CN111223585B - 一种环三磷腈基六磷酸盐类耐高温质子导体的制备方法 - Google Patents
一种环三磷腈基六磷酸盐类耐高温质子导体的制备方法 Download PDFInfo
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- CN111223585B CN111223585B CN202010028548.2A CN202010028548A CN111223585B CN 111223585 B CN111223585 B CN 111223585B CN 202010028548 A CN202010028548 A CN 202010028548A CN 111223585 B CN111223585 B CN 111223585B
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- hexaphosphate
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- 239000004020 conductor Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 125000004122 cyclic group Chemical group 0.000 title claims description 7
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 title claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000000446 fuel Substances 0.000 claims abstract description 6
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 5
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011973 solid acid Substances 0.000 claims abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 10
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 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
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
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- 238000001816 cooling Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 2
- 230000008020 evaporation Effects 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 claims 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 6
- -1 sensors Substances 0.000 abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
- 239000010452 phosphate Substances 0.000 abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000004693 Polybenzimidazole Substances 0.000 description 10
- 229920002480 polybenzimidazole Polymers 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- CGGUNVYOABLSQD-UHFFFAOYSA-N pyrazine-2,6-dicarboxylic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=N1 CGGUNVYOABLSQD-UHFFFAOYSA-N 0.000 description 5
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 3
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
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- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- DPUCLPLBKVSJIB-UHFFFAOYSA-N cerium;tetrahydrate Chemical compound O.O.O.O.[Ce] DPUCLPLBKVSJIB-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- SRKPIULWFNMOKI-UHFFFAOYSA-N imidazole-1,5-dicarboxylic acid Chemical compound OC(=O)C1=CN=CN1C(O)=O SRKPIULWFNMOKI-UHFFFAOYSA-N 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- CCJLMKQVMJPQNW-UHFFFAOYSA-N nitric acid;dihydrate Chemical compound O.O.O[N+]([O-])=O CCJLMKQVMJPQNW-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 1
- GMIOYJQLNFNGPR-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CN=C(C(O)=O)C=N1 GMIOYJQLNFNGPR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003746 yttrium Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Manufacturing & Machinery (AREA)
- Fuel Cell (AREA)
Abstract
本发明涉及一种环三磷腈基六磷酸盐类耐高温质子导体的制备方法及用途。将适量六氯环三磷腈(HCCP)在搅拌下加入亚磷酸酯中，90～140℃反应6～12h得到六元磷酸酯，在浓盐酸中回流24～72h水解得到六元磷酸，在水相中使该六元磷酸与锆、铈、铁等离子中的一种或多种发生聚合而得到不溶于水的耐高温的质子导体(MTHP)。本发明所述的耐高温质子导体，可用于固体酸催化剂、传感器和燃料电池质子传导材料等领域。
Description
技术领域
本发明涉及一种环三磷腈基六磷酸盐类的耐高温质子导体的制备及其用途。其可作为酸催化剂用于化工生产、生物柴油制取等领域，亦可作为固态酸用于传感器、燃料电池和锂电池等领域。
技术背景
无机磷酸盐一般具有良好的热稳定性，其中未参与成键的羟基表现出一定的酸性，可形成氢键，电离出质子，亦可参与离子交换，具有广泛的用途。
许多金属的磷酸氢盐具有良好的热稳定性，其中暴露的羟基可以电离出质子，表现出一定的酸性，可作为质子导体用于电解、电化学传感、燃料电池等领域，这些金属包括铯、锆、锡、钛等[ZL 100421291C；ZL 102770198B]。其中，铯、铷等的磷酸二氢盐在一定温度下可经历超质子相转变，即在达到转变温度时结构发生重排，利于形成氢键，提高其酸性。锆、钛等的磷酸氢盐则不发生超质子相转变，其具有较强的吸水性和层状结构，依靠暴露的羟基表现酸性。钾、锂等的磷酸氢盐则在较高温度下发生分解。
利用溶胶-凝胶法制备的硅磷酸及其盐也可用于质子传导材料的制备[CN101671120B]。
本发明提供了一种环三磷腈基六磷酸盐耐高温质子导体的制备方法。首先，以HCCP与亚磷酸酯为原料，在无催化剂、无溶剂的条件下，在环三磷腈基母体上通过一步反应引入六个磷酸酯基，直接合成环三磷腈基六磷酸酯(ETHP)。然后，在浓盐酸中对其进行水解，得到环三磷腈基六磷酸(THP)。在水相中，将THP与金属(如铈、锆、铁等)的水溶性盐进行聚合反应，即可制备其盐MTHP。本发明提供的MTHP的制备工艺具有原料廉价易得、工艺简单、条件温和、产率高和后处理简单的优势。这样制备的MTHP具有良好的耐温性能，制备方法简便。更重要的是，由于在反应的第一步中，在环三磷腈基母体上一步引入了六个磷酸酯基，使THP结构中，每个环三磷腈基母体都含六个磷酸基，从空间取向上，六个磷酸基在环三磷腈基母体上互为间位，彼此之间位阻最小，有利于活性基团的充分暴露。在与金属盐反应时，通过二者摩尔比的控制，可以调控磷酸基上多少羟基参与聚合反应，多少羟基暴露出来。参与聚合反应的羟基使产物形成聚合物骨架，且在水中不能溶解，避免使用过程中发生流失；未反应而暴露出的羟基则可以提供酸性和氢键供体，使其具有催化活性、质子传导性能和传感性能。本专利制备的环三磷腈基六磷酸盐耐高温质子导体可作为酸催化剂应用于化工生产、生物柴油制取、制药等行业，亦可作为质子导体用于质子交换膜添加剂、传感器和燃料电池膜电极质子传导材料等领域。
发明内容
本发明制备的环三磷腈基六磷酸基耐高温质子导体结构式为：
式中：M＝H,Ce,Zr,Fe,La,Y,etc.(M为其中的一种或多种)
MTHP的合成步骤为：
首先，利用亚磷酸酯的磷原子上的孤对电子对进攻六氯环三磷腈中的P-Cl上的磷原子，发生亲核取代反应，得到RTHP。ETHP在浓盐酸中水解得到THP。THP在水中与锆、铈、铁等离子中的一种或多种发生聚合而得到不溶于水的MTHP，MTHP是有机-无机复合结构的耐高温质子导体。
式中，M＝Ce时，合成反应方程式如下：
本发明所制备的六磷酸基有机-无机复合耐高温质子导体的用途是用于酸催化、传感器和燃料电池的质子传导材料。
本发明在合成工艺和性能方面具有如下优点：
(1)合成工艺上的优点。本发明提供的六磷酸基耐高温质子导体的制备工艺，可以在环三磷腈基母体上一步引入六个磷酸基，所用原料廉价易得，制备工艺简单，条件温和，后处理简便，环境友好，产率高。
(2)产品性能上的优点。本发明所制备的耐高温质子导体具有良好的热稳定性、传感性能、催化性能和离子传导性能。
(3)本发明制备的磷酸基耐高温质子导体，其酸度以及氢键给体和受体的含量可调节，具有一定的吸水性，容易电离构筑离子键，也便于形成氢键网络结构，通过氢键的断裂-形成过程进行质子传导，在中高温和不同湿度尤其是低湿度下具有良好的质子传导性能。另外，其有机-无机复合结构能提高其与聚合物的相容性，避免出现相分离。
具体实施方式
[实施例1]：ETHP的制备：
将20.9g HCCP(0.06mol)在搅拌下2h内分三批慢慢加入60mL亚磷酸三乙酯(TEP,0.34mol)中，升温至120℃反应6h，冷却后加入石油醚静置过夜，得到的沉淀抽滤得到黄色固体，即环三磷腈基六元磷酸乙酯(ETHP)，产率86％。
采用相同反应步骤，以不同亚磷酸酯或在不同条件进行反应的产率汇总如表1所示：
表1不同亚磷酸酯反应制备RTHP的反应条件及产率
[实施例2]：THP的制备：
将46.5g ETHP(0.05mol)加入100mL浓盐酸中，磁力搅拌下回流72h，冷却至50℃，减压蒸去HCl，浓缩至40mL，用90mL乙酸乙酯萃取三次，以除去未水解的TTP。将水相浓缩至近干，在真空干燥箱中120℃下干燥至恒重，得到29.5g白色固体，即六磷酸基环三磷腈(THP，产率：95％)。
采用相同反应步骤，只是用二氯甲烷、苯、甲苯或石油醚萃取，产率分别为89％，85％，87％和82％。
采用相同的反应步骤，在浓盐酸中回流24h，在70℃下减压蒸馏，用乙酸乙酯萃取，产率为71％。
不同酯基的RTHP水解反应结果如表2所示。
表2不同酯基的RTHP水解制备THP的产率
[实施例3]：CeTHP-1:2的制备
取24.8g THP(0.04mol)加入60mL去离子水中，室温搅拌1h使其充分溶解。取11.0g二水合硝酸铈铵(0.02mol)溶于50mL 0.1mol L-1稀盐酸中(避免水解生成难溶的氢氧化高铈)。将硝酸铈铵的盐酸溶液滴加到THP的水溶液中，室温搅拌12h，使THP上的磷酸基与Ce4+之间充分进行聚合反应，得到黄色悬浊液。离心，用去离子水洗涤至滤液pH＝7，以充分除去未反应的原料，在120℃下干燥12h，得24.3g黄色固体(产率86％)，其中铈和THP的摩尔比为1:2，记为CeTHP-1:2)。
其它配比的铈盐的制备同上，只是改变铈盐与THP摩尔比，其结果见表3所示。采用其他高价金属离子的可溶性盐替代硝酸铈铵所制备的MTHP盐，制备工艺条件和性能如表3，表4所示。
[实施例4]：CeTHP-1:2的应用：
以CeTHP-1:2为催化剂催化油脂(以油酸甘油三酯为例)的水解反应：称取2g的油酸甘油三酯溶于20mL甲苯和20mL水的混合液中加热、搅拌乳化，加入0.01g CeTHP-1:2，加热、搅拌、回流6h，测得油酸的产率达90％。
[实施例5]：以CeTHP-1:2为催化剂催化生物柴油制备过程中的酯交换反应，以棉籽油与甲醇为原料：称取5g棉籽油加入100mL的甲醇中，加入0.2g的CeTHP-1:2，加热、搅拌、回流12h，得到脂肪酸甲酯收率达93％。
[实施例6]：以CeTHP-1:2作为质子导体，在180℃，100％相对湿度下质子电导率达0.147S/cm；在180℃，50％相对湿度下质子电导率达0.086S/cm；在180℃，干燥条件下质子电导率达0.0041S/cm。采用其他高价金属离子的可溶性盐替代硝酸铈铵所制备的MTHP盐，其压片测的的电导率如表4所示。
[实施例7]：以CeTHP-1:2作为质子导体用于高温质子交换膜的制备。(1)含有吡嗪基团的聚苯并咪唑(PzPBI)的制备：用2,6-吡嗪二甲酸与3,3’-二氨基联苯胺(DABz)反应制备，具体反应步骤为：在装有电动搅拌和氮气保护的三口烧瓶中加入多聚磷酸(PPA)(100g)，氮气保护下160℃搅拌1h以除去多余的水分及空气。将DABz(4.00g,18.7mmol)以及2,6-吡嗪二甲酸(3.14g,18.7mmol)混合均匀，慢慢加入到三口烧瓶中。控制氮气流速，防止DABz被氧化，同时将反应温度提升到200℃并继续保温、搅拌反应5～8h。随着反应时间的增加，聚合体系逐渐变得粘稠。待粘度合适时停止反应，反应混合液慢慢转移到大量去离子水中抽丝，洗净、烘干，粉碎，去离子水多次洗涤以除去多聚磷酸和未反应的反应物，即得到PzPBI，用乌氏粘度计测定PzPBI的分子量。其粘均分子量为4.5万到5.5万。
(2)其它带吡嗪基团的PBI的制备方法：同(1)的方法，只是将2,6-吡嗪二甲酸分别换成2,5-吡嗪二甲酸或2,3-吡嗪二甲酸即可，其它操作同(1)，即可得到含有不同吡啶基团的PzPBI，产品分别记为：3,5-PzPBI或2,3-PzPBI。
(3)CeTHP-1:2掺杂到聚苯并咪唑(PzPBI)的复合质子交换膜的制备：以CeTHP-1:2掺杂40％为例。取1.0g PzPBI加入10mL N,N’-二甲基乙酰胺(DMAc)中，在80℃下磁力搅拌24h使其充分溶解，抽滤除去不溶物。在50℃下向滤液中加入交联剂0.05g TGIC，继续搅拌2.5h使其充分溶解。再加入0.70g CeTHP-1:2，继续搅拌3h使其充分分散在铸膜液中。超声振荡1h以除去气泡，而后将其浇铸在玻璃板上，在60℃下流延12h，120℃下加热12h除去溶剂，而后在160℃下加热6h使PBI和TGIC进行充分交联。将得到的膜在0.1mol L-1H2SO4水溶液中室温下浸泡24h，使掺杂到膜中的CeTHP-1:2的充分酸化而后在去离子水中浸泡24h(每6h换水一次)以洗去膜中的硫酸，得到PzPBI-TGIC(5％)/CeTHP-1:2(40％)复合膜。
(4)其他PBI制备方法同实施例7中的(1)部分。只是将2,6-吡嗪二羧酸改为其他二羧酸(如，间苯二甲酸、2,6-吡啶二羧酸、1,8-萘二羧酸，1,5-咪唑二羧酸或4,4’-联苯二甲酸等)
(5)其他交联剂交联，其他CeTHP-1:2掺杂量的PBI复合膜的制备方法同实施例7中实验(3)部分，只是把交联剂TGIC改为其他交联剂，CeTHP-1:2的用量0.7g改为其他量即可。其复合膜的测试结果与表5所示。
[实施例8]：采用实施例3相同的方法，只是把硝酸铈铵分别换成氯氧锆、三氯化铁、硝酸钇或硝酸镧，按照不同的摩尔配比，即可分别得到不同配比的锆盐、铁盐、钇盐或镧盐。分别采用实施例4、实施例5、实施例6和实施例7的方法研究这些盐的性能，其制备工艺和性能如表3，表4所示。
表3MTHP类质子导体的制备工艺条件及性能对比
注：IEC的单位为meq.g-1。
表4MTHP类质子导体在180℃下不同性低湿度下的质子电导率(S/cm)
表5MTHP掺杂到PBI制备的复合膜在不同性低湿度下的质子电导率(S/cm)
注：2，6-PzPBI：2，6-吡嗪二甲酸与3，3’-二氨基联苯胺缩合得到的新型PBI
2，5-TpPBI：2，5-噻吩二甲酸与3，3’-二氨基联苯胺缩合得到的新型PBI
2，6-PyPBI：2，6-吡啶二甲酸与3，3’-二氨基联苯胺缩合得到的新型PBI
Claims (4)
1.一种环三磷腈基六磷酸盐类耐高温质子酸的制备方法，其特征在于：以六氯环三磷腈HCCP为原料与亚磷酸酯反应，得到环三磷腈基六磷酸酯RTHP，在浓盐酸中水解得到环三磷腈基六元磷酸THP，将六元磷酸在水相中与高价过渡金属离子发生反应得到不溶于水的环三磷腈基六磷酸高价过渡金属离子盐MTHP；将HCCP在搅拌下0.5～2h内分批慢慢加入亚磷酸酯中，升温至90～140℃反应6～12h，冷却后加入石油醚中过夜，抽滤得到RTHP；将RTHP在浓盐酸中加热、搅拌、回流反应24～72h，在50℃～70℃下，减压蒸出HCl、醇和水，用水和有机溶剂萃取，将水相浓缩，真空干燥得THP；将THP溶于水，按照一定的比例加入高价过渡金属离子的水溶性的盐，搅拌反应12～24h，将得到的沉淀抽滤、洗涤至pH为7，得到不溶于水的MTHP；MTHP作为有机-无机复合耐温质子酸用于固体酸催化剂、质子导体、质子交换膜添加剂、传感器、燃料电池膜电极质子传导材料。
2.根据权利要求1所述的一种环三磷腈基六磷酸盐类耐高温质子酸的制备方法，其亚磷酸酯选用：亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三丙酯或亚磷酸三异丙酯中的一种或几种的混合物，其特征在于：水解反应生成的醇沸点低，容易被蒸发去除。
3.根据权利要求1所述的一种环三磷腈基六磷酸盐类耐高温质子酸的制备方法，其高价过渡金属离子选用：Zr4+、Ce4+、Fe3+、Co3+、La3+或Y3+中的一种或多种，其特征在于：其盐可溶于水，溶液中能电离出金属离子，选用其醋酸盐、盐酸盐、硝酸盐中的一种或几种。
4.根据权利要求1所述的一种环三磷腈基六磷酸盐类耐高温质子酸的制备方法，萃取用的有机溶剂为乙酸乙酯、二氯甲烷、苯、甲苯和石油醚中的一种或多种。
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