CN113307966A - Copolymer containing tetramethyl piperidine oxide quaternary ammonium salt and preparation method and application thereof - Google Patents

Copolymer containing tetramethyl piperidine oxide quaternary ammonium salt and preparation method and application thereof Download PDF

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CN113307966A
CN113307966A CN202110597918.9A CN202110597918A CN113307966A CN 113307966 A CN113307966 A CN 113307966A CN 202110597918 A CN202110597918 A CN 202110597918A CN 113307966 A CN113307966 A CN 113307966A
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刘磊
苗沙沙
刘志茹
柏丽
褚晓萌
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Anhui Normal University
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Abstract

The invention provides a copolymer containing tetramethyl piperidine oxide quaternary ammonium salt and a preparation method and application thereof, firstly preparing halogenated alkylated polymer, then taking halogen at the tail end of an alkyl chain as a reaction active site to carry out functional grafting on the polymer by an atom transfer radical coupling reaction of a cationic group with stable nitroxide free radical, wherein the cyclic piperidine group can enhance the steric hindrance effect of the cation and improve the stability of the cationic functional group, meanwhile, the existence of a six-membered ring of the nitroxide free radical can reduce the swelling rate of the water absorption of the membrane, and an alkaline anion exchange membrane material with high alkali resistance stability, high ion conductivity and low water absorption swelling rate can be obtained through the processes of membrane casting and ion exchange. The anion exchange membrane for the electrochemical device is prepared by the novel method with simple process, can be applied to the fields of alkaline fuel cells, electrolytic water, flow batteries and the like, and has good development prospect.

Description

Copolymer containing tetramethyl piperidine oxide quaternary ammonium salt and preparation method and application thereof
Technical Field
The invention belongs to the technical field of synthesis and preparation of alkaline anion exchange membranes for electrochemical devices, and particularly relates to a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt prepared by utilizing atom transfer radical coupling reaction, a preparation method thereof and application thereof in preparing an anion exchange membrane.
Background
Anion Exchange Membranes (AEMs) are high molecular polymer membranes containing cationic functional groups and having selective permeability to anions. Anion exchange membranes have played a significant role and received much attention in the conventional industries such as chlor-alkali industry, heavy metal recovery, water treatment, hydrometallurgy and the like. In recent years, with the increasing demand for alternative energy in the world, the application of anion exchange membranes in energy electrochemical devices is also receiving more and more attention of researchers, and the anion exchange membranes can be applied to the fields of alkaline fuel cells, water electrolysis and the like and have good development prospects. Anion exchange membranes are required in these emerging application fields to have higher ionic conductivity, better mechanical, thermal and chemical stability.
However, in a high-temperature and alkaline environment, the trimethylamine Quaternary Ammonium Salt (QAs) group commonly used in the anion exchange membrane undergoes degradation reactions through hoffmann elimination, nucleophilic substitution, ylide intermediate formation or other rearrangement reactions, resulting in loss of cation functional groups. Therefore, AEM still has the problems of low ion conductivity, poor alkali-resistant stability, short service life and the like, which limits the development of anion exchange membranes and corresponding energy devices, and still needs to be researched and researched more deeply. Therefore, the development of an anion exchange polymer membrane with high alkali-resistant stability, high ion conductivity and long service life becomes a great challenge for the development of an alkaline polymer electrolyte energy device.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt and a preparation method thereof.
The invention also aims to provide application of the copolymer containing tetramethylpiperidine oxide quaternary ammonium salt to preparation of an anion exchange membrane with low water absorption swelling ratio and high ionic conductivity, and the prepared anion exchange membrane material can be applied to the fields of fuel cells, alkaline electrolyzed water and the like.
The specific technical scheme of the invention is as follows:
a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt has a structural general formula:
Figure BDA0003091859100000021
wherein x is the degree of substitution, and x is more than 0 and less than or equal to 100;
preferably, the polymer skeleton is polyphenylene ether
Figure BDA0003091859100000022
Polystyrene
Figure BDA0003091859100000023
Polyphenyl, polyphenyl granules and their use
Figure BDA0003091859100000024
Polysulfone
Figure BDA0003091859100000025
Polyether ether ketone
Figure BDA0003091859100000026
Poly (styrene-b-isobutylene-b-styrene)
Figure BDA0003091859100000027
Hydrostyrene butadiene block copolymers
Figure BDA0003091859100000028
Styrene-butadiene-styrene block copolymers
Figure BDA0003091859100000029
Or biphenyl type polysulfones
Figure BDA00030918591000000210
Wherein x, y, z, m, n is the degree of polymerization of the polymer, and the molecular weight of the polymer is preferably 20000-100000.
R1Is an all carbon chain
Figure BDA00030918591000000211
Or carbon chains containing ether oxygen chains
Figure BDA00030918591000000212
Preferably, R1N in the whole carbon chain is 1-6, and m in the carbon chain of the ether oxygen chain is 1-6.
R2Is single or multiple quaternary ammonium salt;
preferably, said R is2Is one of the following structures:
Figure BDA0003091859100000031
wherein R is2In the structural formulan is 1 to 12;
wherein R is3、R4、R5is-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-CH(CH3)2、-CHCH3CH2CH3One of (1), R3、R4And R5May be the same or different.
The invention provides a preparation method of a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt, which comprises the following steps:
1) preparing quaternary ammonium salt containing stable nitroxide radical;
2) preparing a polymer containing halomethyl groups;
3) dissolving a polymer containing halogenated methyl groups in an organic solvent, adding quaternary ammonium salt containing stable nitroxide free radicals, halogenated cuprous salt and an organic ligand, carrying out at least three times of freezing-unfreezing cycle degassing, then placing in vacuum for reaction, removing impurities from a product, and drying to obtain the copolymer containing the tetramethylpiperidine oxide quaternary ammonium salt.
Preferably, the specific preparation method in the step 1) comprises the following steps: taking monomers of 2,2,6, 6-tetramethyl diphenyl piperate (TEMPO) as initial raw materials, and reacting Menschutkin (reaction of tertiary amine and halogenated hydrocarbon to generate quaternary ammonium salt) to prepare quaternary ammonium salt containing stable nitroxide free radical, so as to obtain a cationic functional monomer;
in the step 1), the monomer of 2,2,6, 6-tetramethyl diphenyl piperazine ester (TEMPO) is 4-amido-2, 2,6, 6-tetramethyl diphenyl piperazine ester or 4-hydroxy-2, 2,6, 6-tetramethyl diphenyl piperazine ester.
Preferably, the specific preparation method in the step 2) comprises the following steps: chloromethylation, bromomethylation or an alkyl chain containing chloromethyl and bromomethyl, wherein the substitution degree of the polymer skeleton is modified by chloromethylation, bromomethylation or Friedel-crafts alkylation operation, wherein the substitution degree is more than 0 and less than or equal to 100;
step 2) preparing an atom transfer radical coupling reaction polymer precursor; the polymer skeleton in the step 2) is polyphenylEther compounds
Figure BDA0003091859100000041
Polystyrene
Figure BDA0003091859100000042
Polyphenyl, polyphenyl granules and their use
Figure BDA0003091859100000043
Polysulfone
Figure BDA0003091859100000044
Polyether ether ketone
Figure BDA0003091859100000045
Poly (styrene-b-isobutylene-b-styrene)
Figure BDA0003091859100000046
Hydrostyrene butadiene block copolymers
Figure BDA0003091859100000047
Styrene-butadiene-styrene block copolymers
Figure BDA0003091859100000048
Or biphenyl type polysulfones
Figure BDA0003091859100000049
Wherein x, y, z, m, n is the degree of polymerization of the polymer, and the molecular weight of the polymer is preferably 20000-100000.
The reaction in the step 3) is specifically as follows: reacting for 2-4h at 20-100 ℃;
in the step 3), impurity removal refers to that reactants are deposited in a poor solvent and washed for 3-5 times to remove impurities;
the drying in the step 3) refers to vacuum drying at 40-70 ℃ for 24-48 h.
At least three freeze-thaw cycles are degassed in step 3) to remove oxygen and water therein.
The organic solvent in the step 3) is one or a mixture of more of tetrahydrofuran, chloroform, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone in any proportion.
The poor solvent in the step 3) is one or a mixture of several solvents of toluene, diethyl ether, acetone or xylene.
The polymer containing halogenated methyl groups in the step 3) is used as a polymer precursor;
the mole ratio of halogenated methyl group, quaternary ammonium salt containing stable nitroxide free radical, halogenated cuprous salt and organic ligand contained in the polymer precursor in the step 3) is 1: 1-8: 0.25-2: 0.8 to 6.4.
In the step 3), the concentration of the quaternary ammonium salt containing stable nitroxide radicals in the organic solvent is 0.08-0.6 mmol/ml.
The halogenated cuprous salt in the step 3) is one or two of cuprous bromide and cuprous chloride.
In the step 3), the organic ligand is any one or more of 2, 2-bipyridine, 1,4,7, 7-pentamethyldiethylenetriamine and 1,1,4,7,10, 10-hexamethyltriethylenetetramine.
The invention provides a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt, which is prepared by the method.
The invention provides an application of a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt, which is used for preparing an anion exchange membrane, and the specific method for preparing the anion exchange membrane comprises the following steps: dissolving a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt in an organic solvent to prepare a casting solution, coating the obtained casting solution on a planar substrate, and evaporating the solvent to obtain a solid film material; and soaking and stripping the obtained membrane material, soaking in alkali liquor, and washing with deionized water to obtain the anion exchange membrane material.
The prepared anion exchange membrane has the thickness of 40-60 mu m;
the mass fraction of the casting solution is 5-15 wt%.
The organic solvent is one or a mixture of more of tetrahydrofuran, chloroform, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone in any proportion.
The temperature of the evaporation solvent is 60-100 ℃, and the volatilization time is 24-48 hours;
the obtained membrane material is soaked and stripped, namely the obtained membrane material is soaked in deionized water and stripped;
the alkali liquor is sodium hydroxide solution or potassium hydroxide solution, and the concentration of the alkali liquor is 0.5-1 mol/L.
And soaking in alkali liquor for 48-72 h.
The washing is deionized water washing.
The anion exchange membrane prepared by the invention is used in the field of fuel cells or alkaline electrolyzed water.
The invention utilizes the novel method of atom transfer radical coupling reaction to introduce cations or ion clusters with stable nitroxide radicals into the polymer main chain to prepare the anion exchange membrane material, can improve the ion conductivity of the anion exchange membrane material, reduce the swelling water absorption and maintain the stability of the membrane size.
The design idea of the invention is as follows: by changing the steric hindrance and the position distribution of the cationic group, OH can be effectively relieved-And the AEM with good alkali resistance and stability is obtained by the attack on organic cationic groups. The nitrogen heterocyclic quaternary ammonium salt cation is not easy to generate nucleophilic substitution and elimination reaction due to the inherent ring strain force, so that the nitrogen heterocyclic quaternary ammonium salt cation has excellent alkali stability. The invention combines the quaternary ammonium salt with a ring structure and a steric effect to prepare the corresponding anion exchange membrane material with high ionic conductivity and low swelling ratio, and is an effective solution for solving the problems faced by AEM. The simple and efficient synthesis method provided by the invention is used for quantitatively grafting the cyclic steric hindrance type quaternary ammonium salt to the main polymer chain by utilizing the simple and efficient atom transfer radical coupling reaction to prepare the anion exchange membrane material with high ion exchange capacity, high ion conductivity and low swelling ratio, can break through the 'trade-off' effect between the ion conductivity and the water absorption swelling ratio, is simple in preparation process, has good application prospect, and is expected to promote the development of AEM corresponding energy devices.
Compared with the prior art, the preparation process is simple, firstly, the halogenated alkylated polymer is prepared, then the functional grafting is carried out on the polymer by taking halogen at the tail end of an alkyl chain as a reactive active site and carrying out atom transfer radical coupling reaction on a cationic group with stable nitroxide free radical, the steric hindrance effect of the cation can be enhanced by a cyclic piperidine group, the stability of the cationic functional group is improved, meanwhile, the water absorption swelling rate of the membrane can be reduced by the existence of a six-membered ring of the nitroxide free radical, and the alkaline anion exchange membrane material with high alkali resistance stability, high ion conductivity and low water absorption swelling rate can be obtained by the processes of membrane casting and ion exchange. Moreover, the anion exchange membrane material synthesized and prepared by the method is simple to operate, has high process feasibility, and has a good application prospect in electrochemical energy devices.
Drawings
FIG. 1 is the nuclear magnetic resonance hydrogen spectrum of a copolymer PPO-TEMPO-QA-40 prepared from a stabilized nitroxide radical containing trimethylamine quaternary ammonium salt and a polyphenylene oxide PPO main chain in example 1;
FIG. 2 shows the procedure of example 1;
FIG. 3 is a graph comparing the stability of membrane materials of PPO-TEMPO-QA-30 and PPO-TMA-30.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt comprises the following steps:
1) 4-amino-2, 2,6, 6-tetramethyl diphenyl piperazine ester (4-NH)2-TEMPO) (5.1378g,30mmol) is dissolved in 60mL of acetone solution, methyl iodide (11.2058mL,180mmol) is added, stirring is carried out overnight at room temperature, the filtered product is washed with 15mL of acetone each time, 3 times in total, and after drying in vacuum at 50 ℃ for 24h, stable nitroxide radical TEMPO-QA containing trimethylamine quaternary ammonium salt at the terminal position is prepared, and the structural formula is as follows:
Figure BDA0003091859100000071
2) adding chlorobenzene (60mL), polyphenylene oxide PPO (6g, 50mmol containing benzene ring), N-bromosuccinimide NBS (5.3395g, 30mmol) and azobisisobutyronitrile AIBN (0.3695g, 2.25mmol) into a 250mL flask, uniformly mixing, stirring at 135 ℃ for 3h, cooling to room temperature after the reaction is finished, pouring the mixture into excessive methanol (800mL), collecting the fiber polymer, washing with methanol, and drying the obtained PPO-Br-40 copolymer at 60 ℃ overnight in vacuum, wherein the yield is 90%; preparing polyphenyl ether PPO-Br-40 with bromomethyl substitution degree of 40;
3) polyphenylene oxide PPO-Br-40(0.5g, containing bromomethyl 1.32mmol) and TEMPO-QA (1.3498g, 3.96mmol) having a bromomethyl substitution of 40 were dissolved in 14mL of N-methyl-pyrrolidone (NMP), the solution was charged into a reaction vessel, purged with argon for 30 minutes, after adding CuBr (0.142g, 0.99mmol) and 2, 2' -bipyridine (0.4936g, 3.16mmol), the reaction solution was circulated by a freeze-vacuum-thaw method for 3 times, and then reacted at 80 ℃ for 4 hours, the reaction mixture was precipitated into ether, filtered and washed with water for 3 times, and vacuum-dried at 60 ℃ for 24 hours to obtain copolymer PPO-TEMPO-QA-40(0.6763g, yield 80%), structural formula:
Figure BDA0003091859100000081
the copolymer containing tetramethylpiperidine oxide quaternary ammonium salt prepared in example 1 is used for preparing an anion exchange membrane, and the specific preparation method comprises the following steps:
0.5g of PPO-TEMPO-QA-40 polymer was dissolved in N-methyl-pyrrolidonePreparing 8 wt% membrane building liquid in NMP solution, pouring the membrane building liquid on a clean glass plate for natural casting, evaporating the solvent for 24h at 80 ℃ to obtain a membrane material, soaking the glass in deionized water, soaking and stripping, and soaking the membrane material in 1M NaOH aqueous solution for 48h for OH-Ion exchange is carried out to obtain the TEMPO-QA modified PPO-based anion exchange membrane. The ion exchange capacity of the polymer was calculated by nuclear magnetic analysis, the thickness of the membrane was measured with a vernier caliper, and the ionic conductivity of the membrane was analyzed by an electrochemical workstation test. The film is cut into 4cm by 4cm size, and the swelling rate and water absorption rate of the film are tested by testing the size and weight change of the wet film after soaking for 24 hours at a certain temperature in a dry state.
And (3) testing results: the ion exchange capacity is 1.88 g/mmol; the film thickness was 42 μm; HCO of anion exchange membrane at 20 DEG C3 -Has an ionic conductivity of 11.5 mS/cm; OH at 20 DEG C-Has an ionic conductivity of 38.3 mS/cm; the swelling ratio was 6.4%; the water absorption was 18.4%.
Example 2
A preparation method of a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt comprises the following steps:
1) same as step 1) in example 1;
2) substantially similar to step 2) of example 1, except that: NBS (4.4496g, 25mmol), AIBN (0.3104g, 1.89 mmol); PPO-Br-30 with the bromomethyl substitution degree of 30;
3) PPO-Br-30(0.498g, containing 1.04mmol of bromomethyl) having a bromomethyl substitution of 30 and TEMPO-QA, (1.068g, 3.13mmol) were dissolved in 14mL of N-methyl-pyrrolidone (NMP); the solution was charged to a reaction vessel, purged with argon for 30 minutes, after adding CuBr (0.1119g, 0.78mmol) and 2, 2' -bipyridine (0.3905g, 2.5mmol), the reaction solution was cycled 3 times by freeze-pump-thaw method, then reacted at 80 ℃ for 4h, the reaction mixture was precipitated in ether, filtered and washed 3 times with water, and dried under vacuum at 60 ℃ for 24h to give copolymer PPO-TEMPO-QA-30(0.6392g, 83% yield).
The copolymer containing tetramethylpiperidine oxide quaternary ammonium salt prepared in example 2 is used for preparing an anion exchange membrane, and the specific preparation method is as follows:
dissolving 0.5g of PPO-TEMPO-QA-30 polymer in N methyl-pyrrolidone (NMP) solution to prepare 8 wt% membrane building solution, pouring the membrane building solution on a clean glass plate for natural casting, evaporating the solvent for 24h at 80 ℃ to obtain a membrane material, soaking the membrane material in deionized water, soaking and stripping the membrane material, and soaking the membrane material in 1M NaOH aqueous solution for 48h to perform OH-Ion exchange is carried out to obtain the TEMPO-QA modified PPO-based anion exchange membrane.
And (3) testing results: the ion exchange capacity is 1.59 g/mmol; the film thickness was 41 μm; HCO of anion exchange membrane at 20 DEG C3 -Has an ionic conductivity of 8.2 mS/cm; OH at 20 DEG C-Has an ionic conductivity of 26.2 mS/cm; the swelling ratio was 5.3%; the water absorption was 15.2%.
Example 3
A preparation method of a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt comprises the following steps:
1) same as step 1) in example 1;
2) substantially similar to step 2) of example 1, except that: NBS (3.5597g, 20mmol), AIBN (0.2463g, 1.5 mmol); preparing polyphenyl ether PPO-Br-20 with bromomethyl substitution degree of 20;
3) polyphenylene oxide PPO-Br-20(0.5024g, containing 0.74mmol of bromomethyl group) having a degree of bromomethyl substitution of 20 and TEMPO-QA, (0.7542g, 2.21mmol) were dissolved in 14mL of N-methyl-pyrrolidone (NMP), the solution was charged into a reaction vessel, purged with argon for 30 minutes, and after adding CuBr (0.0789g, 0.55mmol) and 2, 2' -bipyridine (0.2765g, 1.77mmol), the reaction solution was circulated by 3 cycles of freeze-vacuum-thaw method and then reacted at 80 ℃ for 4 hours. The reaction mixture was precipitated into diethyl ether, filtered and washed 3 times with water, and dried under vacuum at 60 ℃ for 24h to give the copolymer PPO-TEMPO-QA-20(0.5915g, 85% yield).
The copolymer containing tetramethylpiperidine oxide quaternary ammonium salt prepared in example 3 is used for preparing an anion exchange membrane, and the specific preparation method is as follows:
dissolving 0.5g of PPO-TEMPO-QA-20 polymer in N methyl-pyrrolidone (NMP) solution to prepare 8 wt% of membrane building solution, and mixing the membrane building solutionPouring on a clean glass plate for natural flow casting, evaporating the solvent at 80 ℃ for 24h to obtain a membrane material, soaking in deionized water, soaking and stripping, and soaking the membrane material in 1M NaOH aqueous solution for 48h for OH-Ion exchange is carried out to obtain the TEMPO-QA modified PPO-based anion exchange membrane.
And (3) testing results: the ion exchange capacity is 1.2 g/mmol; the thickness of the film is 40 μm; HCO of anion exchange membrane at 20 DEG C3 -Has an ionic conductivity of 6.8 mS/cm; OH group-Has an ionic conductivity of 14.4 mS/cm; the swelling ratio was 3.5%; the water absorption was 12.0%.
Example 4
A preparation method of a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt comprises the following steps:
1) 4-amino-2, 2,6, 6-tetramethyl diphenyl piperazine ester (4-NH)2TEMPO) (5.1378g,30mmol) in 60mL of acetone, bromoethane (13.527mL,180mmol) was added, stirring was carried out overnight at 60 ℃ and the product was washed with 15mL of acetone each time, 3 times in total, dried under vacuum at 50 ℃ for 24h,
preparing stable nitroxide radical TEMPO-DQA with para-position triethylamine quaternary ammonium salt, wherein the structural formula is as follows:
Figure BDA0003091859100000111
2) same as step 2) in example 1;
3) polyphenylene oxide PPO-Br-40(0.5g, containing 1.32mmol of bromomethyl) having a degree of bromomethyl substitution of 40 and TEMPO-DQA, (1.3319g, 3.96mmol) were dissolved in 7 mLN-methyl-pyrrolidone (NMP), and the solution was charged to a reaction vessel and purged with argon for 30 minutes. After adding CuBr (0.142g, 0.99mmol) and 2, 2' -bipyridine (0.4936g, 3.16mmol), the reaction solution was circulated 3 times by the freeze-vacuum-thaw method and then reacted at 80 ℃ for 4 hours. The reaction mixture was precipitated in diethyl ether, filtered and washed 3 times with water, and dried under vacuum at 60 ℃ for 24h to give the copolymer PPO-TEMPO-DQA-40(0.6544g, yield 78%), formula
Figure BDA0003091859100000112
The copolymer containing tetramethylpiperidine oxide quaternary ammonium salt prepared in example 4 is used for preparing an anion exchange membrane, and the specific preparation method is as follows:
dissolving 0.5g of PPO-TEMPO-DQA-40 polymer in N methyl-pyrrolidone (NMP) solution to prepare 8 wt% membrane building solution, pouring the membrane building solution on a clean glass plate for natural casting, evaporating the solvent for 24h at 80 ℃ to obtain a membrane material, soaking the membrane material in deionized water, soaking and stripping the membrane material, and soaking the membrane material in 1M NaOH aqueous solution for 48h to perform OH-Ion exchange is carried out to obtain the TEMPO-DQA modified PPO-based anion exchange membrane.
And (3) testing results: the ion exchange capacity is 1.75 g/mmol; the film thickness was 44 μm; HCO of anion exchange membrane at 20 DEG C3 -Has an ionic conductivity of 9 mS/cm; OH at 20 DEG C-Has an ionic conductivity of 19.8 mS/cm; the swelling ratio was 5.9%; the water absorption was 17.5%.
Example 5
A preparation method of a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt comprises the following steps:
1) same as step 1) in example 1;
2) polysulfone (5.00g, containing repeat units 11.3mmol), paraformaldehyde (3.39g, containing repeat units 113mmol) and trimethylchlorosilane (14.31mL,113mmol) were dissolved in 200mL CHCl in a three-hole round-bottom flask with magnetic stirrer3Then, anhydrous tin tetrachloride (0.27mL, 2.27mmol) and CHCl were added dropwise at constant pressure at 45 deg.C3(50mL), at 50 ℃ N2Stirring for 3 days under the atmosphere; precipitating the mixed solution in methanol to obtain a white precipitate, and washing with methanol; the copolymer was dried under vacuum at 60 ℃ for 24H, and the degree of chloromethylation (value x) of the PSU-Cl-x copolymer was calculated from the 1H NMR spectrum and can be controlled by adjusting the reaction time. The polysulfone PSU-Cl-100 is prepared, and the structural formula is as follows:
Figure BDA0003091859100000121
3) polysulfone PSU-Cl-100(0.3032g, chloromethyl-containing 0.61mmol) and TEMPO-QA (0.6245g, 1.83mmol) was dissolved in 8mL of N-methyl-pyrrolidone (NMP), the solution was charged into a reaction vessel, purged with argon for 30 minutes, and after adding CuBr (0.066g, 0.46mmol) and 2, 2' -bipyridine (0.2296g, 1.47mmol), the reaction solution was circulated 3 times by freeze-vacuum-thaw method and then reacted at 80 ℃ for 4 hours; the reaction mixture is precipitated in ether, filtered and washed with water for 3 times; after drying at 60 ℃ for 24h under vacuum, the copolymer PSU-TEMPO-QA-100(796.87) n (0.3889g, 80% yield) is obtained, of the formula:
Figure BDA0003091859100000122
the copolymer containing tetramethylpiperidine oxide quaternary ammonium salt in example 5 is used for preparing an anion exchange membrane, and the specific preparation method is as follows:
dissolving 0.3g of PSU-TEMPO-QA-100 polymer in N methyl-pyrrolidone (NMP) solution to prepare 8 wt% membrane building solution, pouring the membrane building solution on a clean glass plate for natural casting, evaporating the solvent for 24h at 80 ℃ to obtain a membrane material, soaking and stripping the membrane material in deionized water, and soaking the membrane material in 1M NaOH aqueous solution for 48h for OH-Ion exchange is carried out to obtain the TEMPO-QA modified PSU-based anion exchange membrane.
And (3) testing results: the ion exchange capacity is 1.46 g/mmol; the film thickness was 43 μm; HCO of anion exchange membrane at 20 DEG C3 -Has an ionic conductivity of 6.3 mS/cm; OH at 20 DEG C-Has an ionic conductivity of 14.3 mS/cm; the swelling ratio was 5.6%; the water absorption was 15.8%.
Example 6
A preparation method of a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt comprises the following steps:
1) in a 100mL round bottom flask was added 10mL of tetrahydrofuran THF and NaH (60% mineral oil, 0.4g,10mmol), HO-TEMPO (M ═ 172.245) (1.4985g,8.7mmol) at 0 ℃ and stirred at room temperature for 1 h. 3-bromopropyl-dimethyl- (3-trimethylammoniopropyl) ammonium dibromide (4.6977g, 11mmol) was added dropwise at 0 deg.C, stirred for 45min, stirred at room temperature for a further 24h, saturated NH added4Quenching reaction by using a Cl aqueous solution; the stable nitroxyl radical quaternary ammonium salt TEMPO-O-2QA is prepared by rotary evaporation, and the structureFormula (II):
Figure BDA0003091859100000131
2) SEBS (3.9918g, containing 19.3mmol of benzene ring), paraformaldehyde (5.79g, containing 193mmol of repeating units) and chlorotrimethylsilane (24.44mL, 193mmol) were added in N2Dissolved in 110mL of CHCl in a three-necked round-bottomed flask equipped with a reflux tube and a magnetic stirrer under an atmosphere3Performing the following steps; then, anhydrous tin tetrachloride (0.4541mL, 3.88mmol) and CHCl were added dropwise at 45 deg.C3(50mL) of the solution. Mixing the mixture in N2Stirring for 7h at 50 ℃ under the atmosphere; the product obtained from this solution was precipitated in methanol as a white flocculent precipitate and washed with methanol; finally, the SEBS-Cl copolymer was dried in vacuo at 60 ℃ for 24 hours; the degree of chloromethylation (value x) in the SEBS-Cl copolymer was calculated from the 1H NMR spectrum and can be controlled by adjusting the reaction time. The SEBS-Cl-7 prepared has the structural formula:
Figure BDA0003091859100000141
3) SEBS-Cl-7(0.5g, chloromethyl-containing 0.61mmol) having a degree of substitution of 7 and TEMPO-O-2QA, (0.9487g, 1.83mmol) were dissolved in 14mL of N-methyl-pyrrolidone (NMP), the solution was charged into a reaction vessel, purged with argon for 30 minutes, after CuBr (0.066g, 0.46mmol) and 2, 2' -bipyridine (0.2296g, 1.47mmol) were added, the reaction solution was circulated 3 times by a freeze-vacuum-thaw method, and then reacted at 80 ℃ for 4 hours; the reaction mixture is precipitated in ether, filtered and washed with water for 3 times; after drying at 60 ℃ for 24h in vacuo, the copolymer SEBS-TEMPO-O-2QA-7(0.6444g, 80% yield) was obtained, of the formula:
Figure BDA0003091859100000142
the copolymer containing tetramethylpiperidine oxide quaternary ammonium salt prepared in example 6 is used for preparing an anion exchange membrane, and the specific preparation method is as follows:
take 0.5Dissolving SEBS-TEMPO-O-2QA-7 polymer in N methyl-pyrrolidone (NMP) solution to prepare 8 wt% membrane building solution, pouring the membrane building solution on a clean glass plate for natural casting, evaporating the solvent at 80 ℃ to obtain a membrane material, soaking and stripping, and soaking the membrane material in 1M NaOH aqueous solution for 48h for OH-Ion exchange is carried out to obtain the TEMPO-O-2QA modified SEBS anion exchange membrane.
And (3) testing results: the ion exchange capacity is 1.67 g/mmol; the film thickness was 40 μm; HCO of anion exchange membrane at 20 DEG C3 -Has an ionic conductivity of 9 mS/cm; OH group-Has an ionic conductivity of 30 mS/cm; the swelling ratio was 7.6%; the water absorption was 18.2%.
Example 7
A preparation method of a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt comprises the following steps:
1) 4-amino-2, 2,6, 6-tetramethyl diphenyl piperazine ester (4-NH)2-TEMPO)(0.3425g,2mmol)、Pd/TiO2And methanol (99.5% with 0.05% water, 50mL) into a glass tube (100 mL); bubbling argon through the solution for 5 minutes; the tube was sealed with a rubber cap. Irradiating the reaction mixture with an LED lamp (λ 365nm) under magnetic stirring at room temperature for 10-15 hours; adding 100mg of biphenyl and 50mL of ethanol, and carrying out quantitative analysis by GC-FID (Agilent 6890A); after removal of the catalyst by filtration, the product is isolated by vacuum distillation to give TEMPO-N (CH)3)2The structural formula is as follows:
Figure BDA0003091859100000151
TEMPO-N (CH)3)2(0.299g, 1.5mmol) and 3-bromopropyltrimethylammonium bromide (0.4306g,1.65mmol) in 10mL of chloroform and reacted at 60 ℃ for 12 h; removing residual liquid reagent under vacuum at 80 deg.C; preparing stable nitroxide radical quaternary ammonium salt TEMPO-2QA, wherein the structural formula is as follows:
Figure BDA0003091859100000152
2) polystyrene PS copolymers of different degrees of substitution were synthesized by the Friedel-Crafts reaction, PS (2.9952g, containing 28.8mmol of benzene rings), paraformaldehyde (8.64g, containing 288mmol of repeating units), chlorotrimethylsilane (36.47mL, 288mmol) were dissolved in 100mL of chloroform and stirred to dissolve completely. Tin tetrachloride (0.68mL, 5.77mmol) and chloroform (50mL) were added dropwise under reflux using a constant pressure dropping funnel, and the reaction temperature was raised to 50 ℃ and the mixture was reacted under reflux for 3 h. After cooling, the reaction solution was precipitated into a large amount of methanol. The polymer was filtered and washed several times with methanol, after which the residue was redissolved in chloroform (130mL) and precipitated again into a large amount of methanol. The resulting PS-10 copolymer was dried overnight under vacuum at 50 ℃ and the degree of chloromethylation was determined1H-NMR calculation was performed and designated PS-10 (yield 96%, where 10 indicates an average of 0.1 chloromethyl groups per PS repeating unit). The prepared PS-Cl-10 has a structural formula as follows:
Figure BDA0003091859100000161
3) PS-Cl-10(0.5g, chloromethyl-containing 0.46mmol) and TEMPO-2QA (0.6352g, 1.38mmol) having a degree of substitution of 10 were dissolved in 14mL of N-methyl-pyrrolidone (NMP), the solution was charged into a reaction vessel, purged with argon for 30 minutes, after adding CuBr (0.0495g, 0.345mmol) and 2, 2' -bipyridine (0.1718g, 1.1mmol), the reaction solution was circulated 3 times by the freeze-vacuum-thaw method, and then reacted at 80 ℃ for 4 hours. The reaction mixture was precipitated into ether, filtered and washed 3 times with water. After drying in vacuo at 60 ℃ for 24h, copolymer PS-TEMPO-2QA-10(0.557g, 80% yield) was obtained, of the formula:
Figure BDA0003091859100000162
the copolymer containing tetramethylpiperidine oxide quaternary ammonium salt prepared in example 7 is used for preparing an anion exchange membrane, and the specific preparation method is as follows:
0.5g of PS-TEMPO-2QA-10 polymer was dissolved in N-methyl-pyrrolidone (NMP) solution,preparing 8 wt% membrane building liquid, pouring the membrane building liquid on a clean glass plate for natural casting, evaporating the solvent at 80 ℃ to obtain a membrane material, soaking and stripping, and soaking the membrane material in 1M NaOH aqueous solution for 48h for OH-Ion exchange is carried out to obtain the TEMPO-2QA modified PS anion exchange membrane.
And (3) testing results: the ion exchange capacity was 1.44g/mmol, and the membrane thickness was 42 μm; HCO of anion exchange membrane at 20 DEG C3 -Has an ionic conductivity of 8 mS/cm; OH group-Has an ionic conductivity of 25 mS/cm; the swelling ratio was 5.3%; the water absorption was 12.4%.
Comparative example 1
A polymer membrane material PPO-TMA-30 containing traditional trimethylamine cations has the following structural formula:
Figure BDA0003091859100000171
preparation of polymer containing traditional trimethylamine quaternary ammonium salt: PPO-Br-30(0.498g, bromomethyl 1.04mmol) and trimethylamine in tetrahydrofuran (2mmol/mL) (2.6mL, 5.2mmol) were dissolved in 10mL of N-methyl-pyrrolidone (NMP). The reaction was carried out overnight at 60 ℃, precipitated in ether and washed 3 times with water. The obtained product PPO-TMA-30 was 0.5374g, with a yield of 96%.
Preparation of anion exchange membrane: dissolving 0.5g of PPO-TMA-30 polymer in N methyl-pyrrolidone (NMP) solution to prepare 8% (w/v) membrane building solution, pouring the membrane building solution on a clean glass plate for natural casting, evaporating the solvent at 80 ℃ to obtain a membrane material, immersing the membrane material in 1M NaOH aqueous solution for 48h, and carrying out OH treatment-And (4) carrying out ion exchange to obtain a TMA modified PPO-based anion exchange membrane with the membrane thickness of 44 mu m.
The anion exchange membrane PPO-TMA-30 prepared in the comparative example 1 is subjected to the nuclear magnetic test to calculate that the IEC value is 2.1g/mmol, and the ion conductivity test is carried out to test the HCO of the anion exchange membrane at 20 DEG C3 -Has an ionic conductivity of 6.1mS/cm, OH-Has an ionic conductivity of 26.4 mS/cm. Compared with example 2, PPO-TEMPO-QA-30 with an ion exchange capacity of 1.59g/mmol (HCO at 20 ℃)3 -Has an ionic conductivity of 8.2mS/cm, OH-Has an ionic conductivity of 26.2mS/cm), which has a higher ion exchange capacity but does not increase the ionic conductivity, indicating that grafting a quaternary ammonium salt containing a nitroxide radical six-membered ring can increase the ionic conductivity under the same IEC. Meanwhile, the membrane materials of PPO-TEMPO-QA-30 and PPO-TMA-30 are subjected to a comparison test of alkali resistance stability at 60 ℃ in 1M NaOH, and the result is shown in FIG. 3, and it can be seen that under the same condition, PPO-TEMPO-QA-30 has higher alkali resistance stability due to the steric hindrance type six-membered ring structure, and can well maintain the ion conductivity.
The above embodiments are merely illustrative of the technical idea and features of the present invention, and the purpose thereof is to make people understand the content of the present invention and implement the invention, and not to limit the protection scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.

Claims (10)

1. The copolymer containing the quaternary ammonium salt of the tetramethylpiperidine oxide is characterized by comprising the following structural general formula:
polymer skeleton
Figure FDA0003091859090000011
Wherein x is the degree of substitution, and x is more than 0 and less than or equal to 100;
R1is a full carbon chain or a carbon chain containing an ether oxygen chain;
R2is single or multiple quaternary ammonium salt.
2. The method for preparing the copolymer containing tetramethylpiperidine oxide quaternary ammonium salt according to claim 1, comprising the steps of:
1) preparing quaternary ammonium salt containing stable nitroxide radical;
2) preparing a polymer containing halomethyl groups;
3) dissolving a polymer containing halogenated methyl groups in an organic solvent, adding quaternary ammonium salt containing stable nitroxide free radicals, halogenated cuprous salt and an organic ligand, carrying out at least three times of freezing-unfreezing cycle degassing, then placing in vacuum for reaction, removing impurities from a product, and drying to obtain the copolymer containing the tetramethylpiperidine oxide quaternary ammonium salt.
3. The preparation method according to claim 2, wherein the specific preparation method in step 1) is as follows: the method is characterized in that a monomer of 2,2,6, 6-tetramethyl diphenylpiperate is used as an initial raw material, and a quaternary ammonium salt containing stable nitroxide free radical is prepared through a Menschutkin reaction to obtain a cationic functional monomer.
4. The preparation method according to claim 1, wherein the specific preparation method in step 2) is as follows: chloromethylation, bromomethylation or alkyl chain containing chloromethyl and bromomethyl with the degree of substitution x is modified on the polymer skeleton through chloromethylation reaction, bromomethylation, Grignard reaction or friedel-crafts alkylation operation, wherein the degree of substitution is 0< x < 100.
5. The method according to claim 2, wherein the reaction in step 3) is specifically: reacting for 2-4h at 20-100 ℃.
6. The method according to claim 2, wherein the molar ratio of the halogenated methyl group contained in the polymer containing a halogenated methyl group in step 3), the quaternary ammonium salt containing a stable nitroxide radical, the halogenated cuprous salt, and the organic ligand is 1: 1-8: 0.25-2: 0.8 to 6.4.
7. The method according to claim 2, wherein the organic ligand in step 3) is any one or more selected from the group consisting of 2, 2-bipyridine, 1,4,7, 7-pentamethyldiethylenetriamine and 1,1,4,7,10, 10-hexamethyltriethylenetetramine.
8. The method according to claim 2, wherein the cuprous halide salt in step 3) is one or both of cuprous bromide and cuprous chloride.
9. The preparation method according to claim 2, wherein the organic solvent in step 3) is one or more of tetrahydrofuran, chloroform, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone.
10. Use of a copolymer containing tetramethylpiperidine oxide quaternary ammonium salt prepared by the process according to any one of claims 2 to 9 for the preparation of an anion exchange membrane.
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