CN110564150A - long side chain type quaternized polybenzimidazole crosslinked membrane and preparation method thereof - Google Patents
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Abstract
The invention discloses a long-side-chain type quaternized polybenzimidazole crosslinking membrane and a preparation method thereof. The crosslinking density can be controlled by controlling the mass ratio of the long side chain type quaternized polybenzimidazole to the epoxy resin. The all-vanadium redox flow battery assembled by the prepared long-side chain type quaternized polybenzimidazole crosslinked membrane has excellent charge and discharge performance, very low self-discharge rate and very good cycle stability, and is remarkably superior to the all-vanadium redox flow battery assembled by a Nafion commercial membrane.
Description
Technical Field
the invention relates to the field of chemistry, in particular to a long-side-chain type quaternized polybenzimidazole crosslinked membrane and a preparation method thereof.
background
as one of large-scale energy storage technologies, the all-vanadium redox flow battery (VRB) has the advantages of high safety, long life cycle, high cost performance, flexible design, high response speed, small environmental damage and the like, is accepted by the market, and becomes the first choice of the large-scale electrochemical energy storage technology. The diaphragm is one of the key components of the VRB, and functions as: 1) the positive and negative electrolytes are isolated, so that the cross contamination of the electrolytes is avoided, and an oxidation-reduction reaction is generated; 2) conducting protons. The performance of the diaphragm is directly related to the conversion energy storage efficiency and the cycle life of the vanadium battery. Currently commercialized membranes are mainly proton exchange membranes based on perfluorosulfonic acid resins, such as: nafion, which has high proton conductivity and excellent chemical stability, but has poor vanadium resistance, and electrolyte permeates mutually to cause serious self-discharge phenomenon, so that the coulomb efficiency of the battery is reduced, and the charge-discharge capacity is attenuated; in addition, the water migration phenomenon of the membrane is severe, and concentration polarization occurs on electrolyte on two sides. Although the literature reports that the vanadium resistance of the Nafion membrane can be improved by modifying the Nafion membrane, so that the coulomb efficiency of the battery is improved, the conductivity of the membrane is reduced, so that the voltage efficiency is reduced, and the manufacturing cost of the membrane is further increased. Compared with Nafion, sulfonated hydrocarbon membranes (such as sulfonated polystyrene, sulfonated polyether sulfone, sulfonated polyether ketone, sulfonated polyimide and the like) generally have the advantages of low cost, good heat resistance, higher mechanical strength and modulus, lower fuel and vanadium ion permeability, abundant and various chemical structures and the like, but most sulfonated hydrocarbon membranes have much poorer chemical stability than Nafion, so that the service life of the battery is short, and the requirements of practical use cannot be met. Polybenzimidazole is an aromatic heterocyclic polymer, and has excellent chemical stability compared with most hydrocarbon polymers. However, the imidazole group in the polybenzimidazole structure has basicity and is neutralized with a sulfonic acid group to generate imidazolium sulfonate, thereby greatly reducing proton conductivity of the membrane.
disclosure of Invention
in order to solve the problems, the invention discloses a long side chain type quaternized polybenzimidazole crosslinked membrane and a preparation method thereof.
The technical scheme of the invention is as follows: a long side chain type quaternized polybenzimidazole crosslinked membrane has the following chemical structure:
wherein x + y + z = 1, and x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1; n = 50-1000.
a method for preparing a long side chain type quaternized polybenzimidazole crosslinked membrane comprises the following steps:
Step 1) Synthesis of Monoquaternary ammonium salt intermediate
The reaction equation is as follows:
Under the protection of nitrogen, sequentially adding toluene, acetonitrile, N, N, N ', N' -tetramethyl-1, 6-hexanediamine and 1-bromo-N-hexane into a dry and clean three-neck flask, stirring for 30min at room temperature, heating to 50-80 ℃, reacting for 2-20 h at the temperature, cooling to room temperature after the reaction is finished, removing a mixed solvent of the toluene and the acetonitrile by a reduced pressure distillation method, washing the product with petroleum ether for 3-4 times, separating out the upper layer liquid each time, and carrying out reduced pressure distillation again to recover the unreacted N, N, N ', N' -tetramethyl-1, 6-hexanediamine, wherein the lower layer light yellow liquid is a reaction product named as quaternary ammonium salt B;
Step 2) Synthesis of Monoepoxy-terminated BiQuaternary ammonium salt
the reaction equation is as follows:
sequentially adding the prepared quaternary ammonium salt intermediate B and acetone into a dry and clean three-neck flask under the protection of nitrogen, magnetically stirring until the quaternary ammonium salt intermediate B and the acetone are completely dissolved, adding 1-bromo-5, 6-epoxyhexane, reacting at room temperature for 20-80 h, separating out a white solid, washing the product for 3-4 times by using the acetone as a solvent after the reaction is finished, and removing unreacted 1-bromo-5, 6-epoxyhexane to prepare a white solid mono-epoxy-terminated biquaternary ammonium salt D;
Step 3) synthesis of long side chain type quaternized polybenzimidazole
The reaction equation is as follows:
Wherein x + y + z = 1, and x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1; n = 50-1000;
The amino (-NH 2) in the structure of the polybenzimidazole containing side amino (H2N-PBI) reacts with the epoxy group in the structure of quaternary ammonium salt D to generate the quaternized polybenzimidazole with long side chain, and the Ion Exchange Capacity (IEC) of the quaternized polybenzimidazole product can be controlled by controlling the molar ratio of the amino (-NH 2) to the quaternary ammonium salt D;
Sequentially adding a solvent containing lateral amino polybenzimidazole (H2N-PBI) and dimethyl sulfoxide (DMSO) into a dry and clean three-neck flask under the protection of nitrogen, magnetically stirring for 30min, heating to 60-90 ℃, cooling to room temperature after the polymer is completely dissolved, adding quaternary ammonium salt D, continuously stirring for 30min under the protection of nitrogen, heating to 50-120 ℃, reacting for 2-20H at the temperature, cooling to room temperature, pouring a highly viscous solution in a reaction bottle into a large amount of acetone, separating out the polymer, washing with acetone, and drying for 10H under vacuum at 50 ℃ to obtain long-side-chain type quaternized polybenzimidazole;
Step 4) preparation of long side chain type quaternized polybenzimidazole crosslinked membrane
unreacted amino groups in the long-side-chain quaternized polybenzimidazole structure and hydroxyl groups formed in the quaternization reaction process can be subjected to crosslinking reaction with common epoxy resin to prepare a long-side-chain quaternized polybenzimidazole crosslinking film; the crosslinking density can be controlled by controlling the mass ratio of the long-side chain type quaternized polybenzimidazole to the epoxy resin; the epoxy resin includes bisphenol A type epoxy resin (BADGE), Ethylene Glycol Diglycidyl Ether (EGDE), etc.
Dissolving the long side chain type quaternized polybenzimidazole in dimethyl sulfoxide to prepare a 2-20 w/v% solution, adding an epoxy resin crosslinking agent, fully and uniformly stirring, filtering the solution, defoaming under negative pressure, directly casting the solution on a dry and clean glass plate, and drying the glass plate for 4-10 hours in a constant-temperature forced air drying oven at 60-100 ℃ to prepare the long side chain type quaternized polybenzimidazole crosslinking membrane.
The crosslinking reaction mechanism is based on the reaction between unreacted amino groups in the long-side chain type quaternized polybenzimidazole structure and hydroxyl groups formed in the quaternization reaction process and epoxy groups in the epoxy resin, and the crosslinking density can be controlled by controlling the mass ratio of the long-side chain type quaternized polybenzimidazole to the epoxy resin.
preferably, the preparation method of the long ~ side ~ chain type quaternized polybenzimidazole crosslinked membrane is characterized in that a mixture of toluene and acetonitrile in the step 1) is used as a reaction medium, the volume ratio of the toluene to the acetonitrile is 1:5 ~ 5:1, and the toluene, the acetonitrile and the 1 ~ bromo ~ N ~ hexane are used as reactants, the molar ratio of the toluene to the acetonitrile is 20:1 ~ 2:1, and the concentration of the reactants is 2 ~ 50 w/v%.
preferably, the concentration of the reactants in step 2) is between 20 and 300 w/v%.
preferably, the molar ratio of the amino (~ NH 2) in the side amino polybenzimidazole structure to the epoxy group in the quaternary ammonium salt D structure in the step 3) is 1:0.1 ~ 1:1.9, and the reactant concentration is 2 ~ 30 w/v%.
preferably, the epoxy resin cross ~ linking agent in the step 4) is a common industrial industrialized epoxy resin, the epoxy resin cross ~ linking agent is bisphenol A type epoxy resin (BADGE) or Ethylene Glycol Diglycidyl Ether (EGDE), and the mass ratio of the long ~ side chain type quaternized polybenzimidazole to the epoxy resin is 50:1 ~ 2: 1.
the long-side-chain type quaternized polybenzimidazole crosslinked membrane is mainly used as a diaphragm of an all-vanadium redox flow battery, and can be used in other fields such as: the alkaline anion exchange membrane fuel cell, the ion exchange resin, the electrolyzed water and the like also have potential application prospects.
The invention discloses a long side chain type quaternized polybenzimidazole crosslinked membrane and a preparation method thereof, aiming at improving the proton conductivity of a polybenzimidazole membrane and further improving the vanadium resistance of the polybenzimidazole membrane. On one hand, as the quaternary ammonium group and the polybenzimidazole main chain have no strong interaction, the proton conductivity of the diaphragm can be obviously improved by improving the ion exchange capacity of the diaphragm; on the other hand, the long side chain of quaternary ammonium salt is beneficial to the formation of a micro-phase separation structure of the membrane, thereby being beneficial to proton conduction. In addition, the vanadium resistance of the diaphragm can be further improved by the repulsion effect (Tangna effect) between the quaternary ammonium salt and the vanadium ions, and the swelling of the diaphragm can be obviously inhibited by valence-supplying crosslinking, so that good mechanical properties are maintained and the service life is prolonged.
the invention has the advantages that: the all-vanadium redox flow battery assembled by the prepared long-side chain type quaternized polybenzimidazole crosslinked membrane has excellent charge and discharge performance, very low self-discharge rate and very good cycle stability, and is remarkably superior to the all-vanadium redox flow battery assembled by a Nafion commercial membrane.
Drawings
FIG. 1 is a chart of the hydrogen nuclear magnetic resonance spectrum of intermediate B which is a quaternary ammonium salt (solvent: DMSO-d 6);
FIG. 2 is a NMR spectrum of a mono-epoxy-terminated diquaternary ammonium salt D (solvent: DMSO-D6);
FIG. 3 is a self ~ discharge curve of an all ~ vanadium liquid flow single cell assembled from long side chain type quaternized polybenzimidazole crosslinked membranes of examples 1 ~ 5 and a commercial membrane of Nafion212, respectively;
FIG. 4 is a charge-discharge cycle curve at a current density of 80 mA cm-2 for an all-vanadium flow cell assembled from long side chain type quaternized polybenzimidazole crosslinked membrane NH2PBI-D (1:0.8) -CL of example 1.
Detailed Description
for the purpose of enhancing understanding of the present invention, the following detailed description will be given in conjunction with examples, which are provided for illustration only and do not limit the scope of the present invention.
example 1
step 1) synthesis of a mono-quaternary ammonium salt intermediate B:
Adding 75 mL of toluene and 75 mL of acetonitrile into a 100 mL dry clean three-neck flask in sequence, magnetically stirring under the protection of nitrogen until the toluene and the acetonitrile are completely and uniformly mixed, then adding 25.8 g N, N, N ', N' -tetramethyl-1, 6-hexanediamine and 2.475 g of 1-bromon-hexane in sequence, stirring at room temperature for 30min, heating to 70 ℃ for reaction, reacting for 12 h, finishing the reaction, and cooling to room temperature. Removing the mixed solvent of toluene and acetonitrile by reduced pressure distillation, repeatedly washing the product with petroleum ether for 3 times, separating the upper layer liquid each time, and recovering the unreacted N, N, N ', N' -tetramethyl-1, 6-hexanediamine by reduced pressure distillation again. The lower pale yellow liquid was reaction product B in 91% yield. The NMR spectrum of the product (solvent: DMSO-d 6) is shown in FIG. 1, and the spectrum analysis result is consistent with the chemical structure.
The NMR spectrum of the product (solvent: DMSO-d 6) is shown in FIG. 1, the peak assignments are labeled in the figure, and the spectrum analysis result is consistent with the chemical structure.
step 2) synthesis of mono-epoxy-terminated bis-quaternary ammonium salt D:
In a 100 mL dry clean three-necked flask, 9.07 g of the quaternary ammonium salt prepared in example 1 and 10 mL of acetone were sequentially added, and after magnetic stirring was performed under nitrogen protection until complete and uniform mixing, 4.77 g of 1-bromo-5, 6-epoxyhexane was added, and the mixture was reacted at room temperature for 48 hours, whereby a white solid was precipitated. After the reaction is finished, repeatedly washing the product for 3 times by using acetone as a solvent, and removing unreacted 1-bromo-5, 6-epoxyhexane to obtain a white solid, namely the bifunctional group single epoxy end group quaternary ammonium salt D, wherein the yield is 97%.
The NMR spectrum of the product (solvent: DMSO-d 6) is shown in FIG. 2, the peak assignments are labeled in the figure, and the spectrum analysis result is consistent with the chemical structure.
Step 3) synthesis of long side chain type quaternized polybenzimidazole NH2PBI-D (1: 0.8):
0.2 g of side-amino-containing polybenzimidazole (H2N-PBI) and 5 mL of dimethyl sulfoxide (DMSO) solvent are sequentially added into a 100 mL dry clean three-neck flask under the protection of nitrogen, magnetic stirring is carried out for 30min, then the temperature is raised to about 80 ℃, after the polymer is completely dissolved, the temperature is cooled to room temperature, 0.2556 g of quaternary ammonium salt D prepared in the step 2 is added, stirring is continued for 30min under the protection of nitrogen, then the temperature is raised to 80 ℃, and reaction is carried out for 10H at the temperature. After cooling to room temperature, the highly viscous solution in the reaction flask was poured into 50 mL of acetone, and the precipitated polymer was washed three times with acetone and dried under vacuum at 50 ℃ for 10 h to give a long side-chain quaternized polybenzimidazole, named: NH2PBI-D (1: 0.8).
Step 4) preparation of long side chain type quaternized polybenzimidazole crosslinked membrane NH2PBI-D (1:0.8) -CL:
dissolving 0.50g of long side chain type quaternized polybenzimidazole NH2PBI-D (1:0.8) prepared in the step 3 in dimethyl sulfoxide to prepare a 5 w/v% solution, adding 0.18g of bisphenol A type epoxy resin crosslinking agent, fully and uniformly stirring, filtering the solution, defoaming under negative pressure, directly casting on a dry and clean glass plate, and placing in a constant temperature forced air drying oven to dry for 6 hours at the temperature of 80 ℃ to prepare the long side chain type quaternized polybenzimidazole crosslinking membrane, which is named as: NH2PBI-D (1:0.8) -CL. Film thickness: 33 μm and a tensile strength of 39MPa and an elongation at break of 4.1% measured at room temperature, 50% relative humidity and a tensile rate of 2 mm/min.
example 2
step 1) ~ step 2) are the same as example 1;
Step 3) synthesis of long side chain type quaternized polybenzimidazole NH2PBI-D (1: 0.6):
0.2 g of side-amino-containing polybenzimidazole (H2N-PBI) and 5 mL of dimethyl sulfoxide (DMSO) solvent are sequentially added to a 100 mL dry clean three-necked flask under the protection of nitrogen, magnetically stirred for 30min, heated to about 80 ℃, cooled to room temperature after the polymer is completely dissolved, added with 0.1917 g of the quaternary ammonium salt D prepared in step 2 of example 1, stirred for 30min under the protection of nitrogen, heated to 80 ℃, and reacted at the temperature for 10H. After cooling to room temperature, the highly viscous solution in the reaction flask was poured into 50 mL of acetone, and the precipitated polymer was washed three times with acetone and dried under vacuum at 50 ℃ for 10 h to give a long side-chain quaternized polybenzimidazole, named: NH2PBI-D (1: 0.6).
Step 4) preparation of long side chain type quaternized polybenzimidazole crosslinked membrane NH2PBI-D (1:0.6) -CL:
A long side chain type quaternized polybenzimidazole NH2PBI-D (1:0.6) -CL prepared by step 3 of example 1 was replaced with long side chain type quaternized polybenzimidazole NH2PBI-D (1:0.8) prepared by step 3 of example 1 under the same conditions as in step 4 of example 1 to obtain a long side chain type quaternized polybenzimidazole crosslinked membrane NH2PBI-D (1:0.6) -CL. Film thickness: 34 μm, a tensile strength of 52MPa and an elongation at break of 8.5% measured at room temperature, 50% relative humidity and a tensile rate of 2 mm/min.
Example 3
step 1) ~ step 2) are the same as example 1;
Step 3) synthesis of long side chain type quaternized polybenzimidazole NH2PBI-D (1: 1):
0.2 g of side-amino-containing polybenzimidazole (H2N-PBI) and 5 mL of dimethyl sulfoxide (DMSO) solvent are sequentially added to a 100 mL dry clean three-necked flask under the protection of nitrogen, magnetically stirred for 30min, heated to about 80 ℃, cooled to room temperature after the polymer is completely dissolved, added with 0.3195 g of the quaternary ammonium salt D prepared in step 2 of example 1, stirred for 30min under the protection of nitrogen, heated to 80 ℃, and reacted at the temperature for 10H. After cooling to room temperature, the highly viscous solution in the reaction flask was poured into 50 mL of acetone, and the precipitated polymer was washed three times with acetone and dried under vacuum at 60 ℃ for 12 h to obtain a long side chain type quaternized polybenzimidazole, named: NH2PBI-D (1: 1).
Step 4) preparation of long side chain type quaternized polybenzimidazole crosslinked membrane NH2PBI-D (1:1) -CL:
a long side chain type quaternized polybenzimidazole crosslinked membrane, designated as: NH2PBI-D (1:1) -CL. Film thickness: 36 μm, a tensile strength of 37MPa and an elongation at break of 9.1% measured at room temperature, 50% relative humidity and a tensile rate of 2 mm/min.
example 4
step 1) ~ step 2) are the same as example 1;
step 3) synthesis of long side chain type quaternized polybenzimidazole NH2PBI-D (1: 0.5):
0.2 g of side-amino-containing polybenzimidazole (H2N-PBI) and 5 mL of dimethyl sulfoxide (DMSO) solvent are sequentially added to a 100 mL dry clean three-necked flask under the protection of nitrogen, magnetically stirred for 30min, heated to about 80 ℃, cooled to room temperature after the polymer is completely dissolved, added with 0.1598 g of the quaternary ammonium salt D prepared in step 2 of example 1, stirred for 30min under the protection of nitrogen, heated to 80 ℃, and reacted at the temperature for 10H. After cooling to room temperature, the highly viscous solution in the reaction flask was poured into 50 mL of acetone, and the precipitated polymer was washed three times with acetone and dried under vacuum at 50 ℃ for 10 h to give a long side-chain quaternized polybenzimidazole, named: NH2PBI-D (1: 0.5).
Step 4) preparation of long side chain type quaternized polybenzimidazole crosslinked membrane NH2PBI-D (1:0.5) -CL:
A long side chain type quaternized polybenzimidazole crosslinked membrane, named: NH2PBI-D (1:0.5) -CL. Film thickness: 31 μm and a tensile strength of 61MPa and an elongation at break of 12.7% measured at room temperature, 50% relative humidity and a tensile rate of 2 mm/min.
Example 5
all-vanadium liquid flow monocells were assembled with the four long side chain type quaternized polybenzimidazole crosslinked membranes NH2PBI-D (1:0.8) -CL, NH2PBI-D (1:0.6) -CL, NH2PBI-D (1:1) -CL, and NH2PBI-D (1:0.5) -CL prepared in examples 1-4 as separators and the commercial Nafion212 separator of the comparative example, respectively, under the following assembly conditions:
The separator was sandwiched between two graphite felt electrodes (separator effective area: 12 cm 2) and graphite paper was used as the current collector. The electrolyte of the positive electrode and the electrolyte of the negative electrode are respectively a sulfuric acid solution (sulfuric acid concentration: 2.0M) of 2.0 + 2.0M V2+/V3+ and a sulfuric acid solution (sulfuric acid concentration: 2.0M) of 2.0M VO2+/VO2+, the volumes of the electrolyte on the two sides of the positive electrode and the negative electrode are both 10 mL, and the circulation rate of the electrolyte is 10 mL min < -1 >.
and (3) carrying out charge and discharge tests on the single cells under a fixed current density by adopting a blue test system, wherein the charge and discharge current density range is 10 ~ 80 mA ~ cm & lt ~ 2 & gt, and the charge and discharge voltage range is controlled to be 0.8 ~ 1.7V.
the evaluation of the self-discharge test of the single cell is carried out according to the following conditions: the assembled VRB is charged at a current density of 40 mA cm-2, the charging is stopped when the charged charge reaches 60% (capacity of 300 mA h), the test is started when the open circuit state is maintained, and the test is ended when the voltage is lower than 0.8V.
in the VRB life cycle test, the current density is 80 mA · cm < ~ 2 > to carry out charge ~ discharge cycle, the test voltage range is 0.8 ~ 1.7V, and the coulombic efficiency, the voltage efficiency and the energy efficiency are calculated by the following formulas:
In the formula CdAnd CcRespectively, discharge capacity and charge capacity, EdAnd EcRespectively, discharge energy and charge energy.
The table I shows the coulombic efficiency, the voltage efficiency and the energy efficiency of the all-vanadium redox flow battery under the conditions that the current density is 10 and 80 mA cm & lt-2 & gt respectively. It can be seen that the energy efficiency of the all vanadium flow battery assembled from long side chain quaternized polybenzimidazole crosslinked membranes is significantly higher than that of the all vanadium flow battery assembled from Nafion212, both at low current density (10 mA · cm "2) and at high current density (80 mA · cm" 2).
watch 1
the self-discharge performance of the all-vanadium liquid flow single cells respectively assembled by the long-side chain type quaternized polybenzimidazole crosslinked membranes NH2PBI-D (1:0.8) -CL and the Nafion212 commercial membranes in the examples 1-4 is shown in FIG. 3.
FIG. 4 is a charge-discharge cycle curve of the all-vanadium redox flow battery cell assembled by the long-side chain type quaternized polybenzimidazole crosslinked membrane NH2PBI-D (1:0.8) -CL in example 1 at a current density of 80 mA cm-2, and it can be seen that after 100 cycles of charge-discharge, there is no any attenuation in the coulombic efficiency, voltage efficiency and energy efficiency of the battery, and the battery is proved to have excellent cycle stability. The residual discharge capacity is slightly reduced along with the increase of the number of charging and discharging operations of the battery, and finally the residual discharge capacity is kept at 72.4%, while the residual discharge capacity of all-vanadium liquid flow single batteries respectively assembled by Nafion212 commercial membranes under the same conditions is only 41.6% after 100 charging and discharging cycles.
Claims (6)
1. a long side chain type quaternized polybenzimidazole crosslinked membrane is characterized in that the chemical structure is as follows:
wherein x + y + z = 1, and x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1; n = 50-1000.
2. The method for preparing a long-side-chain quaternized polybenzimidazole crosslinked membrane according to claim 1, comprising the steps of:
Step 1) Synthesis of Monoquaternary ammonium salt intermediate
the reaction equation is as follows:
Under the protection of nitrogen, sequentially adding toluene, acetonitrile, N, N, N ', N' -tetramethyl-1, 6-hexanediamine and 1-bromo-N-hexane into a dry and clean three-neck flask, stirring for 5-60min at room temperature, heating to 50-80 ℃, reacting for 2-20 h at the temperature, cooling to room temperature after the reaction is finished, removing a mixed solvent of the toluene and the acetonitrile by a reduced pressure distillation method, washing the product with petroleum ether for 3-4 times, separating out the upper layer liquid each time, and recovering the unreacted N, N, N ', N' -tetramethyl-1, 6-hexanediamine by reduced pressure distillation again, wherein the lower layer of light yellow liquid is a reaction product named as quaternary ammonium salt B;
Step 2) Synthesis of Monoepoxy-terminated BiQuaternary ammonium salt
the reaction equation is as follows:
Sequentially adding the prepared quaternary ammonium salt intermediate B and acetone into a dry and clean three-neck flask under the protection of nitrogen, magnetically stirring until the quaternary ammonium salt intermediate B and the acetone are completely dissolved, adding 1-bromo-5, 6-epoxyhexane, reacting at room temperature for 20-80 h, separating out a white solid, washing the product for 3-4 times by using the acetone as a solvent after the reaction is finished, and removing unreacted 1-bromo-5, 6-epoxyhexane to prepare a white solid mono-epoxy-terminated biquaternary ammonium salt D;
step 3) synthesis of long side chain type quaternized polybenzimidazole
The reaction equation is as follows:
Wherein x + y + z = 1, and x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1; n = 50-1000;
Sequentially adding a solvent containing lateral amino polybenzimidazole (H2N-PBI) and dimethyl sulfoxide (DMSO) into a dry and clean three-neck flask under the protection of nitrogen, magnetically stirring for 5-60min, heating to 60-90 ℃, cooling to room temperature after the polymer is completely dissolved, adding quaternary ammonium salt D, continuously stirring for 30min under the protection of nitrogen, heating to 50-120 ℃, reacting for 2-20H at the temperature, cooling to room temperature, pouring a highly viscous solution in a reaction bottle into a large amount of acetone, washing the separated polymer with acetone, and drying for 1-30H at 30-80 ℃ under vacuum to obtain long-side-chain quaternized polybenzimidazole;
Step 4) preparation of long side chain type quaternized polybenzimidazole crosslinked membrane
Dissolving the long side chain type quaternized polybenzimidazole in dimethyl sulfoxide to prepare a 2-20 w/v% solution, adding an epoxy resin crosslinking agent, fully and uniformly stirring, filtering the solution, defoaming under negative pressure, directly casting the solution on a dry and clean glass plate, and drying the glass plate for 4-10 hours in a constant-temperature forced air drying oven at 60-100 ℃ to prepare the long side chain type quaternized polybenzimidazole crosslinking membrane.
3. the method for preparing the long ~ side ~ chain quaternized polybenzimidazole crosslinked membrane according to claim 2, wherein the mixture of toluene and acetonitrile in step 1) is used as a reaction medium, the volume ratio of toluene to acetonitrile is 1:5 ~ 5:1, and the molar ratio of toluene to acetonitrile is 20:1 ~ 2:1, and the concentration of the reactants is 2 ~ 50 w/v%.
4. The method for preparing a long side chain type quaternized polybenzimidazole crosslinked membrane according to claim 2, characterized in that: the concentration of the reactant in the step 2) is 20-300 w/v%.
5. the method for preparing a long-side-chain quaternized polybenzimidazole crosslinked membrane according ~ claim 2, wherein the molar ratio of amino groups (-NH 2) in the structure of the pendant amino polybenzimidazole ~ epoxy groups in the structure of the quaternary ammonium salt D in the step 3) is 1:0.1 ~ 1:1.9, and the reactant concentration is 2 ~ 30 w/v%.
6. the method for preparing the long ~ side ~ chain quaternized polybenzimidazole crosslinked film according to claim 2, wherein the epoxy resin crosslinking agent in the step 4) is a commonly used industrial and industrial epoxy resin, the epoxy resin crosslinking agent is bisphenol A epoxy resin (BADGE) or Ethylene Glycol Diglycidyl Ether (EGDE), and the mass ratio of the long ~ side ~ chain quaternized polybenzimidazole to the epoxy resin is 50:1 ~ 2: 1.
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| CN113471498A (en) * | 2021-07-07 | 2021-10-01 | 长春工业大学 | Multi-quaternary ammonium side long-chain type polysulfone anion-exchange membrane and preparation method thereof |
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