JP2017048145A - Metal complex as well as adsorbent, occlusion material and separation material comprising the same - Google Patents
Metal complex as well as adsorbent, occlusion material and separation material comprising the same Download PDFInfo
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- JP2017048145A JP2017048145A JP2015172558A JP2015172558A JP2017048145A JP 2017048145 A JP2017048145 A JP 2017048145A JP 2015172558 A JP2015172558 A JP 2015172558A JP 2015172558 A JP2015172558 A JP 2015172558A JP 2017048145 A JP2017048145 A JP 2017048145A
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- Prior art keywords
- metal complex
- acid compound
- group
- acid
- ion
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 114
- 239000000463 material Substances 0.000 title claims description 18
- 239000003463 adsorbent Substances 0.000 title claims description 17
- 238000000926 separation method Methods 0.000 title abstract description 15
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 124
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylene diamine Substances C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000001424 substituent group Chemical group 0.000 claims description 20
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 44
- 239000007789 gas Substances 0.000 description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 33
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 28
- 229910052751 metal Inorganic materials 0.000 description 26
- 239000002184 metal Substances 0.000 description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 14
- 235000019253 formic acid Nutrition 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000013110 organic ligand Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229960004424 carbon dioxide Drugs 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEVGGTGPGPKZHF-UHFFFAOYSA-N Epilaurene Natural products CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 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
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 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
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
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- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
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- YUWKPDBHJFNMAD-UHFFFAOYSA-N 2-fluoroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(F)=C1 YUWKPDBHJFNMAD-UHFFFAOYSA-N 0.000 description 1
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
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- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
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- 230000023556 desulfurization Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- ZRKSVHFXTRFQFL-UHFFFAOYSA-N isocyanomethane Chemical compound C[N+]#[C-] ZRKSVHFXTRFQFL-UHFFFAOYSA-N 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
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- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- 229910052754 neon Inorganic materials 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
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- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 150000003681 vanadium Chemical class 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
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Abstract
Description
本発明は、金属錯体、並びにそれからなる吸着材、吸蔵材および分離材に関する。 The present invention relates to a metal complex, and an adsorbent, occlusion material and separation material comprising the same.
これまで、種々の吸着材が開発されている。活性炭はその代表例であり、活性炭の優れた吸着性能を利用して、空気浄化、脱硫、脱硝、有害物質除去など各種工業において広く使用されている。近年は半導体製造プロセスなどへ窒素の需要が増大しており、かかる窒素を製造する方法として、分子ふるい炭を使用して圧力スイング吸着法や温度スイング吸着法により空気から窒素を製造する方法が使用されている。また、分子ふるい炭は、メタノール分解ガスからの水素精製など各種ガス分離精製にも応用されている。 Various adsorbents have been developed so far. Activated carbon is a representative example, and is widely used in various industries such as air purification, desulfurization, denitration, and removal of harmful substances by utilizing the excellent adsorption performance of activated carbon. In recent years, the demand for nitrogen has increased for semiconductor manufacturing processes, etc., and as a method for producing such nitrogen, a method of producing nitrogen from air by pressure swing adsorption method or temperature swing adsorption method using molecular sieve charcoal is used. Has been. Molecular sieve charcoal is also applied to various gas separation and purification such as hydrogen purification from methanol cracked gas.
圧力スイング吸着法や温度スイング吸着法により混合ガスを分離する際には、一般に、分離吸着材として分子ふるい炭やゼオライトなどを使用し、その平衡吸着量または吸着速度の差により分離を行っている。しかしながら、平衡吸着量の差によって混合ガスを分離する場合、これまでの吸着材では除去したいガスのみを選択的に吸着することができないため分離係数が小さくなり、装置の大型化は不可避であった。また、吸着速度の差によって混合ガスを分離する場合、ガスの種類によっては除去したいガスのみを吸着できるが、吸着と脱着を交互に行う必要があり、この場合も装置は依然として大型にならざるを得なかった。 When separating mixed gas by pressure swing adsorption method or temperature swing adsorption method, generally, molecular sieve charcoal or zeolite is used as the separation adsorbent, and separation is performed by the difference in the equilibrium adsorption amount or adsorption rate. . However, when separating the mixed gas based on the difference in the amount of equilibrium adsorption, the conventional adsorbents cannot selectively adsorb only the gas to be removed, so the separation factor becomes small, and the size of the apparatus is inevitable. . In addition, when separating the mixed gas based on the difference in adsorption speed, only the gas to be removed can be adsorbed depending on the type of gas, but it is necessary to perform adsorption and desorption alternately, and in this case, the apparatus still has to be large. I didn't get it.
一方、より優れた吸着性能を与える吸着材として、高分子金属錯体が開発されている。高分子金属錯体は、（１）広い表面積と高い空隙率、（２）高い設計性、といった特徴を有しており、既存の吸着材にはない吸着特性が期待される。 On the other hand, polymer metal complexes have been developed as adsorbents that give better adsorption performance. The polymer metal complex has characteristics such as (1) a large surface area and high porosity, and (2) high designability, and is expected to have adsorption characteristics that are not found in existing adsorbents.
例えば、ギ酸などの有機酸を触媒として添加することを特徴とする、中心金属と、カルボキシレート基を有する有機配位子と、該中心金属に二座配位可能な架橋配位子とからなる金属錯体の製造方法が開示されている（特許文献１参照）。しかし、特許文献１に記載の方法において有機酸は触媒として用いられ、有機酸を構成要素として含む金属錯体は記載されていない。 For example, comprising a central metal, an organic ligand having a carboxylate group, and a bridging ligand capable of bidentate coordination with the central metal, wherein an organic acid such as formic acid is added as a catalyst A method for producing a metal complex is disclosed (see Patent Document 1). However, in the method described in Patent Document 1, an organic acid is used as a catalyst, and a metal complex containing an organic acid as a constituent element is not described.
高分子金属錯体を用いたガス吸着材、分離材等の実用化に際しては、吸着容量と吸着選択性の向上が求められている。 In the practical application of gas adsorbents and separators using polymer metal complexes, improvements in adsorption capacity and adsorption selectivity are required.
本発明の目的は、従来よりも吸着容量と吸着選択性に優れるガス吸着材、ガス吸蔵材或いはガス分離材として使用できる金属錯体を提供することにある。 An object of the present invention is to provide a metal complex that can be used as a gas adsorbent, gas occlusion material, or gas separation material, which is superior in adsorption capacity and adsorption selectivity than conventional ones.
本発明は以下の通りである。
項１．２価の金属イオンと、置換基を有してもよい多価カルボン酸化合物と、置換基を有してもよいトリエチレンジアミン化合物と、炭素数１または２のモノカルボン酸化合物を含有する多孔質の金属錯体であって、
該金属錯体を構成する前記多価カルボン酸化合物と炭素数１または２の前記モノカルボン酸化合物との組成比が多価カルボン酸化合物：炭素数１または２の前記モノカルボン酸化合物＝１：１〜３，０００：１、かつ、比表面積が３５０ｍ２／ｇ以上であることを特徴とする金属錯体。
項２．該金属イオンが２価の亜鉛イオンまたは銅イオンであることを特徴とする項１に記載の金属錯体。
項３．該多価カルボン酸化合物が不飽和ジカルボン酸化合物であることを特徴とする項１または２に記載の金属錯体。
項４．多価カルボン酸化合物が、テレフタル酸または２−ニトロテレフタル酸であることを特徴とする項１〜３のいずれか一項に記載された金属錯体。
項５．項１〜４のいずれか一項に記載された金属錯体を含むことを特徴とする吸着材。
項６．項１〜４のいずれか一項に記載された金属錯体を含むことを特徴とする吸蔵材。
項７．項１〜４のいずれか一項に記載された金属錯体を含むことを特徴とする分離材。
The present invention is as follows.
Item 1.2 A valent metal ion, a polyvalent carboxylic acid compound that may have a substituent, a triethylenediamine compound that may have a substituent, and a monocarboxylic acid compound having 1 or 2 carbon atoms A porous metal complex,
The composition ratio of the polyvalent carboxylic acid compound constituting the metal complex to the monocarboxylic acid compound having 1 or 2 carbon atoms is a polyvalent carboxylic acid compound: the monocarboxylic acid compound having 1 or 2 carbon atoms = 1: 1. A metal complex having a specific surface area of 350 m 2 / g or more and ˜3,000: 1.
Item 2. Item 2. The metal complex according to Item 1, wherein the metal ion is a divalent zinc ion or a copper ion.
Item 3. Item 3. The metal complex according to Item 1 or 2, wherein the polyvalent carboxylic acid compound is an unsaturated dicarboxylic acid compound.
Item 4. Item 4. The metal complex according to any one of Items 1 to 3, wherein the polyvalent carboxylic acid compound is terephthalic acid or 2-nitroterephthalic acid.
Item 5. Item 5. An adsorbent comprising the metal complex according to any one of Items 1 to 4.
Item 6. Item 5. An occlusion material comprising the metal complex according to any one of Items 1 to 4.
Item 7. Item 5. A separation material comprising the metal complex according to any one of Items 1 to 4.
本発明により、２価の金属イオンと、置換基を有してもよい多価カルボン酸化合物と、置換基を有してもよいトリエチレンジアミン化合物と、炭素数１または２のモノカルボン酸化合物とを含有し、多価カルボン酸化合物と炭素数１または２のモノカルボン酸化合物との組成比が多価カルボン酸化合物：炭素数１または２のモノカルボン酸化合物＝１：１〜３，０００：１の範囲内にあり、かつ、比表面積が３５０ｍ２／ｇ以上である多孔質の金属錯体を提供することができる。本発明の金属錯体は、様々なガスの組み合わせから、特定のガスのみを高選択に吸着する。 According to the present invention, a divalent metal ion, a polyvalent carboxylic acid compound that may have a substituent, a triethylenediamine compound that may have a substituent, a monocarboxylic acid compound having 1 or 2 carbon atoms, The composition ratio of the polyvalent carboxylic acid compound and the monocarboxylic acid compound having 1 or 2 carbon atoms is polyvalent carboxylic acid compound: monocarboxylic acid compound having 1 or 2 carbon atoms = 1: 1 to 3,000: 1 and a porous metal complex having a specific surface area of 350 m 2 / g or more can be provided. The metal complex of the present invention adsorbs only a specific gas with high selectivity from various gas combinations.
本発明の金属錯体は、各種ガスの吸着性能に優れているので、炭素数１〜４の炭化水素、二酸化炭素、水素、一酸化炭素、酸素、窒素、希ガス、硫化水素、アンモニア、硫黄酸化物、窒素酸化物、シロキサン、水蒸気または有機蒸気などのガスを吸着するための吸着材として使用することができる。 Since the metal complex of the present invention is excellent in the adsorption performance of various gases, it is a hydrocarbon having 1 to 4 carbon atoms, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, rare gas, hydrogen sulfide, ammonia, sulfur oxidation. It can be used as an adsorbent for adsorbing gases such as substances, nitrogen oxides, siloxane, water vapor or organic vapor.
また、本発明の金属錯体は、各種ガスの吸蔵性能に優れているので、炭素数１〜４の炭化水素、二酸化炭素、水素、一酸化炭素、酸素、窒素、希ガス、硫化水素、アンモニア、水蒸気または有機蒸気などのガスを吸蔵するための吸蔵材としても使用することができる。 Moreover, since the metal complex of the present invention is excellent in the occlusion performance of various gases, it is a hydrocarbon having 1 to 4 carbon atoms, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, rare gas, hydrogen sulfide, ammonia, It can also be used as a storage material for storing gas such as water vapor or organic vapor.
さらに、本発明の金属錯体は、各種ガスの分離性能に優れているので、炭素数１〜４の炭化水素、二酸化炭素、水素、一酸化炭素、酸素、窒素、希ガス、硫化水素、アンモニア、硫黄酸化物、窒素酸化物、シロキサン、水蒸気または有機蒸気などのガスを分離するための分離材としても使用することができる。 Furthermore, since the metal complex of the present invention is excellent in the separation performance of various gases, it is a hydrocarbon having 1 to 4 carbon atoms, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, rare gas, hydrogen sulfide, ammonia, It can also be used as a separating material for separating gases such as sulfur oxide, nitrogen oxide, siloxane, water vapor or organic vapor.
本発明の金属錯体は、２価の金属イオンと、置換基を有してもよい多価カルボン酸化合物と、置換基を有してもよいトリエチレンジアミン化合物と、炭素数１または２のモノカルボン酸化合物とを含む。 The metal complex of the present invention includes a divalent metal ion, a polyvalent carboxylic acid compound that may have a substituent, a triethylenediamine compound that may have a substituent, and a monocarboxylic acid having 1 or 2 carbon atoms. Acid compound.
２価の金属イオンとしては、例えば、マグネシウムイオン、カルシウムイオン、スカンジウムイオン、ランタノイドイオン（ランタンイオン、テルビウムイオン、ルテチウムイオンなど）、アクチノイドイオン（アクチニウムイオン、ローレンシウムイオンなど）、ジルコニウムイオン、バナジウムイオン、クロムイオン、モリブデンイオン、マンガンイオン、鉄イオン、コバルトイオン、ニッケルイオン、銅イオン、亜鉛イオン、カドミウムイオン、アルミニウムイオンなどが挙げられ、中でもマンガンイオン、コバルトイオン、ニッケルイオン、銅イオンおよび亜鉛イオンが好ましく、銅イオンがより好ましい。金属イオンは、単一の金属イオンを使用することが好ましいが、２種類以上の金属イオンを混合して用いてもよい。また、本発明の金属錯体は、単一の金属イオンからなる金属錯体を２種以上混合したものでもよい。 Examples of the divalent metal ion include magnesium ion, calcium ion, scandium ion, lanthanoid ion (such as lanthanum ion, terbium ion, and lutetium ion), actinoid ion (such as actinium ion and lauren ion), zirconium ion, vanadium ion, Examples include chromium ion, molybdenum ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, cadmium ion, aluminum ion, etc., among which manganese ion, cobalt ion, nickel ion, copper ion and zinc ion Preferably, copper ion is more preferable. The metal ion is preferably a single metal ion, but two or more kinds of metal ions may be mixed and used. The metal complex of the present invention may be a mixture of two or more metal complexes composed of a single metal ion.
該金属イオンは金属塩の形で用いてもよい。金属塩としては、例えば、マグネシウム塩、カルシウム塩、スカンジウム塩、ランタノイド塩（ランタン塩、テルビウム塩、ルテチウム塩など）、アクチノイド塩（アクチニウム塩、ローレンシウム塩など）、ジルコニウム塩、バナジウム塩、クロム塩、モリブデン塩、マンガン塩、鉄塩、コバルト塩、ニッケル塩、銅塩、亜鉛塩、カドミウム塩、アルミニウム塩などを使用することができ、中でもマンガン塩、コバルト塩、ニッケル塩、銅塩および亜鉛塩が好ましく、銅塩がより好ましい。金属塩は、単一の金属塩を使用することが好ましいが、２種以上の金属塩を混合して用いてもよい。また、これらの金属塩としては、酢酸塩、ギ酸塩などの有機酸塩、硫酸塩、硝酸塩、塩酸塩、臭化水素酸塩、炭酸塩などの無機酸塩を使用することができる。 The metal ion may be used in the form of a metal salt. Examples of metal salts include magnesium salts, calcium salts, scandium salts, lanthanoid salts (such as lanthanum salts, terbium salts, and lutetium salts), actinoid salts (such as actinium salts and lauren salts), zirconium salts, vanadium salts, chromium salts, Molybdenum salt, manganese salt, iron salt, cobalt salt, nickel salt, copper salt, zinc salt, cadmium salt, aluminum salt etc. can be used, among which manganese salt, cobalt salt, nickel salt, copper salt and zinc salt are Preferably, a copper salt is more preferable. The metal salt is preferably a single metal salt, but two or more metal salts may be mixed and used. Further, as these metal salts, organic acid salts such as acetates and formates, inorganic acid salts such as sulfates, nitrates, hydrochlorides, hydrobromides and carbonates can be used.
本発明に用いられる多価カルボン酸化合物としては、特に限定されるものではないが、ジカルボン酸化合物、トリカルボン酸化合物、テトラカルボン酸化合物などが挙げられる。ジカルボン酸化合物としては、例えば、コハク酸、１，４−シクロヘキサンジカルボン酸、フマル酸、ムコン酸、２，３−ピラジンジカルボン酸、イソフタル酸、テレフタル酸、１，４−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、４，４’−ビフェニルジカルボン酸、２，５−ピリジンジカルボン酸、３，５−ピリジンジカルボン酸、２，５−チオフェンジカルボン酸、２，２’−ジチオフェンジカルボン酸などが挙げられる。トリカルボン酸化合物としては、例えば、トリメシン酸、トリメリット酸、ビフェニル−３，４’，５−トリカルボン酸、１，３，５−トリス（４−カルボキシフェニル）ベンゼン、１，３，５−トリス（４’−カルボキシ［１，１’−ビフェニル］−４−イル）ベンゼンなどが挙げられる。テトラカルボン酸化合物としては、例えば、ピロメリット酸、［１，１’：４’，１’’］ターフェニル−３，３’’，５，５’’−テトラカルボン酸、１，２，４，５−テトラキス（４−カルボキシフェニル）ベンゼンなどが挙げられる。これらの中でもジカルボン酸化合物が好ましく、不飽和ジカルボン酸化合物（例えば、フマル酸、２，３−ピラジンジカルボン酸、イソフタル酸、テレフタル酸、１，４−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、９，１０−アントラセンジカルボン酸、４，４’−ビフェニルジカルボン酸、４，４’−スチルベンジカルボン酸、２，５−ピリジンジカルボン酸、３，５−ピリジンジカルボン酸、２，５−チオフェンジカルボン酸、２，２’−ジチオフェンジカルボン酸など。）がより好ましい。多価カルボン酸化合物は、単独で用いてもよく、２種以上の多価カルボン酸化合物を混合して用いてもよい。また、本発明の金属錯体は、単一の多価カルボン酸化合物からなる金属錯体を２種以上混合したものでもよい。 Although it does not specifically limit as a polyvalent carboxylic acid compound used for this invention, A dicarboxylic acid compound, a tricarboxylic acid compound, a tetracarboxylic acid compound, etc. are mentioned. Examples of the dicarboxylic acid compound include succinic acid, 1,4-cyclohexanedicarboxylic acid, fumaric acid, muconic acid, 2,3-pyrazinedicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,5-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,2 ' -Dithiophene dicarboxylic acid etc. are mentioned. Examples of the tricarboxylic acid compound include trimesic acid, trimellitic acid, biphenyl-3,4 ', 5-tricarboxylic acid, 1,3,5-tris (4-carboxyphenyl) benzene, 1,3,5-tris ( 4'-carboxy [1,1'-biphenyl] -4-yl) benzene and the like. Examples of the tetracarboxylic acid compound include pyromellitic acid, [1,1 ′: 4 ′, 1 ″] terphenyl-3,3 ″, 5,5 ″ -tetracarboxylic acid, 1,2,4. , 5-tetrakis (4-carboxyphenyl) benzene and the like. Among these, dicarboxylic acid compounds are preferable, and unsaturated dicarboxylic acid compounds (for example, fumaric acid, 2,3-pyrazine dicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 9,10-anthracene dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 4,4′-stilbene dicarboxylic acid, 2,5-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,5-thiophene dicarboxylic acid, 2,2′-dithiophene dicarboxylic acid, etc.) are more preferred. The polyvalent carboxylic acid compound may be used alone, or two or more polyvalent carboxylic acid compounds may be mixed and used. The metal complex of the present invention may be a mixture of two or more metal complexes composed of a single polyvalent carboxylic acid compound.
本発明に用いられる多価カルボン酸化合物は置換基を有していてもよい。置換基としては、特に限定されないが、例えばアルキル基（メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基などの直鎖または分岐を有する炭素数１〜５のアルキル基）、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）、アルコキシ基（メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基，ｎ−ブトキシ基、イソブトキシ基、ｔｅｒｔ−ブトキシ基など）、アミノ基、モノアルキルアミノ基（メチルアミノ基など）、ジアルキルアミノ基（ジメチルアミノ基など）、ホルミル基、エポキシ基、アシロキシ基（アセトキシ基、ｎ−プロパノイルオキシ基、ｎ−ブタノイルオキシ基、ピバロイルオキシ基、ベンゾイルオキシ基など）、アルコキシカルボニル基（メトキシカルボニル基、エトキシカルボニル基、ｎ−ブトキシカルボニル基など）、ニトロ基、シアノ基、水酸基、アセチル基、トリフルオロメチル基などが挙げられる。具体的には、多価カルボン酸化合物としては、無置換のテレフタル酸に加え、２−ニトロテレフタル酸、２−フルオロテレフタル酸、１，２，３，４−テトラフルオロテレフタル酸、２，４，６−トリフルオロ−１，３，５−ベンゼントリカルボン酸などが挙げられる。 The polyvalent carboxylic acid compound used in the present invention may have a substituent. Although it does not specifically limit as a substituent, For example, linear or branched, such as an alkyl group (Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, etc.). Having a C1-C5 alkyl group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, Isobutoxy group, tert-butoxy group, etc.), amino group, monoalkylamino group (methylamino group etc.), dialkylamino group (dimethylamino group etc.), formyl group, epoxy group, acyloxy group (acetoxy group, n-propanoyl) Oxy group, n-butanoyloxy group, pivaloyloxy group, benzoyloxy group, etc.), alcohol Aryloxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc. n- butoxycarbonyl group), a nitro group, a cyano group, a hydroxyl group, an acetyl group, and a trifluoromethyl group. Specifically, as the polyvalent carboxylic acid compound, in addition to unsubstituted terephthalic acid, 2-nitroterephthalic acid, 2-fluoroterephthalic acid, 1,2,3,4-tetrafluoroterephthalic acid, 2,4,4 Examples include 6-trifluoro-1,3,5-benzenetricarboxylic acid.
置換基を有してもよい多価カルボン酸化合物は、単独で用いてもよく、２種以上の置換基を有してもよい多価カルボン酸化合物を混合して用いてもよい。また、本発明の金属錯体は、単一の置換基を有してもよい多価カルボン酸化合物からなる金属錯体を２種以上混合したものでもよい。 The polyvalent carboxylic acid compound which may have a substituent may be used alone, or a polyvalent carboxylic acid compound which may have two or more substituents may be mixed and used. In addition, the metal complex of the present invention may be a mixture of two or more metal complexes composed of a polyvalent carboxylic acid compound which may have a single substituent.
多価カルボン酸化合物は、酸無水物やアルカリ金属塩の形で用いてもよい。 The polyvalent carboxylic acid compound may be used in the form of an acid anhydride or an alkali metal salt.
本発明に用いられるトリエチレンジアミン化合物は置換基を有していてもよい。置換基としては、特に限定されないが、例えばアルキル基（メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基などの直鎖または分岐を有する炭素数１〜５のアルキル基）、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）、アルコキシ基（メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基，ｎ−ブトキシ基、イソブトキシ基、ｔｅｒｔ−ブトキシ基など）、アミノ基、モノアルキルアミノ基（メチルアミノ基など）、ジアルキルアミノ基（ジメチルアミノ基など）、ホルミル基、エポキシ基、アシロキシ基（アセトキシ基、ｎ−プロパノイルオキシ基、ｎ−ブタノイルオキシ基、ピバロイルオキシ基、ベンゾイルオキシ基など）、アルコキシカルボニル基（メトキシカルボニル基、エトキシカルボニル基、ｎ−ブトキシカルボニル基など）、ニトロ基、シアノ基、水酸基、アセチル基、トリフルオロメチル基などが挙げられる。置換基を有してもよいトリエチレンジアミン化合物は、単独で用いてもよく、２種以上の置換基を有してもよいトリエチレンジアミン化合物を混合して用いてもよい。また、本発明の金属錯体は、単一の置換基を有してもよいトリエチレンジアミンからなる金属錯体を２種以上混合したものでもよい。 The triethylenediamine compound used in the present invention may have a substituent. Although it does not specifically limit as a substituent, For example, linear or branched, such as an alkyl group (Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, etc.). Having a C1-C5 alkyl group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, Isobutoxy group, tert-butoxy group, etc.), amino group, monoalkylamino group (methylamino group etc.), dialkylamino group (dimethylamino group etc.), formyl group, epoxy group, acyloxy group (acetoxy group, n-propanoyl) Oxy group, n-butanoyloxy group, pivaloyloxy group, benzoyloxy group, etc.), alcohol Aryloxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc. n- butoxycarbonyl group), a nitro group, a cyano group, a hydroxyl group, an acetyl group, and a trifluoromethyl group. The triethylenediamine compound which may have a substituent may be used alone, or a mixture of triethylenediamine compounds which may have two or more substituents may be used. The metal complex of the present invention may be a mixture of two or more metal complexes composed of triethylenediamine which may have a single substituent.
本発明に用いられる炭素数１または２のモノカルボン酸化合物としては、例えば、ギ酸、酢酸、トリフルオロ酢酸などを使用することができ、中でもギ酸または酢酸が好ましく、酢酸が特に好ましい。モノカルボン酸化合物は、単独で用いてもよく、２種以上のモノカルボン酸化合物を混合して用いてもよい。また、本発明の金属錯体は、単一のモノカルボン酸化合物からなる金属錯体を２種以上混合したものでもよい。 As the monocarboxylic acid compound having 1 or 2 carbon atoms used in the present invention, for example, formic acid, acetic acid, trifluoroacetic acid and the like can be used. Among them, formic acid or acetic acid is preferable, and acetic acid is particularly preferable. A monocarboxylic acid compound may be used independently and may mix and use 2 or more types of monocarboxylic acid compounds. The metal complex of the present invention may be a mixture of two or more metal complexes composed of a single monocarboxylic acid compound.
該モノカルボン酸化合物は、金属錯体製造時において酸無水物やアルカリ金属塩の形で用いてもよい。また、原料金属塩のカウンターアニオンとして用いることによっても、本発明の金属錯体構成中にモノカルボン酸化合物を含ませることができる。例えば、金属イオンとして銅イオン、モノカルボン酸化合物として酢酸を用いる場合、原料金属塩として酢酸銅を用いてもよい。該モノカルボン酸化合物は、反応初期から共存させても、反応後期（例えば、モノカルボン酸化合物以外の成分を反応させた後）に添加してもよい。 The monocarboxylic acid compound may be used in the form of an acid anhydride or an alkali metal salt during the production of the metal complex. Moreover, a monocarboxylic acid compound can also be included in the metal complex structure of this invention also by using as a counter anion of a raw material metal salt. For example, when copper ion is used as the metal ion and acetic acid is used as the monocarboxylic acid compound, copper acetate may be used as the raw metal salt. The monocarboxylic acid compound may coexist from the beginning of the reaction or may be added in the late stage of the reaction (for example, after reacting components other than the monocarboxylic acid compound).
本発明の金属錯体を構成する多価カルボン酸化合物と炭素数１または２のモノカルボン酸化合物との組成比は、多価カルボン酸化合物：炭素数１または２のモノカルボン酸化合物＝１：１〜３，０００：１の範囲内であり、３：１〜２，５００：１の範囲内であると好ましい。金属錯体中の多価カルボン酸とモノカルボン酸の比率がこのような範囲にあると、高い吸着量と高い吸着選択性が得られる。 The composition ratio between the polycarboxylic acid compound constituting the metal complex of the present invention and the monocarboxylic acid compound having 1 or 2 carbon atoms is as follows: polycarboxylic acid compound: monocarboxylic acid compound having 1 or 2 carbon atoms = 1: 1 It is in the range of ˜3,000: 1 and is preferably in the range of 3: 1 to 2,500: 1. When the ratio between the polyvalent carboxylic acid and the monocarboxylic acid in the metal complex is in such a range, a high adsorption amount and a high adsorption selectivity can be obtained.
本発明の金属錯体を構成する多価カルボン酸化合物と炭素数１または２のモノカルボン酸化合物の組成比は、金属錯体を分解して均一な溶液とした後に、ガスクロマトグラフィー、高速液体クロマトグラフィーまたはＮＭＲなどを用いて分析することで決定することができるが、これらに限定されるものではない。
また、本発明の金属錯体の比表面積が３５０ｍ２／ｇ以上である。比表面積が３５０ｍ２／ｇ以上であることにより、高い吸着量が得られる。
The composition ratio of the polyvalent carboxylic acid compound constituting the metal complex of the present invention to the monocarboxylic acid compound having 1 or 2 carbon atoms is determined by gas chromatography or high performance liquid chromatography after the metal complex is decomposed to obtain a uniform solution. Alternatively, it can be determined by analysis using NMR or the like, but is not limited thereto.
Moreover, the specific surface area of the metal complex of this invention is 350 m < 2 > / g or more. A high adsorption amount can be obtained when the specific surface area is 350 m 2 / g or more.
本発明の金属錯体は、本発明の効果を損なわない範囲で、さらに単座有機配位子を含んでいてもよい。単座有機配位子とは、非共有電子対で金属イオンに対して配位する部位を１箇所持つ中性配位子を意味する。単座有機配位子としては、例えば、置換または無置換の、フラン、チオフェン、ピリジン、キノリン、イソキノリン、アクリジン、トリメチルホスフィン、トリフェニルホスフィン、トリフェニルホスファイト、メチルイソシアニドなどを使用することができ、中でもピリジンが好ましい。単座有機配位子は炭素数１〜２３の炭化水素基を置換基として有してもよい。 The metal complex of the present invention may further contain a monodentate organic ligand as long as the effects of the present invention are not impaired. The monodentate organic ligand means a neutral ligand having one site coordinated to a metal ion by an unshared electron pair. As the monodentate organic ligand, for example, substituted or unsubstituted furan, thiophene, pyridine, quinoline, isoquinoline, acridine, trimethylphosphine, triphenylphosphine, triphenylphosphite, methylisocyanide, etc. can be used. Of these, pyridine is preferred. The monodentate organic ligand may have a hydrocarbon group having 1 to 23 carbon atoms as a substituent.
本発明の金属錯体が前記単座有機配位子を含む場合、その割合は本発明の効果を損なわない限り特に限定されるものではない。例えば、置換基を有してもよいトリエチレンジアミン化合物と単座有機配位子との組成比は、１：５〜１：１，０００のモル比の範囲内が好ましく、１：１０〜１：１００の範囲内であることがより好ましい。当該組成比は、ガスクロマトグラフィー、高速液体クロマトグラフィーまたはＮＭＲなどを用いて分析することで決定することができるが、これらに限定されるものではない。 When the metal complex of this invention contains the said monodentate organic ligand, the ratio will not be specifically limited unless the effect of this invention is impaired. For example, the composition ratio of the triethylenediamine compound which may have a substituent and the monodentate organic ligand is preferably in the range of a molar ratio of 1: 5 to 1: 1,000, and 1:10 to 1: 100. It is more preferable to be within the range. The composition ratio can be determined by analysis using gas chromatography, high performance liquid chromatography, NMR, or the like, but is not limited thereto.
本発明の金属錯体は、２価の金属イオンと、多価カルボン酸化合物と、トリエチレンジアミン化合物と、炭素数１または２のモノカルボン酸化合物と、必要に応じて単座有機配位子とを、気相、液相または固相のいずれかで反応させることで製造することができる。本発明の金属錯体は、常圧下、溶媒中で数時間から数日間反応させ、析出させて製造することが好ましい。このとき、超音波またはマイクロウェーブ照射下で反応を行ってもよい。例えば、金属塩の水溶液または有機溶媒溶液と、多価カルボン酸化合物と、トリエチレンジアミン化合物を含有する水溶液または有機溶媒溶液とを、常圧下で混合して反応させることにより本発明の金属錯体を得ることができる。 The metal complex of the present invention comprises a divalent metal ion, a polyvalent carboxylic acid compound, a triethylenediamine compound, a monocarboxylic acid compound having 1 or 2 carbon atoms, and a monodentate organic ligand as necessary. It can be produced by reacting in either the gas phase, liquid phase or solid phase. The metal complex of the present invention is preferably produced by reacting and precipitating for several hours to several days in a solvent under normal pressure. At this time, the reaction may be performed under ultrasonic wave or microwave irradiation. For example, an aqueous solution or organic solvent solution of a metal salt, a polyvalent carboxylic acid compound, and an aqueous solution or organic solvent solution containing a triethylenediamine compound are mixed and reacted under normal pressure to obtain the metal complex of the present invention. be able to.
金属錯体を製造するときの金属塩と多価カルボン酸化合物の混合比率は、金属塩：多価カルボン酸化合物＝１：５〜８：１のモル比の範囲内が好ましく、１：３〜６：１のモル比の範囲内がより好ましい。 The mixing ratio of the metal salt and the polyvalent carboxylic acid compound when producing the metal complex is preferably in the range of a molar ratio of metal salt: polyvalent carboxylic acid compound = 1: 5 to 8: 1, and 1: 3 to 6 A molar ratio in the range of 1 is more preferable.
金属錯体を製造するときの金属塩とトリエチレンジアミン化合物の混合比率は、金属塩：トリエチレンジアミン化合物＝１：３〜３：１のモル比の範囲内が好ましく、１：２〜２：１のモル比の範囲内がより好ましい。この範囲で反応を行うと、目的とする金属錯体が高い収率で得られ、未反応の金属塩の残留が少なく、得られた金属錯体の精製が容易である。 The mixing ratio of the metal salt and the triethylenediamine compound when producing the metal complex is preferably within the range of a molar ratio of metal salt: triethylenediamine compound = 1: 3 to 3: 1, and a mole ratio of 1: 2 to 2: 1. A ratio within the range is more preferable. When the reaction is carried out in this range, the target metal complex is obtained in a high yield, there is little residual unreacted metal salt, and the resulting metal complex can be easily purified.
金属錯体を製造するときの多価カルボン酸化合物と炭素数１または２のモノカルボン酸化合物の混合比率は、多価カルボン酸化合物：モノカルボン酸化合物＝１：１，０００〜５，０００：１のモル比の範囲内が好ましく、１：１００〜１，０００：１のモル比の範囲内がより好ましい。この範囲で反応を行うと、目的とする金属錯体が高い収率で得られ、未反応の金属塩の残留が少なく、得られた金属錯体の精製が容易である。 The mixing ratio of the polyvalent carboxylic acid compound and the monocarboxylic acid compound having 1 or 2 carbon atoms when producing the metal complex is as follows: polyvalent carboxylic acid compound: monocarboxylic acid compound = 1: 1,000 to 5,000: 1 Is preferably within the range of the molar ratio of 1: 100 to 1,000: 1. When the reaction is carried out in this range, the target metal complex is obtained in a high yield, there is little residual unreacted metal salt, and the resulting metal complex can be easily purified.
本発明の金属錯体は、用いる炭素数１または２のモノカルボン酸化合物の種類および使用量により、粒径や粒形を制御することができる。 In the metal complex of the present invention, the particle size and particle shape can be controlled by the type and amount of the monocarboxylic acid compound having 1 or 2 carbon atoms used.
金属錯体を製造するための混合溶液における多価カルボン酸化合物のモル濃度は、０．０１〜５．０ｍｏｌ／Ｌが好ましく、０．０５〜２．０ｍｏｌ／Ｌがより好ましい。この濃度範囲で反応を行うと、目的とする金属錯体が高い収率で得られ、溶解性が良好で、反応が円滑に進行する。 The molar concentration of the polyvalent carboxylic acid compound in the mixed solution for producing the metal complex is preferably 0.01 to 5.0 mol / L, more preferably 0.05 to 2.0 mol / L. When the reaction is carried out in this concentration range, the target metal complex is obtained in a high yield, the solubility is good, and the reaction proceeds smoothly.
金属錯体を製造するための混合溶液における金属塩のモル濃度は、０．０１〜５．０ｍｏｌ／Ｌが好ましく、０．０５〜２．０ｍｏｌ／Ｌがより好ましい。この濃度範囲で反応を行うと、目的とする金属錯体が高い収率で得られ、未反応の金属塩の残留が少なく、得られた金属錯体の精製が容易である。 The molar concentration of the metal salt in the mixed solution for producing the metal complex is preferably 0.01 to 5.0 mol / L, more preferably 0.05 to 2.0 mol / L. When the reaction is carried out in this concentration range, the target metal complex is obtained in a high yield, there is little residual unreacted metal salt, and the resulting metal complex can be easily purified.
金属錯体を製造するための混合溶液におけるトリエチレンジアミン化合物のモル濃度は、０．００５〜２．５ｍｏｌ／Ｌが好ましく、０．０２５〜１．０ｍｏｌ／Ｌがより好ましい。この濃度範囲で反応を行うと、目的とする金属錯体が高い収率で得られ、溶解性が良好で、反応が円滑に進行する。 The molar concentration of the triethylenediamine compound in the mixed solution for producing the metal complex is preferably 0.005 to 2.5 mol / L, and more preferably 0.025 to 1.0 mol / L. When the reaction is carried out in this concentration range, the target metal complex is obtained in a high yield, the solubility is good, and the reaction proceeds smoothly.
金属錯体の製造に用いる溶媒としては、有機溶媒、水またはそれらの混合溶媒を使用することができる。具体的には、メタノール、エタノール、プロパノール、ジエチルエーテル、ブタノール、ジメトキシエタン、テトラヒドロフラン、ヘキサン、シクロヘキサン、ヘプタン、ベンゼン、トルエン、塩化メチレン、クロロホルム、アセトン、酢酸エチル、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、水またはこれらの混合溶媒を使用することができる。 As a solvent used for producing the metal complex, an organic solvent, water, or a mixed solvent thereof can be used. Specifically, methanol, ethanol, propanol, diethyl ether, butanol, dimethoxyethane, tetrahydrofuran, hexane, cyclohexane, heptane, benzene, toluene, methylene chloride, chloroform, acetone, ethyl acetate, acetonitrile, N, N-dimethylformamide, Water or a mixed solvent thereof can be used.
反応温度としては、使用する溶媒に応じて適宜に選択すればよいが、２５３〜４６３Ｋが好ましく、２９８〜４２３Ｋがより好ましい。 The reaction temperature may be appropriately selected according to the solvent to be used, but is preferably from 253 to 463K, more preferably from 298 to 423K.
反応が終了したことは吸光光度法、ガスクロマトグラフィーまたは高速液体クロマトグラフィーなどにより原料の残存量を定量することにより確認することができるが、これらに限定されるものではない。反応終了後、得られた混合液を吸引濾過に付して沈殿物を集め、有機溶媒による洗浄後、３７３Ｋ程度で数時間真空乾燥することにより、本発明の金属錯体を得ることができる。 The completion of the reaction can be confirmed by quantifying the remaining amount of the raw material by absorptiometry, gas chromatography, high performance liquid chromatography or the like, but is not limited thereto. After completion of the reaction, the obtained mixed solution is subjected to suction filtration to collect a precipitate, washed with an organic solvent, and then vacuum dried at about 373 K for several hours to obtain the metal complex of the present invention.
本発明の金属錯体は多孔質体であり、その細孔中にガスなどの低分子を吸着し、また脱着することができるため、各種ガスの吸着材、吸蔵材および分離材として用いることができる。ただし、製造時に使用した溶媒が吸着した状態ではガスを吸着しない。そのため、本発明の金属錯体を吸着材、吸蔵材、或いは分離材として使用する際には、予め得られた金属錯体について真空乾燥を行い、細孔内の溶媒を取り除くことが必要である。通常は金属錯体が分解しない程度の温度（例えば２９８Ｋ〜５２３Ｋ以下）で真空乾燥を行えばよく、その温度はより低温（例えば２９８Ｋ〜３９３Ｋ以下）であることが好ましい。この操作は、超臨界二酸化炭素による洗浄によっても代えることができ、より効果的である。 Since the metal complex of the present invention is a porous body and can adsorb and desorb low molecules such as gas in its pores, it can be used as an adsorbent, occlusion material, and separation material for various gases. . However, gas is not adsorbed in a state where the solvent used in the production is adsorbed. Therefore, when the metal complex of the present invention is used as an adsorbent, occlusion material, or separation material, it is necessary to vacuum-dry the metal complex obtained in advance to remove the solvent in the pores. Usually, vacuum drying may be performed at a temperature at which the metal complex is not decomposed (for example, 298K to 523K or less), and the temperature is preferably lower (for example, 298K to 393K or less). This operation can be replaced by cleaning with supercritical carbon dioxide, and is more effective.
本発明の金属錯体は、用いる多価カルボン酸化合物、金属イオンおよびトリエチレンジアミン化合物の種類により、一次元、二次元、或いは三次元の集積構造をとる。 The metal complex of the present invention has a one-dimensional, two-dimensional, or three-dimensional integrated structure depending on the type of polyvalent carboxylic acid compound, metal ion, and triethylenediamine compound used.
本発明の金属錯体は、用いるモノカルボン酸化合物の種類および使用量により、粒径やモルフォロジーを制御することができる。 In the metal complex of the present invention, the particle size and morphology can be controlled by the type and amount of the monocarboxylic acid compound used.
金属錯体の粒径は、例えばレーザ回折法、動的光散乱法、画像イメージング法、重力沈降法などにより確認できるが、これらに限定されるものではない。 The particle size of the metal complex can be confirmed by, for example, a laser diffraction method, a dynamic light scattering method, an image imaging method, a gravity sedimentation method, or the like, but is not limited thereto.
多価カルボン酸化合物と金属イオンとを反応させる際に、炭素数１または２のモノカルボン酸化合物を共存させることで、金属イオンと多価カルボン酸化合物との反応と金属イオンとモノカルボン酸化合物との反応が競争することになる。モノカルボン酸化合物が金属イオンに配位した場合、モノカルボン酸化合物の配位部位は１箇所しかないので、その配位箇所における結晶の成長は停止するため、モノカルボン酸化合物は、結晶生長反応における停止剤と見なすことができる。一方で、金属イオンとモノカルボン酸化合物との反応は可逆であるので、結晶核生成速度および結晶成長速度が制御され、粒径や粒形の制御のみならず、結晶欠陥が少ない金属錯体を得ることが可能となる。結晶欠陥が少ない本発明の金属錯体は、細孔サイズの均一性が高く、特定のガスに対して高い吸着選択性を示す。 When the polyvalent carboxylic acid compound is reacted with the metal ion, the reaction of the metal ion with the polyvalent carboxylic acid compound and the metal ion with the monocarboxylic acid compound are allowed to coexist with the monocarboxylic acid compound having 1 or 2 carbon atoms. The reaction with will compete. When a monocarboxylic acid compound is coordinated to a metal ion, since there is only one coordination site of the monocarboxylic acid compound, crystal growth stops at that coordination site, so the monocarboxylic acid compound is a crystal growth reaction. Can be regarded as a terminator. On the other hand, since the reaction between the metal ion and the monocarboxylic acid compound is reversible, the crystal nucleation rate and the crystal growth rate are controlled, and a metal complex with few crystal defects is obtained in addition to controlling the particle size and particle shape. It becomes possible. The metal complex of the present invention having few crystal defects has high uniformity of pore size and high adsorption selectivity for a specific gas.
前記のメカニズムは推定ではあるが、例え前記メカニズムに従っていない場合でも、本発明で規定する要件を満足するのであれば、本発明の技術的範囲に包含される。 Although the above mechanism is presumed, even if it does not follow the mechanism, it is included in the technical scope of the present invention as long as it satisfies the requirements defined in the present invention.
本発明の金属錯体は、各種ガスの吸着性能、吸蔵性能および分離性能に優れている。従って、本発明の金属錯体は、各種ガスの吸着材、吸着材および分離材として有用であり、これらも本発明の権利範囲に含まれる。 The metal complex of the present invention is excellent in various gas adsorption performance, occlusion performance, and separation performance. Therefore, the metal complex of the present invention is useful as an adsorbent, adsorbent and separator for various gases, and these are also included in the scope of the present invention.
本発明の金属錯体は、例えば、二酸化炭素、水素、一酸化炭素、酸素、窒素、炭素数１〜４の炭化水素（メタン、エタン、エチレン、アセチレン、プロパン、プロペン、メチルアセチレン、プロパジエン、ブタン、１−ブテン、イソブテン、１−ブチン、２−ブチン、１，３−ブタジエン、メチルアレンなど）、希ガス（ヘリウム、ネオン、アルゴン、クリプトン、キセノンなど）、硫化水素、アンモニア、硫黄酸化物、窒素酸化物、シロキサン（ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサンなど）、水蒸気または有機蒸気などのガスを吸着、吸蔵、または分離するために好適に使用できる。本発明の分離材にあっては、混合ガス、特に、メタンと二酸化炭素、水素と二酸化炭素、窒素と二酸化炭素、エチレンと二酸化炭素、メタンとエタン、エチレンとエタン、窒素と酸素、酸素とアルゴン、窒素とメタン、空気とメタンなどを、圧力スイング吸着法や温度スイング吸着法により分離するのに適している。 Examples of the metal complex of the present invention include carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, and hydrocarbons having 1 to 4 carbon atoms (methane, ethane, ethylene, acetylene, propane, propene, methylacetylene, propadiene, butane, 1-butene, isobutene, 1-butyne, 2-butyne, 1,3-butadiene, methylallene, etc.), noble gases (such as helium, neon, argon, krypton, xenon), hydrogen sulfide, ammonia, sulfur oxide, nitrogen It can be suitably used to adsorb, occlude or separate gases such as oxides, siloxanes (such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane), water vapor or organic vapor. In the separation material of the present invention, a mixed gas, particularly methane and carbon dioxide, hydrogen and carbon dioxide, nitrogen and carbon dioxide, ethylene and carbon dioxide, methane and ethane, ethylene and ethane, nitrogen and oxygen, oxygen and argon It is suitable for separating nitrogen and methane, air and methane, etc. by pressure swing adsorption method or temperature swing adsorption method.
有機蒸気とは、常温、常圧で液体状の有機物質の気化ガスを意味する。このような有機物質としては、メタノール、エタノールなどのアルコール類；トリメチルアミンなどのアミン類；ホルムアルデヒド、アセトアルデヒドなどのアルデヒド類；ペンタン、イソプレン、ヘキサン、シクロヘキサン、ヘプタン、メチルシクロヘキサン、オクタン、１−オクテン、シクロオクタン、シクロオクテン、１，５−シクロオクタジエン、４−ビニル−１−シクロヘキセン、１，５，９−シクロドデカトリエンなどの炭素数５〜１６の炭化水素；ベンゼン、トルエンなどの芳香族炭化水素；アセトン、メチルエチルケトンなどのケトン類；酢酸メチル、酢酸エチルなどのエステル類；塩化メチル、クロロホルムなどのハロゲン化炭化水素などが挙げられる。 The organic vapor means a vaporized organic substance that is liquid at normal temperature and pressure. Examples of such organic substances include alcohols such as methanol and ethanol; amines such as trimethylamine; aldehydes such as formaldehyde and acetaldehyde; pentane, isoprene, hexane, cyclohexane, heptane, methylcyclohexane, octane, 1-octene, cyclohexane C5-C16 hydrocarbons such as octane, cyclooctene, 1,5-cyclooctadiene, 4-vinyl-1-cyclohexene, 1,5,9-cyclododecatriene; aromatic hydrocarbons such as benzene and toluene Ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; halogenated hydrocarbons such as methyl chloride and chloroform.
本発明の金属錯体または吸着材、吸蔵材および分離材の使用形態は特に限定されない。例えば、粉末のまま用いてもよいし、ペレット、フィルム、シート、プレート、パイプ、チューブ、棒状体、粒状体、各種異形成形体、繊維、中空糸、織布、編布、不織布などに成形して用いてもよい。 The usage form of the metal complex or adsorbent, occlusion material and separation material of the present invention is not particularly limited. For example, it may be used as a powder, or formed into pellets, films, sheets, plates, pipes, tubes, rods, granules, various deformed shapes, fibers, hollow fibers, woven fabrics, knitted fabrics, nonwoven fabrics, etc. May be used.
以下、本発明を実施例によって具体的に説明するが、本発明はこれらに限定されるものではない。以下の実施例および比較例における分析および評価は次のようにして行った。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Analysis and evaluation in the following examples and comparative examples were performed as follows.
（１）炭素数１または２のモノカルボン酸化合物の定量
金属錯体を重溶媒に溶解させて１Ｈ−ＮＭＲ測定を行い、得られたスペクトルの積分比から算出した。分析条件の詳細を以下に記す。
＜分析条件＞
装置：ブルカー・バイオスピン株式会社製Ａｄｖａｎｃｅ６００
共鳴周波数：６００ＭＨｚ
測定溶媒：重アンモニア水
基準物質：３−（トリメチルシリル）プロパン酸ナトリウム−ｄ４
測定温度：２９８Ｋ
(1) Quantification of monocarboxylic acid compound having 1 or 2 carbon atoms The metal complex was dissolved in a heavy solvent, 1 H-NMR measurement was performed, and the obtained spectrum was calculated from the integral ratio of the spectrum. Details of the analysis conditions are described below.
<Analysis conditions>
Apparatus: Advance600 manufactured by Bruker BioSpin Corporation
Resonance frequency: 600 MHz
Solvent for measurement: Deuterated aqueous ammonia Reference material: Sodium 3- (trimethylsilyl) propanoate-d4
Measurement temperature: 298K
（２）比表面積の測定
ガス吸着量測定装置を用いて、容量法により窒素の吸着等温線を測定した。得られた吸着等温線からＢＥＴ法を用いて比表面積を算出した。分析条件の詳細を以下に示す。
＜分析条件＞
測定温度：７７Ｋ
装置：マイクロトラックベル社製ＢＥＬＳＯＲＰ−ｍａｘ
平衡待ち時間：５００秒
(2) Measurement of specific surface area An adsorption isotherm of nitrogen was measured by a volumetric method using a gas adsorption amount measuring device. The specific surface area was calculated from the obtained adsorption isotherm using the BET method. Details of the analysis conditions are shown below.
<Analysis conditions>
Measurement temperature: 77K
Apparatus: BELSORP-max manufactured by Micro Track Bell
Equilibrium waiting time: 500 seconds
（３）メタン吸着量の測定
高圧ガス吸着量測定装置を用いて、容量法によりガス吸脱着量の測定を行い、吸着量を測定した。このとき、測定に先立って試料を３７３Ｋ、０．５Ｐａで５時間乾燥し、吸着水などを除去した。分析条件の詳細を以下に示す。
＜分析条件＞
測定温度：２９３Ｋ
装置：マイクロトラックベル社製ＢＥＬＳＯＲＰ−ＨＰ
平衡待ち時間：５００秒
平衡圧：２ＭＰａ
(3) Measurement of methane adsorption amount Gas adsorption / desorption amount was measured by a volumetric method using a high-pressure gas adsorption amount measuring device, and the adsorption amount was measured. At this time, the sample was dried at 373 K and 0.5 Pa for 5 hours prior to measurement to remove adsorbed water and the like. Details of the analysis conditions are shown below.
<Analysis conditions>
Measurement temperature: 293K
Apparatus: BELSORP-HP manufactured by Microtrack Bell
Equilibrium waiting time: 500 seconds Equilibrium pressure: 2 MPa
（４）吸着ガス中のメタン組成比の分析
多成分吸着量測定装置を用いて、容量法によりガス吸着量の測定を行った。同時に、ガスクロマトグラフィーを用いて、吸着ガス中のメタン組成比の分析を実施した。このとき、測定に先立って試料を３７３Ｋ、０．５Ｐａで５時間乾燥し、吸着水などを除去した。分析条件の詳細を以下に示す。
＜分析条件＞
装置：マイクロトラックベル社製多成分吸着量測定装置ＢＥＬＳＯＲＰ−ＶＣ
吸着ガス：メタン／窒素混合ガス（ｖ／ｖ＝７９．４／２０．６）
測定温度：２９３Ｋ
平衡待ち時間：３００分
平衡圧：２ＭＰａ
(4) Analysis of methane composition ratio in adsorbed gas The gas adsorbed amount was measured by a volumetric method using a multi-component adsorbed amount measuring apparatus. At the same time, analysis of the methane composition ratio in the adsorbed gas was performed using gas chromatography. At this time, the sample was dried at 373 K and 0.5 Pa for 5 hours prior to measurement to remove adsorbed water and the like. Details of the analysis conditions are shown below.
<Analysis conditions>
Apparatus: Multi component adsorption amount measuring apparatus BELSORP-VC manufactured by Microtrack Bell
Adsorption gas: methane / nitrogen mixed gas (v / v = 79.4 / 20.6)
Measurement temperature: 293K
Equilibrium waiting time: 300 minutes Equilibrium pressure: 2 MPa
＜合成例１＞
窒素雰囲気下、酢酸銅一水和物１．９９４ｇ（１０．０ｍｍｏｌ）、テレフタル酸１．６６１ｇ（１０ｍｍｏｌ）、トリエチレンジアミン１．１２０ｇ（１０ｍｍｏｌ）、およびギ酸１０ｍＬをメタノール５００ｍＬに入れ、スラリー状態にて２９８Ｋの条件下、４８時間攪拌した。析出した金属錯体を吸引濾過により回収した後、５００ｍＬのメタノールで５回洗浄した。続いて、３７３Ｋ、５０Ｐａで８時間乾燥し、目的の金属錯体を得た。
<Synthesis Example 1>
In a nitrogen atmosphere, 1.994 g (10.0 mmol) of copper acetate monohydrate, 1.661 g (10 mmol) of terephthalic acid, 1.120 g (10 mmol) of triethylenediamine, and 10 mL of formic acid were added to 500 mL of methanol, and in a slurry state. The mixture was stirred for 48 hours under the condition of 298K. The deposited metal complex was collected by suction filtration, and then washed 5 times with 500 mL of methanol. Then, it dried at 373K and 50Pa for 8 hours, and obtained the target metal complex.
得られた金属錯体１０ｍｇを重アンモニア水８００ｍｇに溶解させ、１Ｈ−ＮＭＲ測定を行った。得られたスペクトルを図１に示す。スペクトルを解析した結果、テレフタル酸の２位、３位、５位および６位のプロトンに帰属される７．９ｐｐｍ（ｓ，４Ｈ）のピークの積分値を１，０００とした際に、ギ酸の１位のプロトンに帰属される８．５ｐｐｍ（ｓ，１Ｈ）のピークの積分値は０．０６４であったことから、金属錯体に含まれるテレフタル酸とギ酸のモル比は、テレフタル酸：ギ酸＝９．６：１であることが分かった。なお、４．１ｐｐｍ付近のブロードなシグナルは水によるものである。 10 mg of the obtained metal complex was dissolved in 800 mg of heavy ammonia water, and 1 H-NMR measurement was performed. The obtained spectrum is shown in FIG. As a result of analyzing the spectrum, when the integrated value of the peak of 7.9 ppm (s, 4H) attributed to protons at the 2nd, 3rd, 5th and 6th positions of terephthalic acid was set to 1,000, Since the integrated value of the 8.5 ppm (s, 1H) peak attributed to the proton at the 1-position was 0.064, the molar ratio of terephthalic acid to formic acid contained in the metal complex was terephthalic acid: formic acid = It was found to be 9.6: 1. The broad signal around 4.1 ppm is due to water.
＜合成例２＞
窒素雰囲気下、酢酸銅一水和物１４．３１４ｇ（７１．７ｍｍｏｌ）、テレフタル酸１１．９１１ｇ（７１．７ｍｍｏｌ）、トリエチレンジアミン８．０４２ｇ（７１．７ｍｍｏｌ）、および酢酸３．５８ｇをメタノール１００ｍＬに入れ、スラリー状態にて３３３Ｋの条件下、１２０時間攪拌した。析出した金属錯体を吸引濾過により回収した後、５００ｍＬのメタノールで５回洗浄した。続いて、３７３Ｋ、５０Ｐａで８時間乾燥し、目的の金属錯体を得た。
<Synthesis Example 2>
In a nitrogen atmosphere, 14.314 g (71.7 mmol) of copper acetate monohydrate, 11.911 g (71.7 mmol) of terephthalic acid, 8.042 g (71.7 mmol) of triethylenediamine, and 3.58 g of acetic acid in 100 mL of methanol. And stirred for 120 hours in a slurry state under the condition of 333K. The deposited metal complex was collected by suction filtration, and then washed 5 times with 500 mL of methanol. Then, it dried at 373K and 50Pa for 8 hours, and obtained the target metal complex.
得られた金属錯体１０ｍｇを重アンモニア水８００ｍｇに溶解させ、１Ｈ−ＮＭＲ測定を行った。得られたスペクトルを図２に示す。スペクトルを解析した結果、テレフタル酸の２位、３位、５位および６位のプロトンに帰属される７．９ｐｐｍ（ｓ，４Ｈ）のピークの積分値を１，０００とした際に、酢酸の１位のプロトンに帰属される１．９ｐｐｍ（ｓ，３Ｈ）のピークの積分値は０．０８７であったことから、金属錯体に含まれるテレフタル酸とギ酸のモル比は、テレフタル酸：酢酸＝８．６：１であることが分かった。なお、４．１ｐｐｍ付近のブロードなシグナルは水によるものである。 10 mg of the obtained metal complex was dissolved in 800 mg of heavy ammonia water, and 1 H-NMR measurement was performed. The obtained spectrum is shown in FIG. As a result of analyzing the spectrum, when the integrated value of the peak of 7.9 ppm (s, 4H) attributed to the 2nd, 3rd, 5th and 6th position protons of terephthalic acid was set to 1,000, acetic acid Since the integrated value of the peak of 1.9 ppm (s, 3H) attributed to the proton at the 1-position was 0.087, the molar ratio of terephthalic acid and formic acid contained in the metal complex was terephthalic acid: acetic acid = It was found to be 8.6: 1. The broad signal around 4.1 ppm is due to water.
＜合成例３＞
窒素雰囲気下、酢酸銅一水和物１．９９４ｇ（１０．０ｍｍｏｌ）、２−ニトロテレフタル酸２．１１０ｇ（１０ｍｍｏｌ）、トリエチレンジアミン１．１２０ｇ（１０ｍｍｏｌ）、およびギ酸１０ｍＬをメタノール５００ｍＬに入れ、スラリー状態にて３１３Ｋの条件下、１１０時間攪拌した。析出した金属錯体を吸引濾過により回収した後、５００ｍＬのメタノールで５回洗浄した。続いて、３７３Ｋ、５０Ｐａで８時間乾燥し、目的の金属錯体を得た。
<Synthesis Example 3>
In a nitrogen atmosphere, 1.994 g (10.0 mmol) of copper acetate monohydrate, 2.110 g (10 mmol) of 2-nitroterephthalic acid, 1.120 g (10 mmol) of triethylenediamine and 10 mL of formic acid were added to 500 mL of methanol, and the slurry The mixture was stirred for 110 hours under conditions of 313K. The deposited metal complex was collected by suction filtration, and then washed 5 times with 500 mL of methanol. Then, it dried at 373K and 50Pa for 8 hours, and obtained the target metal complex.
得られた金属錯体１０ｍｇを重アンモニア水８００ｍｇに溶解させ、１Ｈ−ＮＭＲ測定を行った。得られたスペクトルを図３に示す。スペクトルを解析した結果、２−ニトロテレフタル酸のそれぞれ３位、５位、および６位のプロトンに帰属される８．５ｐｐｍ（ｓ，１Ｈ）、８．２ｐｐｍ（ｓ，１Ｈ）、７．６ｐｐｍ（ｓ，１Ｈ）のピークのそれぞれの積分値を１．０００とした際に、ギ酸の１位のプロトンに帰属される８．５ｐｐｍ（ｓ，１Ｈ）のピークの積分値は０．０００１であったことから、金属錯体に含まれるテレフタル酸とギ酸のモル比は、テレフタル酸：ギ酸＝２５００：１であることが分かった。なお、４．１ｐｐｍ付近のブロードなシグナルは水によるものである。 10 mg of the obtained metal complex was dissolved in 800 mg of heavy ammonia water, and 1 H-NMR measurement was performed. The obtained spectrum is shown in FIG. As a result of analyzing the spectrum, 8.5 ppm (s, 1 H), 8.2 ppm (s, 1 H), and 7.6 ppm (respectively assigned to protons at 3-position, 5-position, and 6-position of 2-nitroterephthalic acid ( The integrated value of the 8.5 ppm (s, 1H) peak attributed to the proton at the 1-position of formic acid was 0.0001 when the integrated value of each peak of the (s, 1H) was 1.000. From this, it was found that the molar ratio of terephthalic acid and formic acid contained in the metal complex was terephthalic acid: formic acid = 2500: 1. The broad signal around 4.1 ppm is due to water.
＜比較合成例１＞
窒素雰囲気下、酢酸銅一水和物１．９９４ｇ（１０．０ｍｍｏｌ）、テレフタル酸１．６６１ｇ（１０ｍｍｏｌ）、トリエチレンジアミン１．１２０ｇ（１０ｍｍｏｌ）、およびギ酸１０ｍＬをメタノール５００ｍＬに入れ、スラリー状態にて室温条件下、１６時間攪拌した。析出した金属錯体を吸引濾過により回収した後、５００ｍＬのメタノールで５回洗浄した。続いて、３７３Ｋ、５０Ｐａで８時間乾燥し、目的の金属錯体を得た。
<Comparative Synthesis Example 1>
In a nitrogen atmosphere, 1.994 g (10.0 mmol) of copper acetate monohydrate, 1.661 g (10 mmol) of terephthalic acid, 1.120 g (10 mmol) of triethylenediamine, and 10 mL of formic acid were added to 500 mL of methanol, and in a slurry state. Stir at room temperature for 16 hours. The deposited metal complex was collected by suction filtration, and then washed 5 times with 500 mL of methanol. Then, it dried at 373K and 50Pa for 8 hours, and obtained the target metal complex.
得られた金属錯体１０ｍｇを重アンモニア水８００ｍｇに溶解させ、１Ｈ−ＮＭＲ測定を行った。得られたスペクトルを図４に示す。スペクトルを解析した結果、テレフタル酸の２位、３位、５位および６位のプロトンに帰属される７．９ｐｐｍ（ｓ，４Ｈ）のピークの積分値を１，０００とした際に、ギ酸の１位のプロトンに帰属される８．５ｐｐｍ（ｓ，１Ｈ）のピークの積分値は０．２８２であったことから、金属錯体に含まれるテレフタル酸とギ酸のモル比は、テレフタル酸：ギ酸＝０．８９：１であることが分かった。なお、４．１ｐｐｍ付近のブロードなシグナルは水によるものである。 10 mg of the obtained metal complex was dissolved in 800 mg of heavy ammonia water, and 1 H-NMR measurement was performed. The obtained spectrum is shown in FIG. As a result of analyzing the spectrum, when the integrated value of the peak of 7.9 ppm (s, 4H) attributed to protons at the 2nd, 3rd, 5th and 6th positions of terephthalic acid was set to 1,000, Since the integrated value of the peak of 8.5 ppm (s, 1H) attributed to the proton at the 1-position was 0.282, the molar ratio of terephthalic acid and formic acid contained in the metal complex was terephthalic acid: formic acid = It was found to be 0.89: 1. The broad signal around 4.1 ppm is due to water.
＜比較合成例２＞
窒素雰囲気下、酢酸銅一水和物２１．８４ｇ（１０９．４ｍｍｏｌ）、テレフタル酸１８．１７ｇ（１０９．４ｍｍｏｌ）および酢酸２６．２８ｇ（４３７．６ｍｍｏｌ）をメタノール２００ｍＬに溶解させ、３３３Ｋで１８時間攪拌した。析出した金属錯体を吸引濾過により回収した後、１Ｌのメタノールで５回洗浄し、中間体を単離した。次に、単離した中間体を窒素雰囲気下でメタノール２００ｍＬ中に分散させ、４，４’−ビピリジル８．５４ｇ（５４．７０ｍｍｏｌ）を添加し、３１３Ｋで３時間攪拌した。金属錯体を吸引濾過により回収した後、１Ｌのメタノールで５回洗浄した。続いて、３７３Ｋ、５０Ｐａで８時間乾燥し、目的の金属錯体を得た。
<Comparative Synthesis Example 2>
Under a nitrogen atmosphere, 21.84 g (109.4 mmol) of copper acetate monohydrate, 18.17 g (109.4 mmol) of terephthalic acid and 26.28 g (437.6 mmol) of acetic acid were dissolved in 200 mL of methanol, and the mixture was treated at 333 K for 18 hours. Stir. The precipitated metal complex was recovered by suction filtration, and then washed 5 times with 1 L of methanol to isolate the intermediate. Next, the isolated intermediate was dispersed in 200 mL of methanol under a nitrogen atmosphere, 8.54 g (54.70 mmol) of 4,4′-bipyridyl was added, and the mixture was stirred at 313 K for 3 hours. The metal complex was recovered by suction filtration and then washed 5 times with 1 L of methanol. Then, it dried at 373K and 50Pa for 8 hours, and obtained the target metal complex.
得られた金属錯体１０ｍｇを重アンモニア水８００ｍｇに溶解させ、１Ｈ−ＮＭＲ測定を行った。得られたスペクトルを図５に示す。スペクトルを解析した結果、テレフタル酸の２位、３位、５位および６位のプロトンに帰属される７．９２０ｐｐｍ（ｓ，４Ｈ）のピークの積分値を１，０００とした際に、酢酸の１位のプロトンに帰属される１．９２９ｐｐｍ（ｓ，４Ｈ）のピークの積分値は０．０１１であったことから、金属錯体に含まれるテレフタル酸と酢酸のモル比は、テレフタル酸：酢酸＝６８：１であることが分かった。なお、３．８ｐｐｍ付近のブロードなシグナルは水によるものである。 10 mg of the obtained metal complex was dissolved in 800 mg of heavy ammonia water, and 1 H-NMR measurement was performed. The obtained spectrum is shown in FIG. As a result of analyzing the spectrum, when the integral value of the peak of 7.920 ppm (s, 4H) attributed to protons at the 2nd, 3rd, 5th and 6th positions of terephthalic acid was set to 1,000, acetic acid Since the integrated value of the 1.929 ppm (s, 4H) peak attributed to the proton at the 1-position was 0.011, the molar ratio of terephthalic acid and acetic acid contained in the metal complex was terephthalic acid: acetic acid = It was found to be 68: 1. The broad signal around 3.8 ppm is due to water.
＜実施例１＞
合成例１で得られた金属錯体について、比表面積と２９３Ｋにおけるメタンの吸着量を容量法により測定した。また、２９３Ｋにてメタン吸着／窒素混合ガスを吸着させ、平衡状態における吸着ガス中のメタン組成比を分析した。結果を表１に示す。
<Example 1>
With respect to the metal complex obtained in Synthesis Example 1, the specific surface area and the amount of methane adsorbed at 293 K were measured by a volumetric method. Further, methane adsorption / nitrogen mixed gas was adsorbed at 293K, and the methane composition ratio in the adsorbed gas in an equilibrium state was analyzed. The results are shown in Table 1.
＜実施例２＞
合成例２で得られた金属錯体について、比表面積と２９３Ｋにおけるメタンの吸着量を容量法により測定した。また、２９３Ｋにてメタン吸着／窒素混合ガスを吸着させ、平衡状態における吸着ガス中のメタン組成比を分析した。結果を表１に示す。
<Example 2>
With respect to the metal complex obtained in Synthesis Example 2, the specific surface area and the amount of methane adsorbed at 293 K were measured by the volumetric method. Further, methane adsorption / nitrogen mixed gas was adsorbed at 293K, and the methane composition ratio in the adsorbed gas in an equilibrium state was analyzed. The results are shown in Table 1.
＜実施例３＞
合成例３で得られた金属錯体について、比表面積と２９３Ｋにおけるメタンの吸着量を容量法により測定した。また、２９３Ｋにてメタン吸着／窒素混合ガスを吸着させ、平衡状態における吸着ガス中のメタン組成比を分析した。結果を表１に示す。
<Example 3>
With respect to the metal complex obtained in Synthesis Example 3, the specific surface area and the amount of methane adsorbed at 293 K were measured by the volumetric method. Further, methane adsorption / nitrogen mixed gas was adsorbed at 293K, and the methane composition ratio in the adsorbed gas in an equilibrium state was analyzed. The results are shown in Table 1.
＜比較例１＞
比較合成例１で得られた金属錯体について、比表面積と２９３Ｋにおけるメタンの吸着量を容量法により測定した。また、２９３Ｋにてメタン吸着／窒素混合ガスを吸着させ、平衡状態における吸着ガス中のメタン組成比を分析した。結果を表１に示す。
<Comparative Example 1>
With respect to the metal complex obtained in Comparative Synthesis Example 1, the specific surface area and the amount of methane adsorbed at 293 K were measured by the volumetric method. Further, methane adsorption / nitrogen mixed gas was adsorbed at 293K, and the methane composition ratio in the adsorbed gas in an equilibrium state was analyzed. The results are shown in Table 1.
＜比較例２＞
比較合成例２で得られた金属錯体について、２９３Ｋにおけるメタンの吸着量を容量法により測定した。また、２９３Ｋにてメタン吸着／窒素混合ガスを吸着させ、平衡状態における吸着ガス中のメタン組成比を分析した。結果を表１に示す。
<Comparative example 2>
For the metal complex obtained in Comparative Synthesis Example 2, the amount of methane adsorbed at 293K was measured by the volumetric method. Further, methane adsorption / nitrogen mixed gas was adsorbed at 293K, and the methane composition ratio in the adsorbed gas in an equilibrium state was analyzed. The results are shown in Table 1.
実施例１、２、３と比較例１の比較より、金属錯体中の多価カルボン酸とモノカルボン酸の比率が本発明の構成要件を満たす場合のみ、高い吸着量と吸着選択性が得られることは明らかである。また、実施例１、２、３と比較例２の比較より、二座配位子としてトリエチレンジアミンを含まない金属錯体は、メタン吸着量が他に比べて著しく低く、吸着量と吸着選択性が両立できていない。
Claims (7)
該金属錯体を構成する前記多価カルボン酸化合物と炭素数１または２の前記モノカルボン酸化合物との組成比が多価カルボン酸化合物：炭素数１または２の前記モノカルボン酸化合物＝１：１〜３，０００：１の範囲内にあり、かつ、比表面積が３５０ｍ２／ｇ以上であることを特徴とする金属錯体。 Porous containing a divalent metal ion, a polyvalent carboxylic acid compound that may have a substituent, a triethylenediamine compound that may have a substituent, and a monocarboxylic acid compound having 1 or 2 carbon atoms Quality metal complex,
The composition ratio of the polyvalent carboxylic acid compound constituting the metal complex and the monocarboxylic acid compound having 1 or 2 carbon atoms is a polyvalent carboxylic acid compound: the monocarboxylic acid compound having 1 or 2 carbon atoms = 1: 1. A metal complex having a specific surface area of 350 m 2 / g or more in a range of ˜3,000: 1.
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