-methylpyrrolidone, maintaining the temperature at 40 ℃ after completely dissolving, adding perfluorotriethylamine (0.002 mol, 0.4275mL, available in the market) to react for 24h to obtain a quaternized product, pouring the reaction solution into a polytetrafluoroethylene mold, carrying out heat treatment at 150 ℃ for 2h, cooling and demolding to obtain the high-conductivity polyphenylene ether anion exchange membrane.
Tests prove that the tensile strength of the anion-exchange membrane prepared in the embodiment is 19.7MPa, the ion exchange capacity is 1.94mmol/g, the conductivity is 0.049S/cm, the conductivity reduction rates of the membrane after the membrane is soaked in lmol/L, 3mol/L and 5mol/LKOH solutions for 8 days at normal temperature are 9.58%, 9.83% and 10.28% respectively, the alkali resistance is good, and the conductivity of the membrane after the membrane is soaked in 3mol/LKOH solutions for 8 days at 60 ℃ is 0.040S/cm.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A preparation method of a high-conductivity polyphenyl ether anion exchange membrane is characterized by comprising the following steps: the polyphenyl ether is brominated and hydroxylated modified to obtain partially hydroxylated brominated polyphenyl ether, then the partially hydroxylated brominated polyphenyl ether is reacted with epoxy chloropropane to generate ether, the obtained product is reacted with a quaternizing agent to introduce a conduction site, and finally a crosslinking structure is generated through heat treatment to obtain the high-conductivity polyphenyl ether anion exchange membrane.
2. The method for preparing a highly conductive polyphenylene ether anion exchange membrane according to claim 1, wherein: the specific preparation method is as follows,
dissolving polyphenyl ether in a solvent, adding a bromination reagent under the condition of introducing nitrogen gas, carrying out bromination reaction to obtain a bromomethylated polyphenyl ether solution, and precipitating and drying to obtain the bromomethylated polyphenyl ether;
soaking the bromomethylated polyphenylene oxide obtained in the step (1) in a sodium hydroxide solution, then reacting at a constant temperature for a period of time to obtain a partially hydroxylated brominated polyphenylene oxide solution, and washing and drying to obtain the partially hydroxylated brominated polyphenylene oxide;
dissolving part of the hydroxylated brominated polyphenylene ether obtained in the step (2) in a solvent to obtain a part of hydroxylated brominated polyphenylene ether solution, slowly dropwise adding epoxy chloropropane under the condition of introducing nitrogen to perform ring opening ether forming reaction, washing by using a saturated sodium bicarbonate solution, and drying to obtain an etherified product;
and (4) dissolving the etherified product obtained in the step (3) in a solvent, adding a quaternization reagent under the condition of introducing nitrogen, carrying out quaternization reaction to obtain a quaternization polyphenyl ether anion exchange membrane solution, then pouring the quaternization polyphenyl ether anion exchange membrane solution into a polytetrafluoroethylene mould disc for heat treatment, cooling and demoulding to obtain the polyphenyl ether anion exchange membrane with high conductivity.
3. The method for preparing a highly conductive polyphenylene ether anion exchange membrane according to claim 2, wherein: the molar ratio of the polyphenyl ether to the brominating reagent in the step (1) is 1: 1, the brominating reagent is liquid bromine, and the solvent is chlorobenzene.
4. The method for preparing a highly conductive polyphenylene ether anion exchange membrane according to claim 2, wherein: in the step (1), the bromination reaction temperature is 135 ℃, and the reaction time is 4-6 h.
5. The method for preparing a highly conductive polyphenylene ether anion exchange membrane according to claim 2, wherein: in the step (2), the molar concentration of the sodium hydroxide solution is 2-4 mol/L, the reaction temperature is 70-90 ℃, and the reaction time is 20-30 h.
6. The method for preparing a highly conductive polyphenylene ether anion exchange membrane according to claim 2, wherein: in the step (3), the molar ratio of the partially hydroxylated brominated polyphenylene ether to the epichlorohydrin is 1: 1-2, wherein the solvent is chlorobenzene.
7. The method for preparing a highly conductive polyphenylene ether anion exchange membrane according to claim 2, wherein: in the step (3), the ring-opening ether-forming reaction temperature is 45-65 ℃, and the reaction time is 5-7 h.
8. The method for preparing a highly conductive polyphenylene ether anion exchange membrane according to claim 2, wherein: in the step (4), the molar ratio of the etherification product to the quaternizing agent is 1: 1-2, wherein the solvent is N-methylpyrrolidone, and the quaternizing agent is one of trimethylamine, triethylamine and perfluorinated triethylamine.
9. The method for preparing a highly conductive polyphenylene ether anion exchange membrane according to claim 2, wherein: in the step (4), the quaternization reaction temperature is 20-40 ℃, and the reaction time is 20-24 h.
10. The method for preparing a highly conductive polyphenylene ether anion exchange membrane according to claim 2, wherein: in the step (4), the heat treatment temperature is 150 ℃, and the heat treatment time is 2 hours.
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