CN113801300B - Anion exchange polymer, preparation method and application thereof - Google Patents
Anion exchange polymer, preparation method and application thereof Download PDFInfo
- Publication number
- CN113801300B CN113801300B CN202111165344.4A CN202111165344A CN113801300B CN 113801300 B CN113801300 B CN 113801300B CN 202111165344 A CN202111165344 A CN 202111165344A CN 113801300 B CN113801300 B CN 113801300B
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- Prior art keywords
- anion exchange
- exchange polymer
- polymer
- hours
- piperidone
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- 229920000642 polymer Polymers 0.000 title claims abstract description 105
- 238000005349 anion exchange Methods 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 29
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims abstract description 44
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 14
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical group O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 239000003011 anion exchange membrane Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 229920006317 cationic polymer Polymers 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 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 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 229930184652 p-Terphenyl Natural products 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 230000002152 alkylating effect Effects 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 6
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 5
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 3
- BDVKAMAALQXGLM-UHFFFAOYSA-N 1-ethylpiperidin-4-one Chemical compound CCN1CCC(=O)CC1 BDVKAMAALQXGLM-UHFFFAOYSA-N 0.000 claims description 3
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 claims description 3
- CCDBCHAQIXKJCG-UHFFFAOYSA-N 1-propan-2-ylpiperidin-4-one Chemical compound CC(C)N1CCC(=O)CC1 CCDBCHAQIXKJCG-UHFFFAOYSA-N 0.000 claims description 3
- YGDZKYYCJUNORF-UHFFFAOYSA-N 1-propylpiperidin-4-one Chemical compound CCCN1CCC(=O)CC1 YGDZKYYCJUNORF-UHFFFAOYSA-N 0.000 claims description 3
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 claims description 2
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000002168 alkylating agent Substances 0.000 claims description 2
- 229940100198 alkylating agent Drugs 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 2
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 40
- 239000000126 substance Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 6
- 150000001768 cations Chemical class 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 4
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- 230000000052 comparative effect Effects 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 238000003892 spreading Methods 0.000 description 9
- 230000007480 spreading Effects 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 7
- 238000005956 quaternization reaction Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KXVUSQIDCZRUKF-UHFFFAOYSA-N bromocyclobutane Chemical compound BrC1CCC1 KXVUSQIDCZRUKF-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VRJHQPZVIGNGMX-UHFFFAOYSA-N piperidine-4-one Natural products O=C1CCNCC1 VRJHQPZVIGNGMX-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/122—Copolymers statistical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides an anion exchange polymer, a preparation method and application thereof, wherein the anion exchange polymer comprises structural units shown in a formula (1), a formula (2) and a formula (3); wherein the R is 1 And R is 2 Each independently selected from C1-C10 chain alkyl or C3-C10 cycloalkyl. The anion exchange polymer provided by the invention simultaneously comprises three structural units of terphenyl, m-terphenyl and piperidone monomers, the main chain of the anion exchange polymer does not contain polar groups such as ether bonds, and the like, has good main chain stability, and the piperidine cyclic quaternary ammonium group has good cation stability, so that the material has excellent chemical stability, meanwhile, the solubility of the anion exchange polymer is improved, and the subsequent molding processability of the anion exchange polymer is facilitated.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to an anion exchange polymer, a preparation method and application thereof.
Background
Anion exchange polymers are key materials in fuel cells, water separators, electrical synthesizers, and electrodialysis devices. Ionic conductivity, chemical stability and mechanical strength are key properties that determine the performance of anion exchange polymers, directly affecting the energy conversion efficiency and the service life of each of the above devices. At present, there are a large number of types of anion exchange polymers which have OH at 80 DEG C - The conductivity exceeds 100mS/cm, and the application requirement can be met. However, the performance of the anion exchange polymer is still to be further improved in terms of chemical stability and mechanical strength under high-temperature strong alkali conditions.
CN105924587a discloses a branched polymer anion exchange membrane and a preparation method thereof. The preparation of the membrane material is based on the preparation of a series of polymers containing branched side chain structures by using chloromethyl polysulfone as a macromolecular initiator and p-chloromethyl styrene as a monomer and utilizing atom transfer radical polymerization reaction. The high-conductivity alkaline anion exchange membrane with low chloromethylation degree can be prepared by using abundant terminal groups with higher chemical reactivity through post-treatment; in addition, by modulating the branching degree of the side chains, microphase separation with different degrees can be formed in the membrane, and the aim of considering the conductivity and the stability of the anion exchange membrane is fulfilled.
CN102945975a discloses a pyridinium salt polymer anion exchange membrane with high conductivity, good chemical stability and thermal stability and a preparation method thereof. The active group of the pyridinium salt polymer anion exchange membrane is pyridinium salt. (1) Adding olefin containing pyridine groups, fluorine-containing acrylate monomers, a solvent and an initiator into a reactor, sealing under the protection of inert gas, carrying out reflux reaction, and obtaining a polymer with pyridine groups after precipitation, washing and drying of the obtained product; (2) Dissolving the polymer obtained in the step (1) in an organic solvent to prepare a polymer solution with the mass percent concentration of 5-20%, casting into a film by a phase inversion method, and drying for later use; (3) And (3) soaking the membrane dried in the step (2) in a quaternizing reagent for reaction, and taking out and drying to obtain the pyridinium salt polymer anion exchange membrane.
CN107910576a discloses a preparation method of an anionic polymer film with high chemical stability, belonging to the field of ionic polymer films. Under the catalysis of mixed super acid, the aryl compound and the N-alkyl 4-piperidone compound undergo an addition condensation reaction to obtain a linear polymer with large molecular weight and narrow molecular weight distribution. Quaternization modification is carried out on the nitrogen-containing heterocycle on the polymer chain by methyl iodide or bromoalkane, the obtained quaternized ionic polymer is soaked in strong alkali solution for ion exchange, washing and drying are carried out, and finally the obtained ionic polymer is dissolved into a casting film.
Although the above-mentioned special scheme can obtain anion exchange polymer with good ionic conductivity, the tortuosity and rotatability of benzene ring on main chain are strong, so that microstructure regularity after film formation of polymer is low, and mechanical strength is still to be further raised. Therefore, there is a need to develop an anion exchange polymer having excellent mechanical strength, high ionic conductivity and high chemical stability, thereby improving the performance of the related electrochemical device.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an anion exchange polymer, a preparation method and application thereof, wherein the anion exchange polymer provided by the invention comprises three structural units of terphenyl, m-terphenyl and piperidone monomers, and the main chain of the anion exchange polymer does not contain polar groups such as ether bonds and the like, has good main chain stability, and the piperidine cyclic quaternary ammonium group has good cation stability, so that the material has excellent chemical stability, and meanwhile, the solubility of the anion exchange polymer is improved, thereby being beneficial to the subsequent molding processability of the anion exchange polymer.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an anion exchange polymer comprising structural units represented by formula (1), formula (2) and formula (3);
wherein the R is 1 And R is 2 Each independently selected from C1-C10 chain alkyl or C3-C10 cycloalkyl;
the anion exchange polymer provided by the invention simultaneously comprises three structural units of terphenyl, m-terphenyl and piperidone monomers, the main chain of the anion exchange polymer does not contain polar groups such as ether bonds, and the like, has good main chain stability, and the piperidine cyclic quaternary ammonium group has good cation stability, so that the material has excellent chemical stability, meanwhile, the solubility of the anion exchange polymer is improved, and the subsequent molding processability of the anion exchange polymer is facilitated.
In a preferred embodiment of the present invention, the number average molecular weight of the anion exchange polymer is 1000 to 100 ten thousand, and for example, 1000, 5000, 1 ten thousand, 10 ten thousand, 20 ten thousand, 30 ten thousand, 40 ten thousand, 50 ten thousand, 60 ten thousand, 70 ten thousand, 80 ten thousand, 90 ten thousand or 100 ten thousand may be used, but the present invention is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the sum of the mole fractions of the structural units of formula (2) and formula (3) is the same as the mole fraction of the structural unit of formula (1).
Preferably, said R 1 And R is 2 Each independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
Preferably, the X - Selected from OH - 、Cl - 、Br - 、I - 、F - 、NO 3 - Or HCO 3 - Any of them is more preferably OH - 。
Preferably, the X - Selected from OH - The ion exchange capacity of the anion exchange polymer is 1.5 to 3.5mmol/g, and may be, for example, 1.6mmol/g, 1.8mmol/g, 2mmol/g, 2.2mmol/g, 2.4mmol/g, 2.6mmol/g, 2.8mmol/g, 3mmol/g, 3.2mmol/g, or 3.4mmol/g, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are applicable.
In a second aspect, the present invention provides a method for preparing the anion exchange polymer of the first aspect, the method comprising:
reacting p-terphenyl shown in formula (2), m-terphenyl shown in formula (3) and piperidone monomer shown in formula (1) under the action of an organic solvent and a catalyst to obtain an intermediate polymer containing piperidine tertiary amine groups;
(II) reacting the intermediate polymer containing the piperidine tertiary amine group obtained in the step (I) with an alkylating reagent under the action of an organic solvent to obtain a piperidine cationic polymer;
(III) carrying out anion exchange on the piperidine cationic polymer obtained in the step (II) to obtain the anion exchange polymer.
As a preferred technical scheme of the invention, the piperidone monomer comprises any one or a combination of at least two of N-methyl-4-piperidone, N-ethyl-4-piperidone, N-propyl-4-piperidone or N-isopropyl-4-piperidone.
Preferably, the organic solvent comprises any one or a combination of at least two of dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid or trifluoromethanesulfonic acid.
Preferably, the catalyst comprises any one or a combination of at least two of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid or heptafluorobutyric acid.
The reaction temperature is preferably 0 to 40 ℃, and may be, for example, 0 ℃,5 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃,30 ℃, 35 ℃, or 40 ℃, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the reaction time is 0.5 to 12 hours, for example, 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, step (i) further comprises: and cleaning, separating and drying the reactants obtained by the reaction in sequence.
Preferably, the washing process includes immersing the reactants in an alkaline solution for 24-36 hours, which may be, for example, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, or 36 hours, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the alkaline solution comprises any one or a combination of at least two of sodium carbonate, potassium bicarbonate, sodium hydroxide or potassium hydroxide.
As a preferred embodiment of the present invention, the alkylating agent in step (II) includes any one or a combination of at least two of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, propyl bromide, butyl bromide or butyl bromide.
Preferably, the organic solvent comprises any one or a combination of at least two of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide.
The reaction temperature is preferably 30 to 120 ℃, and may be, for example, 30 ℃, 40 ℃,50 ℃, 60 ℃, 70 ℃,80 ℃, 90 ℃,100 ℃, 110 ℃, or 120 ℃, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the reaction time is 3 to 24 hours, and may be, for example, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, in step (III), the temperature of the anion exchange is 40 to 95℃and may be, for example, 40℃45℃50℃55℃60℃65℃70℃75℃80℃85℃90℃or 95℃but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the anion exchange time is 4 to 80 hours, and may be, for example, 4 hours, 5 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 45 hours, 50 hours, 55 hours, 60 hours, 65 hours, 70 hours, 75 hours or 80 hours, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a third aspect, an anion exchange polymer solution having a solute that is the anion exchange polymer of the first aspect.
The solvent of the anion exchange polymer solution is any one or a combination of at least two of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol or water.
In a fourth aspect, the present invention provides an anion exchange membrane obtained by curing an anion exchange polymer solution according to the third aspect.
The thickness of the anion exchange membrane is preferably 5 to 500. Mu.m, for example, 5 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm or 500 μm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the X - Selected from OH - The anion exchange membrane has an ionic conductivity of more than 40mS/cm at 25℃and more than 135mS/cm at 80 ℃.
In a fifth aspect, the present invention provides a method for preparing an anion exchange membrane according to the fourth aspect, the method comprising the steps of:
casting or casting the anion exchange polymer solution on a substrate, solidifying and stripping to obtain the anion exchange membrane.
As a preferred technical scheme of the present invention, the substrate comprises any one of a glass plate, a polytetrafluoroethylene plate, a ceramic plate, a steel belt, a polyethylene terephthalate base film, a polyamide base film, a polytetrafluoroethylene porous film, a polyethylene porous film, a polypropylene porous film, a glass fiber or a carbon fiber; .
The curing temperature is preferably 60 to 110 ℃, and may be 60 ℃, 65 ℃, 70 ℃, 75 ℃,80 ℃, 85 ℃, 90 ℃, 95 ℃,100 ℃, 105 ℃, or 110 ℃, for example, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a sixth aspect, the present invention provides the use of an anion exchange membrane according to the fourth aspect in a fuel cell, a water electrolyzer, a metal air cell, a nickel hydrogen cell, a zinc manganese cell, a flow cell, a carbon dioxide reducer, an electromechanical synthesizer, an electrodialyzer, a water processor or a membrane humidifier.
The anion exchange membrane provided by the invention has excellent ionic conductivity and mechanical strength, can keep the internal resistance of the device at a lower value when being applied to electrochemical devices such as fuel cells, water electrolysers and the like, and is beneficial to improving the energy conversion efficiency, and the excellent mechanical strength and swelling resistance are beneficial to improving the service life of the electrochemical devices.
Compared with the prior art, the invention has the beneficial effects that:
the anion exchange polymer provided by the invention simultaneously comprises three structural units of terphenyl, m-terphenyl and piperidone monomers, the main chain of the anion exchange polymer does not contain polar groups such as ether bonds, and the like, has good main chain stability, and the piperidine cyclic quaternary ammonium group has good cation stability, so that the material has excellent chemical stability, meanwhile, the solubility of the anion exchange polymer is improved, and the subsequent molding processability of the anion exchange polymer is facilitated.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of an anion exchange polymer prepared in example 1 of the present invention;
FIG. 2 is a graph showing the change in conductivity with temperature of the anion exchange membrane prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
Example 1
The present example provides a method for preparing an anion exchange polymer, the process route of the preparation method is as follows:
the preparation method specifically comprises the following steps:
(1) Weighing 12mol of p-terphenyl, 12mol of m-terphenyl and 24mol of N-methyl-4-piperidone, putting into a three-neck flask, adding 15mL of organic solvent dichloromethane to dissolve reactants, adding catalyst trifluoroacetic acid, and reacting for 12 hours at 0 ℃ to obtain a viscous deep blue product;
(2) Pouring the deep blue product into 1mol/L sodium carbonate solution, soaking for 24 hours, cleaning, filtering after soaking to obtain a white product, fully washing with deionized water, and drying to obtain an intermediate polymer containing piperidine tertiary amine groups;
(3) Weighing 5g of the intermediate polymer, adding an organic solvent dimethyl sulfoxide, fully dissolving, adding an alkylating reagent methyl iodide, carrying out quaternization reaction for 24 hours at 30 ℃, pouring a reaction product into diethyl ether for precipitation, washing the reaction product for multiple times by diethyl ether, washing the reaction product with deionized water for multiple times, and drying the reaction product to obtain the piperidine cationic polymer containing iodide ions;
(4) Soaking the prepared piperidine cationic polymer in 1mol/L potassium hydroxide solution, and performing anion exchange reaction at 40deg.C for 80 hr to obtain OH - A type of anion exchange polymer.
The prepared OH was subjected to a nuclear magnetic resonance spectrometer (Bruker AVANCE III HD (400 MH)) to obtain - The anion exchange polymer was characterized and analyzed by nuclear magnetic resonance spectroscopy as shown in FIG. 1, using deuterated dimethyl sulfoxide (d 6-DMSO) to dissolve the sample in the test, and Tetramethylsilane (TMS) as an internal standard reagent. The chemical shift (delta) is 2.50ppm of DMSO solvent peak, the main chain contains 9H in different chemical environments, the corresponding multiple characteristic peaks are delta 7.50-7.90ppm, delta 2.9ppm and delta 3.5ppm respectively correspond to the characteristic peak of methylene H on the piperidine ring, and delta 3.15 corresponds to the characteristic peak of H on the methyl connected with nitrogen atoms.
The embodiment also provides a preparation method of the anion exchange membrane, which comprises the following steps:
OH obtained by the above preparation - Dissolving anion exchange polymer in dimethyl sulfoxide solvent, spreading on the surface of substrate, spreading, oven drying at 80deg.C for curing to obtain OH - And (3) an anion exchange membrane, wherein the anion exchange membrane is peeled from the substrate.
Measuring OH of all-wet anion exchange membrane in pure water by four-electrode alternating current impedance method - The ionic conductivity at different temperatures is tested respectively, the test results are summarized and plotted to obtain a curve of the change area of the ionic conductivity at different temperatures as shown in figure 2, and as can be seen from figure 2, the ionic conductivity of the anion exchange membrane prepared in example 1 exceeds 40mS/cm at 25 ℃ and exceeds 135mS/cm at 80 ℃.
Example 2
The embodiment provides a preparation method of an anion exchange polymer, which comprises the following steps:
(1) Weighing 12mol of p-terphenyl, 20mol of m-terphenyl and 32mol of N-ethyl-4-piperidone, putting into a three-neck flask, adding 20mL of organic solvent chloroform to dissolve reactants, adding a catalyst methanesulfonic acid, and reacting for 10 hours at 10 ℃ to obtain a viscous deep blue product;
(2) Pouring the dark blue product into 1mol/L potassium carbonate solution, soaking for 28 hours, cleaning, filtering after soaking to obtain a white product, fully washing with deionized water, and drying to obtain an intermediate polymer containing piperidine tertiary amine groups;
(3) Weighing 5g of the intermediate polymer, adding an organic solvent of 1-methyl-2-pyrrolidone, fully dissolving, adding an alkylating reagent of bromocyclobutane, carrying out quaternization reaction for 20h at 50 ℃, pouring the reaction product into diethyl ether for precipitation, washing for many times by diethyl ether, washing for many times by deionized water, and drying to obtain a piperidine cationic polymer containing bromide ions;
(4) Piperidines prepared by the methodSoaking the cationic polymer in 1mol/L potassium hydroxide solution, and performing anion exchange reaction at 50deg.C for 60 hr to obtain OH - A type of anion exchange polymer.
The embodiment also provides a preparation method of the anion exchange membrane, which comprises the following steps:
OH obtained by the above preparation - Dissolving anion exchange polymer in ethanol, spreading on the surface of substrate after solvent is fully dissolved, spreading, drying and solidifying at 80deg.C to form OH - And (3) an anion exchange membrane, wherein the anion exchange membrane is peeled from the substrate.
Example 3
The embodiment provides a preparation method of an anion exchange polymer, which comprises the following steps:
(1) Weighing 10mol of p-terphenyl, 12mol of m-terphenyl and 22mol of N-propyl-4-piperidone, putting into a three-neck flask, adding 10mL of tetrachloroethane as an organic solvent to dissolve reactants, adding a catalyst trifluoromethanesulfonic acid, and reacting for 5 hours at 20 ℃ to obtain a viscous dark blue product;
(2) Pouring the dark blue product into 1mol/L potassium bicarbonate solution, soaking for 30 hours, cleaning, filtering after soaking to obtain a white product, fully washing with deionized water, and drying to obtain an intermediate polymer containing piperidine tertiary amine groups;
(3) Weighing 5g of the intermediate polymer, adding an organic solvent dimethylformamide, fully dissolving, adding an alkylating reagent iodohexane, carrying out quaternization reaction for 15h at 80 ℃, pouring the reaction product into diethyl ether for precipitation, washing the reaction product for multiple times by diethyl ether, washing the reaction product with deionized water for multiple times, and drying the reaction product to obtain the piperidine cationic polymer containing iodide ions;
(4) Soaking the prepared piperidine cationic polymer in 1mol/L potassium hydroxide solution, and performing anion exchange reaction at 65deg.C for 40 hr to obtain OH - A type of anion exchange polymer.
The embodiment also provides a preparation method of the anion exchange membrane, which comprises the following steps:
OH obtained by the above preparation - Dissolving anion exchange polymer in n-butanol, spreading on the surface of substrate, spreading, oven drying at 80deg.C for curing to obtain OH - And (3) an anion exchange membrane, wherein the anion exchange membrane is peeled from the substrate.
Example 4
The embodiment provides a preparation method of an anion exchange polymer, which comprises the following steps:
(1) Weighing 12mol of p-terphenyl, 18mol of m-terphenyl and 30mol of N-isopropyl-4-piperidone, putting into a three-neck flask, adding 20mL of organic solvent toluene to dissolve reactants, adding catalyst pentafluoropropionic acid, and reacting for 3 hours at 30 ℃ to obtain a viscous dark blue product;
(2) Pouring the deep blue product into 1mol/L sodium bicarbonate solution, soaking for 33 hours, cleaning, filtering after soaking to obtain a white product, fully washing with deionized water, and drying to obtain an intermediate polymer containing piperidine tertiary amine groups;
(3) Weighing 5g of the intermediate polymer, adding an organic solvent dimethylacetamide, fully dissolving, adding an alkylating reagent bromopropane, carrying out quaternization reaction for 10 hours at 100 ℃, pouring the reaction product into diethyl ether for precipitation, washing the reaction product for multiple times by diethyl ether, washing the reaction product with deionized water for multiple times, and drying the reaction product to obtain a piperidine cationic polymer containing bromide ions;
(4) Soaking the prepared piperidine cationic polymer in 1mol/L potassium hydroxide solution, and performing anion exchange reaction at 80deg.C for 20 hr to obtain OH - A type of anion exchange polymer.
The embodiment also provides a preparation method of the anion exchange membrane, which comprises the following steps:
OH obtained by the above preparation - Dissolving anion exchange polymer in solvent 1-methyl-2-pyrrolidone, casting on the surface of substrate after solvent is fully dissolved, drying and solidifying at 80 ℃ after doctor blade coating to form OH - An anion exchange membrane, willThe anion exchange membrane is peeled from the substrate.
Example 5
The embodiment provides a preparation method of an anion exchange polymer, which comprises the following steps:
(1) Weighing 15mol of p-terphenyl, 15mol of m-terphenyl and 30mol of N-methyl-4-piperidone, putting into a three-neck flask, adding 25mL of organic solvent trifluoroacetic acid to dissolve reactants, adding a catalyst heptafluorobutyric acid, and reacting for 0.5h at 40 ℃ to obtain a viscous dark blue product;
(2) Pouring the deep blue product into a 1mol/L sodium hydroxide solution, soaking for 36 hours, cleaning, filtering after soaking to obtain a white product, fully washing with deionized water, and drying to obtain an intermediate polymer containing piperidine tertiary amine groups;
(3) Weighing 5g of the intermediate polymer, adding an organic solvent dimethyl sulfoxide, fully dissolving, adding an alkylating reagent bromohexane, carrying out quaternization reaction for 3 hours at 120 ℃, pouring a reaction product into diethyl ether for precipitation, washing the reaction product for multiple times by diethyl ether, washing the reaction product with deionized water for multiple times, and drying the reaction product to obtain a piperidine cationic polymer containing bromide ions;
(4) Soaking the prepared piperidine cationic polymer in 1mol/L potassium hydroxide solution, and performing anion exchange reaction at 95deg.C for 4 hr to obtain OH - A type of anion exchange polymer.
The embodiment also provides a preparation method of the anion exchange membrane, which comprises the following steps:
OH obtained by the above preparation - Dissolving anion exchange polymer in solvent glycol, spreading on the surface of substrate after solvent is fully dissolved, and oven drying and solidifying at 80deg.C to form OH - And (3) an anion exchange membrane, wherein the anion exchange membrane is peeled from the substrate.
Comparative example 1
This comparative example provides a process for the preparation of an anion exchange polymer, which is disclosed with reference to CN111040137a, the process route is as follows:
the preparation method specifically comprises the following steps:
(1) Weighing 12mol of diphenyl, 12mol of p-terphenyl and 24mol of N-methyl-4-piperidone, putting into a three-neck flask, adding 15mL of organic solvent dichloromethane to dissolve reactants, adding catalyst trifluoroacetic acid, and reacting for 12 hours at 0 ℃ to obtain a viscous purple product;
(2) Pouring the purple product into 1mol/L sodium carbonate solution, soaking for 24 hours, cleaning, filtering after the soaking is finished to obtain a white product, fully washing with deionized water, and drying to obtain an intermediate polymer containing piperidine tertiary amine groups;
(3) Weighing 5g of the intermediate polymer, adding an organic solvent dimethyl sulfoxide, fully dissolving, adding an alkylating reagent methyl iodide, carrying out quaternization reaction for 24 hours at 30 ℃, pouring a reaction product into diethyl ether for precipitation, washing the reaction product for multiple times by diethyl ether, washing the reaction product with deionized water for multiple times, and drying the reaction product to obtain the piperidine cationic polymer containing iodide ions;
(4) Soaking the prepared piperidine cationic polymer in 1mol/L potassium hydroxide solution, and performing anion exchange reaction at 40deg.C for 80 hr to obtain OH - A type of anion exchange polymer.
The comparative example also provides a method for preparing an anion exchange membrane, comprising:
OH obtained by the above preparation - Dissolving anion exchange polymer in dimethyl sulfoxide solvent, spreading on the surface of substrate, spreading, oven drying at 80deg.C for curing to obtain OH - And (3) an anion exchange membrane, wherein the anion exchange membrane is peeled from the substrate.
Solubility test: the prepared anion exchange polymers of examples 1 to 5 and comparative example 1 were respectively tested for solubility using different organic solvents at the same temperature, and the test results are shown in table 1.
TABLE 1
| Sample of | DMF | DMAC | DMSO | NMP |
| Example 1 | +++ | ++ | +++ | +++ |
| Example 2 | +++ | ++ | +++ | +++ |
| Example 3 | +++ | ++ | +++ | +++ |
| Example 4 | +++ | ++ | +++ | +++ |
| Example 5 | +++ | ++ | +++ | +++ |
| Comparative example 1 | ++ | + | ++ | + |
Wherein +represents poorly soluble (solubility in the range of 0.01-1g/100g solvent), ++ stands for soluble (solubility in the range of 1-10g/100g solvent), ++ stands for easily soluble (solubility +.gtoreq.) 10g/100g solvent).
As can be seen from Table 1, the only difference between example 1 and comparative example 1 is that the structural units used are para-terphenyl, meta-terphenyl and piperidone monomers, whereas the solubility of the anion exchange polymer prepared in example 1 is significantly better than that of comparative example 1, with the use of the di-biphenyl, para-terphenyl and piperidone monomers as structural units in comparative example 1.
The anion exchange membranes prepared in examples 1 to 5 and comparative example 1 were tested in the following manner: the ionic conductivity at 25℃at 80℃and the tensile strength and chemical stability at room temperature were measured, and the results are shown in Table 2.
TABLE 2
| Sample of | Ion conductivity at 25 DEG C | Ion conductivity at 80 DEG C | Tensile strength of |
| Example 1 | 60mS/cm | 138mS/cm | 35MPa |
| Example 2 | 63mS/cm | 140mS/cm | 38MPa |
| Example 3 | 62mS/cm | 141mS/cm | 36MPa |
| Example 4 | 65mS/cm | 143mS/cm | 37MPa |
| Example 5 | 64mS/cm | 142mS/cm | 39MPa |
| Comparative example 1 | 32mS/cm | 125mS/cm | 25MPa |
As can be seen from Table 1, the only difference between examples 1 to 5 and comparative example 1 is that the structural units used were p-terphenyl, m-terphenyl and piperidone monomers, whereas the ionic conductivity and tensile strength of the anion exchange membrane prepared in example 1 were significantly better than those of comparative example 1, with respect to comparative example 1 using biphenyl, p-terphenyl and piperidone monomers as structural units.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (30)
1. An anion exchange polymer is characterized in that the anion exchange polymer is a combination of structural units shown in a formula (1), a formula (2) and a formula (3);
wherein the R is 1 And R is 2 Each independently selected from C1-C10 chain alkyl or C3-C10 cycloalkyl;
2. the anion exchange polymer of claim 1, wherein the number average molecular weight of the anion exchange polymer is 1000 to 100 tens of thousands.
3. The anion exchange polymer of claim 1, wherein the sum of the mole fractions of structural units of formula (2) and formula (3) is the same as the mole fraction of structural units of formula (1).
4. The anion exchange polymer of claim 1, wherein R 1 And R is 2 Each independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
5. The anion exchange polymer of claim 1, wherein said X "is selected from the group consisting of OH - 、Cl - 、Br - 、I - 、F - 、NO 3 - Or HCO 3 - Any one of the following.
6. The anion exchange polymer of claim 5, wherein X is - Is OH - 。
7. The anion exchange polymer of claim 1, wherein X is - Selected from OH - The ion exchange capacity of the anion exchange polymer is 1.5-3.5 mmol/g.
8. A process for preparing an anion exchange polymer of claim 1, said process comprising:
reacting p-terphenyl, m-terphenyl and piperidone monomers under the action of an organic solvent and a catalyst to obtain an intermediate polymer containing a piperidine tertiary amine group;
(II) reacting the intermediate polymer containing the piperidine tertiary amine group obtained in the step (I) with an alkylating reagent under the action of an organic solvent to obtain a piperidine cationic polymer;
(III) carrying out anion exchange on the piperidine cationic polymer obtained in the step (II) to obtain the anion exchange polymer.
9. The method of claim 8, wherein in step (i), the piperidone monomer comprises any one or a combination of at least two of N-methyl-4-piperidone, N-ethyl-4-piperidone, N-propyl-4-piperidone, and N-isopropyl-4-piperidone.
10. The method according to claim 8, wherein in the step (i), the organic solvent comprises any one or a combination of at least two of dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid, and trifluoromethanesulfonic acid.
11. The method of claim 8, wherein the catalyst comprises any one or a combination of at least two of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, and heptafluorobutyric acid.
12. The process according to claim 8, wherein in step (i), the temperature of the reaction is 0 to 40 ℃.
13. The process according to claim 8, wherein in step (I), the reaction time is 0.5 to 12 hours.
14. The method of claim 8, wherein step (i) further comprises: and cleaning, separating and drying the reactants obtained by the reaction in sequence.
15. The method of claim 14, wherein the washing process comprises immersing the reactants in an alkaline solution for 24-36 hours.
16. The method of claim 15, wherein the alkaline solution comprises any one or a combination of at least two of sodium carbonate, potassium bicarbonate, sodium hydroxide, or potassium hydroxide.
17. The method according to claim 8, wherein, the alkylating agent in step (II) comprises any one or a combination of at least two of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, propyl bromide, butyl bromide or butyl bromide.
18. The method according to claim 8, wherein in the step (ii), the organic solvent comprises any one or a combination of at least two of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide.
19. The process according to claim 8, wherein in step (ii), the temperature of the reaction is 30 to 120 ℃.
20. The process according to claim 8, wherein in step (ii), the reaction time is 3 to 24 hours.
21. The process according to claim 8, wherein in step (III), the temperature of the anion exchange is 40 to 95 ℃.
22. The process according to claim 8, wherein the anion exchange time is 4 to 80 hours.
23. An anion exchange polymer solution, characterized in that the solute of the anion exchange polymer solution is the anion exchange polymer of any one of claims 1-7;
the solvent of the anion exchange polymer solution is any one or a combination of at least two of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol or water.
24. An anion exchange membrane obtained by curing the anion exchange polymer solution of claim 23.
25. The anion exchange membrane of claim 24, wherein the anion exchange membrane has a thickness of 5 to 500 μm.
26. The anion exchange membrane of claim 24, wherein X is - Selected from OH - The anion exchange membrane has an ionic conductivity of more than 40mS/cm at 25℃and more than 135mS/cm at 80 ℃.
27. A method of preparing an anion exchange membrane according to any one of claims 24 to 26, comprising the steps of:
casting or casting the anion exchange polymer solution on a substrate, solidifying and stripping to obtain the anion exchange membrane.
28. The method of producing according to claim 27, wherein the substrate comprises any one of a glass plate, a polytetrafluoroethylene plate, a ceramic plate, a steel strip, a polyethylene terephthalate-based film, a polyamide-based film, a polytetrafluoroethylene porous film, a polyethylene porous film, a polypropylene porous film, a glass fiber, and a carbon fiber.
29. The method of claim 27, wherein the curing temperature is 60-110 ℃.
30. Use of an anion exchange membrane according to any one of claims 24 to 26 in a fuel cell, a water electrolyzer, a metal air cell, a nickel hydrogen cell, a zinc manganese cell, a flow cell, a carbon dioxide reducer, an electromechanical synthesizer, an electrodialyzer, a water processor or a membrane humidifier.
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