CN117024711A - Free radical resistant low water swelling polymers and uses thereof - Google Patents
Free radical resistant low water swelling polymers and uses thereof Download PDFInfo
- Publication number
- CN117024711A CN117024711A CN202311152004.7A CN202311152004A CN117024711A CN 117024711 A CN117024711 A CN 117024711A CN 202311152004 A CN202311152004 A CN 202311152004A CN 117024711 A CN117024711 A CN 117024711A
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- Prior art keywords
- polymer
- anion exchange
- piperidone
- bromide
- organic solvent
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 26
- 230000008961 swelling Effects 0.000 title abstract description 12
- 150000003254 radicals Chemical class 0.000 title abstract description 11
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 40
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005349 anion exchange Methods 0.000 claims abstract description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 28
- -1 fluorinated aliphatic halogenated hydrocarbon Chemical class 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 16
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 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
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 6
- VRJHQPZVIGNGMX-UHFFFAOYSA-N 4-piperidinone Chemical compound O=C1CCNCC1 VRJHQPZVIGNGMX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 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 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 5
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 claims description 3
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-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
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 claims description 3
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002168 alkylating agent Substances 0.000 claims description 3
- 229940100198 alkylating agent Drugs 0.000 claims description 3
- 230000002152 alkylating effect Effects 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 3
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 3
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 7
- 238000005342 ion exchange Methods 0.000 abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 5
- 150000004945 aromatic hydrocarbons Chemical group 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- NZXVPCQHQVWOFD-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1,2-diiodoethane Chemical compound FC(F)(I)C(F)(F)I NZXVPCQHQVWOFD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 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 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-UHFFFAOYSA-N 0.000 description 1
- WIEYKFZUVTYEIY-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-1,3-diiodopropane Chemical compound FC(F)(I)C(F)(F)C(F)(F)I WIEYKFZUVTYEIY-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- SCOAVUHOIJMIBW-UHFFFAOYSA-N phenanthrene-1,2-dione Chemical group C1=CC=C2C(C=CC(C3=O)=O)=C3C=CC2=C1 SCOAVUHOIJMIBW-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 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 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- 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
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
-
- 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
- C08G2261/124—Copolymers alternating
-
- 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
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Abstract
The invention belongs to the field of new materials, and discloses a polymer resistant to free radical low water swelling and application thereof, wherein the main polymer of an anion exchange membrane material has the structural formula ofOr (b)，X ‑ Ar is aromatic hydrocarbon containing fluorinated alkane chain. The fluorine-containing functional group of the polymer can reduce the benzene electron cloud density, can effectively prevent free radical attack, and can effectively improve the stability of alkali resistance and free radical resistance. The polyfluoro structure may also allow for better phase separation of the membrane, reducing water swelling. The ion exchange capacity of the prepared anion exchange polymer is 1.5-3.5mmol/g, the ion conductivity at 25 ℃ exceeds 30mS/cm, and the conductivity is excellent.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a free radical resistant polymer with low water swelling and application thereof.
Background
The electrochemical kinetics of anion exchange membrane electrolyzed water (anion exchange membrane water electrolysis, AEMWE) hydrogen production in alkaline media for anodic oxygen evolution (oxygen evolution reaction, OER) is faster and the use of less expensive non-platinum group metals (non-platinum group metal, NPGM) as cathode catalysts is receiving increasing attention.
In the use of anion exchange membranes, the following main problems exist:
1. during electrocatalytic processes, a large number of free radicals are generated which attack the anion exchange polymer, causing the polymer to degrade. At the same time OH in solution - And also causes degradation of the anion exchange membrane.
2. In pursuit of high conductivity AEM, polymers tend to have more anion exchange groups, which in turn lead to membrane swelling and poor dimensional stability.
Many patents today increase the alkali resistance stability by introducing new structures such as piperidine, but there are still technical challenges in stability. For example, CN115010907a discloses a polyarylpiperidine type anion exchange membrane containing hydrophilic and hydrophobic side chains and a method for preparing the same, wherein the anion exchange membrane is prepared by grafting hydrophilic bromo 6C-piperidine and hydrophobic bromo n-hexane with different molar ratios on a polyarylpiperidine main chain. The anion exchange membrane takes the polyarylpiperidine without ether bond as a main chain, ensures the alkaline stability, grafts hydrophilic and hydrophobic side chains with different proportions to form a comb-shaped structure so as to promote microphase separation of the anion exchange membrane, and improves the ion conductivity of the anion exchange membrane so as to solve the trade-off problem between the alkaline stability and the ion conductivity of the anion exchange membrane. CN115678073a discloses a branched poly (aryl piperidinium) anion exchange membrane, a preparation method and application thereof, and a novel branched alkaline anion exchange membrane is prepared after ionization by a simple two-step synthesis method. PolymerThe branched structure of (2) produces high rigidity, and greatly reduces the water absorption and expansion ratio of the anion exchange membrane, thereby improving the dimensional stability. CN113471497a discloses a piperidine type anion-exchange membrane and a preparation method thereof, firstly synthesizing piperidine type tri-monomer polymers with different substitution degrees, and then directly quaternizing the polymers with piperidone of the polymers as grafting sites to obtain membrane materials and preparing membranes. CN114874420a discloses a polymer of the formulaWherein n is the degree of polymerization and A is selected from a substituted or unsubstituted benzyl, piperidinyl, phenyl, indolyl, acenaphthenyl or phenanthrenequinone group. The polymer is prepared by acid-catalyzed polyhydroxyalkylation reaction, and can be used as an anion exchange membrane material by introducing quaternary ammonium salt groups into the polymer through post-functionalization, so that the variety of the anion exchange membrane material is enriched, and the method has important significance in expanding the application field of the anion exchange membrane material. The synthetic route of the polymer is simple, the distribution and aggregation conditions of the hydrophilic microphase and the hydrophobic microphase in the membrane are regulated and controlled through the post-functionalization, an anion transmission channel is constructed, and the anion conductivity is improved. Meanwhile, the anion exchange membrane has better alkali stability, lower swelling water absorption and good conductivity and mechanical property.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides a polymer resistant to free radical and low in water swelling and application thereof.
The technical scheme adopted by the invention is as follows:
in a first aspect of the invention, there is provided:
a polymer has a structural general formula shown in formula 1 or formula 2,
wherein:
n is the degree of polymerization and,
R 1 ，R 2 identical or different, alkyl radicals selected from C1 to C10,
X - as a result of the ligand anion,
ar is an aromatic hydrocarbon group containing fluorinated alkane chains and is selected from the following groups:
in the formula, z is an integer between 1 and 6, ar 1 Independently selected from one of the following residues:
。
in some examples of polymers, the polymer has a number average molecular weight of 60000 to 500000 and/or a degree of polymerization n of 100 to 10000.
In some examples of polymers, X - Selected from Br - 、I - 、Cl - 、OH - 、HCO 3 - Or CO 3 2- 。
In some examples of polymers, the polymers have a number average molecular weight of 60000 to 500000 and/or a degree of polymerization n of 100 to 10000, X - Selected from Br - 、I - 、Cl - 、OH - 、HCO 3 - Or CO 3 2- 。
In a second aspect of the invention, there is provided:
the preparation method of the polymer in the first aspect of the invention comprises the following steps:
(1) Dissolving aryl monomers and fluorinated aliphatic halogenated hydrocarbon monomers in an organic solvent, and carrying out catalytic reaction to obtain an intermediate containing fluorinated alkane chain aromatic hydrocarbon;
(2) The intermediate of fluorinated alkane chain aromatic hydrocarbon obtained in the step (1) and a piperidone monomer are subjected to catalytic reaction in an organic solvent to obtain an intermediate polymer containing a piperidinetertiary amine group;
(3) Reacting the intermediate polymer containing the piperidine tertiary amine group obtained in the step (2) with an alkylating reagent under the action of an organic solvent to obtain a polymer containing piperidine quaternary ammonium cations;
(4) Carrying out anion exchange on the polymer containing piperidine quaternary ammonium cations obtained in the step (3) to obtain an anion exchange polymer;
wherein the aryl monomer is selected from at least one of the following monomers:
；
the fluorinated aliphatic halogenated hydrocarbon monomer is selected from at least one of the following monomers:
，X 1 is Cl, br or I, m is an integer of 1 to 6;
the piperidone monomer is at least one of 4-piperidone, N-methyl-4-piperidone, N-ethyl-4-piperidone, N-propyl-4-piperidone or N-isopropyl-4-piperidone;
the alkylating agent is at least one selected from 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 1, 5-dibromopentane.
In some examples of the preparation process, the catalyst of step (1) is selected from at least one of n-butyllithium, methyllithium, and phenyllithium.
In some examples of the preparation process, the catalyst of step (2) is selected from at least one of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, and heptafluorobutyric acid.
In some examples of the preparation process, the catalyst of step (1) is selected from at least one of n-butyllithium, methyllithium, and phenyllithium, and the catalyst of step (2) is selected from at least one of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, and heptafluorobutyric acid.
In some examples of the preparation method, the organic solvent of step (1) is selected from at least one of tetrahydrofuran, n-hexane, toluene, benzene, and cyclohexane.
In some examples of the preparation method, the organic solvent of step (2) is selected from at least one of dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid and trifluoromethanesulfonic acid.
In some examples of the preparation method, the organic solvent of step (3) is selected from at least one of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide and dimethylacetamide.
In some examples of the preparation process, the reaction temperature of step (1) is from-100 to 0 ℃.
In some examples of the preparation process, the reaction temperature of step (2) is from-10 to 30 ℃.
In some examples of the preparation process, the reaction temperature of step (3) is 30 to 120 ℃.
In some examples of the preparation process, the reaction time of step (1) is from 0.5h to 5h.
In some examples of the preparation process, the reaction time of step (2) is from 2h to 72h.
In some examples of the preparation process, the reaction time of step (3) is from 12h to 48h.
In some examples of the preparation process, the reaction temperature in step (1) is-100 to 0 ℃ and the reaction time is 0.5 to 5 hours.
In some examples of the preparation method, the reaction temperature in the step (2) is-10-30 ℃ and the reaction time is 2-72 h.
In some examples of the preparation method, the reaction temperature in the step (3) is 30-120 ℃ and the reaction time is 12-48 hours.
In some examples of the preparation method, the reaction temperature in the step (1) is-100-0 ℃, the reaction time is 0.5-5 h, and no water or oxygen exists in the reaction process.
In a third aspect of the invention, there is provided:
a polymer material comprising the polymer according to the first aspect of the present invention.
In some examples of polymeric materials, they are anion exchange membranes.
In some examples of polymeric materials, the anion exchange membrane is an anion exchange membrane for a fuel cell, a water electrolyzer, a metal air cell, a nickel hydrogen cell, a zinc manganese cell, a flow battery, a carbon dioxide reducer, an electromechanical synthesizer, an electrodialyzer, a water treater, or a membrane humidifier.
In a fourth aspect of the invention, there is provided:
the use of a polymer according to the first aspect of the invention for the preparation of an anion exchange membrane.
In some examples of applications, the anion exchange membrane is an anion exchange membrane for a fuel cell, a water electrolyzer, a metal air cell, a nickel hydrogen cell, a zinc manganese cell, a flow battery, a carbon dioxide reducer, an electromechanical synthesizer, an electrodialyzer, a water processor, or a membrane humidifier.
The beneficial effects of the invention are as follows:
according to the polymer provided by the embodiment of the invention, the main chain is composed of fluorinated aliphatic and aromatic hydrocarbons, and the fluorine-containing functional group can reduce the benzene electron cloud density, effectively prevent free radical attack and effectively improve the alkali resistance and free radical resistance stability. The polyfluoro structure may also allow for better phase separation of the membrane, reducing water swelling. The ligand anion of the polymer is preferably OH - The ion exchange capacity of the anion exchange polymer is 1.5-3.5mmol/g, the ion conductivity at 25 ℃ exceeds 30mS/cm, and the conductivity is excellent.
The polymer of some examples of the invention has simple synthesis method, comprises hydrophobic functionalization of aromatic hydrocarbon under the catalysis of catalyst by using fluorinated aliphatic halogenated hydrocarbon, and then uses super acid to promote polycondensation, thereby being beneficial to reducing synthesis cost.
Drawings
FIG. 1 is a graph of gas flow versus current density in an electrolyzer for the anion exchange membrane of example 1.
FIG. 2 is a graph of voltage-current density in an electrolytic cell for the anion exchange membrane of example 1.
Detailed Description
In a first aspect of the invention, there is provided:
a polymer has a structural general formula shown in formula 1 or formula 2,
wherein:
n is the degree of polymerization and,
R 1 ，R 2 identical or different, alkyl radicals selected from C1 to C10,
X - as a result of the ligand anion,
ar is an aromatic hydrocarbon group containing fluorinated alkane chains and is selected from the following groups:
in the formula, z is an integer between 1 and 6, ar 1 Independently selected from one of the following residues:
。
too low a molecular weight or degree of polymerization may decrease the mechanical properties of the film or even prevent casting into a film. In some examples of polymers, the polymer has a number average molecular weight of 60000 to 500000 and/or a degree of polymerization n of 100 to 10000. This gives a high strength and is easy to cast into films.
In some examples of polymers, X - Selected from Br - 、I - 、Cl - 、OH - 、HCO 3 - Or CO 3 2- 。
In some examples of polymers, the polymers have a number average molecular weight of 60000 to 500000 and/or a degree of polymerization n of 100 to 10000, X - Selected from Br - 、I - 、Cl - 、OH - 、HCO 3 - Or CO 3 2- 。
In a second aspect of the invention, there is provided:
the preparation method of the polymer in the first aspect of the invention comprises the following steps:
(1) Dissolving aryl monomers and fluorinated aliphatic halogenated hydrocarbon monomers in an organic solvent, and carrying out catalytic reaction to obtain an intermediate containing fluorinated alkane chain aromatic hydrocarbon;
(2) The intermediate of fluorinated alkane chain aromatic hydrocarbon obtained in the step (1) and a piperidone monomer are subjected to catalytic reaction in an organic solvent to obtain an intermediate polymer containing a piperidinetertiary amine group;
(3) Reacting the intermediate polymer containing the piperidine tertiary amine group obtained in the step (2) with an alkylating reagent under the action of an organic solvent to obtain a polymer containing piperidine quaternary ammonium cations;
(4) Carrying out anion exchange on the polymer containing piperidine quaternary ammonium cations obtained in the step (3) to obtain an anion exchange polymer;
wherein the aryl monomer is selected from at least one of the following monomers:
；
the fluorinated aliphatic halogenated hydrocarbon monomer is selected from at least one of the following monomers:
，X 1 is Cl, br or I, m is an integer of 1 to 6;
the piperidone monomer is at least one of 4-piperidone, N-methyl-4-piperidone, N-ethyl-4-piperidone, N-propyl-4-piperidone or N-isopropyl-4-piperidone;
the alkylating agent is at least one selected from 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 1, 5-dibromopentane.
In some examples of the preparation process, the catalyst of step (1) is selected from at least one of n-butyllithium, methyllithium, and phenyllithium.
In some examples of the preparation process, the catalyst of step (2) is selected from at least one of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, and heptafluorobutyric acid.
In some examples of the preparation process, the catalyst of step (1) is selected from at least one of n-butyllithium, methyllithium, and phenyllithium, and the catalyst of step (2) is selected from at least one of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, and heptafluorobutyric acid.
In some examples of the preparation method, the organic solvent of step (1) is selected from at least one of tetrahydrofuran, n-hexane, toluene, benzene, and cyclohexane.
In some examples of the preparation method, the organic solvent of step (2) is selected from at least one of dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid and trifluoromethanesulfonic acid.
In some examples of the preparation method, the organic solvent of step (3) is selected from at least one of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide and dimethylacetamide.
In the reaction of step (1), the temperature is too high to cause rearrangement of negative ions, and the yield of the target product is not reduced, and in some examples of the preparation method, the reaction temperature of step (1) is-100-0 ℃. Lower temperatures are more advantageous for improving the purity of the product and improving the yield.
In the reaction of step (2), the elimination reaction is easily caused by the fact that the temperature is too high, and in some examples of the preparation method, the reaction temperature of step (2) is-10 to 30 ℃, preferably-10 to 0 ℃.
In some examples of the preparation process, the reaction temperature of step (3) is 30 to 120 ℃.
In each step, the specific reaction temperature may be adjusted according to the specific reaction speed, yield, purity, etc., to obtain the optimal reaction temperature.
In some examples of the preparation process, the reaction time of step (1) is from 0.5h to 5h.
In some examples of the preparation process, the reaction time of step (2) is from 2h to 72h.
In some examples of the preparation process, the reaction time of step (3) is from 12h to 48h.
In each step, the specific reaction time may be adjusted according to the specific reaction degree, yield, purity, etc., to obtain the optimal reaction time.
In some examples of the preparation process, the reaction temperature in step (1) is-100 to 0 ℃ and the reaction time is 0.5 to 5 hours.
In some examples of the preparation method, the reaction temperature in the step (2) is-10-30 ℃ and the reaction time is 2-72 h.
In some examples of the preparation method, the reaction temperature in the step (3) is 30-120 ℃ and the reaction time is 12-48 hours.
In some examples of the preparation method, the reaction temperature in the step (1) is-100-0 ℃, the reaction time is 0.5-5 h, and no water or oxygen exists in the reaction process.
The technical scheme of the invention is further described below by combining examples.
Example 1
S1) adding biphenyl (44 mmol) and 1, 2-diiodotetrafluoroethane (40 mmol) into hexane (16 ml) solution dissolved with n-butyllithium (88 mmol) under nitrogen environment at-78 ℃ and stirring for 2h, detecting no reactant by thin layer chromatography, adding ethanol into ice bath for quenching reaction, filtering, washing with water, concentrating organic phase, and obtaining 1,2-di ([ 1,1' -biphenyl ] -4-yl) -1, 2-tetrafluoroethane by column chromatography;
s2) dissolving 1,2-di ([ 1,1' -biphenyl ] -4-yl) -1, 2-tetrafluoroethane (16.24 g,40 mmol) and N-methylpiperidone (4.526 g,40 mmol) in dichloromethane (30 mL) at 20-35 ℃, stirring to be uniform, and controlling the concentration of the solution to be 46wt%;
s3) to the solution of step (2) was added dropwise trifluoromethanesulfonic acid (TFSA) (31.8 mL,360 mmol) and trifluoroacetic acid (TFA) (3.06 mL,40 mmol) at 0deg.C. Polymerization is initiated at 0 ℃ and then reacted at room temperature for 2 to 72 hours. After the reaction is finished, pouring the solution into methanol or ethanol to obtain a fibrous polymer, removing excessive acid in the solution by using 1M potassium carbonate solution at 50 ℃, washing the solution with distilled water for multiple times to be neutral, filtering the solution to obtain a fibrous solid polymer, and drying the obtained polymer at 80 ℃ in a vacuum drying oven for 24 hours and weighing the polymer;
s4) dissolving the polymer (3 g) by using a polar solvent NMP, rapidly adding a methyl iodide solution, stirring for more than 12 hours in a dark place, dissolving, precipitating and filtering by using ethyl acetate to obtain a yellow solid, washing by using distilled water, and drying at 80 ℃ for 12 hours to obtain the polymer.
Example 2
Biphenyl (44 mmol) and 1, 3-diiodohexafluoropropane (40 mmol) were added to a hexane (16 ml) solution containing n-butyllithium (40 mmol) dissolved therein at-78deg.C under nitrogen atmosphere, and stirred for 2h to obtain aromatic hydrocarbon 4,4' ' - (perfluoropropane-1, 3-diyl) di-1,1' -biphenyl;
at 20-35 ℃, the aromatic hydrocarbon 4,4' ' - (perfluorpropane-1, 3-diyl) di-1,1' -biphenyl (18.24 g,40 mmol) and N-methylpiperidone (4.526 g,40 mmol) are dissolved in methylene dichloride (30 mL) and stirred until the solution is uniform, and the concentration of the solution is controlled at 46wt%
Reference example 1 further produced a polymer
。
Example 3
Biphenyl (44 mmol) and 1, 4-diiodooctafluorobutane (40 mmol) were added to a solution of n-butyllithium (40 mmol) in hexane (16 ml) at-78℃under nitrogen and stirred for 2h to give 4,4' ' - (perfluor-1, 4-diyl) di-1,1' -biphenyl;
at 20-35 ℃, the aromatic hydrocarbon 4,4' ' - (perfluorobutane-1, 4-diyl) di-1,1' -biphenyl (20.4 g,40 mmol) and N-methylpiperidone (4.526 g,40 mmol) are dissolved in methylene dichloride (30 mL) and stirred until the solution concentration is controlled at 46wt%
Reference example 1 further produced a polymer
。
Example 4
Para-terphenyl (44 mmol) and 1, 2-diiodotetrafluoroethane (40 mmol) were added to a solution of n-butyllithium (40 mmol) in hexane (16 ml) at-78deg.C under nitrogen and stirred for 2h to give 1,2-di ([ 1,1':4',1 "-terphenyl ] -4-yl) -1, 2-tetrafluoroethane;
aromatic hydrocarbon 1,2-di ([ 1,1':4',1'' -terphenyl ] -4-yl) -1, 2-tetrafluoroethane (22.328 g,40 mmol) and N-methylpiperidone (4.526 g,40 mmol) are dissolved in methylene dichloride (30 mL) at 20-35 ℃ and stirred until the solution is uniform, and the concentration of the solution is controlled at 46wt%;
reference example 1 further produced a polymer
。
Example 5
M-terphenyl (44 mmol) and 1, 2-diiodotetrafluoroethane (40 mmol) were added to a solution of n-butyllithium (40 mmol) in hexane (16 ml) at-78deg.C under nitrogen and stirred for 2h to give 1,2-di ([ 1,1':3',1 "-terphenyl ] -4-yl) -1, 2-tetrafluoroethane;
aromatic hydrocarbon 1,2-di ([ 1,1':3',1'' -terphenyl ] -4-yl) -1, 2-tetrafluoroethane (22.328 g,40 mmol) and N-methylpiperidone (4.526 g,40 mmol) are dissolved in methylene dichloride (30 mL) at 20-35 ℃ and stirred until the solution is uniform, and the concentration of the solution is controlled at 46wt%;
reference example 1 further produced a polymer
。
Comparative example 1
At 20-35 ℃, dissolving the straight terphenyl (4.6 g,20 mmol) and the N-methyl piperidone (4.526 g,40 mmol) in methylene dichloride (30 mL), stirring to be uniform, and controlling the concentration of the solution to be 46wt%;
reference example 1 further produced a polymer
。
Performance testing
The polymers obtained in the different examples were dissolved in a polar solvent (NMP, DMF, DMSO, DMAc et al, preferably DMSO) and centrifuged, cast onto glass plates, dried at 80℃for 12h to form a film, and then dried at 100℃for 12h in vacuo, the designed thickness of the film being 40. Mu.m. The membrane was subjected to hydroxide ion exchange at 80℃under 1M sodium hydroxide to give an anion exchange membrane.
The test method is as follows:
swelling ratio: the test method refers to the swelling rate method of the proton exchange membrane GB/T20042.3-2022.
Water absorption rate: the test method refers to the water absorption method of the proton exchange membrane GB/T20042.3-2022.
Fenton test: test film at 80℃2 ppm Fe2+/3% H 2 O 2 Weight loss at 1h of solution.
Ion exchange capacity: the membrane was subjected to chloride ion exchange at 80 ℃ in 1M sodium chloride to obtain a chloride ion exchanged anion exchange membrane, and a chloride ion exchanged anion exchange membrane sample was immersed in a solution containing 0.1. 0.1M sodium nitrate to exchange chloride ions. The chloride ions were titrated with a standard silver nitrate solution at a concentration of about 0.1N, and the ion exchange capacity of the membrane was calculated.
Ion conductivity: the OH-ion conductivity of the full wet anion exchange membrane in pure water is measured by using a four-electrode alternating current impedance method, and specific test parameters are as follows: the membrane material with the area of 5mm multiplied by 10mm and the thickness of 40 mu m is used for carrying out alternating current impedance test within the frequency range of 1Hz to 1000K Hz by using a Chen Hua (CHI 760E) electrochemical workstation, and the ion conductivity is calculated by fitting a curve, and the test temperature is 25 ℃.
Number average molecular weight: measured using a gel chromatography penetrometer (GPC).
The test results are shown in Table 1.
TABLE 1 results of Performance test of anion exchange membranes of different examples
As can be seen from the test results in table 1, the technical scheme according to the invention:
1) The length of the introduced fluorine-containing alkane chain is increased, and the swelling rate of the prepared anion exchange membrane is reduced by 25-38.05%.
2) The length of the introduced fluorine-containing alkane chain is increased, and the water absorption of the prepared anion exchange membrane is reduced by 3.86-16.02%.
3) The length of the introduced fluorine-containing alkane chain is increased, and the Fenton free radical degradation resistance experiment of the prepared anion exchange membrane is improved by 57.55% -73.21%.
According to the voltammogram test method, the current values of the voltage of 1.6V, 1.7V, 1.8V, 1.9V and 2.0V at 45 ℃ and water flow of 1.4L/min are tested and stabilized for 10 minutes, and the current density is calculated through the membrane area. The performance data of the anion exchange membrane of example 1 in the cell was determined. The results are shown in fig. 1, fig. 2 and table 2.
Table 2, performance test data of the anion exchange Membrane of example 1 in an electrolytic tank
SCCM in the table is designated standard cubic centimeterper minute (standard milliliters/min).
From the experimental data, the anion exchange membrane of example 1 has a maximum current density imax=0.528A/cm at a temperature of 45 ℃ 2 Whereas the current density of the commercial AEM film at 45 ℃ is imax=0.4A/cm 2 . The anion exchange membrane prepared by the method can withstand larger current.
The above description of the present invention is further illustrated in detail and should not be taken as limiting the practice of the present invention. It is within the scope of the present invention for those skilled in the art to make simple deductions or substitutions without departing from the concept of the present invention.
Claims (10)
1. A polymer has a structural general formula shown in formula 1 or formula 2,
wherein:
n is the degree of polymerization and,
R 1 ，R 2 identical or different, alkyl radicals selected from C1 to C10,
X - as a result of the ligand anion,
ar is an aromatic hydrocarbon group containing fluorinated alkane chains and is selected from the following groups:
in the formula, z is an integer between 1 and 6, ar 1 Independently selected from one of the following residues:
。
2. the polymer according to claim 1, wherein the polymer has a number average molecular weight of 60000 to 500000 and/or a degree of polymerization n of 100 to 10000.
3. The polymer of claim 1, wherein X - Selected from Br - 、I - 、Cl - 、OH - 、HCO 3 - Or CO 3 2- 。
4. A process for the preparation of a polymer as claimed in any one of claims 1 to 3 comprising the steps of:
(1) Dissolving aryl monomers and fluorinated aliphatic halogenated hydrocarbon monomers in an organic solvent, and carrying out catalytic reaction to obtain an intermediate containing fluorinated alkane chain aromatic hydrocarbon;
(2) The intermediate of fluorinated alkane chain aromatic hydrocarbon obtained in the step (1) and a piperidone monomer are subjected to catalytic reaction in an organic solvent to obtain an intermediate polymer containing a piperidinetertiary amine group;
(3) Reacting the intermediate polymer containing the piperidine tertiary amine group obtained in the step (2) with an alkylating reagent under the action of an organic solvent to obtain a polymer containing piperidine quaternary ammonium cations;
(4) Carrying out anion exchange on the polymer containing piperidine quaternary ammonium cations obtained in the step (3) to obtain an anion exchange polymer;
wherein the aryl monomer is selected from at least one of the following monomers:
；
the fluorinated aliphatic halogenated hydrocarbon monomer is selected from at least one of the following monomers:
，X 1 is Cl, br or I, m is an integer of 1 to 6;
the piperidone monomer is at least one of 4-piperidone, N-methyl-4-piperidone, N-ethyl-4-piperidone, N-propyl-4-piperidone or N-isopropyl-4-piperidone;
the alkylating agent is at least one selected from 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 1, 5-dibromopentane.
5. The method of claim 4, wherein at least one of the following conditions is satisfied:
the catalyst in the step (1) is at least one selected from n-butyl lithium, methyl lithium and phenyl lithium;
the catalyst of the step (2) is at least one selected from trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid and heptafluorobutyric acid.
6. The method of claim 4, wherein at least one of the following conditions is satisfied:
the organic solvent in the step (1) is at least one selected from tetrahydrofuran, normal hexane, toluene, benzene and cyclohexane;
the organic solvent in the step (2) is at least one selected from dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid and trifluoromethanesulfonic acid;
the organic solvent in the step (3) is at least one selected from dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide and dimethylacetamide.
7. The method of claim 4, wherein at least one of the following conditions is satisfied:
the reaction temperature of the step (1) is-100-0 ℃;
the reaction temperature of the step (2) is-10-30 ℃;
the reaction temperature of the step (3) is 30-120 ℃.
8. The production method according to claim 4 or 7, characterized in that at least one of the following conditions is satisfied:
the reaction time of the step (1) is 0.5-5 h;
the reaction time of the step (2) is 2-72 h;
the reaction time of the step (3) is 12-48 h.
9. A polymer material comprising the polymer according to any one of claims 1 to 3.
10. Use of a polymer according to any one of claims 1 to 3 for the preparation of an anion exchange membrane.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0440082A2 (en) * | 1990-02-01 | 1991-08-07 | MERCK PATENT GmbH | Method for the conversion of fluorinated aromatic compounds using electrophiles |
| JPH05140004A (en) * | 1991-11-26 | 1993-06-08 | Nippon Petrochem Co Ltd | Production of ethyl-substituted biphenyl compounds |
| JP2005272375A (en) * | 2004-03-25 | 2005-10-06 | Honshu Chem Ind Co Ltd | 4,4'''-DIALKOXY-p-QUATERPHENYLS AND METHOD FOR PRODUCING THE SAME |
| CN102040731A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工集团公司 | Method for preparing polyether polyol |
| CN104725296A (en) * | 2013-12-24 | 2015-06-24 | 北京鼎材科技有限公司 | Indole derivative and application thereof to organic electroluminescence |
| CN106574074A (en) * | 2014-08-01 | 2017-04-19 | 霓佳斯株式会社 | Crosslinking agent and fluorine-containing aromatic compound |
| CN111040137A (en) * | 2019-12-27 | 2020-04-21 | 惠州市亿纬新能源研究院 | Anion exchange polymer and preparation method and application thereof |
| CN113717310A (en) * | 2021-11-03 | 2021-11-30 | 国家电投集团氢能科技发展有限公司 | Perfluoro ion exchange resin with high-efficiency ion transmission channel and preparation method thereof |
| KR20220061829A (en) * | 2020-11-06 | 2022-05-13 | 인천대학교 산학협력단 | A copolymer having quaternary ammonium functional group, a polymer membrane comprising the same, an anion exchange membrane comprising the polymer membrane, a fuel cell comprising the anion exchange membrane, and a method for manufacturing the copolymer |
| CN115010907A (en) * | 2022-06-14 | 2022-09-06 | 天津市大陆制氢设备有限公司 | Polyarylpiperidine type anion exchange membrane containing hydrophilic and hydrophobic double side chains and preparation method thereof |
| KR20220145751A (en) * | 2021-04-22 | 2022-10-31 | 한양대학교 산학협력단 | Novel aliphatic chain-containing poly(alkyl-aryl piperidinium) ionomer, anion exchange membrane, composite membrane and method for preparing the same |
-
2023
- 2023-09-07 CN CN202311152004.7A patent/CN117024711A/en not_active Withdrawn
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0440082A2 (en) * | 1990-02-01 | 1991-08-07 | MERCK PATENT GmbH | Method for the conversion of fluorinated aromatic compounds using electrophiles |
| JPH05140004A (en) * | 1991-11-26 | 1993-06-08 | Nippon Petrochem Co Ltd | Production of ethyl-substituted biphenyl compounds |
| JP2005272375A (en) * | 2004-03-25 | 2005-10-06 | Honshu Chem Ind Co Ltd | 4,4'''-DIALKOXY-p-QUATERPHENYLS AND METHOD FOR PRODUCING THE SAME |
| CN102040731A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工集团公司 | Method for preparing polyether polyol |
| CN104725296A (en) * | 2013-12-24 | 2015-06-24 | 北京鼎材科技有限公司 | Indole derivative and application thereof to organic electroluminescence |
| CN106574074A (en) * | 2014-08-01 | 2017-04-19 | 霓佳斯株式会社 | Crosslinking agent and fluorine-containing aromatic compound |
| CN111040137A (en) * | 2019-12-27 | 2020-04-21 | 惠州市亿纬新能源研究院 | Anion exchange polymer and preparation method and application thereof |
| KR20220061829A (en) * | 2020-11-06 | 2022-05-13 | 인천대학교 산학협력단 | A copolymer having quaternary ammonium functional group, a polymer membrane comprising the same, an anion exchange membrane comprising the polymer membrane, a fuel cell comprising the anion exchange membrane, and a method for manufacturing the copolymer |
| KR20220145751A (en) * | 2021-04-22 | 2022-10-31 | 한양대학교 산학협력단 | Novel aliphatic chain-containing poly(alkyl-aryl piperidinium) ionomer, anion exchange membrane, composite membrane and method for preparing the same |
| CN113717310A (en) * | 2021-11-03 | 2021-11-30 | 国家电投集团氢能科技发展有限公司 | Perfluoro ion exchange resin with high-efficiency ion transmission channel and preparation method thereof |
| CN115010907A (en) * | 2022-06-14 | 2022-09-06 | 天津市大陆制氢设备有限公司 | Polyarylpiperidine type anion exchange membrane containing hydrophilic and hydrophobic double side chains and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIANG, YIYUAN: "Taming Highly Unstable Radical Anions and 1, 4-Organodilithiums by Flow Microreactors: Controlled Reductive Dimerization of Styrenes", 《JACS AU》, vol. 2, no. 11, pages 2514 * |
| JOHN J. YOUNG: "Interannular interactions in p-substituted diphenylmethane anion radicals", 《J. AM. CHEM. SOC.》, vol. 94, no. 25, pages 8790 - 8794, XP002161109, DOI: 10.1021/ja00780a025 * |
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