CN115594807A - Preparation method and application of hole ether crosslinking type anion exchange membrane based on polyarylene piperidine copolymer - Google Patents
Preparation method and application of hole ether crosslinking type anion exchange membrane based on polyarylene piperidine copolymer Download PDFInfo
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- CN115594807A CN115594807A CN202211356906.8A CN202211356906A CN115594807A CN 115594807 A CN115594807 A CN 115594807A CN 202211356906 A CN202211356906 A CN 202211356906A CN 115594807 A CN115594807 A CN 115594807A
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- piperidine
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229920001577 copolymer Polymers 0.000 title claims abstract description 106
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 82
- 238000004132 cross linking Methods 0.000 title claims abstract description 47
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 238000005266 casting Methods 0.000 claims abstract description 35
- 239000012528 membrane Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005342 ion exchange Methods 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 17
- 150000002367 halogens Chemical class 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 150000002576 ketones Chemical class 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 11
- 239000003930 superacid Substances 0.000 claims abstract description 11
- 125000001033 ether group Chemical group 0.000 claims abstract description 10
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000001291 vacuum drying Methods 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002739 cryptand Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 claims description 13
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 9
- 229930184652 p-Terphenyl Natural products 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 8
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- WPDAVTSOEQEGMS-UHFFFAOYSA-N 9,10-dihydroanthracene Chemical compound C1=CC=C2CC3=CC=CC=C3CC2=C1 WPDAVTSOEQEGMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 125000003386 piperidinyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- QBVHMPFSDVNFAY-UHFFFAOYSA-N 1,1,1-trifluorobutan-2-one Chemical compound CCC(=O)C(F)(F)F QBVHMPFSDVNFAY-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010931 gold Substances 0.000 abstract description 3
- 229910052737 gold Inorganic materials 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 15
- 238000002791 soaking Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- 239000005357 flat glass Substances 0.000 description 8
- AUFVJZSDSXXFOI-UHFFFAOYSA-N 2.2.2-cryptand Chemical compound C1COCCOCCN2CCOCCOCCN1CCOCCOCC2 AUFVJZSDSXXFOI-UHFFFAOYSA-N 0.000 description 6
- IDFLGSYEBJNWMK-UHFFFAOYSA-N 1,2-Bis(chloromethoxy)ethane Chemical compound ClCOCCOCCl IDFLGSYEBJNWMK-UHFFFAOYSA-N 0.000 description 4
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 4
- JITJIMMMQDJOHE-UHFFFAOYSA-N 4,10,15-trioxa-1,7-diazabicyclo[5.5.5]heptadecane Chemical group C1COCCN2CCOCCN1CCOCC2 JITJIMMMQDJOHE-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 4
- -1 1, 2-bis (chloromethoxy) ethaneOne Chemical compound 0.000 description 3
- NIDSRGCVYOEDFW-UHFFFAOYSA-N 1-bromo-4-chlorobutane Chemical compound ClCCCCBr NIDSRGCVYOEDFW-UHFFFAOYSA-N 0.000 description 3
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- PDWBGRKARJFJGI-UHFFFAOYSA-N 2-phenylcyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1C1=CC=CC=C1 PDWBGRKARJFJGI-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000005011 alkyl ether group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a hole ether crosslinking type anion exchange membrane based on a polyarylene piperidine copolymer, and relates to the technical field of preparation of alkaline anion exchange membranes for new energy electrochemical devices. The hole ether crosslinking type anion exchange membrane based on the polyarylene piperidine copolymer is obtained by polymerizing an aromatic hydrocarbon monomer containing an Ar group and a ketone monomer through superacid catalysis to obtain a main chain, grafting an alkyl chain or an ether chain with halogens at two ends after quaternization of the main chain to obtain a copolymer, reacting the copolymer and a hole ether crosslinking monomer through Menshutt gold to obtain a membrane casting solution, casting the membrane to form a membrane, and performing ion exchange. The invention improves the dimensional stability, mechanical property, ionic conductivity and alkali resistance stability of the anion exchange membrane, and has good application prospect in alkaline anion exchange membrane fuel cells, electrolytic water and flow batteries.
Description
Technical Field
The invention relates to the technical field of preparation of alkaline anion exchange membranes for new energy electrochemical devices, in particular to a preparation method and application of a hole ether crosslinking type anion exchange membrane based on a polyarylene piperidine copolymer.
Background
The current Anion Exchange Membranes (AEM) are mainly composed of different polymer backbones grafted with cationic groups, wherein the cationic groups are mainly quaternary ammonium salts. Since anion exchange membranes have been widely used in the fields of electrodialysis, electrolytic water, alkaline fuel cells, flow batteries, electrochemical sensors, and the like in recent years, the performance of anion exchange membranes has been receiving attention from researchers. However, the currently prepared anion exchange membranes generally have the problems of low ionic conductivity, poor membrane dimensional stability, poor alkali stability at high temperature and the like.
Disclosure of Invention
The invention aims to provide a preparation method and application of a cryptand crosslinking type anion exchange membrane based on a polyarylene piperidine copolymer, which aims to solve the problems in the prior art, and improves the dimensional stability and the mechanical property of the membrane by forming a crosslinking network structure; the ionic conductivity and the alkali resistance stability of the anion exchange membrane are improved by introducing cryptate with a hydrophilic cage structure. The invention has simple synthetic route, and the prepared anion exchange membrane material can well balance the contradiction among ion conductivity, mechanical property and alkali resistance stability.
In order to achieve the purpose, the invention provides the following scheme:
in one technical scheme of the invention, the structural general formula of the compound is shown as formula I:
in formula I, 0 y + z is less than or equal to 100,0 is less than or equal to z is less than or equal to y;
m is polymerization degree, and m is a positive integer between 50 and 800;
ar and Ar 1 Are the same or different units containing aromatic ring structures;
x is Br - 、I - 、Cl - 、OH - 、HCO 3 - Or CO 3 2- Any one of the above;
R 1 is an alkyl chain or an ether chain;
R 2 is a structure formed after the polymerization of ketone monomers;
R 3 is a cryptand ether unit structure;
the molecular weight of the compound is 3000-360000.
Further, ar and Ar are 1 Is one or more of the following structural formulas:
the R is 1 Is one of the following structural formulas:
said R is 2 Is one of the following structural formulas:
said R is 3 Is one of the following structural formulas:
the second technical scheme of the invention is a hole ether crosslinking type anion exchange membrane based on polyarylene piperidine copolymer, which comprises the main components of the compound; the thickness is 20-60 μm.
In the third technical scheme of the present invention, the preparation method of the cryptand crosslinking type anion exchange membrane based on the polyarylene piperidine copolymer comprises the following steps:
will contain Ar, ar 1 Performing superacid catalysis polymerization on aromatic hydrocarbon monomers and ketone monomers to obtain a main chain, performing quaternization treatment on the main chain, grafting an alkyl chain or an ether chain with halogens at two ends to obtain a copolymer, performing a Menshute reaction on the copolymer and a cryptate crosslinking monomer to obtain a casting solution, and performing ion exchange after casting to form a membrane to obtain the product based on the metal complexA cryptand crosslinked anion exchange membrane of a polyarylene piperidine copolymer.
Further, the method comprises the following steps:
step 1, ar and Ar are added 1 Dissolving aromatic hydrocarbon monomers of the groups in a solvent to obtain a solution A, then adding ketone monomers into the solution A to dissolve the solution A to obtain a mixed solution, dropwise adding an acid solution into the mixed solution to perform a catalytic reaction, and pouring the mixed solution into a poor solvent after the reaction is finished to obtain a fibrous polymer; sequentially immersing the fibrous polymer into an alkaline solution, washing in water, and drying in vacuum to obtain a polyaryl piperidine copolymer;
step 3, dispersing the copolymer in a polar solvent, adding a cryptand crosslinking monomer, and heating to react to obtain a casting solution; casting the casting solution on a substrate, drying to form a film, and continuing vacuum drying; and immersing the obtained membrane into alkali liquor for ion exchange to obtain the hole ether crosslinking type anion exchange membrane based on the polyarylene piperidine copolymer.
Further, in step 1, the solvent is dichloromethane;
the solid content of the solution A is 20-30%;
the aromatic hydrocarbon monomer containing Ar group is p-terphenyl
9, 10-dihydroanthracene
4,4' -Dimethylbiphenyl
Or biphenyl
One or more of the above;
the ketone monomer is N-methyl-4-piperidone
2, 2-trifluoroacetophenone
Or 1, 1-trifluoro-2-butanone
One or more of the above;
containing Ar, ar 1 The molar ratio of aromatic hydrocarbon monomer to ketone monomer of the group is 1:1 to 1.3;
the molar ratio of the aromatic hydrocarbon monomer to the ketone monomer is lower than 1, the reaction cannot be polymerized, and the reaction polymerization is faster and is not easy to control when the molar ratio is higher than 1.3; therefore, it is preferred according to the invention to define the molar ratio of aromatic hydrocarbon monomer to ketone monomer as 1:1 to 1.3;
the acid solution is a mixed solution of trifluoroacetic acid and trifluoromethanesulfonic acid;
the molar ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid is 1-2;
the dropping condition of the acid solution is 0-5 ℃;
the time of the catalytic reaction is 2 to 48 hours.
Further, in step 1, the poor solvent is one or more of methanol, ethanol, diethyl ether or water;
the immersion in the alkaline solution is specifically immersion in 1-2 mol/L potassium carbonate solution at 50-60 ℃ for 24-48 hours;
the vacuum drying is specifically vacuum drying for 12-24 hours at 60-70 ℃.
Further, in the step 2, the polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone;
the poor solvent is one or more of ethanol, diethyl ether or diethyl ether;
the molar ratio of the piperidine group to the methyl iodide in the polyarylpiperidine copolymer is 1 to 0; the molar ratio of a piperidine group to an alkyl chain or an ether chain with halogens at two ends in the polyaryl piperidine copolymer is 1-10;
the alkyl chain with halogen at two ends is 1, 6-dibromohexane
1-bromo-4-chlorobutane
1, 2-bis (chloromethoxy) ethane
One of (a) and (b);
the temperature of the light-resistant reaction is 40-80 ℃ and the time is 4-24 hours;
the vacuum drying is specifically drying for 20 to 36 hours at a temperature of between 60 and 80 ℃;
the specific steps of grafting alkyl chains or ether chains with halogens at two ends of the quaternized polyarylpiperidine copolymer are as follows: dispersing the quaternized polyarylpiperidine copolymer in a polar solvent (one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone), then adding an alkyl chain or an ether chain with halogen at two ends, heating to 40-80 ℃, reacting in the dark for 4-24 hours, pouring the reaction solution into a poor solvent (one of ethanol, ether or diethyl ether), washing, filtering, and drying in vacuum (drying at 60-80 ℃ for 12-36 hours) to obtain the copolymer.
Further, in the step 3, the polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone;
the molar ratio of the copolymer to the cryptand ether crosslinking monomer is 1;
the cryptand ether crosslinking monomer is 4,10, 15-trioxane-1, 7-diazabicyclo [5.5.5]]Heptadecane
Or 4,7,13,16,21,24-hexaoxy-1, 10-diazabicyclo [8.8.8]Hexacosane (also known as cryptate 222)
The solid content of the casting solution is 3-15%;
the drying film forming is specifically drying for 12 to 24 hours at a temperature of between 60 and 100 ℃;
the vacuum drying is specifically vacuum drying for 12 to 30 hours at a temperature of between 50 and 110 ℃;
the alkali liquor is 1-5M NaOH or KOH solution;
the temperature of the ion exchange is 25-30 ℃, and the time is 48-72 h;
the substrate is plate glass.
The fourth technical scheme of the invention is the application of the hole ether crosslinking anion exchange membrane of the polyarylene piperidine copolymer in water electrolysis and preparation of alkaline fuel cells or flow batteries.
Preferably, in alkaline electrolysis water. When used for alkaline electrolyzed water, the electrolyte is one of potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate or pure water.
Preferably, the flow battery is a vanadium flow battery; the alkaline fuel cell is a hydrogen-oxygen fuel cell, an enzyme biofuel cell or a sodium borohydride fuel cell.
The technical idea of the invention is as follows:
the invention adopts the polyether-free polyaryl polymer as the main chain, has better alkali stability compared with aromatic ether and polyolefin aromatic main chains, and the piperidine tertiary amine group in the side chain has high reactivity with alkyl halide, thus leading the crosslinking reaction to be easier to occur. In addition, because the cryptand has a hydrophilic cage structure and stronger coordination capacity with alkali metal ions, the ionic conductivity of AEM can be effectively improved after the cryptand is grafted to a polymer framework, and the cryptand cannot generate degradation reaction under the working condition of a fuel cell because the cryptand is of a hydrophilic cage structureHas a larger ring structure, and can block OH in an external alkaline environment to a certain extent - Improving the stability of the anion exchange membrane. The invention uses the cryptate ether hydrophilic monomer as a crosslinking unit and introduces the cryptate ether hydrophilic monomer into the polyarylene copolymer through the Menshut gold reaction, and the prepared hydrophilic crosslinking type alkaline anion exchange membrane has higher ionic conductivity, better dimensional stability and alkali-resistant stability.
The invention discloses the following technical effects:
the invention provides a method for preparing a cavity ether crosslinking type anion exchange membrane material based on a polyarylene piperidine copolymer, wherein the anion exchange membrane utilizes a superacid catalysis reaction to introduce piperidine cyclic quaternary ammonium salt cations with excellent alkaline stability into a polymer main chain, and then a cavity ether crosslinking monomer is added to form a net structure, so that the dimensional stability and the mechanical property of the membrane can be effectively improved; the hydrophilic cage-like structure of the crosslinking monomer cryptand ether can improve the ionic conductivity and the alkali resistance stability of the anion exchange membrane. The method is simple and efficient, and has good application prospect in alkaline anion exchange membrane fuel cells, electrolytic water and flow batteries.
The hydrophilic crosslinked anion exchange membrane prepared by the reaction of the polyarylene copolymer and the cryptate crosslinking monomer through Menshut gold can form a crosslinked net structure and a nano ion channel, thereby well balancing the contradiction relationship among the ionic conductivity, the mechanical property and the alkali resistance stability of the membrane.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a FT-IR spectrum of anion exchange membranes prepared in examples 2 and 4 of the present invention.
FIG. 2 is a graph showing the results of temperature rise test of hydroxide ion conductivity of anion exchange membranes prepared in examples 2 and 4 of the present invention.
FIG. 3 is a graph showing the results of mechanical property tests of anion-exchange membranes prepared in examples 2 and 4 of the present invention.
FIG. 4 is a graph showing the results of cell performance tests on anion exchange membranes prepared in examples 2 and 4 of the present invention; wherein, a is a polarization curve and a peak power density curve graph, and b is an HFR curve graph; and (3) testing conditions are as follows: the membrane was tested for single cell performance at 80 ℃ in a fuel cell workstation (850e, sibner, USA). Humidity 100% (100% RH), no back pressure, by sweeping a voltage from 0.9V to 0.3V, a sweep rate of 10mV/s, test H 2 And O 2 And obtaining the initial performance of the fuel cell by the polarization curve and the power density curve of the fuel cell when the flow is 1000 sccm.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The "parts" in the present invention are in parts by mass unless otherwise specified.
Example 1
In this example, the hole ether crosslinking anion exchange membrane based on polyarylene piperidine copolymer is composed of a copolymer having the following repeating structural unit, the main chain of the copolymer is formed by super acid catalyzed polymerization of N-methyl-4-piperidone and p-terphenyl, after grafting of 1, 6-dibromohexane containing halogen at both ends, the crosslinking monomer is 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8] hexacosane, and the structural formula is:
the preparation method of the cavity ether crosslinking type anion exchange membrane based on the polyarylene piperidine copolymer comprises the following specific steps:
(1) Dissolving p-terphenyl (20.00mmol, 4.61g) in dichloromethane (15.00 mL) at room temperature, and mechanically stirring to obtain a mixed solution; n-methyl-4-piperidone (26.30mmol, 3.00mL) was then added and stirred until it was well dissolved. The mixture was maintained at 0 ℃ and trifluoroacetic acid TFA (13.46mmol, 1.00mL) and trifluoromethanesulfonic acid TFSA (187.60mmol, 15.00mL) were slowly added dropwise, and after completion of the addition, the reaction was stirred for 5 hours. After the reaction is finished, the mixture is poured into absolute ethyl alcohol to obtain a fibrous polymer. The above polymer was immersed in a 1mol/L potassium carbonate solution at 50 ℃ for 24 hours, after which the polymer was washed 3 times in deionized water. After completion of the washing, the reaction mixture was dried in a vacuum oven at 60 ℃ for 12 hours to obtain a polyarylaiperidine copolymer (7.23 g, yield 95%, degree of polymerization m: 500).
(2) The polyarylpiperidine copolymer (3.05mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL), and 1, 6-dibromohexane (24.40mol, 3.72mL) was added to the mixture. Then, the system was heated to 80 ℃, reacted for 13 hours in the dark, and then the reaction solution was poured into ether and washed several times with ethanol. After filtration, the product was dried in a vacuum oven at 60 ℃ for 20 hours to give a quaternized polyarylpiperidine copolymer (1.59 g, 90% yield).
(3) This example is a fully crosslinked structure, so no iodomethane is required for quaternization. The quaternized polyarylpiperidine copolymer (2.42mmol, 1.00g) was uniformly dispersed in dimethylsulfoxide (10.00 mL) at a solid content of 10%, and then a crosslinking monomer 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8] hexacosane (1.94mmol, 0.73g, cryptate 222) was added to the mixture. Then, the system was heated to 70 ℃ to obtain a casting solution after 10 hours of reaction. Casting the casting solution on plate glass, drying at 80 ℃ for 12h to form a film, and then placing the film in a vacuum drying oven for vacuum drying at 80 ℃ for 24h; soaking the obtained solid membrane material in deionized water, peeling, soaking in 30 deg.C alkali liquor for 72h for ion exchange, and fully washing with deionized water to obtain a porous ether cross-linked anion exchange membrane (anion exchange membrane for short) based on polyarylene piperidine copolymer with a thickness of 25 μm.
And (3) testing results: the theoretical value of the ion exchange capacity of the anion exchange membrane prepared in the embodiment is 1.22g/mmol, and the anion exchange membrane is HCO at 20 DEG C 3 - Has a conductivity of 6.54mS/cm, an OH-conductivity of 18.36mS/cm, an OH group at 30 DEG - Has a conductivity of 32.57mS/cm and OH at 80 DEG C - The conductivity of (d) was 75.23mS/cm. After the membrane was immersed in 2M NaOH solution at 60 ℃ for 7 days, the OH-conductivity of the membrane at 30 ℃ was still 24.70mS/cm.
Example 2
In this embodiment, the hole ether crosslinking anion exchange membrane based on polyarylene piperidine copolymer is composed of a copolymer having the following repeating structural unit, the main chain of the copolymer is formed by super acid catalyzed polymerization of N-methyl-4-piperidone and p-terphenyl, 1, 6-dibromohexane containing halogen at both ends is grafted after quaternization, the crosslinking monomer is 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8] hexacosane, and the structural formula is:
(1) Same as in step (1) of example 1.
(2) The polyarylpiperidine type copolymer (3.04mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL), and methyl iodide (2.58mmol, 0.16mL) was added to the mixture. Then, the system was heated to 40 ℃, reacted in the dark for 24 hours, and then the reaction solution was poured into ether and washed with ethanol several times. After filtration, the product was dried in a vacuum oven at 80 ℃ for 24 hours to give quaternized polyarylpiperidine copolymer (1.25 g, 95% yield).
(3) The quaternized polyarylpiperidine copolymer (2.95mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL), and 1, 6-dibromohexane (29.50mol, 4.50mL) was added to the mixture. Then, the system was heated to 80 ℃, reacted for 4 hours in the dark, and then the reaction solution was poured into ether and washed several times with ethanol. After filtration, the product was dried in a vacuum oven at 60 ℃ for 20 hours to obtain a copolymer (1.78 g, 96% yield).
(4) The copolymer (2.85mmol, 1.00g) prepared in step (3) was uniformly dispersed in dimethyl sulfoxide (12.50 mL) at a solid content of 8%, and then a crosslinking monomer 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8] hexacosane (0.21mmol, 0.08g, cryptate 222) was added to the mixed solution. Then, the system was heated to 80 ℃ to obtain a casting solution after 10 hours of reaction. Casting the casting solution on flat glass, drying at 60 ℃ for 12h to form a film, and then placing the film in a vacuum drying oven for vacuum drying at 80 ℃ for 12h; soaking the obtained solid membrane material in deionized water, peeling, soaking in 25 ℃ alkali liquor for 48h for ion exchange, and finally fully washing with deionized water to obtain the polyarylenesiperidine copolymer-based hole ether crosslinking type anion exchange membrane (called anion exchange membrane for short) with the thickness of 35 mu m.
And (3) testing results: the theoretical value of the ion exchange capacity of the anion exchange membrane prepared in the embodiment is 2.33g/mmol, and the anion exchange membrane is HCO at 20 DEG C 3 - Has a conductivity of 13.80mS/cm, OH - The conductivity of (b) was 33.40mS/cm, the conductivity of OH-at 30 ℃ was 45.65mS/cm and the conductivity of OH-at 80 ℃ was 90.16mS/cm. Immersing the membrane in 2M NaOH solution at 60 deg.C for 7 days, and then placing the membrane at 30 deg.C with OH - The conductivity was still 41.4mS/cm.
Example 3
In this example, the hole ether cross-linked anion exchange membrane based on polyarylene piperidine copolymer is composed of a copolymer having the following repeating structural unit, the main chain of the copolymer is formed by super acid catalyzed polymerization of N-methyl-4-piperidone and p-terphenyl, after grafting 1, 2-bis (chloromethoxy) ethane containing halogen at both ends, the cross-linking monomer is 4,10, 15-trioxa-1, 7-diazabicyclo [5.5.5] heptadecane, and the structural formula is:
(1) The same procedure as in step (1) of example 1.
(2) The polyarylpiperidine copolymer (3.05mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL), and 1, 2-bis (chloromethoxy) ethane (15.25mol, 2.00mL) was added to the mixture. Then, the system was heated to 70 ℃, reacted in the dark for 6 hours, and then the reaction liquid was poured into ether and washed with ethanol several times. After filtration, the product was dried in a vacuum oven at 70 ℃ for 36 hours to obtain a copolymer (2.72 g, yield 92%).
(3) This example is a fully crosslinked structure, so no iodomethane is required for quaternization. The prepared copolymer (2.42mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (6.00 mL) to have a solid content of 6%, and then 4,10, 15-trioxa-1, 7-diazabicyclo [5.5.5] heptadecane (1.45mmol, 0.35g) was added to the mixed solution. Then, the system was heated to 70 ℃ to obtain a casting solution after 12 hours of reaction. Casting the casting solution on plate glass, drying at 60 ℃ for 24h to form a film, and then placing the film in a vacuum drying oven for vacuum drying at 100 ℃ for 12h; soaking the obtained solid membrane material in deionized water, peeling, soaking in 30 deg.C alkali liquor for 48h for ion exchange, and fully washing with deionized water to obtain a porous ether cross-linked anion exchange membrane (anion exchange membrane for short) based on polyarylene piperidine copolymer, with a thickness of 55 μm.
And (3) testing results: the theoretical value of the ion exchange capacity of the anion exchange membrane prepared in the embodiment is 1.44g/mmol, and the anion exchange membrane is HCO at 20 DEG C 3 - Has a conductivity of 8.52mS/cm, OH - Has a conductivity of 21.34mS/cm and OH at 30 DEG C - Has a conductivity of 38.49mS/cm and an OH temperature of 80 DEG C - The conductivity of (b) was 83.54mS/cm. The membrane was immersed in 2M NaOH solution at 60 ℃ for 7 days, and then the OH of the membrane was 30 ℃ - The conductivity was still 31.91mS/cm.
Example 4
In this embodiment, the cavity ether crosslinked anion exchange membrane based on the polyarylene piperidine copolymer is composed of a copolymer having the following repeating structural unit, the main chain of the copolymer is formed by super acid catalyzed polymerization of N-methyl-4-piperidone, 2-trifluoroacetophenone and p-terphenyl, 1-bromo-4-chlorobutane with halogen at both ends is grafted after quaternization, the crosslinking monomer is 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8] hexacosane, and the structural formula is:
(1) Same as in step (1) of example 1.
(2) The same procedure as in step (2) of example 2 was repeated.
(3) The quaternized polyarylpiperidine copolymer (2.95mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL), and 1-bromo-4 chlorobutane (29.50mol, 3.40mL) was added to the mixture. Then, the system was heated to 70 ℃, reacted for 4 hours in the dark, and then the reaction solution was poured into ether and washed several times with ethanol. After filtration, the product was dried in a vacuum oven at 65 ℃ for 30 hours to obtain a copolymer (3.25 g, yield 95%).
(4) The copolymer (2.88mmol, 1.00g), was uniformly dispersed in dimethyl sulfoxide (12.5 mL) at 8% solids, and then crosslinking monomer cryptate 222 (0.22mmol, 0.08g) was added to the mixture. Then, the system is heated to 80 ℃ and a casting solution is obtained after 10 hours of reaction. Casting the casting solution on flat glass, drying at 60 ℃ for 22h to form a film, and then placing the film in a vacuum drying oven for vacuum drying at 100 ℃ for 16h; soaking the obtained solid membrane material in deionized water, peeling, soaking in 25 deg.C alkali liquor for 48h for ion exchange, and fully washing with deionized water to obtain a porous ether cross-linked anion exchange membrane (anion exchange membrane for short) based on polyarylene piperidine copolymer, with a thickness of 35 μm.
And (3) testing results: the theoretical value of the ion exchange capacity of the anion exchange membrane prepared in the embodiment is 2.35g/mmol, and the anion exchange membrane is HCO at 20 DEG C 3 - Has a conductivity of 15.00mS/cm, OH - Has a conductivity of 38.40mS/cm and OH at 30 DEG C - Has a conductivity of 53.28mS/cm, OH at 80 DEG - The conductivity of (a) was 95.69mS/cm. Immersing the membrane in 2M NaOH solution at 60 deg.C for 7 days, and then placing the membrane at 30 deg.C with OH - The conductivity was still 49.76mS/cm.
The performance of the anion exchange membranes prepared in example 2 and example 4 was examined, and the results are shown in FIGS. 1 to 4, wherein example 2 is shown in FIGS. 2 to 4, and example 4 is shown in FIG. 4.
FIG. 1 is a FT-IR spectrum of anion exchange membranes prepared in examples 2 and 4 of the present invention, in which PPT + CH 3 I represents the infrared structure spectrum of the quaternized polyarylene copolymer. 1042cm can be seen from FIG. 1 -1 Characteristic peaks for ether linkages appear indicating successful grafting of the hole ether crosslinking agent onto the polyarylene copolymer.
FIG. 2 is a graph showing the results of temperature rise test of hydroxide ion conductivity of anion exchange membranes prepared in examples 2 and 4 of the present invention. It can be seen from fig. 2 that as the temperature increases, the OH "ion conductivity also increases.
FIG. 3 is a graph showing the results of mechanical property tests of anion-exchange membranes prepared in examples 2 and 4 of the present invention. It can be seen from fig. 3 that the prepared anion-exchange membrane has good mechanical properties.
FIG. 4 is a graph showing the results of cell performance tests on anion exchange membranes prepared in examples 2 and 4 of the present invention; wherein, a is a polarization curve and a peak power density curve graph, and b is an HFR curve graph; and (3) testing conditions are as follows: the membrane was tested for single cell performance at 80 ℃ in a fuel cell workstation (850e, sibner, USA). Humidity 100% (100% RH), no back pressure, by sweeping voltage from 0.9V to 0.3V, sweep rate 10mV/s, test H 2 And O 2 And obtaining the initial performance of the fuel cell by the polarization curve and the power density curve of the fuel cell when the flow is 1000 sccm. It can be seen from fig. 4 that the prepared films all had a higher open circuit voltage, indicating that the permeability of the film was low; example 4 has a greater power density of 666.07mW/cm 2 Because of its higher conductivity.
Example 5
In this embodiment, the hole ether crosslinking anion exchange membrane based on polyarylene piperidine copolymer is composed of a copolymer having the following repeating structural unit, the main chain of the copolymer is formed by super acid catalyzed polymerization of N-methyl-4-piperidone, 2-trifluoroacetophenone and p-terphenyl, 1, 6-dibromohexane containing halogen at both ends is grafted after quaternization, the crosslinking monomer is 4,10, 15-trioxa-1, 7-diazabicyclo [5.5.5] heptadecane, and the structural formula is:
(1) Biphenyl (21.71mmol, 3.35g) was dissolved in dichloromethane at room temperature, and mixed solution was obtained under mechanical stirring; then N-methyl-4-piperidone (14.21mmol, 1.62mL), 2-trifluoroacetophenone (2.49mmol, 0.34mL) was added and stirred until it was sufficiently dissolved. The mixture was kept at 3 ℃ and trifluoroacetic acid TFA (13.46mmol, 1.00mL) and trifluoromethanesulfonic acid TFSA (150.08mmol, 12.00mL) were slowly added dropwise, and after completion of the addition, the reaction was stirred for 6 hours. After the reaction, the reaction solution was poured into a large amount of methanol to obtain a polymer. The polymer was immersed in a 2mol/L potassium carbonate solution at 60 ℃ for 36 hours, after which the polymer was washed 4 times with deionized water. After the completion of the washing, the polymer was dried in a vacuum oven at 70 ℃ for 12 hours to obtain a polyarylaiperidine copolymer (4.77 g, yield 96%, polymerization degree m 600).
(2) The above-mentioned polyarylaiperidine type copolymer (3.84mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL), and methyl iodide (1.54mol, 0.10 mL) was added to the mixture. Then, the system was heated to 50 ℃, reacted in the dark for 20 hours, and then the reaction solution was poured into ether and washed with ethanol several times. After filtration, the product was dried in a vacuum oven at 60 ℃ for 20 hours to give quaternized polyarylpiperidine copolymer (1.25 g, 95% yield).
(3) The quaternized polyarylpiperidine copolymer (3.90mmol, 1.00g) described above was uniformly dispersed in dimethyl sulfoxide (10.00 mL), and 1, 6-dibromohexane (14.04mol, 2.14mL) was then added to the mixture. Then, the system was heated to 75 ℃, reacted for 5 hours in the dark, and then the reaction solution was poured into ether and washed with ethanol several times. After filtration, the product was dried in a vacuum oven at 75 ℃ for 28 hours to obtain a copolymer (1.26 g, yield 93%).
(4) The copolymer (3.28mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL) to have a solid content of 10%, and 4,10, 15-trioxa-1, 7-diazabicyclo [5.5.5] heptadecane (0.74mmol, 0.18g) was added to the mixed solution. Then, the system was heated to 75 ℃ and a casting solution was obtained after 11 hours of reaction. Casting the casting solution on flat glass, drying at 70 ℃ for 24h to form a film, and then placing the film in a vacuum drying oven for vacuum drying at 60 ℃ for 24h; soaking the obtained solid membrane material in deionized water, peeling, soaking in 30 ℃ alkali liquor for 60h for ion exchange, and finally fully washing with deionized water to obtain the hole ether crosslinking type anion exchange membrane (called anion exchange membrane for short) based on the polyarylene piperidine copolymer, wherein the thickness of the hole ether crosslinking type anion exchange membrane is 25 micrometers.
And (3) testing results:the theoretical value of the ion exchange capacity of the anion exchange membrane prepared in the embodiment is 2.29g/mmol, and the anion exchange membrane is HCO at 20 DEG C 3 - Has a conductivity of 12.75mS/cm, OH - Has a conductivity of 35.72mS/cm and OH at 30 DEG C - Has a conductivity of 43.35mS/cm and OH at 80 DEG C - The conductivity of (d) was 89.93mS/cm. Immersing the membrane in 2M NaOH solution at 60 deg.C for 7 days, and then placing the membrane at 30 deg.C with OH - The conductivity was still 38.00mS/cm.
Example 6
In this embodiment, the hole ether crosslinking anion exchange membrane based on polyarylene piperidine copolymer is composed of a copolymer having the following repeating structural unit, the main chain of the copolymer is polymerized by super acid catalysis from N-methyl-4-piperidone, 9, 10-dihydroanthracene and p-terphenyl, 1, 2-bis (chloromethoxy) ethane containing halogen at both ends is grafted after quaternization, the crosslinking monomer is 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8] hexacosane, and the structural formula is:
(1) P-terphenyl (18.63mmol, 4.29g) and 9, 10-dihydroanthracene (3.29mmol, 0.59g) are dissolved in dichloromethane at room temperature, and mixed solution is obtained under mechanical stirring; n-methyl-4-piperidone (24.22mmol, 2.98mL) was then added and stirred until it was fully dissolved. The mixture was maintained at 5 ℃ and trifluoroacetic acid TFA (13.46mmol, 1.00mL) and trifluoromethanesulfonic acid TFSA (187.60mmol, 15.00mL) were added slowly dropwise, after which the reaction was stirred for 7 hours. After the reaction, the reaction mixture was poured into diethyl ether to obtain a polymer. The polymer was immersed in a 1mol/L potassium carbonate solution at 55 ℃ for 24 hours, after which the polymer was washed 5 times with deionized water. After the completion of the washing, the polymer was dried in a vacuum oven at 60 ℃ for 24 hours to obtain a polyarylaiperidine copolymer (5.32 g, yield 98%, polymerization degree m: 500).
(2) The above-mentioned polyarylaiperidine type copolymer (3.12mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL), methyl iodide (0.47mol, 0.03mL) was then added, the system was heated to 40 ℃ and reacted in the dark for 12 hours, and then the reaction solution was poured into ether and washed with ethanol several times. After filtration, the product was dried in a vacuum oven at 80 ℃ for 36 hours to give quaternized polyarylpiperidine copolymer (1.82 g, 96% yield).
(3) The quaternized polyarylpiperidine copolymer (3.00mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL), then 1, 2-bis (chloromethoxy) ethane (12.75mol, 1.66mL) was added to the mixed solution, the system was heated to 75 ℃, reacted in the dark for 6 hours, and then the reaction solution was poured into ether and washed with ethanol several times. After filtration, the product was dried in a vacuum oven at 60 ℃ for 20 hours to obtain a copolymer (1.35 g, yield 90%).
(4) The copolymer (2.51mmol, 1.00g), was uniformly dispersed in dimethyl sulfoxide (5.00 mL) at 5% solids, and then crosslinked monomer cryptate 222 (2.13mmol, 0.80g) was added to the mixture. Then, the system was heated to 70 ℃ and a casting solution was obtained after 12 hours of reaction. Casting the casting solution on flat glass, drying at 100 ℃ for 12h to form a film, and then placing the film in a vacuum drying oven for vacuum drying at 100 ℃ for 12h; soaking the obtained solid membrane material in deionized water, peeling, soaking in 30 deg.C alkali liquor for 60h for ion exchange, and fully washing with deionized water to obtain a porous ether cross-linked anion exchange membrane (anion exchange membrane for short) based on polyarylene piperidine copolymer, with a thickness of 55 μm.
And (3) testing results: the theoretical value of the ion exchange capacity of the anion exchange membrane prepared in the embodiment is 1.34g/mmol, and the anion exchange membrane is HCO at 20 DEG C 3 - Has a conductivity of 7.93mS/cm, OH - Has a conductivity of 19.85mS/cm and OH at 30 DEG C - Has a conductivity of 37.29mS/cm and OH at 80 DEG C - The conductivity of (a) was 79.37mS/cm. The membrane was immersed in 2M NaOH solution at 60 ℃ for 7 days, and then the OH of the membrane was 30 ℃ - The conductivity was still 30.79mS/cm.
Example 7
In this example, the poly (arylene piperidine) copolymer-based cryptand-ether cross-linked anion exchange membrane is composed of a copolymer having the following repeating structural unit, wherein the main chain of the copolymer is prepared by super acid catalyzed polymerization of N-methyl-4-piperidone, 4' -dimethylbiphenyl and p-terphenyl, 1, 6-dibromohexane containing halogen at both ends is grafted after quaternization, and the cross-linking monomer is 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8] hexacosane, and the structural formula is:
(1) P-terphenyl (18.63mmol, 4.29g) and 4,4' -dimethylbiphenyl (3.29mmol, 0.60g) were dissolved in dichloromethane at room temperature, and a mixed solution was obtained under mechanical stirring; n-methyl-4-piperidone (24.22mmol, 2.98mL) was then added and stirred until it was fully dissolved. The mixture was maintained at 0 ℃ and trifluoroacetic acid TFA (13.46mmol, 1.00mL) and trifluoromethanesulfonic acid TFSA (125.07mmol, 10.00mL) were slowly added dropwise, and the reaction was stirred for 4 hours after the addition. After the reaction, the mixture was poured into a large amount of ethanol to obtain a polymer. The polymer was immersed in a 2mol/L potassium carbonate solution at 55 ℃ for 24 hours, after which the polymer was washed 3 times with deionized water. After the final suction filtration, the polymer solid fiber was dried in a vacuum oven at 65 ℃ for 20 hours to obtain a polyarylamide copolymer (5.56 g, yield 95%, degree of polymerization m 600).
(2) The above-mentioned polyarylpiperidine copolymer (3.02mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL), methyl iodide (0.45mol, 0.03mL) was then added to the mixed solution, the system was heated to 45 ℃ and reacted in the dark for 22 hours, and then the reaction solution was poured into ether and washed with ethanol several times. After filtration, the product was dried in a vacuum oven at 75 ℃ for 30 hours to give quaternized polyarylpiperidine copolymer (1.75 g, 90% yield).
(3) The quaternized polyarylpiperidine copolymer (2.97mmol, 1.00g) was uniformly dispersed in dimethyl sulfoxide (10.00 mL), and then 1, 6-dibromohexane (11.88mol, 1.81mL) was added to the mixed solution, the system was heated to 80 ℃ and reacted in the dark for 6 hours, and then the reaction solution was poured into ether and washed with ethanol several times. After filtration, the product was dried in a vacuum oven at 60 ℃ for 20 hours to obtain a copolymer (1.58 g, yield 90%).
(4) The copolymer (2.53mmol, 1.00g) is evenly dispersed in dimethyl sulfoxide (10.00 mL) with the solid content of 10%, then crosslinking monomer cryptand 222 (1.08mmol, 0.41g) is added into the mixed solution, the system is heated to 80 ℃, and the casting solution is obtained after 10 hours of reaction. Casting the casting solution on plate glass, drying at 90 ℃ for 10h to form a film, and then placing the film in a vacuum drying oven for vacuum drying at 120 ℃ for 30h; soaking the obtained solid membrane material in deionized water, peeling, soaking in 25 deg.C alkali liquor for 72h for ion exchange, and fully washing with deionized water to obtain a porous ether cross-linked anion exchange membrane (anion exchange membrane for short) based on polyarylene piperidine copolymer with a thickness of 25 μm.
And (3) testing results: the theoretical value of the ion exchange capacity of the anion exchange membrane prepared in the embodiment is 1.34g/mmol, and the anion exchange membrane is HCO at 20 DEG C 3 - Has a conductivity of 7.94mS/cm, OH - Has a conductivity of 19.25mS/cm, an OH-conductivity of 36.58mS/cm at 30 ℃ and an OH-conductivity of 80 DEG C - The conductivity of (3) was 77.26mS/cm. Immersing the membrane in 2M NaOH solution at 60 deg.C for 7 days, and then placing the membrane at 30 deg.C with OH - The conductivity was still 29.36mS/cm.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A compound having a general structural formula as shown in formula I:
in formula I, 0 y + z is less than or equal to 100,0 is less than or equal to z is less than or equal to y;
m is polymerization degree, and m is a positive integer between 50 and 800;
ar and Ar 1 Are the same or different units containing aromatic ring structures;
x is Br - 、I-、Cl - 、OH - 、HCO 3 - Or CO 3 2- Any one of the above;
R 1 is an alkyl chain or an ether chain;
R 2 is a structure formed after the polymerization of ketone monomers;
R 3 is a cryptand ether unit structure.
2. The compound of claim 1, wherein Ar, ar are 1 Is one or more of the following structural formulas:
the R is 1 Is one of the following structural formulas:
the R is 2 Is one of the following structural formulas:
the R is 3 Is one of the following structural formulas:
3. a cryptand-crosslinked anion exchange membrane of a polyarylene piperidine copolymer, characterized in that the main component is the compound according to claim 1.
4. A method for preparing a cryptand-crosslinked anion exchange membrane of the polyarylene piperidine copolymer as claimed in claim 3, which comprises the steps of:
carrying out super acid catalytic polymerization on an aromatic hydrocarbon monomer containing Ar groups and a ketone monomer to obtain a main chain, carrying out quaternization treatment on the main chain, grafting an alkyl chain or an ether chain with halogens at two ends to obtain a copolymer, carrying out Menshute reaction on the copolymer and a cavity ether crosslinking monomer to obtain a casting solution, and carrying out ion exchange after casting film forming to obtain the cavity ether crosslinking type anion exchange membrane based on the polyarylene piperidine copolymer.
5. The method of claim 4, comprising the steps of:
step 1, adding Ar and Ar 1 Dissolving aromatic hydrocarbon monomers of the groups in a solvent to obtain a solution A, then adding ketone monomers into the solution A to dissolve the ketone monomers to obtain a mixed solution, dropwise adding an acid solution into the mixed solution to perform catalytic reaction, and pouring the mixed solution into a poor solvent after the reaction is finished to obtain a polymer; immersing the polymer into an alkaline solution, washing in water, and drying in vacuum to obtain a polyarylpiperidine copolymer;
step 2, dispersing the polyarylpiperidine copolymer in a polar solvent, adding methyl iodide, reacting in a dark place, pouring a reaction solution into a poor solvent after the reaction is finished, washing, filtering and drying in vacuum to obtain the quaternized polyarylpiperidine copolymer; grafting an alkyl chain or an ether chain with halogen at two ends of the quaternized polyaryl piperidine copolymer to obtain a copolymer;
step 3, dispersing the copolymer in a polar solvent, adding a cryptand crosslinking monomer, and heating to react to obtain a casting solution; casting the casting solution on a substrate, drying to form a film, and then drying in vacuum; and immersing the obtained membrane into alkali liquor for ion exchange to obtain the hole ether crosslinking type anion exchange membrane based on the polyarylene piperidine copolymer.
6. The method according to claim 5, wherein in step 1, the solvent is dichloromethane;
the solid content of the solution A is 20-30%;
containing Ar and Ar 1 The aromatic hydrocarbon monomer of the group is one or more of p-terphenyl, 9, 10-dihydroanthracene, 4' -dimethyl biphenyl or biphenyl;
the ketone monomer is one or more of N-methyl-4-piperidone, 2-trifluoro acetophenone or 1, 1-trifluoro-2-butanone;
containing Ar, ar 1 The molar ratio of aromatic hydrocarbon monomer to ketone monomer of the group is 1:1 to 1.3;
the acid solution is a mixed solution of trifluoroacetic acid and trifluoromethanesulfonic acid;
the molar ratio of the trifluoroacetic acid to the trifluoromethanesulfonic acid is 1-2;
the dropping condition of the acid solution is 0-5 ℃;
the time of the catalytic reaction is 2 to 48 hours.
7. The preparation method according to claim 5, wherein in the step 1, the poor solvent is one or more of methanol, ethanol, diethyl ether or water;
the immersion in the alkaline solution is specifically immersion in 1-2 mol/L potassium carbonate solution at 50-60 ℃ for 24-48 hours;
the vacuum drying is specifically vacuum drying for 12-24 hours at 60-70 ℃.
8. The preparation method according to claim 5, wherein in the step 2, the polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone;
the poor solvent is one or more of ethanol, diethyl ether or diethyl ether;
the molar ratio of the piperidine group to the methyl iodide in the polyarylpiperidine copolymer is 1; the molar ratio of a piperidine group to an alkyl chain or an ether chain with halogens at two ends in the polyaryl piperidine copolymer is 1-10;
the temperature of the light-resistant reaction is 40-80 ℃ and the time is 4-24 hours;
the vacuum drying is specifically drying for 20 to 36 hours at a temperature of between 60 and 80 ℃.
9. The preparation method according to claim 5, wherein in the step 3, the polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone;
the molar ratio of the copolymer to the cryptand ether crosslinking monomer is 1;
the solid content of the casting solution is 3-15%;
the drying film forming is specifically drying for 12 to 24 hours at a temperature of between 60 and 100 ℃;
the vacuum drying is specifically vacuum drying for 12 to 24 hours at the temperature of between 50 and 110 ℃;
the alkali liquor is 1-5M NaOH or KOH solution;
the temperature of the ion exchange is 25-30 ℃, and the time is 48-72 h.
10. Use of the cryptand-crosslinked anion exchange membrane of the polyarylene piperidine copolymer as claimed in claim 3 for the electrolysis of water, for the preparation of alkaline fuel cells or flow batteries.
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| CN117229463A (en) * | 2023-11-15 | 2023-12-15 | 国家电投集团氢能科技发展有限公司 | Non-fluorine sulfonic acid resin, proton exchange membrane and preparation method and application thereof |
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| CN117024924A (en) * | 2023-10-08 | 2023-11-10 | 佛山科学技术学院 | Ultralow-swelling anti-free radical polyaryl anion exchange membrane and preparation method thereof |
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| CN117229463A (en) * | 2023-11-15 | 2023-12-15 | 国家电投集团氢能科技发展有限公司 | Non-fluorine sulfonic acid resin, proton exchange membrane and preparation method and application thereof |
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