CN111303360A - Polymer containing piperidine tertiary amine group, anion exchange polymer, and preparation methods and applications thereof - Google Patents
Polymer containing piperidine tertiary amine group, anion exchange polymer, and preparation methods and applications thereof Download PDFInfo
- Publication number
- CN111303360A CN111303360A CN202010070181.0A CN202010070181A CN111303360A CN 111303360 A CN111303360 A CN 111303360A CN 202010070181 A CN202010070181 A CN 202010070181A CN 111303360 A CN111303360 A CN 111303360A
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- China
- Prior art keywords
- anion exchange
- phenanthrene
- formula
- polymer
- tertiary amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 140
- 238000005349 anion exchange Methods 0.000 title claims abstract description 93
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 80
- -1 piperidine tertiary amine Chemical class 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- XXPBFNVKTVJZKF-UHFFFAOYSA-N 9,10-dihydrophenanthrene Chemical compound C1=CC=C2CCC3=CC=CC=C3C2=C1 XXPBFNVKTVJZKF-UHFFFAOYSA-N 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 18
- 239000003011 anion exchange membrane Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 238000005342 ion exchange Methods 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 229930184652 p-Terphenyl Natural products 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 9
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 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 8
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 8
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002168 alkylating agent Substances 0.000 claims description 6
- 229940100198 alkylating agent Drugs 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 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 description 4
- BDVKAMAALQXGLM-UHFFFAOYSA-N 1-ethylpiperidin-4-one Chemical compound CCN1CCC(=O)CC1 BDVKAMAALQXGLM-UHFFFAOYSA-N 0.000 claims description 4
- CCDBCHAQIXKJCG-UHFFFAOYSA-N 1-propan-2-ylpiperidin-4-one Chemical compound CC(C)N1CCC(=O)CC1 CCDBCHAQIXKJCG-UHFFFAOYSA-N 0.000 claims description 4
- YGDZKYYCJUNORF-UHFFFAOYSA-N 1-propylpiperidin-4-one Chemical compound CCCN1CCC(=O)CC1 YGDZKYYCJUNORF-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- JURXVMQHSBALPL-UHFFFAOYSA-N 9,10-diethylphenanthrene Chemical compound C1=CC=C2C(CC)=C(CC)C3=CC=CC=C3C2=C1 JURXVMQHSBALPL-UHFFFAOYSA-N 0.000 claims description 4
- JUEORGSHIXFSSI-UHFFFAOYSA-N 9,10-dimethylphenanthrene Chemical compound C1=CC=C2C(C)=C(C)C3=CC=CC=C3C2=C1 JUEORGSHIXFSSI-UHFFFAOYSA-N 0.000 claims description 4
- 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 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 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- GPRIERYVMZVKTC-UHFFFAOYSA-N p-quaterphenyl Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 GPRIERYVMZVKTC-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 2
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 claims description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 2
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-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
- KXVUSQIDCZRUKF-UHFFFAOYSA-N bromocyclobutane Chemical compound BrC1CCC1 KXVUSQIDCZRUKF-UHFFFAOYSA-N 0.000 claims description 2
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 claims description 2
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 claims description 2
- LKXYJYDRLBPHRS-UHFFFAOYSA-N bromocyclopropane Chemical compound BrC1CC1 LKXYJYDRLBPHRS-UHFFFAOYSA-N 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 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
- 239000007789 gas Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 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
- 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
- 239000010959 steel Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 150000003512 tertiary amines Chemical group 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 13
- 150000001768 cations Chemical class 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 14
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 125000003386 piperidinyl group Chemical group 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 239000012265 solid product Substances 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
- RYCFMDRSMPBMEB-UHFFFAOYSA-N 10,10-dimethyl-9h-phenanthrene Chemical compound C1=CC=C2C(C)(C)CC3=CC=CC=C3C2=C1 RYCFMDRSMPBMEB-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
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/30—Chemical modification by after-treatment
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- 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
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- 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
- C08J5/2287—After-treatment
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- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a polymer containing piperidine tertiary amine groups, an anion exchange polymer, a preparation method and application thereof, wherein the polymer containing piperidine tertiary amine groups comprises phenanthrene structural units shown in a formula (1A) and/or a formula (2A) and piperidine tertiary amine structural units shown in a formula (3'A); the anion exchange polymer comprises a phenanthrene structural unit shown in a formula (1A) and/or a formula (2A) and a piperidine quaternary ammonium structural unit shown in a formula (3A). The main chain of the polymer containing the piperidine tertiary amine group and the anion exchange polymer provided by the invention contains the phenanthrene structural unit, so that the material has excellent mechanical strength performance, the twisting property and the rotation property of a benzene ring on the main chain are weak, the main chain stability is good, and meanwhile, the cation of the anion exchange polymer is a high-stability piperidine cyclic quaternary ammonium group, so that the material has good chemical stability.
Description
Technical Field
The invention relates to the technical field of high molecular materials, in particular to a polymer containing piperidine tertiary amine groups, an anion exchange polymer, and a preparation method and application thereof.
Background
Anion exchange polymers are key materials in fuel cells, water electrolyzers, electrosynthesizers and electrodialyzers. 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 service life of each of the above devices. Currently, many types of anion exchange polymers have an OH-conductivity of more than 100mS/cm (j.pan, et al.structural high way in alkaline polymer electrolytes, energy environ.sci., 2014,7,354) at 80 ℃, which can meet the application requirements. However, the performance of the anion exchange polymer has yet to be further improved in terms of chemical Stability and mechanical strength under high temperature and strong alkali conditions (m.g. marino, k.d. kreuer. Alkali Stability of quaternary ammonium cations for alkaline fuel cells and ionic liquids, chemsus chem.2014,7,1).
CN105924587A discloses a branched polymer anion exchange membrane and a preparation method thereof. The preparation of the membrane material is based on that chloromethylated polysulfone is used as a macroinitiator, p-chloromethyl styrene is used as a monomer, and Atom Transfer Radical Polymerization (ATRP) reaction is utilized to synthesize a series of polymers containing branched side chain structures. The abundant end group with higher chemical reaction activity is utilized to prepare the low-chloridization degree high-conductivity alkaline anion exchange membrane through post-treatment; in addition, micro-phase separation of different degrees can be formed in the membrane by modulating the branching degree of the side chain, so as to achieve the aim of taking account of the conductivity and the stability of the anion exchange membrane.
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, a fluorine-containing acrylate monomer, a solvent and an initiator into a reactor, sealing and carrying out reflux reaction under the protection of inert gas, and precipitating, washing and drying the obtained product to obtain a polymer with the pyridine groups; 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 the solution into a film by a phase conversion method, and drying the film for later use; 3) Soaking the membrane dried in the step 2) in a quaternization reagent for reaction, taking out and drying to obtain the pyridinium salt polymer anion exchange membrane.
Although the above patent application can obtain anion exchange polymer with good ionic conductivity, the distortion and rotation of the benzene ring on the main chain are strong, which results in low microstructure regularity of the polymer after film formation, and the mechanical strength needs to be further improved.
Therefore, it is required 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
In view of the disadvantages of the prior art, it is an object of the present invention to provide a polymer containing a piperidine tertiary amine group, which has both excellent mechanical strength and high chemical stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a polymer containing a piperidine tertiary amine group, which comprises a phenanthrene structural unit shown in a formula (1A) and/or a formula (2A) and a piperidine tertiary amine structural unit shown in a formula (3'A);
the R is 1 And R 2 Each independently selected from hydrogen, C1-C10 (e.g. C2, C3, C4, C5, C6, C7, C8 or C9) chain alkyl or C3-C10 (e.g. C4, C5, C9, etc.),C6, C7, C8 or C9, etc.);
said R is 3 Is selected from any one of C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9) chain alkyl or C3-C10 (such as C4, C5, C6, C7, C8 or C9) cycloalkyl.
The polymer containing the piperidine tertiary amine group comprises the phenanthrene group on the chemical structure of the main chain, so that the material has excellent mechanical strength performance, the twisting property and the rotation property of a benzene ring on the main chain are weak, the microstructure regularity of the polymer after film forming is higher, and the polymer has good main chain stability.
Preferably, the polymer containing piperidine tertiary amine groups further comprises aryl structural units represented by formula (4A) and/or formula (5A);
the m is an integer of 0 to 3, for example 1 or 2.
Preferably, the molar ratio of the phenanthrene structural unit to the piperidine tertiary amine structural unit is (0.01 to 1) 1, for example, 0.02.
Preferably, the sum of the mole fractions of the phenanthrene structural unit and the aryl structural unit is equal to the mole fraction of the piperidine tertiary amine structural unit.
Preferably, the number average molecular weight of the anion exchange polymer is 0.5 to 35 ten thousand, for example, 1 ten thousand, 2 ten thousand, 3 ten thousand, 4 ten thousand, 5 ten thousand, 6 ten thousand, 7 ten thousand, 8 ten thousand, 9 ten thousand, 10 ten thousand, 11 ten thousand, 12 ten thousand, 13 ten thousand, 14 ten thousand, 15 ten thousand, 16 ten thousand, 17 ten thousand, 18 ten thousand, 19 ten thousand, 20 ten thousand, 21 ten thousand, 22 ten thousand, 23 ten thousand, 24 ten thousand, 25 ten thousand, 26 ten thousand, 27 ten thousand, 28 ten thousand, 29 ten thousand, 30 ten thousand, 31 ten thousand, 32 ten thousand, 33 ten thousand, 34 ten thousand, or the like.
Preferably, said R is 1 And R 2 Each independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl.
Preferably, said R is 3 Is selected fromAny one of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
The second object of the present invention is to provide a method for producing a polymer containing a piperidine tertiary amine group, the method comprising: polymerizing the monomer to obtain a polymer containing piperidine tertiary amine groups;
the monomer comprises a phenanthrene monomer shown in a formula (1 a) and/or a formula (2 a) and a piperidone monomer shown in a formula (3 a);
said R is 1 And R 2 Each independently selected from any one of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkyl;
the R is 3 Is selected from any one of C1-C10 chain alkyl or C3-C10 cycloalkyl.
Preferably, the monomer further comprises an aromatic monomer.
Preferably, the aryl monomer comprises any one or at least two of benzene, biphenyl, p-terphenyl, m-terphenyl or p-quaterphenyl.
Preferably, the phenanthrene monomer comprises any one or at least two of phenanthrene, 9,10-dimethyl phenanthrene, 9,10-diethyl phenanthrene or 9,10-dihydro phenanthrene.
Preferably, the piperidone monomer comprises any one or at least two of N-methyl-4-piperidone, N-ethyl-4-piperidone, N-propyl-4-piperidone or N-isopropyl-4-piperidone.
Preferably, the solvent for the polymerization reaction includes any one or a combination of at least two of dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid, or trifluoromethanesulfonic acid.
Preferably, the polymerization reaction is carried out in the presence of a catalyst comprising any one or a combination of at least two of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, or heptafluorobutyric acid.
Preferably, the reaction temperature is-10 to 35 ℃, such as-10 degrees C, -5 degrees C, 0 degrees C, 5 degrees C, 10 degrees C, 15 degrees C, 20 degrees C, 25 degrees C, 30 degrees C.
Preferably, the reaction time is 0.5 to 24 hours, such as 1 hour, 5 hours, 10 hours, 15 hours, 20 hours, 23h, and the like.
The invention also provides application of the polymer containing the piperidine tertiary amine group, which is applied to high-temperature proton membrane fuel cells, water treatment devices, gas separators or preparation of anion exchange polymers.
The fourth object of the present invention is to provide an anion exchange polymer comprising a phenanthrene structural unit represented by formula (1A) and/or formula (2A), and a piperidine quaternary ammonium structural unit represented by formula (3A);
the R is 1 And R 2 Each independently selected from any one of hydrogen, C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9) chain alkyl or C3-C10 (such as C4, C5, C6, C7, C8 or C9) cycloalkyl;
the R is 3 And R 4 Each independently selected from any one of C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9) chain alkyl or C3-C10 (such as C4, C5, C6, C7, C8 or C9) naphthenic base;
said X - Is an anion.
The main chain of the anion exchange polymer comprises phenanthrene structural units, so that the material has higher mechanical strength. Meanwhile, the anion exchange polymer has weak twisting property and rotation property of a benzene ring on a main chain, the microstructure regularity of the polymer after film forming is higher, and cations are high-stability piperidine cyclic quaternary ammonium groups, so that the material has good chemical stability, the ion exchange capacity can exceed 2.5mmol/g, and good ion conductivity can be obtained.
The anion exchange polymer provided by the invention has excellent mechanical strength, high ionic conductivity and high chemical stability, and is suitable for being applied to electrochemical devices such as fuel cells, water electrolyzers and the like.
Preferably, the anion exchange polymer further comprises an aryl-based structural unit represented by formula (4A) and/or formula (5A);
m is an integer of 0 to 3, for example 1 or 2.
In the preferred scheme of the invention, the rotation and flexibility of the main chain are adjusted by copolymerizing aryl monomers, so that the mechanical properties of the polymer are further improved.
Preferably, the molar ratio of the phenanthrene structural unit to the piperidine quaternary ammonium structural unit is (0.01 to 1) 1, for example, 0.02.
Preferably, the sum of the mole fractions of the phenanthrene-based structural units and the aryl-based structural units is equal to the mole fraction of the piperidine quaternary ammonium-based structural units.
Preferably, the anion exchange polymer has a number average molecular weight of 0.5 to 35 ten thousand, for example, 1 ten thousand, 2 ten thousand, 3 ten thousand, 4 ten thousand, 5 ten thousand, 6 ten thousand, 7 ten thousand, 8 ten thousand, 9 ten thousand, 10 ten thousand, 11 ten thousand, 12 ten thousand, 13 ten thousand, 14 ten thousand, 15 ten thousand, 16 ten thousand, 17 ten thousand, 18 ten thousand, 19 ten thousand, 20 ten thousand, 21 ten thousand, 22 ten thousand, 23 ten thousand, 24 ten thousand, 25 ten thousand, 26 ten thousand, 27 ten thousand, 28 ten thousand, 29 ten thousand, 30 ten thousand, 31 ten thousand, 32 ten thousand, 33 thousand, 34 ten thousand, or the like.
Preferably, said X - Is selected from OH - 、Cl - 、Br - 、I - 、F - 、NO 3 - Or HCO 3 - More preferably OH - 。
Preferably, said X - Is OH - The anion exchange polymer has an ion exchange capacity of 0.5 to 3.5mmol/g, for example, 1mmol/g, 1.2mmol/g, 1.4mmol/g, 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, 3.4mmol/g, etc.
Preferably, said R is 1 And R 2 Each independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl.
Preferably, said R is 3 And R 4 Each independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
The fifth object of the present invention is to provide a method for producing the anion exchange polymer according to the fourth object, the method comprising: reacting the polymer containing a piperidine tertiary amine group according to one of the objects with an alkylating agent to obtain the anion exchange polymer.
Preferably, the preparation method comprises the following steps:
(1) Polymerizing the monomer to obtain a polymer containing piperidine tertiary amine groups;
the monomer comprises a phenanthrene monomer shown in a formula (1 a) and/or a formula (2 a) and a piperidone monomer shown in a formula (3 a);
the R is 1 And R 2 Each independently selected from any one of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkyl;
said R is 3 Any one selected from C1-C10 chain alkyl or C3-C10 cycloalkyl;
(2) Reacting the polymer containing piperidine tertiary amine groups with an alkylating agent to obtain the anion exchange polymer.
In the preparation method of the anion exchange polymer, the reaction temperature of the step (1) is-15 ℃ to 35 ℃, such as-10 ℃, 5 ℃, 0 ℃, 5 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ and the like, the reaction time is 0.5h to 24h, such as 1h, 5h, 10h, 15h, 20h, 23h and the like, the molecular weight of the polymerization product can be regulated and controlled by changing the reaction temperature and the reaction time, and the higher the reaction temperature is, the shorter the reaction time is, and the lower the molecular weight of the polymerization product is; the reaction temperature of the step (2) is 25 ℃ to 120 ℃, such as 30 ℃,35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃,60 ℃, 65 ℃, 70 ℃, 75 ℃,80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ and the like, the reaction time is 1h to 72h, such as 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h and the like, the regulation of the ion exchange capacity of the anion exchange polymer can be realized by changing the reaction temperature and the reaction time, and the higher the reaction temperature is, the longer the reaction time is, and the larger the ion exchange capacity of the anion exchange polymer is. By changing the reaction conditions, anion exchange polymers with different molecular weights and different ion exchange capacities can be obtained, thereby meeting the differentiated requirements of devices such as fuel cells, water electrolyzers, electrodialyzers and the like on the anion exchange polymers.
Preferably, step (3) is performed after step (2): and (3) carrying out anion exchange on the anion exchange polymer obtained in the step (2) to obtain the anion exchange polymer with target anions.
Preferably, the monomer further comprises an aromatic monomer.
Preferably, the aryl monomer comprises any one or at least two of benzene, biphenyl, p-terphenyl, m-terphenyl and p-quaterphenyl.
Preferably, the phenanthrene monomer comprises any one or at least two of phenanthrene, 9,10-dimethyl phenanthrene, 9,10-diethyl phenanthrene or 9,10-dihydro phenanthrene.
Preferably, the piperidone monomer comprises any one or at least two of N-methyl-4-piperidone, N-ethyl-4-piperidone, N-propyl-4-piperidone or N-isopropyl-4-piperidone.
Preferably, in the step (1), the solvent for the polymerization reaction includes any one or at least two combinations of dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid or trifluoromethanesulfonic acid.
Preferably, in step (1), the polymerization reaction is carried out in the presence of a catalyst comprising any one or a combination of at least two of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, or heptafluorobutyric acid.
Preferably, in the step (2), the solvent for the reaction includes any one or a combination of at least two of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide.
Preferably, in the step (2), the alkylating agent includes any one or 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, cyclopropyl bromide, cyclobutyl bromide, cyclopentyl bromide or cyclohexyl bromide.
Preferably, in step (1), the reaction temperature is-10 to 35 ℃, such as-10 ℃, -5 ℃, 0 ℃, 5 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ and the like.
Preferably, in step (1), the reaction time is 0.5 to 24 hours, such as 1 hour, 5 hours, 10 hours, 15 hours, 20 hours, 23 hours and the like.
Preferably, in step (2), the reaction temperature is 25-120 ℃, such as 30 ℃,35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃,60 ℃, 65 ℃, 70 ℃, 75 ℃,80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ and the like.
Preferably, in step (2), the reaction time is 1 to 72h, such as 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h, and the like.
The sixth object of the present invention is to provide an anion exchange polymer solution comprising the anion exchange polymer described in the fourth object and a solvent.
Preferably, the solvent includes 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.
The seventh object of the present invention is to provide an anion exchange membrane obtained by solidifying the anion exchange polymer solution according to the sixth object.
Preferably, the anion exchange membrane has a thickness of 5 to 500. Mu.m, such as 10. Mu.m, 50. Mu.m, 100. Mu.m, 150. Mu.m, 200. Mu.m, 250. Mu.m, 300. Mu.m, 350. Mu.m, 400. Mu.m, 450. Mu.m, or the like.
Preferably, said X - Is OH - The anion exchange membrane has an ionic conductivity at 25 ℃ of greater than 30mS/cm, e.g., 40mS/cm, 50mS/cm, 60mS/cm, 70mS/cm, 80mS/cm, 90mS/cm, 100mS/cm, 110mS/cm, 120mS/cm, 130mS/cm, 140mS/cm, 150mS/cm, 160mS/cm, 170mS/cm, 180mS/cm, etc., and an ionic conductivity at 80 ℃ of greater than 100mS/cm, e.g., 110mS/cm, 120mS/cm, 130mS/cm, 140mS/cm, 150mS/cm, 160mS/cm, 165mS/cm, 170mS/cm, 175mS/cm, 180mS/cm, etc.
Preferably, the preparation method of the ion exchange membrane comprises the following steps: casting or casting the anion exchange polymer solution described in the sixth purpose on a substrate, and performing drying treatment.
Preferably, the substrate includes any one or a combination of at least two 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, or a carbon fiber.
An eighth object of the present invention is to provide a use of the anion exchange polymer according to the fourth object for a fuel cell, a water electrolyzer, a metal air battery, a nickel-hydrogen battery, a zinc-manganese battery, a flow battery, a carbon dioxide reducer, an organic electric synthesizer, an electrodialyzer, a water treater, or a membrane humidifier.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polymer containing piperidine tertiary amine groups and the anion exchange polymer provided by the invention contain phenanthrene groups in a main chain chemical structure, so that the material has excellent mechanical strength performance, the twisting property and the rotation property of a benzene ring on the main chain are weak, the microstructure regularity of the polymer after film forming is higher, and the polymer has good main chain stability.
(2) The anion exchange polymer provided by the invention contains phenanthrene groups on the chemical structure of the main chain, so that the material has excellent mechanical strength performance, and the tensile strength at room temperature is higher than 40MPa; the anion exchange polymer has weak twisting property and rotation property of benzene rings on the main chain, the microstructure regularity of the polymer after film forming is higher, the polymer has good main chain stability, and the piperidine cyclic quaternary ammonium group has good cation stability, so that the material has excellent chemical stability, the mechanical strength of the material is not obviously changed after the material is soaked in 1M (mol/L) NaOH solution for 5000 hours at the temperature of 80 ℃, and the cation residual rate is higher than 95 percent; the anion exchange polymer has ion exchange capacity over 2.5mmol/g and excellent ionic conductivity, and has OH at 80 deg.c of 2.5mmol/g - The ionic conductivity can reach 155mS/cm. When the high-performance anion exchange polymer is applied to devices such as fuel cells, water electrolyzers, electrodialyzers and the like, the performances such as energy conversion efficiency, durability and the like can be improved relative to the prior level.
In a further preferred scheme, the aryl structural unit shown in the formula (4A) and/or the formula (5A) is introduced, and the rotation and flexibility of the main chain are adjusted through copolymerization of the aryl monomer, so that the mechanical properties of the polymer are further improved.
(3) The preparation method of the anion exchange polymer has the advantages of low cost, simplicity, high efficiency and controllable conditions, and is suitable for industrial application.
Drawings
FIG. 1 shows examples 1 to 5 of the present invention and comparative example 12 anion exchange Polymer OH at 80 deg.C - Graph comparing ionic conductivity.
FIG. 2 is a graph comparing the tensile strength at room temperature of examples 1 to 5 of the present invention with comparative examples 1 to 2.
FIG. 3 is a graph comparing the residual rate of cations after soaking examples 1 to 5 of the present invention and comparative examples 1 to 2 in NaOH solution at 80 ℃ for 5000 hours.
FIG. 4 shows the nuclear magnetic H spectrum of the anion exchange polymer obtained in example 1 of the present invention.
FIG. 5 shows the nuclear magnetic H spectrum of the anion exchange polymer obtained in example 2 of the present invention.
FIG. 6 is a nuclear magnetic H spectrum of the anion exchange polymer obtained in example 3 of the present invention.
FIG. 7 shows the nuclear magnetic H spectrum of the anion exchange polymer obtained in example 4 of the present invention.
FIG. 8 shows the nuclear magnetic H spectrum of the anion exchange polymer obtained in example 5 of the present invention.
FIG. 9 is a nuclear magnetic H spectrum of the anion exchange polymer obtained in comparative example 1.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides an anion exchange polymer having the structure:
the preparation route is as follows:
(1) And (3) synthesizing a polymer containing piperidine tertiary amine groups. 8.56g (48.0 mmol) of phenanthrene was weighed into a 100mL three-necked flask, 5.43g (48.0 mmol) of N-methyl-4-piperidone was added, and 10mL of dichloromethane was added to dissolve the reaction product. 50mL of a mixed acid of trifluoromethanesulfonic acid and trifluoroacetic acid (both in a volume ratio of 12. The viscous purple product was poured into 1M K 2 CO 3 And soaking the solution at room temperature for 24 hours, filtering to obtain a white solid product, fully washing the white solid product with deionized water, and drying to obtain the polymer containing the piperidine tertiary amine group.
(2) And (4) carrying out quaternization. 10.0g of the above intermediate polymer was weighed, 100mL of 1-methyl-2-pyrrolidone was added, and after complete dissolution, 18mL of methyl iodide was added, and the reaction was carried out at 60 ℃ for 10 hours. Pouring the reaction product into ether for precipitation to obtain yellow precipitate, washing with ether for several times, washing with water, and oven drying to obtain anion I - The anion exchange polymer of (1).
(3) Film formation and ion exchange. Weighing 1g of the anion exchange polymer, adding 50mL of dimethyl sulfoxide, fully dissolving, pouring into a groove of a flat glass plate, drying at 80 ℃ to form a film, and stripping the film from the glass plate. Soaking the anion exchange membrane in 1M KOH solution, and performing ion exchange at 60 ℃ for 24 hours to obtain OH as an anion - The alkaline membrane of (1).
The number average molecular weight of the product obtained in the step (3) is 21000. The anion exchange polymer obtained was characterized and analyzed by means of a nuclear magnetic resonance spectrometer, model Bruker AVANCE III HD (400 MHz), with a nuclear magnetic hydrogen spectrum as shown in FIG. 4, using deuterated dimethyl sulfoxide (d) in the test 6 -DMSO) dissolved samples and Tetramethylsilane (TMS) used as internal standard reagent. The peak at chemical shift (. Delta.) 2.50ppm is the DMSO solvent peak, the peaks at. Delta.2.85 ppm and. Delta.3.35 ppm correspond to the characteristic peaks of methylene H on the piperidine ring, and the peak at. Delta.3.15 ppm corresponds to the characteristic peak of methyl H directly attached to the nitrogen atom. Delta 7.60-8.00 ppm and delta 8.80ppm are multiple characteristic peaks of H on a benzene ring in a phenanthrene structural unit and coexist in H in four different chemical environments. .
Example 2
This example provides an anion exchange polymer having the structure:
the preparation route is as follows:
the preparation process differs from example 1 only in that 8.56g of phenanthrene are replaced by 8.65g (48.0 mmol) of 9,10-dihydrophenanthrene, and the other conditions are exactly the same as in example 1.
The obtained anion exchange polymer had a number average molecular weight of 160000. The nuclear magnetic hydrogen spectrum diagram is shown in figure 5, a DMSO solvent peak is at a chemical shift (delta) of 2.50ppm, characteristic peaks of methylene H on a piperidine ring are corresponding to delta 2.85ppm and delta 3.35ppm, a characteristic peak of methyl H directly connected with a nitrogen atom is corresponding to delta 3.15ppm, multiple characteristic peaks of H on a benzene ring in a 9,10-dihydrophenanthrene structural unit are coexisted in H in three different chemical environments, and a characteristic peak of methylene H in a 9,10-dihydrophenanthrene structural unit is corresponding to delta 3.50-7.80 ppm.
Example 3
This example provides an anion exchange polymer having the structure:
the preparation route is as follows:
the preparation process differs from example 1 only in that 8.56g of phenanthrene are replaced by 5.70g (32.0 mmol) of phenanthrene and 2.47g (16.0 mmol) of biphenyl, and the other conditions are exactly the same as in example 1.
The resulting anion exchange polymer had a number average molecular weight of 185000. The nuclear magnetic hydrogen spectrum is shown in figure 6, a DMSO solvent peak is at a chemical shift (delta) of 2.50ppm, characteristic peaks of methylene H on a piperidine ring are corresponding to delta 2.85ppm and delta 3.35ppm, characteristic peaks of methyl H directly connected with a nitrogen atom are corresponding to delta 3.15ppm, and delta 7.50-8.00 ppm and delta 8.80ppm are multiple characteristic peaks of H on benzene rings in a phenanthrene structural unit and a biphenyl structural unit and coexist in H in six different chemical environments.
Example 4
This example provides an anion exchange polymer having the structure:
the preparation method is different from that of example 1 only in that 8.56g of phenanthrene is replaced by 5.70g (32.0 mmol) of phenanthrene and 3.68g (16.0 mmol) of p-terphenyl, and the other conditions are identical compared with example 1.
The resulting anion exchange polymer had a number average molecular weight of 235000. The nuclear magnetic hydrogen spectrum diagram is shown in figure 7, a DMSO solvent peak is at a chemical shift (delta) of 2.50ppm, characteristic peaks of methylene H on a piperidine ring are corresponding to delta 2.85ppm and delta 3.35ppm, characteristic peaks of methyl H directly connected with a nitrogen atom are corresponding to delta 3.15ppm, and multiple characteristic peaks of H on a benzene ring in a phenanthrene structural unit and a p-terphenyl structural unit are corresponding to delta 7.50-8.00 ppm and delta 8.80ppm, and the H coexists in seven different chemical environments.
Example 5
This example provides an anion exchange polymer having the structure:
the preparation process differs from example 1 only in that 8.56g of phenanthrene are replaced by 5.77g (32.0 mmol) of 9,10-dihydrophenanthrene and 3.68g (16.0 mmol) of p-terphenyl, and the other conditions are exactly the same as in example 1.
The number average molecular weight of the obtained anion exchange polymer was 225000. The nuclear magnetic hydrogen spectrum diagram is shown in figure 8, a DMSO solvent peak is at a chemical shift (delta) of 2.50ppm, characteristic peaks of methylene H on a piperidine ring are corresponding to delta 2.85ppm and delta 3.35ppm, a characteristic peak of methyl H directly connected with a nitrogen atom is corresponding to delta 3.15ppm, multiple characteristic peaks of H on a benzene ring in a 9,10-dihydrophenanthrene structural unit and a p-terphenyl structural unit are coexisted in H in six different chemical environments, and a characteristic peak of methylene H in a 9,10-dihydrophenanthrene structural unit is corresponding to delta 3.00 ppm.
Example 6
This example provides an anion exchange polymer having the structure:
the preparation method differs from example 1 only in that 8.56g of phenanthrene are replaced by 6.60g (32.0 mmol) of 9,9-dimethylphenanthrene and 3.68g (16.0 mmol) of p-terphenyl, and the other conditions are identical compared with example 1.
Comparative example 1
This comparative example provides an anion exchange polymer having the following structure:
the preparation process differs from example 1 only in that 8.56g of phenanthrene are replaced by 11.04g (48.0 mmol) of p-terphenyl, and the other conditions are exactly the same as in example 1.
The number average molecular weight of the obtained anion exchange polymer was 270000. The nuclear magnetic hydrogen spectrum diagram is shown in figure 9, a DMSO solvent peak is at a chemical shift (delta) of 2.50ppm, characteristic peaks of methylene H on a piperidine ring are corresponding to delta 2.85ppm and delta 3.35ppm, a characteristic peak of methyl H directly connected with a nitrogen atom is corresponding to delta 3.15ppm, delta 7.40-7.90 ppm is a multiple characteristic peak of H on a benzene ring in a main chain p-terphenyl structural unit, and three kinds of H in different chemical environments coexist.
Comparative example 2
This comparative example provides an anion exchange polymer having the following structure:
the anion exchange polymer is purchased from Shanghai Gao energy equipment Co., ltd, and is under the brand name AT-01.
And (3) performance testing:
the anion exchange polymers obtained in the above examples 1 to 6 and comparative examples 1 to 2 were subjected to the following performance tests:
(1) Ion exchange Capacity test
The H spectrum in the nuclear magnetic test is used for measuring the ion exchange capacity of the anion exchange membrane, and the method specifically comprises the following steps: and (3) performing characterization analysis on the obtained anion exchange polymer by using a nuclear magnetic resonance spectrometer with the model number of Bruker AVANCE III HD (400 MHz), performing area integration on a hydrogen peak on a methyl group connected with quaternary ammonium nitrogen and a hydrogen peak on a main chain benzene ring respectively, and calculating the ion exchange capacity by the peak area ratio of the two peaks.
(2)OH - Ion conductivity test
Method for measuring OH of full-wet anion exchange membrane in pure water by utilizing four-electrode alternating current impedance method - The ionic conductivity, the specific test parameters are as follows: taking the area of 1X 1cm 2 And the membrane material with the thickness of 25 mu m is subjected to alternating current impedance test in the frequency range of 1 Hz-1000K Hz by using a Metrohm Autolab electrochemical workstation, and the curve is fitted to calculate ionsElectrical conductivity.
(3) Tensile Strength test
Tensile strength of the anion-exchange membrane at room temperature was measured using a tensile tester (manufacturer: san corporation, model: powerTest _ Sooc).
(4) Stability test
The residual rate of the cations in the anion exchange membrane is measured by soaking the anion exchange membrane in 1M NaOH solution at 80 ℃, observing the nuclear magnetic H spectrum change after 5000H. The results of the above performance tests are shown in table 1.
TABLE 1
FIG. 1 shows OH at 80 ℃ of the anion exchange polymers of examples 1 to 5 and comparative examples 1 to 2 - Ion conductivity comparison graph, from Table 1 above and FIG. 1, it can be seen that the ion exchange capacity of examples 1-5 can reach above 2.5mmol/g, so that the ion conductivity at 80 ℃ of examples 1-6 can exceed 150mS/cm. Comparative example 2 is a quaternized polysulfone type anion exchange polymer with an ion exchange capacity of 1.56mmol/g and an ionic conductivity of only 105mS/cm at 80 ℃. The anion exchange polymer has high ionic conductivity, is applied to electrochemical devices such as fuel cells, water electrolyzers and the like, and is beneficial to improving the energy conversion efficiency.
FIG. 2 is a graph comparing the room-temperature tensile strengths of examples 1 to 5 with those of comparative examples 1 to 2, and it can be seen from the above Table 1 and FIG. 2 that the room-temperature tensile strengths of examples 1 to 6 exceed 40MPa. The molecular structure of comparative example 1 was composed of p-terphenyl and quaternary ammonium piperidine groups, and it contained no phenanthrene structure, the planarity and regularity of the main chain were low, and the tensile strength thereof was therefore 35.9MPa, which is lower than those of examples 1 to 6, and comparative example 2 was a quaternized polysulfone type anion exchange polymer, which contained no phenanthrene structure, and the ether bond in the main chain thereof had strong rotational properties, and the tensile strength was only 20.6MPa. The anion exchange polymer has good mechanical property, is convenient for processing and operation, and can better meet the application requirements of various devices.
FIG. 3 is a graph comparing the residual rate of cations after soaking examples 1-5 of the present invention and comparative examples 1-2 in NaOH solution at 80 ℃ for 5000h, and it can be seen from the above Table 1 and FIG. 3 that the residual rate of cations after soaking examples 1-6 in 1M NaOH solution at 80 ℃ for 5000h is higher than 95%. The quaternized polysulfone material of comparative example 2 has a main chain containing polar groups such as ether bonds and the cation is not a high-stability piperidine cyclic cation, and thus has no good chemical stability and the cation residual rate is only 62.2%. The anion exchange polymer provided by the invention has good chemical stability, and is beneficial to the improvement of the durability of devices such as fuel cells and water electrolyzers.
In conclusion, the polymer ion exchange membrane disclosed by the invention has the advantages of higher high ionic conductivity, good mechanical property and good chemical stability, and has better application prospect.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modifications to the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A polymer containing a piperidine tertiary amine group is characterized in that the polymer containing the piperidine tertiary amine group comprises a phenanthrene structural unit shown in a formula (1A) and/or a formula (2A) and a piperidine tertiary amine structural unit shown in a formula (3'A);
the R is 1 And R 2 Each independently selected from any of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkylThe method is as follows;
the R is 3 Is selected from any one of C1-C10 chain alkyl or C3-C10 cycloalkyl.
2. The polymer containing a piperidine tertiary amine group according to claim 1, further comprising an aryl-based structural unit represented by formula (4A) and/or formula (5A);
and m is an integer of 0 to 3.
3. The polymer having a piperidinic tertiary amine group of claim 1 or 2, wherein the molar ratio of the phenanthrene structural unit to the piperidinic tertiary amine structural unit is (0.01 to 1): 1;
preferably, the sum of the mole fractions of the phenanthrene structural units and the aryl structural units is equal to the mole fraction of the piperidine tertiary amine structural units;
preferably, the number average molecular weight of the polymer containing a piperidine tertiary amine group is 0.5 to 35 ten thousand;
preferably, said R is 1 And R 2 Each independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl;
preferably, said R is 3 Is selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
4. A method for producing a polymer containing a piperidine tertiary amine group according to any one of claims 1 to 3, comprising: polymerizing the monomer to obtain a polymer containing piperidine tertiary amine groups;
the monomer comprises a phenanthrene monomer shown in a formula (1 a) and/or a formula (2 a) and a piperidone monomer shown in a formula (3 a);
the R is 1 And R 2 Each independently selected from any one of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkyl;
the R is 3 Any one selected from C1-C10 chain alkyl or C3-C10 cycloalkyl;
preferably, the monomer further comprises an aromatic monomer;
preferably, the aryl monomer comprises any one or at least two of benzene, biphenyl, p-terphenyl, m-terphenyl and p-quaterphenyl;
preferably, the phenanthrene monomer comprises any one or at least two of phenanthrene, 9,10-dimethyl phenanthrene, 9,10-diethyl phenanthrene or 9,10-dihydro phenanthrene;
preferably, the piperidone monomer comprises any one or at least two of N-methyl-4-piperidone, N-ethyl-4-piperidone, N-propyl-4-piperidone or N-isopropyl-4-piperidone;
preferably, the solvent for the polymerization reaction comprises any one or a combination of at least two of dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid or trifluoromethanesulfonic acid;
preferably, the polymerization reaction is carried out in the presence of a catalyst comprising any one or a combination of at least two of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, or heptafluorobutyric acid;
preferably, the temperature of the reaction is-10 to 35 ℃;
preferably, the reaction time is 0.5 to 24 hours.
5. Use of the polymer containing a piperidine tertiary amine group according to any one of claims 1 to 3 in a high temperature proton membrane fuel cell, a water treatment plant, a gas separator or for the preparation of an anion exchange polymer.
6. An anion exchange polymer, which is characterized by comprising a phenanthrene structural unit shown in a formula (1A) and/or a formula (2A) and a piperidine quaternary ammonium structural unit shown in a formula (3A);
the R is 1 And R 2 Each independently selected from any one of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkyl;
the R is 3 And R 4 Each independently selected from any one of C1-C10 chain alkyl or C3-C10 cycloalkyl;
said X - Is an anion;
preferably, the anion exchange polymer further comprises an aryl-based structural unit represented by formula (4A) and/or formula (5A);
m is an integer of 0 to 3;
preferably, the molar ratio of the phenanthrene structural unit to the piperidine quaternary ammonium structural unit is (0.01-1): 1;
preferably, the sum of the mole fractions of the phenanthrene-based structural units and the aryl-based structural units is equal to the mole fraction of the piperidine quaternary ammonium-based structural units;
preferably, the number average molecular weight of the anion exchange polymer is from 0.5 to 35 ten thousand;
preferably, said X - Selected from OH - 、Cl - 、Br - 、I - 、F - 、NO 3 - Or HCO 3 - More preferably OH - ；
Preferably, said X - Is OH - Said anion exchange polymerizationThe ion exchange capacity of the compound is 0.5-3.5 mmol/g;
preferably, said R is 1 And R 2 Each independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl;
preferably, said R is 3 And R 4 Each independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
7. A method of making the anion exchange polymer of claim 6, wherein the method of making comprises: reacting the polymer containing a piperidine tertiary amine group of any one of claims 1-3 with an alkylating agent to provide the anion exchange polymer;
preferably, the preparation method comprises the following steps:
(1) Polymerizing the monomer to obtain a polymer containing piperidine tertiary amine groups;
the monomer comprises a phenanthrene monomer shown in a formula (1 a) and/or a formula (2 a) and a piperidone monomer shown in a formula (3 a);
the R is 1 And R 2 Each independently selected from any one of hydrogen, C1-C10 chain alkyl or C3-C10 cycloalkyl;
said R is 3 Any one selected from C1-C10 chain alkyl or C3-C10 cycloalkyl;
(2) Reacting the polymer containing piperidine tertiary amine groups with an alkylating agent to obtain the anion exchange polymer;
preferably, step (3) is performed after step (2): carrying out anion exchange on the anion exchange polymer obtained in the step (2) to obtain an anion exchange polymer with target anions;
preferably, the monomer further comprises an aromatic monomer;
preferably, the aryl monomer comprises any one or at least two of benzene, biphenyl, p-terphenyl, m-terphenyl and p-quaterphenyl;
preferably, the phenanthrene monomer comprises any one or at least two of phenanthrene, 9,10-dimethyl phenanthrene, 9,10-diethyl phenanthrene or 9,10-dihydro phenanthrene;
preferably, the piperidone monomer comprises any one or at least two of N-methyl-4-piperidone, N-ethyl-4-piperidone, N-propyl-4-piperidone or N-isopropyl-4-piperidone;
preferably, in the step (1), the solvent for the polymerization reaction comprises any one or at least two of dichloromethane, chloroform, tetrachloroethane, toluene, trifluoroacetic acid or trifluoromethanesulfonic acid;
preferably, in the step (1), the polymerization reaction is carried out in the presence of a catalyst, and the catalyst comprises any one or at least two of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid or heptafluorobutyric acid;
preferably, in the step (2), the solvent for the reaction comprises any one or at least two of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide;
preferably, in step (2), the alkylating agent includes any one or 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, cyclopropyl bromide, cyclobutyl bromide, cyclopentyl bromide or cyclohexyl bromide;
preferably, in the step (1), the temperature of the reaction is-10-35 ℃;
preferably, in the step (1), the reaction time is 0.5-24 h;
preferably, in the step (2), the temperature of the reaction is 25-120 ℃;
preferably, in the step (2), the reaction time is 1-72 h.
8. An anion exchange polymer solution, wherein the anion exchange polymer solution comprises the anion exchange polymer of claim 6 and a solvent;
preferably, the solvent includes 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.
9. An anion exchange membrane obtained by solidifying the anion exchange polymer solution of claim 8;
preferably, the thickness of the anion exchange membrane is 5 to 500 μm;
preferably, said X - Is OH - The anion exchange membrane has an ionic conductivity greater than 30mS/cm at 25 ℃ and greater than 100mS/cm at 80 ℃;
preferably, the preparation method of the ion exchange membrane comprises the following steps: casting or casting the anion exchange polymer solution of claim 8 on a substrate and drying;
preferably, the substrate includes any one or a combination of at least two 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, or a carbon fiber.
10. Use of the anion exchange polymer of claim 6 in fuel cells, water electrolyzers, metal air batteries, nickel hydrogen batteries, zinc manganese batteries, flow batteries, carbon dioxide reducers, organic electrosynthesizers, electrodialysers, water treatment or membrane humidifiers.
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