CN114072454A - 具有对苯二甲酸系配体的金属有机结构体 - Google Patents
具有对苯二甲酸系配体的金属有机结构体 Download PDFInfo
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- CN114072454A CN114072454A CN202080045215.9A CN202080045215A CN114072454A CN 114072454 A CN114072454 A CN 114072454A CN 202080045215 A CN202080045215 A CN 202080045215A CN 114072454 A CN114072454 A CN 114072454A
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title abstract description 18
- 239000003446 ligand Substances 0.000 title description 6
- 239000007789 gas Substances 0.000 claims abstract description 26
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 12
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 239000013110 organic ligand Substances 0.000 claims description 103
- 239000000203 mixture Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 7
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 125000004353 pyrazol-1-yl group Chemical group [H]C1=NN(*)C([H])=C1[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- -1 2, 5-disubstituted terephthalic acid Chemical class 0.000 abstract description 139
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 24
- 125000001424 substituent group Chemical group 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 87
- 239000007787 solid Substances 0.000 description 66
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 62
- 238000004519 manufacturing process Methods 0.000 description 45
- 239000000843 powder Substances 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 27
- 239000006228 supernatant Substances 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 238000005119 centrifugation Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 20
- 239000012621 metal-organic framework Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 14
- NSJVYHOPHZMZPN-UHFFFAOYSA-N (2-methylphenyl)boronic acid Chemical compound CC1=CC=CC=C1B(O)O NSJVYHOPHZMZPN-UHFFFAOYSA-N 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000010908 decantation Methods 0.000 description 11
- 125000003808 silyl group Chemical class [H][Si]([H])([H])[*] 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 10
- 235000019341 magnesium sulphate Nutrition 0.000 description 10
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 8
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000003367 polycyclic group Chemical group 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 4
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- WXRSDHICEYICMV-UHFFFAOYSA-N diethyl 2,5-dibromobenzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC(Br)=C(C(=O)OCC)C=C1Br WXRSDHICEYICMV-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 4
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000013132 MOF-5 Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 3
- JNSBEPKGFVENFS-UHFFFAOYSA-N [2-(trifluoromethyl)phenyl]boronic acid Chemical compound OB(O)C1=CC=CC=C1C(F)(F)F JNSBEPKGFVENFS-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 description 3
- 235000011009 potassium phosphates Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- BWRRWBIBNBVHQF-UHFFFAOYSA-N 4-(3-pyridin-2-yl-1,2,4-oxadiazol-5-yl)butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2N=CC=CC=2)=N1 BWRRWBIBNBVHQF-UHFFFAOYSA-N 0.000 description 2
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 description 2
- ROMPPAWVATWIKR-UHFFFAOYSA-N 4-[3-(4-chlorophenyl)-1,2,4-oxadiazol-5-yl]butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2C=CC(Cl)=CC=2)=N1 ROMPPAWVATWIKR-UHFFFAOYSA-N 0.000 description 2
- 241000282836 Camelus dromedarius Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000013254 iso-reticular metal–organic framework Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000000786 liquid-assisted grinding Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
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- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 description 1
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- 125000002757 morpholinyl group Chemical group 0.000 description 1
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- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000005184 naphthylamino group Chemical group C1(=CC=CC2=CC=CC=C12)N* 0.000 description 1
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
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- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 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
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000005554 pyridyloxy group Chemical group 0.000 description 1
- 125000005030 pyridylthio group Chemical group N1=C(C=CC=C1)S* 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- QNMBSXGYAQZCTN-UHFFFAOYSA-N thiophen-3-ylboronic acid Chemical compound OB(O)C=1C=CSC=1 QNMBSXGYAQZCTN-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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Abstract
尽管存在贮藏的气体的量、种类根据取代基的种类而产生变化的可能性,但是,以往仅以具有限定范围的取代基的对苯二甲酸来制作金属有机结构体。本发明的目的在于提供一种使用2,5‑二取代对苯二甲酸的新颖的金属有机结构体。式(I)表示的羧酸离子与多价金属离子键合而成的金属有机结构体为新颖的金属有机结构体,能够高效率地贮藏氢气、氮气等气体。(在式(I)中,X表示无取代或取代的环烷基、无取代或取代的芳基、无取代或取代的杂环基或‑Si(R1)(R2)(R3),Y表示单键、亚烷基、‑O‑、‑S‑、‑S(O)‑、‑SO2‑、或‑N(R4)‑、或者将它们组合而得到的基团,其中,作为X‑Y‑,不包括为苯基、苄氧基、吡唑‑1‑基、以及式(II)表示的基团且m为3、6、8、9、10、11和12的情况。)
Description
技术领域
本发明涉及一种新颖的金属有机结构体、使用该金属有机结构体的气体贮藏方法。
本申请主张基于2019年6月25日提出申请的日本专利申请第2019-117163号的优先权,在此引用其内容。
背景技术
金属有机结构体(以下有时称为“MOF”)是通过将金属离子与连结它们的交联性的有机配体进行组合而具有在内部具有空间(即细孔)的高分子结构的固体状的物质,作为具有气体的贮藏、分离等功能的多孔性材料,这十几年来一直受到较多的关注。
作为交联性的有机配体,大多使用氧供体配体和氮供体配体。
已知:通过将对苯二甲酸作为交联性的有机配体使用且在N,N-二甲基甲酰胺中使用Zn(NO3)2·6H2O的溶剂热法,可以得到MOF-5,在温度77K、4MPa的条件下,对于MOF-5能够贮藏7.1质量%的氢(参照非专利文献1~3)。
另外,还已知:即便使用在对苯二甲酸的2,5-位具有正丙氧基、正戊氧基的对苯二甲酸衍生物,仍可得到与MOF-5同构的IRMOF(同构网状金属有机框架(isoreticularMetal-Organic Framework))(参照非专利文献2)。
已知:作为使用2,5-二取代对苯二甲酸的MOF的例子,有使用在2、5位具有如下基团的对苯二甲酸作为有机配体的MOF,即,ω-(咔唑-9-基)烷氧基(亚烷基链的碳原子数为3、6和8-12)(参照非专利文献4和5)、烷氧基(碳原子数为6-14)(参照非专利文献6)、甲基、甲氧基、氯基、乙基和乙氧基(参照专利文献1)、羟基和乙酰氧基(参照非专利文献7)、异丙氧基、烯丙氧基和炔丙氧基(参照非专利文献8)、吡唑-1-基(参照非专利文献9)、4-甲基苯甲酰基(参照非专利文献10)、苯甲酰基(参照非专利文献11)、苄氧基(参照非专利文献12)、溴基(参照非专利文献13)和苯基(参照非专利文献14)。
现有技术文献
专利文献
专利文献1:美国专利公开公报2010-75123号公报
非专利文献
非专利文献1:H.Li,M.Eddaudi,M.O'Keefe,O.M.Yaghi,Nature,402,276(1999)
非专利文献2:M.Eddaudi,J.Kim,N.Rosi,D.Vodak,J.Wachter,M.O'Keefe,O.M.Yaghi,Science 2002,295(5554),469.
非专利文献3:S.Kaye,A.Daily,O.M.Yaghi,J.Long,J.Am.Chem.Soc.2007,129(46),14176.
非专利文献4:E.Y.Choi,S.H.Lee,O.P.Kwon,Bull.Korean Chem.Soc.2012,33(7),2431.
非专利文献5:E.Y.Choi,S.B.Lee,H.Yun,S.H.Lee,C.Gao,Y.Shin,O.P.Kwon,Bull.Korean Chem.Soc.2013,34(12),3903.
非专利文献6:E.Y.Choi,C.Gao,H.J.Lee,O.P.Kwon,S.H.Lee,Chem.Comunn.2009,7563.
非专利文献7:T.Yamada,H.Kitagawa,Supramolecular Chemistry 2011,23,315.
非专利文献8:A.Schneemann,E.D.Bloch,S.Henke,P.L.Llewellyn,J.R.Long,R.A.Fischer,Eur.Chem.J.2015,21,18764.
非专利文献9:E.Gao,J.Xing,Y.Qu,X,Qiu,M.Zhu,Appl.Organometal Chem.2018,32,e4469
非专利文献10:X.Zheng,S.Q.Guo,X.Y.Yu,J.K.Hu,Y.H.Luo,H.Zhang,X.Chen,Inorganic Chemistry Communication2012,18,29.
非专利文献11:F.Yue,B.Li,X.Zhu,Y.Luo,J.Hu,X.Wang,H.Zhang,Journal ofCoordination Chemistry,2013,66(2),243.
非专利文献12:h.Deng,C.J.Doona,H.Furukawa,R.B.Ferreira,J.Towne,C.B.Knobler,B.Wang,O.M.Yaghi,Science 2010,327,846.
非专利文献13:J.Gascon,M.D.Hernandez-Alonson,A.R.Almeida,G.P.M.vanKlink,F.Kapteijin,G.Mui,ChemSusChem 2008,1,981.
非专利文献14:E.R.Engel,A.Jouaiti,C.X.Bezuidenhout,M.W.Hosseini,L.J.Barbour,Angew.Chem.Int.Ed.2017,56,8874.
发明内容
如非专利文献8中所记载的那样,尽管存在贮藏的气体的量、种类根据取代基的种类而产生变化的可能性,但是,以往只制作了使用具有上述限定的范围的取代基的对苯二甲酸的MOF。
本发明的目的在于提供一种新颖的MOF,其使用了2,5-二取代对苯二甲酸。
本发明人等为了解决上述问题进行了深入研究,结果发现,通过使用以往没有的2,5-二取代对苯二甲酸与各种金属盐的组合,能够提供新颖的MOF,从而完成本发明。
即,本发明是由以下事项所确定的如下的发明。
[1]一种金属有机结构体,其由式(I)表示的羧酸离子与多价金属离子键合而成。
(在式(I)中,
X表示无取代或取代的环烷基、无取代或取代的芳基、无取代或取代的杂环基、或-Si(R1)(R2)(R3),R1~R3各自独立地表示氢原子、无取代或取代的烷基、或者无取代或取代的芳基,
Y表示单键、亚烷基、-O-、-S-、-S(O)-、-SO2-、-N(R4)-、或者将它们组合而得到的基团,
R4表示氢原子、无取代或取代的烷基、无取代或取代的环烷基、无取代或取代的芳烷基、无取代或取代的芳基、或者无取代或取代的杂环基。
其中,作为X-Y-,不包括为苯基、苄氧基、吡唑-1-基、以及式(II)表示的基团且m为3、6、8、9、10、11和12的情况。)
[2]如[1]所述的金属有机结构体,其中,多价金属离子为选自元素周期表的第2族~第13族的金属中的至少1种金属的离子。
[3]如[1]或[2]所述的金属有机结构体,其中,多价金属离子为选自Zn、Fe、Co、Ni、Cu、Al、Zr和Mg中的至少1种金属的离子。
[4]如[1]至[3]中任一项所述的金属有机结构体,其中,进一步包含除了式(I)所示的有机配体以外的有机配体作为构成成分。
[5]一种气体贮藏方法,具有如下工序:使气体与如[1]至[4]中任一项所述的金属有机结构体接触,使上述气体吸附在上述金属有机结构体的内部。
本发明的MOF为新颖的MOF,在气体贮藏中有着表现出与以往的MOF不同的性能的可能性。
具体实施方式
本发明的MOF是式(I)表示的羧酸离子与多价金属离子键合而成的MOF。
本发明中使用的多价金属离子只要是2价以上的金属的离子,就没有特别限定,优选为选自元素周期表的第2族~第13族的金属中的至少1种金属的离子,进一步优选为选自Zn、Fe、Co、Ni、Cu、Al、Zr和Mg中的至少1种金属的离子,再进一步优选为选自Co、Ni、Cu和Zn中的至少1种金属的离子。
这些多价金属离子以各种盐的形式被供给,例如,可例示硝酸盐、过氯酸盐、氯化物离子盐等,具体而言,可例示Zn(NO3)2·6H2O、Zn(NO3)2·4H2O、Ni(NO3)2·6H2O、Mg(NO3)2·6H2O、Cu(NO3)2·xH2O、Cu(NO3)2·2.5H2O、Co(NO3)2·6H2O、Al(NO3)3·6H2O、ZrCl4等。进而,如果考虑到盐的纯度、金属离子与有机配体的键合的容易程度等,可优选例示硝酸盐。
本发明的MOF中包含式(I)表示的羧酸离子。
式(I)中,X表示无取代或取代的环烷基、无取代或取代的芳基、无取代或取代的杂环基或-Si(R1)(R2)(R3)。
此处,在本发明中,“无取代(unsubstituted)”的用语是指仅仅作为母核的基团。在没有“取代”的记载且又仅记载作为母核的基团的名称时,只要没有特别说明,就是指“无取代”的意思。
另一方面,“取代(substituted)”是指作为母核的基团的任一氢原子被结构与母核相同或不同的官能团(取代基)取代。因此,“取代基”是指与作为母核的官能团键合的其它官能团。取代基可以是1个,也可以是2个以上。2个以上的取代基可以相同,也可以不同。
“C1~6”等用语表示作为母核的基团(位于“C1~6”的语句后的官能团)的碳原子数为1~6个等。该碳原子数中,不包含取代基中的碳原子的数量。例如,具有乙氧基作为取代基的丁基被分类为C2烷氧基C4烷基。
“取代基”只要在化学上允许,且具有本发明的效果,就没有特别限定。以下例示可作为“取代基”的基团。
甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、正己基等C1~6烷基;
乙烯基、1-丙烯基、2-丙烯基(烯丙基)、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基等C2~6烯基;
乙炔基、1-丙炔基、2-丙炔基(炔丙基)、1-丁炔基、2-丁炔基、3-丁炔基、1-甲基-2-丙炔基等C2~6炔基;
环丙基、环丁基、环戊基、环己基、立方烷基(Cubanyl group)等C3~8环烷基;
苯基、萘基等C6~10芳基;
苄基、苯乙基等C6~10芳基C1~6烷基;
3~6元杂环基;
3~6元杂环基C1~6烷基;
氧基;
羟基;
甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基等C1~6烷氧基;
乙烯氧基、烯丙氧基、丙烯氧基、丁烯氧基等C2~6烯氧基;
乙炔氧基、炔丙氧基等C2~6炔氧基;
苯氧基、萘氧基等C6~10芳氧基;
苄氧基、苯乙氧基等C6~10芳基C1~6烷氧基;
噻唑氧基、吡啶氧基等5~6元杂芳氧基;
噻唑基甲氧基、吡啶基甲氧基等5~6元杂芳基C1~6烷氧基;
甲酰基;
乙酰基、丙酰基等C1~6烷基羰基;
甲酰氧基;
乙酰氧基、丙酰氧基等C1~6烷基羰氧基;
苯甲酰基等C6~10芳基羰基;
甲氧基羰基、乙氧基羰基、正丙氧基羰基、异丙氧基羰基、正丁氧基羰基、叔丁氧基羰基等C1~6烷氧基羰基;
甲氧基羰氧基、乙氧基羰氧基、正丙氧基羰氧基、异丙氧基羰氧基、正丁氧基羰氧基、叔丁氧基羰氧基等C1~6烷氧基羰氧基;
羧基;
氟基、氯基、溴基、碘基等卤素基团;
氟甲基、二氟甲基、三氟甲基、2,2,2-三氟乙基、五氟乙基、3,3,3-三氟丙基、2,2,3,3,3-五氟丙基、全氟丙基、2,2,2-三氟-1-三氟甲基乙基、全氟异丙基、4-氟丁基、2,2,3,3,4,4,4-七氟丁基、全氟丁基、全氟戊基、全氟己基、氯甲基、溴甲基、二氯甲基、二溴甲基、三氯甲基、三溴甲基、1-氯乙基、2,2,2-三氯乙基、4-氯丁基、全氯己基、2,4,6-三氯己基等C1~6卤代烷基;
2-氯-1-丙烯基、2-氟-1-丁烯基等C2~6卤代烯基;
4,4-二氯-1-丁炔基、4-氟-1-戊炔基、5-溴-2-戊炔基等C2~6卤代炔基;
三氟甲氧基、2-氯正丙氧基、2,3-二氯丁氧基等C1~6卤代烷氧基;
2-氯丙烯氧基、3-溴丁烯氧基等C2~6卤代烯氧基;
氯乙酰基、三氟乙酰基、三氯乙酰基等C1~6卤代烷基羰基;
氨基;
甲基氨基、二甲基氨基、二乙基氨基等C1~6烷基取代氨基;
苯胺基、萘氨基等C6~10芳氨基;
苄基氨基、苯乙基氨基等C6~10芳基C1~6烷基氨基;
甲酰氨基;
乙酰氨基、丙酰氨基、丁酰氨基、异丙基羰基氨基等C1~6烷基羰基氨基;
甲氧基羰基氨基、乙氧基羰基氨基、正丙氧基羰基氨基、异丙氧基羰基氨基等C1~6烷氧基羰基氨基;
S,S-二甲基磺酰亚氨基(S,S-ジメチルスルホキシイミノ基)等C1~6烷基磺酰亚氨基(アルキルスルホキシイミノ基);
氨基羰基、二甲基氨基羰基、苯基氨基羰基、N-苯基-N-甲基氨基羰基等无取代或具有取代基的氨基羰基;
亚氨基甲基、1-亚氨基乙基、1-亚氨基正丙基等亚氨基C1~6烷基;
N-羟基-亚氨基甲基、1-(N-羟基亚氨基)乙基、1-(N-羟基亚氨基)丙基、N-甲氧基亚氨基甲基、1-(N-甲氧基亚氨基)乙基等取代或无取代的N-羟基亚氨基C1~6烷基;
羟基亚氨基;
甲氧基亚氨基、乙氧基亚氨基、正丙氧基亚氨基、异丙氧基亚氨基、正丁氧基亚氨基等C1~6烷氧基亚氨基;
氨基羰氧基;
乙基氨基羰氧基、二甲基氨基羰氧基等C1~6烷基取代氨基羰氧基;
硫基;
巯基;
甲硫基、乙硫基、正丙硫基、异丙硫基、正丁硫基、异丁硫基、仲丁硫基、叔丁硫基等C1~6烷硫基;
三氟甲硫基、2,2,2-三氟乙硫基等C1~6卤代烷硫基;
苯硫基、萘硫基等C6~10芳硫基;
噻唑硫基、吡啶硫基等5~6元杂芳硫基;
甲基亚磺酰基、乙基亚磺酰基、叔丁基亚磺酰基等C1~6烷基亚磺酰基;
三氟甲基亚磺酰基、2,2,2-三氟乙基亚磺酰基等C1~6卤代烷基亚磺酰基;
苯基亚磺酰基等C6~10芳基亚磺酰基;
噻唑基亚磺酰基、吡啶基亚磺酰基等5~6元杂芳基亚磺酰基;
甲基磺酰基、乙基磺酰基、叔丁基磺酰基等C1~6烷基磺酰基;
三氟甲基磺酰基、2,2,2-三氟乙基磺酰基等C1~6卤代烷基磺酰基;
苯基磺酰基等C6~10芳基磺酰基;
噻唑基磺酰基、吡啶基磺酰基等5~6元杂芳基磺酰基;
磺基;
甲基磺酰氧基、乙基磺酰氧基、叔丁基磺酰氧基等C1~6烷基磺酰氧基;
三氟甲基磺酰氧基、2,2,2-三氟乙基磺酰氧基等C1~6卤代烷基磺酰氧基;
三甲基甲硅烷基、三乙基甲硅烷基、叔丁基二甲基甲硅烷基等三C1~6烷基取代甲硅烷基;
三苯基甲硅烷基等三C6~10芳基取代甲硅烷基;
烯丙基二甲基甲硅烷基、乙烯基二甲基甲硅烷基等C2~C6烯基C1~C6二烷基取代甲硅烷基;
叔丁基二苯基甲硅烷基、二苯基甲基甲硅烷基等C1~C6烷基二C6~C10芳基取代甲硅烷基;
二甲基苯基甲硅烷基等二C1~C6烷基C6~C10芳基取代甲硅烷基;
苄基二甲基甲硅烷基、3-苯基丙基二甲基甲硅烷基等(C6~C10苯基C1~C6烷基)二C1~C6烷基甲硅烷基;
甲基苯基乙烯基甲硅烷基等C1~C6烷基C6~C10苯基C2~C6烯基甲硅烷基;
三甲氧基甲硅烷基、三乙氧基甲硅烷基等三C1~C6烷氧基取代甲硅烷基;
二甲基甲硅烷基、二乙基甲硅烷基等二C1~C6烷基取代甲硅烷基;
二甲氧基甲硅烷基、二乙氧基甲硅烷基等二C1~C6烷氧基取代甲硅烷基;
甲氧基二甲基甲硅烷基等C1~C6烷氧基C1~C6烷基取代甲硅烷基;
叔丁氧基二苯基甲硅烷基等C1~C6烷氧基C6~C10芳基取代甲硅烷基;
甲基二甲氧基甲硅烷基等C1~C6烷基二C1~C6烷氧基取代甲硅烷基;
氰基;
硝基。
另外,在这些“取代基”中,该取代基中的任一氢原子也可以被结构不同的基团取代。作为该情况下的“取代基”,可举出C1~6烷基、C1~6卤代烷基、C1~6烷氧基、C1~6卤代烷氧基、卤素基团、氰基、硝基等。
另外,上述“3~6元杂环基”包含选自氮原子、氧原子和硫原子中的1~4个杂原子来作为环的构成原子。杂环基可以是单环和多环中任一者。多环杂环基只要至少一个环是杂环即可,剩下的环可以是饱和脂环、不饱和脂环或芳香环中任一者。作为“3~6元杂环基”,可举出3~6元饱和杂环基、5~6元杂芳基、5~6元部分不饱和杂环基等。
作为3~6元饱和杂环基,可举出氮丙啶基、环氧基、吡咯啶基、四氢呋喃基、噻唑烷基、哌啶基、哌嗪基、吗啉基、二氧杂戊环基、二氧杂环己基等。
作为6元杂芳基,可举出吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基等。
式(I)的X中,作为“无取代或取代的环烷基”的“环烷基”,可举出环丙基、环丁基、环戊基、环己基、立方烷基等。
式(I)的X中,“无取代或取代的芳基”的“芳基”可以是单环和多环中任一者。多环芳基只要至少一个环是芳香环即可,剩下的环可以是饱和脂环、不饱和脂环或芳香环中任一者。
式(I)的X中,作为“无取代或取代的杂环基”的“杂环基”,可举出与“取代基”的“3~6元杂环基”中所例示的“杂环基”相同的“杂环基”。
式(I)的X中,“-Si(R1)(R2)(R3)”的R1~R3各自独立地表示氢原子、无取代或取代的烷基、或者无取代或取代的芳基。
“无取代或取代的烷基”的“烷基”可以是直链,也可以是支链,可举出甲基、乙基、正丙基、正丁基、正戊基、正己基、异丙基、异丁基、仲丁基、叔丁基、异戊基、新戊基、2-甲基正丁基、异己基等。
“无取代或取代的芳基”的“芳基”可以是单环和多环中任一者,多环芳基只要至少一个环为芳香环即可,剩下的环可以是饱和脂环、不饱和脂环或芳香环中任一者,可举出苯基、1-萘基、2-萘基、基、茚基、二氢茚基、四氢萘基等。
作为“-Si(R1)(R2)(R3)”,可举出甲硅烷基、三甲基甲硅烷基、三乙基甲硅烷基、三异丙基甲硅烷基、三(正丁基)甲硅烷基、叔丁基二甲基甲硅烷基、3-氰基丙基二甲基甲硅烷基、二甲基(正丁基)甲硅烷基、二甲基(正壬基)甲硅烷基、二甲基(正十一烷基)甲硅烷基、二乙基异丙基甲硅烷基、二甲基异丙基甲硅烷基、二甲基(正丙基)甲硅烷基、二甲基(正己基)甲硅烷基、二甲基硬脂基甲硅烷基、二甲基乙基甲硅烷基、二甲基(1,1,2-三甲基丙基)甲硅烷基、三苯基甲硅烷基、二苯基甲基甲硅烷基、二苯基(叔丁基)甲硅烷基、二甲基(3-苯基丙基)甲硅烷基、二甲基苯基甲硅烷基、苄基二甲基甲硅烷基、溴甲基二甲基甲硅烷基、氯甲基二甲基甲硅烷基、二甲基甲硅烷基、二异丙基甲硅烷基、二苯基甲硅烷基等。
式(I)中,Y表示单键、亚烷基、-O-、-S-、-S(O)-、-SO2-、-N(R4)-、或者将它们组合而得到的基团。
作为亚烷基,可举出亚甲基、亚乙基、1,3-亚丙基、1,2-亚丙基、2,2-亚丙基、1,4-亚丁基、1,3-亚丁基、1,2-亚丁基等。
R4表示氢原子、无取代或取代的烷基、无取代或取代的环烷基、无取代或取代的芳烷基、无取代或取代的芳基、或者无取代或取代的杂环基。
作为烷基,可举出与R1中举出的烷基相同的烷基,作为环烷基、芳基和杂环基,可举出与X中所举出的环烷基、芳基和杂环基相同的环烷基、芳基和杂环基,作为芳烷基,可举出苄基、苯乙基、3-苯基丙基等。
作为式(I)中的Y的将单键、亚烷基、-O-、-S-、-S(O)-、-SO2-和-N(R4)-组合而成的基团,只要为化学上所允许的范围即可,其组合、组合的数量等没有特别限定,可以自由地组合。作为如此组合而成的基团,可举出-NHO-、-CH2O-、-CH2CH2O-、-CH2S-、-CH2CH2S-、-OCH2CH2O-、-SCH2CH2S-、-OCH2CH2S-、-CH2OCH2CH2O-、-SO2NH-、-SO2N(CH3)-等。对于在哪个位置与苯基和X键合,可以在化学上允许的范围内任意地选择。即,在Y为-CH2O-的情况下,包含以下任一情况。
作为式(I)表示的羧酸离子,可举出以下所示的化合物等。
本发明的金属有机结构体可包含除了式(I)表示的有机配体以外的有机配体。作为该有机配体,具体而言,可例示对苯二甲酸、邻苯二甲酸、间苯二甲酸、5-氰基间苯二甲酸、1,3,5-苯三甲酸、1,3,5-三(4-羧基苯基)苯、4,4'-二羧基联苯、3,5-二羧基吡啶、2,3-二羧基吡嗪、1,3,5-三(4-羧基苯基)苯、1,2,4,5-四(4-羧基苯基)苯、9,10-蒽二羧酸、2,6-萘二甲酸、[1,1':4',1”]联三苯基-3,3”,5,5”-四羧酸、联苯-3,3',5,5'-四羧酸、3,3',5,5'-四羧基二苯甲烷、1,3,5-三(4'-羧基[1,1'-联苯]-4-基)苯、1,3,5-三(4-羧基苯基)三嗪、1,2-双(4-羧基-3-硝基苯基)乙烯、1,2-双(4-羧基-3-氨基苯基)乙烯、反式,反式-粘康酸、富马酸、苯并咪唑、咪唑、1,4-二氮杂双环[2.2.2]辛烷(DABCO)、吡嗪、4,4'-联吡啶、1,2-二(4-吡啶基)乙烯、2,7-二氮杂芘、4,4'-偶氮双吡啶、双(3-(4-吡啶基)-2,4-戊二酮)合铜等。
在将式(I)表示的有机配体与除了式(I)以外的有机配体混合使用时的混合摩尔比没有特别限定,例如,如果是利用柱状分子进行交联来构筑柱撑层型之类的三维结构时的柱状分子,则优选相对于式(I)表示的有机配体过量地使用除了式(I)以外的有机配体。
作为本发明的金属有机结构体的制造方法,没有特别限定,可使用以下方法中的任一方法:溶剂扩散法、溶剂搅拌法、水热法等溶液法;对反应溶液照射微波而将体系整体在短时间内均匀地加热的微波法;超声波法,即,通过对反应容器照射超声波,在反应容器中反复产生压力的变化,通过该压力的变化,出现溶剂形成气泡并崩解的被称为气蚀的现象,此时约5000K、10000bar的高能量场成为局部地形成的结晶的各生成的反应场;在不使用溶剂的情况下将金属离子产生源与有机配体混合的固相合成法;添加结晶水程度的水,将金属离子产生源与有机配体混合的LAG(液体辅助研磨(liquid assisted grinding))法等。
例如具备如下工序:分别制备含有成为金属离子的产生源的金属化合物和溶剂的第一溶液、含有作为式(I)表示的有机配体的前体的羧酸和溶剂的第二溶液、以及根据需要含有其它成为多齿配体的化合物和溶剂的第三溶液的工序;以及,通过将第一溶液与第二溶液和第三溶液进行混合而制备反应液,并将该反应液进行加热,从而得到金属有机结构体的工序。不需要分别制备第一~第三溶液,例如可将上述金属化合物、作为式(I)表示的有机配体的前体的羧酸、其它成为多齿配体的化合物和溶剂一次性混合,从而制备1种溶液。
上述金属化合物与式(I)表示的有机配体的混合摩尔比可根据得到的金属有机结构体的细孔尺寸、表面特性而任意地选择,相对于式(I)表示的有机配体1摩尔,优选使用金属化合物1摩尔以上,进一步优选使用1.1摩尔以上,进一步优选使用1.2摩尔以上,进一步优选使用1.5摩尔以上,进一步优选使用2摩尔以上,进一步优选使用3摩尔以上。
另外,反应液体中的上述金属离子的浓度优选为25~200mmol/L的范围。
式(1)表示的有机配体在反应液体中的浓度优选为10~100mmol/L的范围。
除了式(I)以外的有机配体在反应液体中的浓度优选为25~100mmol/L。
作为使用的溶剂,可使用选自N,N-二甲基甲酰胺(以下有时记载为“DMF”)、N,N-二乙基甲酰胺(以下有时记载为“DEF”)、N,N-二甲基乙酰胺和水中的1种或2种以上。在它们之中,优选单独使用N,N-二甲基甲酰胺、N,N-二乙基甲酰胺或二甲基乙酰胺中任一者,或者优选使用N,N-二甲基甲酰胺/水混合溶剂、N,N-二乙基甲酰胺/水混合溶剂或N,N-二甲基乙酰胺/水混合溶剂。
反应液的加热温度没有特别限定,优选为室温~140℃的范围。
本发明的MOF为多孔性配位高分子,利用其细孔的表面积较大,可考虑气体的贮藏、气体的分离、或作为非均相催化剂的应用,其中,可优选用于气体的贮藏。可贮藏的气体没有特别限定,通过适当调整细孔的大小,能够贮藏氢、氮、二氧化碳、低级烃。
使用了本发明的MOF的气体的贮藏方法没有特别限定,优选为使本发明的MOF与气体接触的方法,接触的方法没有特别限定。例如,可举出在罐中填充本发明的MOF,使气体流入至罐内的方法;使本发明的MOF担载在构成罐的内壁的表面,使气体流入至罐内的方法;以及用包含MOF的材料形成罐并使气体流入至罐内的方法等。
实施例
以下,使用实施例详细地说明本发明,但本发明并不限定于实施例的范围。
将实施例中使用的作为式(I)表示的有机配体1~31的前体的羧酸(以下,包含作为前体的羧酸在内,称为“有机配体”)的结构示于表1。
应予说明,表1中的符号表示以下含义。
Me:甲基、Ph:苯基、Py:吡啶基、c-Pr:环丙基、c-Hex:环己基、O:氧原子、N:氮原子、S:硫原子、Cl:氯原子、F:氟原子、H:氢原子、C:碳原子。
表1中的X-Y-中的数字表示取代位点。例如,2-MePh表示以苯基键合在式(I)中的苯环的位置作为1位、且在2位上取代有甲基的2-甲基苯基。
[表1]
有机配体序号 | X-Y- | 有机配体序号 | X-Y- |
1 | 2-MePh | 17 | 4-MePhO |
2 | 3-MePh | 18 | 4-ClPhO |
3 | 4-MePh | 19 | PhNH |
4 | 2,6-diMePh | 20 | Me<sub>3</sub>Si |
5 | 2-ClPh | 21 | 2-萘基-O |
6 | 3-ClPh | 22 | 4-MeOPhO |
7 | 2-CF<sub>3</sub>Ph | 23 | 3-噻吩基 |
8 | 3-CF<sub>3</sub>Ph | 24 | 4-ClPh |
9 | 4-CF<sub>3</sub>Ph | 25 | 4-MeOPh |
10 | 3-Py | 26 | 3-MeOPh |
11 | 4-PyO | 27 | 2-MeOPh |
12 | c-Pr | 28 | 3-呋喃基 |
13 | c-Hex | 29 | 2-MeSPh |
14 | PhO | 30 | 3-MeSPh |
15 | 3-MePhO | 31 | 4-MeSPh |
16 | 2-MePhO |
[制造例1]有机配体1的合成
将2,5-二溴对苯二甲酸二乙酯(5.0mmol)、邻甲基苯基硼酸(12.5mmol)、四(三苯基膦)钯(0.05mmol)、2M的碳酸钠水溶液10mL、甲苯35mL、乙醇10mL在氮气下以90℃加热36小时。恢复至室温,加入水进行分液,用硫酸镁使有机层干燥,并进行过滤。减压蒸馏除去滤液,将得到的固体使用硅胶柱色谱法(氯仿)进行纯化。作为黄色固体而得到了1.5g(3.7mmol)的2,5-二(邻甲基苯基)对苯二甲酸二乙酯。对得到的黄色固体加入氢氧化钾(100mmol)、乙醇50mL、水40mL,在100℃加热2小时。恢复至室温,加入浓盐酸。以乙酸乙酯进行萃取,以硫酸镁干燥后,进行过滤。减压蒸馏除去滤液,得到了1.2g(3.46mmol)的有机配体1。
[制造例2]有机配体2的合成
使用间甲基苯基硼酸来代替邻甲基苯基硼酸,除此之外,按照与制造例1相同的操作,得到了有机配体2。
[制造例3]有机配体4的合成
使2,5-二溴对苯二甲酸二乙酯(5.0mmol)、2,6-二甲基苯基硼酸(12.5mmol)、三(二亚苄基丙酮)二钯(0.25mmol)、2-二环己基膦-2',6'-二甲氧基联苯(1.0mmol)、磷酸钾(15mmol)、甲苯50mL在氮气下回流两天。恢复至室温,进行硅藻土过滤,减压蒸馏除去滤液,并将得到的固体使用硅胶柱色谱法(氯仿)进行纯化。利用己烷清洗固体并干燥,从而作为无色固体而得到了2.1mmol的2,5-双(2,6-二甲基苯基)对苯二甲酸二乙酯。对得到的固体加入氢氧化钾(40mmol)、乙醇50mL、水20mL,在100℃加热15小时。恢复至室温,加入浓盐酸。以乙酸乙酯进行萃取,以硫酸镁干燥后,进行过滤。减压蒸馏除去滤液,得到了0.8g(2.1mmol)的有机配体4。
[制造例4]有机配体5的合成
使用邻氯苯基硼酸来代替邻甲基苯基硼酸,除此之外,按照与制造例1相同的操作,得到了有机配体5。
[制造例5]有机配体6的合成
使用间氯苯基硼酸来代替邻甲基苯基硼酸,除此之外,按照与制造例1相同的操作,得到了有机配体6。
[制造例6]有机配体7的合成
使2,5-二溴对苯二甲酸二乙酯(5.0mmol)、邻三氟甲基苯基硼酸(12.0mmol)、[1,1'-双(二苯基膦)二茂铁]钯(II)二氯化物二氯甲烷加成物(0.25mmol)、磷酸钾(20mmol)、二甲氧基乙烷20mL在氮气下回流一天。恢复至室温,进行水洗,用乙酸乙酯进行萃取后,用硫酸镁进行干燥。过滤后,减压蒸馏除去滤液,将得到的固体使用硅胶柱色谱法(氯仿)进行纯化。用己烷清洗固体并干燥,从而作为无色固体而得到了2.2mmol的2,5-双(邻三氟甲基苯基)对苯二甲酸二乙酯。对得到的固体加入氢氧化钾(40mmol)、乙醇50mL、水20mL,在100℃加热15小时。恢复至室温,加入浓盐酸。以乙酸乙酯进行萃取,以硫酸镁干燥后,进行过滤。减压蒸馏除去滤液,得到了0.8g(1.9mmol)的有机配体7。
[制造例7]有机配体8的合成
使用间三氟甲基苯基硼酸来代替邻三氟甲基苯基硼酸,除此之外,按照与制造例6相同的操作,得到了有机配体8。
[制造例8]有机配体9的合成
使用对三氟甲基苯基硼酸来代替邻三氟甲基苯基硼酸,除此之外,按照与制造例6相同的操作,得到了有机配体9。
[制造例9]有机配体10的合成
使2,5-二溴对二甲苯(5.0mmol)、3-吡啶基硼酸(12.0mmol)、四(三苯基膦)钯(0.5mmol)、氢氧化钠(20mmol)、甲苯20mL、乙醇15mL、水10mL在氮气下回流一天。恢复至室温,进行水洗,用乙酸乙酯进行萃取后,用硫酸镁进行干燥。过滤后,减压蒸馏除去滤液,并将得到的固体使用硅胶柱色谱法(乙酸乙酯→氯仿:甲醇=9:1)进行纯化。作为无色固体而得到了3.4mmol的2,5-二(3-吡啶基)对二甲苯。对得到的固体加入高锰酸钾(20mmol)、水15mL,并加热整夜。恢复至室温,进行过滤后,用热水充分清洗残渣。在滤液中加入盐酸,调整为pH3。减压蒸馏除去滤液,将得到的固体充分进行水洗,并进行干燥,从而得到了0.3g(0.6mmol)的有机配体10。
[制造例10]有机配体11的合成
加入2,5-二溴对苯二甲酸(10.0mmol)、4-羟基吡啶(40mmol)、铜粉(3.0mmol)、碘化铜(0.8mmol)、二甲基甲酰胺100mL、二氮杂双环十一烯(60.0mmol)、吡啶0.2mL,加热回流整夜。恢复至室温,加入盐酸,过滤出析出的固体,将过滤物用水充分清洗。使其干燥,作为白色固体而得到了3.0g(6.0mmol)的有机配体11。
[制造例11]有机配体12的合成
将2,5-二溴对苯二甲酸二乙酯(5.0mmol)、环丙基硼酸(12.0mmol)、乙酸钯(0.05mmol)、磷酸钾(16mmol)、三环己基膦(1.0mmol)、甲苯20mL、水1mL在氮气下以100℃加热整夜。加入水并用乙酸乙酯进行萃取,以硫酸镁使有机层干燥,并进行过滤。减压蒸馏除去滤液,将得到的固体使用硅胶柱色谱法(氯仿)进行纯化。作为无色固体而得到了2,5-二环丙基对苯二甲酸二乙酯。对得到的无色固体加入氢氧化钾(50mmol)、乙醇50mL、水20mL,在100℃加热2小时。恢复至室温,加入浓盐酸。以乙酸乙酯进行萃取,以硫酸镁干燥后,进行过滤。减压蒸馏除去滤液,得到了1.7g(4.2mmol)的有机配体12。
[制造例12]有机配体13的合成
在对二(环己基)苯(30mmol)中加入碘(3.0mmol)并使其溶解在氯仿中。向其中滴加溴(60mmol),并搅拌48小时。加入20%氢氧化钠,并用二乙醚进行萃取。用硫酸镁使所萃取的溶液干燥,并进行过滤,将滤液进行减压蒸馏,从而得到了2,5-二溴-1,4-二环己基苯(27mmol)。在得到的二溴化物(10mmol)中加入氰化铜(30mmol),并使其溶解在二甲基甲酰胺30mL中。使其整夜回流,恢复至室温,之后,加入氨水100mL。过滤分离出所析出的固体,用水充分清洗,并使其溶解在氯仿中。用硫酸镁进行干燥后,进行过滤,将滤液进行减压蒸馏。将得到的粗产物用己烷进行重结晶,从而作为无色固体而得到了2,5-二氰基-1,4-二环己基苯(9.5mmol)。在得到的二氰化物(5.0mmol)中加入10M的氢氧化钠水溶液75mmol份,使其溶解在乙二醇50mL中,之后,回流一整夜。恢复至室温后,加入100mL的水,加入盐酸,将pH值调整至pH1。过滤分离出所析出的固体,并使其充分干燥,从而得到了2.2g(4.6mmol)的有机配体13。
[制造例13]有机配体15的合成
使用间甲酚来代替4-羟基吡啶,除此之外,按照与制造例10相同的操作,得到了有机配体15。
[制造例14]有机配体16的合成
使用邻甲酚来代替4-羟基吡啶,除此之外,按照与制造例10相同的操作,得到了有机配体16。
[制造例15]有机配体17的合成
使用对甲酚来代替4-羟基吡啶,除此之外,按照与制造例10相同的操作,得到了有机配体17。
[制造例16]有机配体18的合成
使用对氯苯酚来代替4-羟基吡啶,除此之外,按照与制造例10相同的操作,得到了有机配体18。
[制造例17]有机配体21的合成
使用2-萘酚来代替4-羟基吡啶,除此之外,与制造例10同样地进行操作,得到了有机配体21。
[制造例18]有机配体22的合成
使用4-甲氧基苯酚来代替4-羟基吡啶,除此之外,与制造例10同样地进行操作,得到了有机配体22。
[制造例19]有机配体23的合成
使用3-噻吩基硼酸来代替邻甲基苯基硼酸,除此之外,与制造例1同样地进行操作,得到了有机配体23。
[制造例20]有机配体24的合成
使用对氯苯基硼酸来代替邻甲基苯基硼酸,除此之外,与制造例1同样地进行操作,得到了有机配体24。
[制造例21]有机配体25的合成
使用对甲氧基苯基硼酸来代替邻甲基苯基硼酸,除此之外,与制造例1同样地进行操作,得到了有机配体25。
[制造例22]有机配体26的合成
使用间甲氧基苯基硼酸来代替邻甲基苯基硼酸,除此之外,与制造例1同样地进行操作,得到了有机配体26。
[制造例23]有机配体27的合成
使用邻甲氧基苯基硼酸来代替邻甲基苯基硼酸,除此之外,与制造例1同样地进行操作,得到了有机配体27。
[制造例24]有机配体28的合成
使用3-呋喃基硼酸来代替邻甲基苯基硼酸,除此之外,与制造例1同样地进行操作,得到了有机配体28。
[制造例25]有机配体29的合成
使用邻甲基噻吩基硼酸来代替邻甲基苯基硼酸,除此之外,与制造例1同样地进行操作,得到了有机配体29。
[制造例26]有机配体30的合成
使用间甲基噻吩基硼酸来代替邻甲基苯基硼酸,除此之外,与制造例1同样地进行操作,得到了有机配体30。
[制造例27]有机配体31的合成
使用对甲基噻吩基硼酸来代替邻甲基苯基硼酸,除此之外,与制造例1同样地进行操作,得到了有机配体31。
[比较例1]
将对苯二甲酸166.7mg溶解在13mL的DMF中,并向其中加入三乙基胺0.28mL。向其中滴加乙酸锌二水合物557.7mg的DMF溶液17mL。在室温下搅拌2.5小时,将得到的固体用离心分离进行分离。将上清液除去,并将固体浸渍在20mL的DMF中一夜。之后进行离心分离,将上清液除去,使用氯仿进行置换。将离心分离出的固体浸渍在氯仿20mL中一夜,再次进行离心分离的操作重复3次。然后,将离心分离出的固体在150℃真空干燥5小时,从而作为白色粉末而得到了142.9mg的金属有机结构体A。
[比较例2]
在2,5-二甲基对苯二甲酸0.492g、硝酸锌六水合物1.49g中加入50mL的DMF,用烘箱(反应条件:120℃、24小时)进行加热。恢复至室温,并将上清液除去。加入50ml的DMF,并将上清液除去,将溶剂换为氯仿。加入氯仿50ml,浸渍一整夜。将固体进行吸滤,并将得到的固体以150℃进行真空干燥5小时,得到了0.709g的金属有机结构体B。
[实施例1-1]
对有机配体1(0.375mmol)、硝酸锌六水合物(0.375mmol)、1,4-二氮杂双环[2.2.2]辛烷(0.20mmol)和7.5mL的DMF,一边在室温下施加超声波,一边搅拌15分钟。然后,将进行了离心分离、过滤处理的滤液加入高压釜中,用烘箱(反应条件:120℃、66小时)进行加热。恢复至室温,将上清液丢弃,之后用DMF清洗结晶。然后,将结晶浸渍在DMF中一夜。然后,将上清液除去,置换为氯仿后,浸渍一天。在离心分离后除去上清液的工序重复3次。将通过进行离心分离并将上清液除去得到的固体以150℃进行真空干燥,从而作为白色粉末而得到了金属有机结构体1-1。
[实施例1-2]~[实施例1-24]
使用下述表2所示的有机配体和溶剂,以表2所示的反应条件进行反应,除此之外,进行与实施例1-1相同的操作,得到了金属有机结构体1-2~1-24。将其结果示于表2。
[表2]
[实施例2-1]
使有机配体20(0.5mmol)溶解在7mL的DMF中。向其中滴加乙酸锌二水合物(1.27mmol)的8mL的DMF溶液。在室温下搅拌2.5小时,将得到的固体用离心分离进行分离。将上清液除去,并将固体浸渍在20mL的DMF中一夜。之后进行离心分离,将上清液除去,使用氯仿进行置换。将离心分离出的固体浸渍在氯仿20mL中一夜,再次进行离心分离的清洗操作重复3次。然后,将离心分离出的固体在150℃真空干燥5小时,从而作为白色粉末而得到了金属有机结构体2-1。
[实施例2-2]~[实施例2-15]
使用下述表3所示的有机配体和溶剂,以表3所示的反应条件进行反应,除此之外,进行与实施例2-1相同的操作,得到了金属有机结构体2-2~2-15。将其结果示于表3。
[表3]
[实施例3-1]
使有机配体20(1.0mmol)溶解在13mL的DMF中,并向其中添加三乙基胺(0.0038mmol)。向其中滴加乙酸锌二水合物(2.5mmol)的17mL的DMF溶液。在室温下搅拌2.5小时,将得到的固体用离心分离进行分离。将上清液除去,并将固体浸渍在20mL的DMF中一夜。之后进行离心分离,将上清液除去,使用氯仿进行置换。将离心分离出的固体在氯仿20mL中浸渍一夜,再次进行离心分离的清洗操作重复3次。然后,将离心分离出的固体在150℃真空干燥5小时,从而作为白色粉末而得到了金属有机结构体3-1。
[实施例3-2]~[实施例3-12]
使用下述表4所示的有机配体和溶剂,以表4所示的反应条件进行反应,除此之外,进行与实施例3-1相同的操作,得到了金属有机结构体3-2~3-12。将其结果示于表4。
[表4]
[实施例4-1]
在有机配体14(0.3mmol)、硝酸锌六水合物(0.4mmol)中加入10mL的DMF,并搅拌5分钟。向其中滴加三乙基胺(0.0068mmol),并在室温下搅拌5分钟。将其静置20分钟后进行离心分离10分钟,并将上清液除去。在残渣中加入10mL的DMF,再次进行离心分离10分钟,并将上清液除去。在DMF中浸渍一整夜后,进行离心分离10分钟,将上清液除去,之后,加入氯仿10mL。将离心分离出的固体在氯仿20mL中浸渍一夜,再次进行离心分离的清洗操作重复3次。然后,将离心分离出的固体在150℃真空干燥5小时,从而作为淡黄色粉末而得到了金属有机结构体4-1。
[实施例4-2]~[实施例4-20]
使用下述表5所示的有机配体,除此之外,进行与实施例4-1相同的操作,得到了金属有机结构体4-2~4-20。将其结果示于表5。
[表5]
实施例 | 有机配体 | 性状 |
4-1 | 14 | 淡黄色粉末 |
4-2 | 12 | 白色粉末 |
4-3 | 1 | 白色粉末 |
4-4 | 18 | 淡绿色粉末 |
4-5 | 5 | 白色粉末 |
4-6 | 6 | 白色粉末 |
4-7 | 16 | 淡黄色粉末 |
4-8 | 15 | 黄色粉末 |
4-9 | 3 | 白色粉末 |
4-10 | 20 | 白色粉末 |
4-11 | 17 | 白色粉末 |
4-12 | 2 | 白色粉末 |
4-13 | 9 | 淡灰色粉末 |
4-14 | 8 | 白色粉末 |
4-15 | 21 | 绿褐色粉末 |
4-16 | 24 | 浅驼色粉末 |
4-17 | 25 | 无色粉末 |
4-18 | 26 | 无色粉末 |
4-19 | 27 | 无色粉末 |
4-20 | 11 | 无色粉末 |
[实施例5-1]
在有机配体14(0.175mmol)、硝酸锌六水合物(0.352mmol)中加入3.8mL的DMF,用烘箱(反应条件:100℃、161小时)进行加热。恢复至室温,进行离心分离后,将上清液除去。加入10m1的DMF,进行离心分离后,将溶剂除去,并将溶剂换为氯仿。加入氯仿10ml,浸渍一整夜。通过离心分离将氯仿除去,之后以150℃进行真空干燥5小时,作为淡橙色结晶而得到了金属有机结构体5-1。
[实施例5-2]~[实施例5-86]
使用下述表6所示的有机配体和溶剂,以表6所示的反应条件进行反应,除此之外,进行与实施例5-1相同的操作,得到了金属有机结构体5-2~5-86。将其结果示于表6。
[表6]
(续表6)
(续表6)
*1:与实施例5-1相比,以稀释2倍的方式加入DEF。
[实施例6-1]
将有机配体12(0.38mmol)的DMF溶液3mL、1,4-二氮杂双环[2.2.2]辛烷(0.2mmol)的DMF溶液2.5mL缓慢滴加在乙酸锌二水合物(0.38mmol)的2mL的DMF溶液中。在室温下搅拌2.5小时,之后进行离心分离,并将上清液除去。加入DMF浸渍一夜后,将上清液除去,并置换为氯仿,加入氯仿10mL浸渍一天。进行离心分离,将溶剂除去,再次加入氯仿浸渍一夜,进行离心分离后除去上清液的工序重复3次。将通过进行离心分离并将上清液除去得到的固体以150℃进行真空干燥,从而作为无色结晶而得到了金属有机结构体6-1。
[实施例7-1]
在0.152g的有机配体25、硝酸镍六水合物0.233g中加入9mL的THF、水1mL,用烘箱(反应条件:100℃、48小时)进行加热。恢复至室温,进行离心分离后,进行倾析,得到了固体。在该固体中加入DMF,进行离心分离,并进行倾析的操作重复3次,加入DMF,浸渍一整夜。将上清液除去,对该固体加入氯仿,进行离心分离,并进行倾析的操作重复3次,并将溶剂换为氯仿,加入氯仿,浸渍一整夜。将固体进行倾析,并将得到的固体在150℃进行真空干燥5小时,得到了0.178g的金属有机结构体7-1。
[实施例7-2]~[实施例7-17]
使用下述表7所示的有机配体和表7所示的反应条件,除此之外,进行与实施例7-1相同的操作,得到了金属有机结构体7-2~7-17。将其结果示于表7。
[表7]
[实施例8-1]
对于0.114g的有机配体25、氯化锆0.0702g、水0.0625g、乙酸0.5406g和4mL的DMF,一边在室温下施加超声波,一边搅拌5分钟。然后,用烘箱(反应条件:120℃、24小时)进行加热。恢复至室温,进行离心分离后,进行倾析,得到了固体。在该固体中加入DMF,进行离心分离,并进行倾析的操作重复3次。将上清液除去,加入DMF,浸渍一整夜。离心分离后,进行倾析,在得到的固体中加入丙酮,进行离心分离,并进行倾析的操作重复3次。将上清液除去,加入丙酮,浸渍一整夜。进行离心分离并倾析,将得到的固体在150℃进行真空干燥5小时,得到了0.0826g的金属有机结构体8-1。
[实施例8-2]~[实施例8-10]
使用下述表8所示的有机配体,除此之外,进行与实施例8-1相同的操作,得到了金属有机结构体8-2~8-10。将其结果示于表8。
[表8]
实施例 | 有机配体 | 性状 |
8-1 | 25 | 无色粉末 |
8-2 | 26 | 白色粉末 |
8-3 | 14 | 黄色固体 |
8-4 | 18 | 褐色固体 |
8-5 | 3 | 无色粉末 |
8-6 | 16 | 淡黄色固体 |
8-7 | 15 | 淡黄色粉末 |
8-8 | 17 | 浅驼色固体 |
8-9 | 2 | 无色粉末 |
8-10 | 8 | 无色粉末 |
[实施例9-1]
加入0.0759g的有机配体25、硝酸铜三水合物0.0484g、4mL的DMF并进行搅拌,之后进行过滤。然后,用烘箱(反应条件:120℃、24小时)进行加热。恢复至室温,进行离心分离后,进行倾析,得到了固体。在该固体中加入DMF,进行离心分离,并进行倾析的操作重复3次,加入DMF,浸渍一整夜。将上清液除去,将溶剂换为氯仿。加入氯仿,清洗、加压过滤的操作重复3次,加入氯仿,浸渍一整夜。将固体进行加压过滤,将得到的固体在150℃进行真空干燥5小时,得到了0.0670g的金属有机结构体9-1。
[实施例9-2]~[实施例9-32]
使用下述表9所示的有机配体,除此之外,进行与实施例9-1相同的操作,得到了金属有机结构体9-2~9-32。将其结果示于表9。
[表9]
[实施例10-1和10-2]
将0.1839g的有机配体11、乙酸铜一水合物0.0521g、乙酸0.1098g、10mL的DMF加入至小瓶中,进行5分钟超声波处理。然后,用烘箱(反应条件:70℃、7天)进行加热。恢复至室温,得到了浅蓝色和白色的固体。分别以目视分离,在离心分离后进行倾析,分别得到了固体。在各固体中加入DMF,浸渍一整夜。通过进行离心分离并倾析,从而将DMF除去,将溶剂交换为氯仿。对于蓝色固体,重复3次该工序,并将得到的固体在150℃进行真空干燥5小时,得到了0.0538g的金属有机结构体10-1。对于白色的固体,离心分离、加压过滤的操作重复3次后,将得到的固体在150℃进行真空干燥5小时,从而得到了0.0258g的金属有机结构体10-2。
(BET比表面积测定和氢贮藏量测定)
对于得到的金属有机结构体的一部分,测定BET比表面积和77K-大气压下的氢贮藏量。另外,对于金属有机结构体的一部分,测定298K-10MPa下的氢贮藏量。
BET比表面积和77K-大气压下的氢贮藏量的测定使用气体吸附量测定装置Tristar-II(Micromeritics公司制)进行。
BET比表面积按照如下方法算出。将50mg左右的金属有机结构体加入至玻璃比色槽的内部。玻璃比色槽的内部是以135℃的温度减压至真空,并使其干燥6小时。将玻璃比色槽安装于气体吸附量测定装置,并浸渍在装入液氮的恒温槽中。使玻璃比色槽中所含有的氮的压力缓缓增加。直至导入至玻璃比色槽的内部的氮的压力成为1.0×105Pa为止,进行测定。
77K常压下的氢贮藏量按照如下方法算出。在氮的测定后,将气体种类变更为氢而进行测定。使玻璃比色槽中所含有的氢的压力缓缓增加。进行测定,直至导入至玻璃比色槽的内部的氢的压力成为1.0×105Pa为止。
将测得的BET比表面积的结果示于表10。
将测得的77K-大气压下的氢贮藏量示于表11。
[表10]
[表11]
产业上的可利用性
本发明的金属有机结构体能够以实用的水平来贮藏氢气、氮气等气体。其结果,随着氢社会的到来,氢的利用会变得更容易。
Claims (5)
1.一种金属有机结构体,其由式(I)表示的羧酸离子与多价金属离子键合而成,
在式(I)中,
X表示:
无取代或取代的环烷基、
无取代或取代的芳基、
无取代或取代的杂环基、
或-Si(R1)(R2)(R3),
R1~R3各自独立地表示:
氢原子、
无取代或取代的烷基、
或者无取代或取代的芳基,
Y表示:
单键、
亚烷基、
-O-、
-S-、
-S(O)-、
-SO2-、
-N(R4)-、
或者将它们组合而得到的基团,
R4表示:
氢原子、
无取代或取代的烷基、
无取代或取代的环烷基、
无取代或取代的芳烷基、
无取代或取代的芳基、
或者无取代或取代的杂环基,
其中,
作为X-Y-,不包括为苯基、苄氧基、吡唑-1-基、以及式(II)表示的基团且m为3、6、8、9、10、11和12的情况,
2.根据权利要求1所述的金属有机结构体,其中,多价金属离子为选自元素周期表的第2族~第13族的金属中的至少1种金属的离子。
3.根据权利要求1或2所述的金属有机结构体,其中,多价金属离子为选自Zn、Fe、Co、Ni、Cu、Al、Zr和Mg中的至少1种金属的离子。
4.根据权利要求1~3中任一项所述的金属有机结构体,其中,进一步包含除了式(I)所示的有机配体以外的有机配体作为构成成分。
5.一种气体贮藏方法,具有如下工序:使气体与权利要求1~4中任一项所述的金属有机结构体接触,使所述气体吸附在所述金属有机结构体的内部。
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