CN107286337B - A kind of piperazine functionalized polyphenylene ether basic anion exchange membrane and preparation method thereof - Google Patents
A kind of piperazine functionalized polyphenylene ether basic anion exchange membrane and preparation method thereof Download PDFInfo
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- CN107286337B CN107286337B CN201710466664.0A CN201710466664A CN107286337B CN 107286337 B CN107286337 B CN 107286337B CN 201710466664 A CN201710466664 A CN 201710466664A CN 107286337 B CN107286337 B CN 107286337B
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- CN
- China
- Prior art keywords
- piperazine
- polyphenylene oxide
- acid
- preparation
- solvent
- Prior art date
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- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001955 polyphenylene ether Polymers 0.000 title abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 89
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 89
- 238000005917 acylation reaction Methods 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 230000010933 acylation Effects 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical group CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical compound FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 claims description 7
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000003252 repetitive effect Effects 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 5
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Chemical group O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- -1 carboxylic acid halides Chemical class 0.000 claims description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical group O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical class ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- YKSVXVKIYYQWBB-UHFFFAOYSA-N 1-butylpiperazine Chemical compound CCCCN1CCNCC1 YKSVXVKIYYQWBB-UHFFFAOYSA-N 0.000 claims description 2
- UUWUIWUPMVSNGJ-UHFFFAOYSA-N 1-decylpiperazine Chemical compound CCCCCCCCCCN1CCNCC1 UUWUIWUPMVSNGJ-UHFFFAOYSA-N 0.000 claims description 2
- GFFSNSPNXPELQE-UHFFFAOYSA-N 1-heptylpiperazine Chemical compound CCCCCCCN1CCNCC1 GFFSNSPNXPELQE-UHFFFAOYSA-N 0.000 claims description 2
- WRFUXAYDZDQDKY-UHFFFAOYSA-N 1-hexylpiperazine Chemical compound CCCCCCN1CCNCC1 WRFUXAYDZDQDKY-UHFFFAOYSA-N 0.000 claims description 2
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 claims description 2
- OGSJMFCWOUHXHN-UHFFFAOYSA-N 1-iodononane Chemical compound CCCCCCCCCI OGSJMFCWOUHXHN-UHFFFAOYSA-N 0.000 claims description 2
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 claims description 2
- JXSIBFCQEWUEDI-UHFFFAOYSA-N 1-nonylpiperazine Chemical compound CCCCCCCCCN1CCNCC1 JXSIBFCQEWUEDI-UHFFFAOYSA-N 0.000 claims description 2
- RRZDZQLIIMBIDL-UHFFFAOYSA-N 1-octylpiperazine Chemical compound CCCCCCCCN1CCNCC1 RRZDZQLIIMBIDL-UHFFFAOYSA-N 0.000 claims description 2
- MJWWNBHUIIRNDZ-UHFFFAOYSA-N 1-pentylpiperazine Chemical compound CCCCCN1CCNCC1 MJWWNBHUIIRNDZ-UHFFFAOYSA-N 0.000 claims description 2
- QLEIDMAURCRVCX-UHFFFAOYSA-N 1-propylpiperazine Chemical compound CCCN1CCNCC1 QLEIDMAURCRVCX-UHFFFAOYSA-N 0.000 claims description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 2
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 claims description 2
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims description 2
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 claims description 2
- GHICCUXQJBDNRN-UHFFFAOYSA-N 4-iodobenzoic acid Chemical compound OC(=O)C1=CC=C(I)C=C1 GHICCUXQJBDNRN-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- YAPJPSFOWOSMRG-UHFFFAOYSA-N CCCCCCCCCC.[I] Chemical compound CCCCCCCCCC.[I] YAPJPSFOWOSMRG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- ZHGVBKGHGOWFOG-UHFFFAOYSA-N [I].CCCCCCC Chemical compound [I].CCCCCCC ZHGVBKGHGOWFOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000003729 cation exchange resin Chemical group 0.000 claims description 2
- 150000001768 cations Chemical group 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000011964 heteropoly acid Chemical group 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 2
- 150000002576 ketones Chemical class 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 21
- 239000012528 membrane Substances 0.000 abstract description 10
- 238000007306 functionalization reaction Methods 0.000 abstract description 9
- 230000007423 decrease Effects 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006482 condensation reaction Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- QASKCGNZJHBTDJ-UHFFFAOYSA-N [SiH4].BrCCCCC Chemical compound [SiH4].BrCCCCC QASKCGNZJHBTDJ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- WBSYROANJZFFNF-UHFFFAOYSA-N CCCCCCCC.[I] Chemical compound CCCCCCCC.[I] WBSYROANJZFFNF-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-BJUDXGSMSA-N iodomethane Chemical group I[11CH3] INQOMBQAUSQDDS-BJUDXGSMSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
-
- 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
- C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to technical field of membrane, a kind of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane and preparation method thereof is provided.A kind of preparation method of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane firstly, polyphenylene ether carries out acylation reaction, then is condensed, then realize functionalization with N- alkyl piperazine.Obtain the polyphenylene oxide membrane material of the functional group containing piperazine shown in formula I.For alkaline anion-exchange membrane prepared by the present invention at 80 DEG C, hydroxide ion conductivity has reached 128mS cm‑1；After impregnating 500h in 60 DEG C, 1M NaOH solution, hydroxide ion conductivity and ion exchange capacity do not decline with the extension of soaking time.Much higher than the performance for the alkaline anion-exchange membrane reported at present.
Description
Technical field
The invention belongs to technical field of membrane, and in particular to a kind of system of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane
Preparation Method.
Background technique
Alkaline anion-exchange membrane fuel cell has the advantages that can be used base metal as catalyst, is seen as new
Generation fuel cell technology and be widely studied.Core of the alkaline anion-exchange membrane as alkaline anion-exchange membrane fuel cell
One of center portion part is largely fixed performance and the service life of battery.High nucleophilicity hydroxide ion in alkaline membrane structure
In the presence of and alkaline membrane fuel cell operation temperature (generally greater than 60 DEG C) Yi Yinqi membrane structure degradation, so as to cause from
Sub- exchange capacity (IEC), the decline of hydroxide ion conductivity and mechanical strength seriously affect performance and the service life of battery.Mesh
Before, the hydroxide ion conductivity of alkaline membrane is low, alkali stability is poor, has become the Important Problems urgently broken through.Largely
Research has shown that: compared to other quaternary ammonium groups, cyclammonium has better chemical stability under strongly alkaline conditions.But at present
Lack and feasible method is facilitated to introduce on polymer.
Summary of the invention
The present invention is directed to improve the hydroxide ion conductivity of alkaline anion-exchange membrane and improve its alkali stability, mention
It has supplied a kind of using piperazine as polyphenylene ether polymer of functional group and preparation method thereof；By friedel-craft be acylated, end group fluorine with it is secondary
The reaction of amine, iodomethane functionalization introduce piperazine on main polymer chain, effectively improve the micro- of alkaline anion-exchange membrane
It sees phase separation structure and can be used as alkali anion to improve the hydroxide ion conductivity and alkali stability of alkaline membrane
Exchange membrane material.
Technical solution of the present invention:
A kind of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane, the piperazine functionalized polyphenylene oxide alkali anion exchange
The structure of film is as shown in formula I:
Formula I；
Wherein, 0.01≤x≤0.99；0.01≤y≤0.99；Methylene number n=0~10；The molecular weight of the material is
500-500000。
A kind of preparation method of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane, steps are as follows:
(1) acylation of polyphenylene oxide main chain: under inert gas protection, polyphenylene oxide being dissolved in solvent A, lewis acid or
Proton acid as catalyst, carboxylic acid halides, acid anhydrides or carboxylic acid make acylting agent, under the conditions of 20~130 DEG C react 1~for 24 hours；It again will be anti-
In the excessive precipitating reagent of solution addition after answering, washing is dry to get the polyphenylene oxide for arriving acylation；
The structure of the polyphenylene oxide of the acylation is as shown in formula II, and z is defined as being acylated the functionality of polyphenylene oxide in formula,
0≤z≤1:
Formula II；
Mass percent concentration of the polyphenylene oxide in solvent A is not more than 60%；
The molar ratio of the acylting agent and polyphenylene oxide repetitive unit is 0.01~2, catalyst and acylting agent
Molar ratio be 0.1~5；
(2) under inert gas atmosphere, the polyphenylene oxide of acylation is dissolved in solvent B, N- alkyl piperazine and dehydration is added
Agent reacts 1~96h under basic catalyst effect at 50~150 DEG C；Reaction solution is added in excessive precipitating reagent again, washing,
It dries to get polymer is arrived；
Mass percent concentration of the polyphenylene oxide of the acylation in solvent B is 1%~50%；
The volume ratio of the dehydrating agent and solvent B is not more than 2；
The molar ratio of the polyphenylene oxide repetitive unit of the N- alkyl piperazine and acylation is 0.1~10；
The molar ratio of the polyphenylene oxide repetitive unit of the basic catalyst and acylation is 0.1~10；
(3) suitable polymer containing piperazine is dissolved in solvent C, functionalized reagent is added, is reacted at 10~150 DEG C
0.5~96h；Reaction solution is added in excessive precipitating reagent again, washing obtains piperazine functionalized polymer material after dry；
Mass percent concentration of the polymer containing piperazine in solvent C is 1%~50%；
The molar ratio of the functionalized reagent and the polymer repeat unit containing piperazine is 0.3~10.
The solvent A is methylene chloride, chloroform, carbon tetrachloride, dichloroethanes or 1,1,2,2- tetrachloroethanes；
The solvent B is dimethyl sulfoxide, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide or N- methylpyrrole
Alkanone, sulfolane or tetrachloroethanes；
The solvent C is dimethyl sulfoxide, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide or N- methylpyrrole
Alkanone, sulfolane or tetrachloroethanes.
The catalyst is alchlor, tin tetrachloride, zinc chloride, ferric trichloride, Antimony pentachloride, boron trifluoride, four
Titanium chloride, hydrofluoric acid, sulfuric acid, phosphorus pentoxide, phosphoric acid, heteropoly acid, cation exchange resin, cation exchanged montmorillonite or negative
Load type AlCl3；
The basic catalyst is potassium carbonate, sodium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide or potassium hydroxide.
The acylting agent is to fluorobenzoyl chloride, parachlorobenzoyl chloride, 4- fluobenzoic acid acid anhydride, 4- chlorobenzoic acid
Acid anhydride, 4- fluobenzoic acid, 4- chlorobenzoic acid, 4- bromobenzoic acid or 4- iodo-benzoic acid.
The precipitating reagent is methanol, ethyl alcohol, acetonitrile, acetone, ethyl acetate or ether.
The N- alkyl piperazine is N methyl piperazine, n-ethylpiperazine, N- propylpiperazine, N- butyl piperazine, N- amyl
Piperazine, N- hexyl piperazine, N- heptyl piperazine, N- octyl piperazine, N- nonyl piperazine or N- decyl piperazine.
The dehydrating agent is mixed for one or more of toluene, benzene, dimethylbenzene, hexamethylene, isoamyl alcohol, petroleum ether
It closes.
The functionalized reagent is iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodine heptane, iodine
Octane, iodononane or iodine decane；Iodine is replaced by bromine.
Beneficial effects of the present invention: at 80 DEG C, hydroxide ion passes alkaline anion-exchange membrane prepared by the present invention
Conductance has reached 128mS cm-1；After impregnating 500h in 60 DEG C, 1M NaOH solution, hydroxide ion conductivity and ion
Exchange capacity does not decline with the extension of soaking time.Much higher than the performance for the alkaline anion-exchange membrane reported at present.
Specific embodiment
Below in conjunction with technical solution, in detail narration a specific embodiment of the invention.
Embodiment 1
The acylation (PPOCOPhF) of polyphenylene oxide
5.4g polyphenylene oxide (PPO) is added in 250mL round-bottomed flask, 80mL1,2- dichloroethanes, magnetic agitation are added
Under, it dissolves by heating.Under nitrogen atmosphere, 55mL 1,2- dichloroethanes, 0.2 molar equivalent (PPO) nothing are added in three-necked flask
To fluorobenzoyl chloride, then under conditions of ice-water bath magnetic agitation 0.2 molar equivalent (PPO) is added dropwise in water alchlor dropwise
Polyphenylene oxide (PPO) solution dissolved, 60 DEG C of reaction 10h is added, reaction terminates.After solution is cooling, solution is poured into anhydrous
Solid polymer is precipitated in methanol, is washed again with anhydrous methanol, after dry, with chloroform again finished polymer.
It is acylated the condensation reaction of polyphenylene oxide (PPOCOPhF) and N methyl piperazine
Under nitrogen atmosphere, 100mL N-Methyl pyrrolidone is added into three-necked flask, 5g is acylated polyphenylene oxide
(PPOCOPhF), after stirring and dissolving, 2 molar equivalent Anhydrous potassium carbonates are added, 5 molar equivalent N methyl piperazines are heated to 100
DEG C reaction 48h, stops reaction, after solution is cooling, is centrifuged off insoluble matter, solution is poured into dehydrated alcohol, polymerization is precipitated
Object obtains yellow polymer (PPOCOPh-Pi) after suction filtration, is washed repeatedly with dehydrated alcohol 3 times, 60 DEG C of vacuum drying.
Iodomethane is connect, is realized functionalization (PPOCOPh-Pi-1)
It is added 2g PPOCOPh-Pi polymer into round-bottomed flask, 27mL N-Methyl pyrrolidone, after stirring and dissolving,
3 molar equivalent CH are added under the conditions of being protected from light3I is heated to 40 DEG C of reaction 48h.Stop reaction, after solution is cooling, dehydrated alcohol
It is precipitated with the mixed solvent of ethyl acetate, obtains polymer solids after suction filtration, washed repeatedly with dehydrated alcohol 3 times, 60 DEG C of vacuum
It is dry.
Test indicate that the water absorption rate of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane prepared in the present embodiment
It is 23%, swellbility 10%, and be not swollen with the raising of temperature within the scope of 30-80 DEG C.At 30 DEG C, hydroxide ion is passed
Conductance is 10mS cm-1, at 80 DEG C, hydroxide ion conductivity has reached 28mS cm-1。
Embodiment 2
The acylation (PPOCOPhF) of polyphenylene oxide
5.4g polyphenylene oxide (PPO) is added in 250mL round-bottomed flask, 80mL1,2- dichloroethanes, magnetic agitation are added
Under, it dissolves by heating.Under nitrogen atmosphere, 55mL 1,2- dichloroethanes, 0.4 molar equivalent (PPO) nothing are added in three-necked flask
To fluorobenzoyl chloride, then under conditions of ice-water bath magnetic agitation 0.4 molar equivalent (PPO) is added dropwise in water alchlor dropwise
Polyphenylene oxide (PPO) solution dissolved, 60 DEG C of reaction 10h is added, reaction terminates.After solution is cooling, solution is poured into anhydrous
Solid polymer is precipitated in methanol, is washed again with anhydrous methanol, after dry, with chloroform again finished polymer.
It is acylated the condensation reaction of polyphenylene oxide (PPOCOPhF) and N methyl piperazine: with embodiment 1
Iodomethane is connect, is realized functionalization (PPOCOPh-Pi-1): with embodiment 1
Test indicate that the water absorption rate of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane prepared in the present embodiment
It is 32%, swellbility 15%, and be not swollen with the raising of temperature within the scope of 30-80 DEG C.At 30 DEG C, hydroxide ion is passed
Conductance is 39mS cm-1, at 80 DEG C, hydroxide ion conductivity has reached 88mS cm-1。
Embodiment 3
The acylation (PPOCOPhF) of polyphenylene oxide
5.4g polyphenylene oxide (PPO) is added in 250mL round-bottomed flask, 80mL1,2- dichloroethanes, magnetic agitation are added
Under, it dissolves by heating.Under nitrogen atmosphere, 55mL 1,2- dichloroethanes, 0.6 molar equivalent (PPO) nothing are added in three-necked flask
To fluorobenzoyl chloride, then under conditions of ice-water bath magnetic agitation 0.6 molar equivalent (PPO) is added dropwise in water alchlor dropwise
Polyphenylene oxide (PPO) solution dissolved, 60 DEG C of reaction 10h is added, reaction terminates.After solution is cooling, solution is poured into anhydrous
Solid polymer is precipitated in methanol, is washed again with anhydrous methanol, after dry, with chloroform again finished polymer.
It is acylated the condensation reaction of polyphenylene oxide (PPOCOPhF) and N methyl piperazine: with embodiment 1
Iodomethane is connect, is realized functionalization (PPOCOPh-Pi-1): with embodiment 1
Test indicate that the water absorption rate of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane prepared in the present embodiment
It is 90%, swellbility 27%, at 30 DEG C, hydroxide ion conductivity is 69mS cm- 1, at 80 DEG C, hydroxide ion conduction
Rate has reached 128mS cm-1.Show piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane prepared in the present embodiment molten
It is swollen it is low under conditions of, have high hydroxide ion conductivity.
Embodiment 4
The acylation (PPOCOPhF) of polyphenylene oxide
5.4g polyphenylene oxide (PPO) is added in 250mL round-bottomed flask, 80mL1,2- dichloroethanes, magnetic agitation are added
Under, it dissolves by heating.Under nitrogen atmosphere, 55mL 1,2- dichloroethanes, 0.8 molar equivalent (PPO) nothing are added in three-necked flask
To fluorobenzoyl chloride, then under conditions of ice-water bath magnetic agitation 0.8 molar equivalent (PPO) is added dropwise in water alchlor dropwise
Polyphenylene oxide (PPO) solution dissolved, 60 DEG C of reaction 10h is added, reaction terminates.After solution is cooling, solution is poured into anhydrous
Solid polymer is precipitated in methanol, is washed again with anhydrous methanol, after dry, with chloroform again finished polymer.
It is acylated the condensation reaction of polyphenylene oxide (PPOCOPhF) and N methyl piperazine: with embodiment 1
Iodomethane is connect, is realized functionalization (PPOCOPh-Pi-1): with embodiment 1
Test indicate that the water absorption rate of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane prepared in the present embodiment
It is 120%, swellbility 35%, at 30 DEG C, hydroxide ion conductivity is 75mS cm-1。
Embodiment 5
The acylation (PPOCOPhF) of polyphenylene oxide
5.4g polyphenylene oxide (PPO) is added in 250mL round-bottomed flask, 80mL1,2- dichloroethanes, magnetic agitation are added
Under, it dissolves by heating.Under nitrogen atmosphere, addition 55mL 1,2- dichloroethanes, 1 molar equivalent (PPO) are anhydrous in three-necked flask
Alchlor is added dropwise 1 molar equivalent (PPO) to fluorobenzoyl chloride dropwise, is then added under conditions of ice-water bath magnetic agitation
Polyphenylene oxide (PPO) solution dissolved, 60 DEG C of reaction 10h, reaction terminate.After solution is cooling, solution is poured into anhydrous methanol
Middle precipitation solid polymer is washed again with anhydrous methanol, after dry, with chloroform again finished polymer.
It is acylated the condensation reaction of polyphenylene oxide (PPOCOPhF) and N methyl piperazine: with embodiment 1
Iodomethane is connect, is realized functionalization (PPOCOPh-Pi-1): with embodiment 1
Test indicate that the water absorption rate of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane prepared in the present embodiment
It is 160%, swellbility 42%, at 30 DEG C, hydroxide ion conductivity is 87mS cm- 1。
Embodiment 6
The acylation (PPOCOPhF) of polyphenylene oxide: with embodiment 2
It is acylated the condensation reaction of polyphenylene oxide (PPOCOPhF) and N methyl piperazine: with embodiment 2
N-Propyl Bromide is connect, is realized functionalization (PPOCOPh-Pi-3): 3.8g PPOCOPh-Pi polymerization being added into round-bottomed flask
Object, 63mL N-Methyl pyrrolidone after stirring and dissolving, are added 5 molar equivalent N-Propyl Bromides, are heated to 60 DEG C of reaction 96h.Stop
Reaction is precipitated polymer, obtains polymer solids after suction filtration after solution is cooling, after washing repeatedly, 60 DEG C of vacuum drying.
Test indicate that the hydroxyl of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane prepared in the present embodiment
Ionic conductivity is 44mS cm at 30 DEG C- 1, at 80 DEG C, hydroxide ion conductivity has reached 103mS cm-1。
Embodiment 7
The acylation (PPOCOPhF) of polyphenylene oxide: with embodiment 2
It is acylated the condensation reaction of polyphenylene oxide (PPOCOPhF) and N methyl piperazine: with embodiment 2
Bromo pentane silane is connect, is realized functionalization (PPOCOPh-Pi-5): 3.8g PPOCOPh-Pi polymerization being added into round-bottomed flask
Object, 63mL N-Methyl pyrrolidone after stirring and dissolving, are added 5 molar equivalent bromo pentane silanes, are heated to 60 DEG C of reaction 96h.Stop
Reaction is precipitated polymer, obtains polymer solids after suction filtration after solution is cooling, after washing repeatedly, 60 DEG C of vacuum drying.
Test indicate that the hydroxyl of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane prepared in the present embodiment
Ionic conductivity is 34mS cm at 30 DEG C-1, at 80 DEG C, hydroxide ion conductivity is 86mS cm-1。
Embodiment 8
Alkali stability test: 1 gained long-chain branch polyphenylene oxide anion-exchange membrane of embodiment is immersed in 1mol/L NaOH
In after 60 DEG C of immersion 500h, then with deionized water be dipped to neutrality.
Test indicate that piperazine functionalized polyphenylene oxide anion-exchange membrane prepared in the present embodiment is impregnating 500h
Afterwards, hydroxide ion conductivity and ion exchange capacity do not reduce, show alkali anion prepared in the present embodiment
Exchange membrane has good alkali stability.
Claims (10)
1. a kind of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane, which is characterized in that the piperazine functionalized polyphenylene oxide alkalinity
The structure of anion-exchange membrane is as shown in formula I:
Wherein, 0.01≤x≤0.99；0.01≤y≤0.99；Methylene number n=0~10；The piperazine functionalized polyphenylene oxide alkali
Property anion-exchange membrane molecular weight be 500-500000.
2. the preparation method of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane described in claim 1, which is characterized in that step
It is rapid as follows:
(1) acylation of polyphenylene oxide main chain: under inert gas protection, polyphenylene oxide being dissolved in solvent A, lewis acid or proton
Acid as catalyst, carboxylic acid halides, acid anhydrides or carboxylic acid make acylting agent, under the conditions of 20~130 DEG C react 1~for 24 hours；After reacting again
Solution be added in excessive precipitating reagent, washing is dry to get to the polyphenylene oxide being acylated；
The structure of the polyphenylene oxide of the acylation is as shown in formula II, and z is defined as being acylated the functionality of polyphenylene oxide, 0 < z in formula
≤ 1:
Mass percent concentration of the polyphenylene oxide in solvent A is not more than 60%；
The molar ratio of the acylting agent and polyphenylene oxide repetitive unit is 0.01~2, and catalyst and acylting agent rub
You are than being 0.1~5；
(2) under inert gas atmosphere, the polyphenylene oxide of acylation is dissolved in solvent B, N- alkyl piperazine and dehydrating agent is added,
Under basic catalyst effect, 1~96h is reacted at 50~150 DEG C；Reaction solution is added in excessive precipitating reagent again, is washed, it is dry,
Obtain polymer；
Mass percent concentration of the polyphenylene oxide of the acylation in solvent B is 1%~50%；
The volume ratio of the dehydrating agent and solvent B is not more than 2；
The molar ratio of the polyphenylene oxide repetitive unit of the N- alkyl piperazine and acylation is 0.1~10；
The molar ratio of the polyphenylene oxide repetitive unit of the basic catalyst and acylation is 0.1~10；
(3) suitable polymer containing piperazine is dissolved in solvent C, functionalized reagent is added, reacts 0.5 at 10~150 DEG C
~96h；Reaction solution is added in excessive precipitating reagent again, washing obtains piperazine functionalized polymer material after dry；
Mass percent concentration of the polymer containing piperazine in solvent C is 1%~50%；
The molar ratio of the functionalized reagent and the polymer repeat unit containing piperazine is 0.3~10.
3. preparation method according to claim 2, which is characterized in that
The solvent A is methylene chloride, chloroform, carbon tetrachloride, dichloroethanes or 1,1,2,2- tetrachloroethanes；
The solvent B is dimethyl sulfoxide, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide or N- crassitude
Ketone, sulfolane or tetrachloroethanes；
The solvent C is dimethyl sulfoxide, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide or N- crassitude
Ketone, sulfolane or tetrachloroethanes.
4. preparation method according to claim 2 or 3, which is characterized in that
The catalyst is alchlor, tin tetrachloride, zinc chloride, ferric trichloride, Antimony pentachloride, boron trifluoride, four chlorinations
Titanium, hydrofluoric acid, sulfuric acid, phosphorus pentoxide, phosphoric acid, heteropoly acid, cation exchange resin, cation exchanged montmorillonite or support type
AlCl3；
The basic catalyst is potassium carbonate, sodium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide or potassium hydroxide.
5. the preparation method according to claim 4, which is characterized in that
The acylting agent is to fluorobenzoyl chloride, parachlorobenzoyl chloride, 4- fluobenzoic acid acid anhydride, 4- chlorobenzoic acid acid anhydride, 4-
Fluobenzoic acid, 4- chlorobenzoic acid, 4- bromobenzoic acid or 4- iodo-benzoic acid.
6. preparation method according to claim 5, which is characterized in that
The precipitating reagent is methanol, ethyl alcohol, acetonitrile, acetone, ethyl acetate or ether.
7. preparation method according to claim 6, which is characterized in that the N- alkyl piperazine is N methyl piperazine, N-
Ethyl piperazidine, N- propylpiperazine, N- butyl piperazine, N- amyl piperazine, N- hexyl piperazine, N- heptyl piperazine, N- octyl piperazine, N-
Nonyl piperazine or N- decyl piperazine.
8. preparation method according to claim 7, which is characterized in that
The dehydrating agent is the mixing of one or more of toluene, benzene, dimethylbenzene, hexamethylene, isoamyl alcohol, petroleum ether.
9. according to preparation method described in claim 2,3,5,6,7 or 8, which is characterized in that
The functionalized reagent is that iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodine heptane, iodine are pungent
Alkane, iodononane or iodine decane.
10. preparation method according to claim 9, which is characterized in that replace iodine by bromine.
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