WO2014189120A1 - 固体触媒、およびその固体触媒を用いたイソシアネート化合物の製造方法 - Google Patents
固体触媒、およびその固体触媒を用いたイソシアネート化合物の製造方法 Download PDFInfo
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- WO2014189120A1 WO2014189120A1 PCT/JP2014/063619 JP2014063619W WO2014189120A1 WO 2014189120 A1 WO2014189120 A1 WO 2014189120A1 JP 2014063619 W JP2014063619 W JP 2014063619W WO 2014189120 A1 WO2014189120 A1 WO 2014189120A1
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- Prior art keywords
- compound
- solid catalyst
- silica
- group
- catalyst
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- -1 isocyanate compound Chemical class 0.000 title claims abstract description 181
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 134
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 88
- 239000012948 isocyanate Substances 0.000 title claims abstract description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 185
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 72
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000001179 sorption measurement Methods 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 23
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000011148 porous material Substances 0.000 claims description 27
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 18
- 229910052753 mercury Inorganic materials 0.000 claims description 18
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 6
- 238000002459 porosimetry Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 229940043430 calcium compound Drugs 0.000 claims description 4
- 150000001674 calcium compounds Chemical class 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- 150000003388 sodium compounds Chemical class 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 65
- 229910052784 alkaline earth metal Chemical class 0.000 abstract description 9
- 150000002739 metals Chemical group 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 32
- 229910004298 SiO 2 Inorganic materials 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005259 measurement Methods 0.000 description 16
- 229910002027 silica gel Inorganic materials 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 14
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 14
- 238000010304 firing Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000012442 inert solvent Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- DWLVWMUCHSLGSU-UHFFFAOYSA-M n,n-dimethylcarbamate Chemical compound CN(C)C([O-])=O DWLVWMUCHSLGSU-UHFFFAOYSA-M 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000002638 heterogeneous catalyst Substances 0.000 description 5
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000004436 sodium atom Chemical group 0.000 description 4
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical group C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000006627 ethoxycarbonylamino group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 125000006838 isophorone group Chemical group 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- CNPWIVIIZHULCN-UHFFFAOYSA-N methyl n-[3-(methoxycarbonylamino)-4-methylphenyl]carbamate Chemical group COC(=O)NC1=CC=C(C)C(NC(=O)OC)=C1 CNPWIVIIZHULCN-UHFFFAOYSA-N 0.000 description 2
- BAMOLHXSXMKLAA-UHFFFAOYSA-N methyl n-[3-[(methoxycarbonylamino)methyl]-3,5,5-trimethylcyclohexyl]carbamate Chemical compound COC(=O)NCC1(C)CC(NC(=O)OC)CC(C)(C)C1 BAMOLHXSXMKLAA-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- AYDIPERXFQBZQX-UHFFFAOYSA-N 1,2,3-triethyl-4-phenylbenzene Chemical group CCC1=C(CC)C(CC)=CC=C1C1=CC=CC=C1 AYDIPERXFQBZQX-UHFFFAOYSA-N 0.000 description 1
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 description 1
- VUMCUSHVMYIRMB-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 VUMCUSHVMYIRMB-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 description 1
- UMSGIWAAMHRVQI-UHFFFAOYSA-N 1-ethyl-4-(4-ethylphenyl)benzene Chemical group C1=CC(CC)=CC=C1C1=CC=C(CC)C=C1 UMSGIWAAMHRVQI-UHFFFAOYSA-N 0.000 description 1
- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001255 actinides Chemical group 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000006630 butoxycarbonylamino group Chemical group 0.000 description 1
- RAGMJVZPRKJQCP-UHFFFAOYSA-N butyl N-[[4-[(butoxycarbonylamino)methyl]cyclohexyl]methyl]carbamate Chemical compound CCCCOC(=O)NCC1CCC(CNC(=O)OCCCC)CC1 RAGMJVZPRKJQCP-UHFFFAOYSA-N 0.000 description 1
- DIFMKDPWLDQOED-UHFFFAOYSA-N butyl n-(dicyclohexylmethyl)carbamate Chemical compound C1CCCCC1C(NC(=O)OCCCC)C1CCCCC1 DIFMKDPWLDQOED-UHFFFAOYSA-N 0.000 description 1
- AGIKINZLPGZPSN-UHFFFAOYSA-N butyl n-[3-(butoxycarbonylamino)-2-methylphenyl]carbamate Chemical compound CCCCOC(=O)NC1=CC=CC(NC(=O)OCCCC)=C1C AGIKINZLPGZPSN-UHFFFAOYSA-N 0.000 description 1
- UESWNOJFEKZPNC-UHFFFAOYSA-N butyl n-[4-(butoxycarbonylamino)butyl]carbamate Chemical compound CCCCOC(=O)NCCCCNC(=O)OCCCC UESWNOJFEKZPNC-UHFFFAOYSA-N 0.000 description 1
- HXARNQOAWLBABV-UHFFFAOYSA-N butyl n-[4-(butoxycarbonylamino)cyclohexyl]carbamate Chemical compound CCCCOC(=O)NC1CCC(NC(=O)OCCCC)CC1 HXARNQOAWLBABV-UHFFFAOYSA-N 0.000 description 1
- JSWNMQAQCWHTII-UHFFFAOYSA-N butyl n-[4-[4-(butoxycarbonylamino)phenyl]phenyl]carbamate Chemical group C1=CC(NC(=O)OCCCC)=CC=C1C1=CC=C(NC(=O)OCCCC)C=C1 JSWNMQAQCWHTII-UHFFFAOYSA-N 0.000 description 1
- ILPOVPZIWGHRLX-UHFFFAOYSA-N butyl n-[6-(butoxycarbonylamino)hexyl]carbamate Chemical compound CCCCOC(=O)NCCCCCCNC(=O)OCCCC ILPOVPZIWGHRLX-UHFFFAOYSA-N 0.000 description 1
- GSKPMNCZJHPUGE-UHFFFAOYSA-N butyl n-[6-(butoxycarbonylamino)naphthalen-2-yl]carbamate Chemical compound C1=C(NC(=O)OCCCC)C=CC2=CC(NC(=O)OCCCC)=CC=C21 GSKPMNCZJHPUGE-UHFFFAOYSA-N 0.000 description 1
- UOYGRADABAWATD-UHFFFAOYSA-N butyl n-[8-(butoxycarbonylamino)octyl]carbamate Chemical compound CCCCOC(=O)NCCCCCCCCNC(=O)OCCCC UOYGRADABAWATD-UHFFFAOYSA-N 0.000 description 1
- FHQKIZGBOZXRFT-UHFFFAOYSA-N butyl n-[9-(butoxycarbonylamino)nonyl]carbamate Chemical compound CCCCOC(=O)NCCCCCCCCCNC(=O)OCCCC FHQKIZGBOZXRFT-UHFFFAOYSA-N 0.000 description 1
- CSFSCCJINPUJJZ-UHFFFAOYSA-N butyl n-[[2-[(butoxycarbonylamino)methyl]-5-bicyclo[2.2.1]heptanyl]methyl]carbamate Chemical compound C1C2C(CNC(=O)OCCCC)CC1C(CNC(=O)OCCCC)C2 CSFSCCJINPUJJZ-UHFFFAOYSA-N 0.000 description 1
- UITVMUKLPUTSDF-UHFFFAOYSA-N butyl n-[[3-[(butoxycarbonylamino)methyl]-5-bicyclo[2.2.1]heptanyl]methyl]carbamate Chemical compound C1C(CNC(=O)OCCCC)C2C(CNC(=O)OCCCC)CC1C2 UITVMUKLPUTSDF-UHFFFAOYSA-N 0.000 description 1
- ZLYCRSFXTUHWJT-UHFFFAOYSA-N butyl n-[[4-[(butoxycarbonylamino)methyl]phenyl]methyl]carbamate Chemical compound CCCCOC(=O)NCC1=CC=C(CNC(=O)OCCCC)C=C1 ZLYCRSFXTUHWJT-UHFFFAOYSA-N 0.000 description 1
- CKKIQIYBHGMKOO-UHFFFAOYSA-N butyl n-benzhydrylcarbamate Chemical compound C=1C=CC=CC=1C(NC(=O)OCCCC)C1=CC=CC=C1 CKKIQIYBHGMKOO-UHFFFAOYSA-N 0.000 description 1
- XGWVZANXYSUDKG-UHFFFAOYSA-N butyl n-dodecylcarbamate Chemical compound CCCCCCCCCCCCNC(=O)OCCCC XGWVZANXYSUDKG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- PUFGCEQWYLJYNJ-UHFFFAOYSA-N didodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCC PUFGCEQWYLJYNJ-UHFFFAOYSA-N 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
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JXPLWXPINNWUTN-UHFFFAOYSA-N ethyl n-(dicyclohexylmethyl)carbamate Chemical compound C1CCCCC1C(NC(=O)OCC)C1CCCCC1 JXPLWXPINNWUTN-UHFFFAOYSA-N 0.000 description 1
- QNJPOHYCQROUCT-UHFFFAOYSA-N ethyl n-[3-(ethoxycarbonylamino)-2-methylphenyl]carbamate Chemical compound CCOC(=O)NC1=CC=CC(NC(=O)OCC)=C1C QNJPOHYCQROUCT-UHFFFAOYSA-N 0.000 description 1
- FWKGEANWQNXYRM-UHFFFAOYSA-N ethyl n-[6-(ethoxycarbonylamino)hexyl]carbamate Chemical compound CCOC(=O)NCCCCCCNC(=O)OCC FWKGEANWQNXYRM-UHFFFAOYSA-N 0.000 description 1
- BQBKYSPXQYHTIP-UHFFFAOYSA-N ethyl n-butylcarbamate Chemical compound CCCCNC(=O)OCC BQBKYSPXQYHTIP-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002602 lanthanoids Chemical group 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- AEDRVIDHGSOCTB-UHFFFAOYSA-N methyl N-[9-(methoxycarbonylamino)nonyl]carbamate Chemical compound COC(=O)NCCCCCCCCCNC(=O)OC AEDRVIDHGSOCTB-UHFFFAOYSA-N 0.000 description 1
- PFHFEBFOJYQIRG-UHFFFAOYSA-N methyl n-(dicyclohexylmethyl)carbamate Chemical compound C1CCCCC1C(NC(=O)OC)C1CCCCC1 PFHFEBFOJYQIRG-UHFFFAOYSA-N 0.000 description 1
- RUDDKVKIAVQINV-UHFFFAOYSA-N methyl n-[10-(methoxycarbonylamino)decyl]carbamate Chemical compound COC(=O)NCCCCCCCCCCNC(=O)OC RUDDKVKIAVQINV-UHFFFAOYSA-N 0.000 description 1
- CSIDQAACVLDAJD-UHFFFAOYSA-N methyl n-[12-(methoxycarbonylamino)dodecyl]carbamate Chemical compound COC(=O)NCCCCCCCCCCCCNC(=O)OC CSIDQAACVLDAJD-UHFFFAOYSA-N 0.000 description 1
- JNNLWOJZIPJIQG-UHFFFAOYSA-N methyl n-[3-(methoxycarbonylamino)-2-methylphenyl]carbamate Chemical compound COC(=O)NC1=CC=CC(NC(=O)OC)=C1C JNNLWOJZIPJIQG-UHFFFAOYSA-N 0.000 description 1
- OQNSLWFDULDLQM-UHFFFAOYSA-N methyl n-[4-(methoxycarbonylamino)butyl]carbamate Chemical compound COC(=O)NCCCCNC(=O)OC OQNSLWFDULDLQM-UHFFFAOYSA-N 0.000 description 1
- RPCPEKVNPMGVJL-UHFFFAOYSA-N methyl n-[4-(methoxycarbonylamino)cyclohexyl]carbamate Chemical compound COC(=O)NC1CCC(NC(=O)OC)CC1 RPCPEKVNPMGVJL-UHFFFAOYSA-N 0.000 description 1
- ASJZPQFCFNYJJX-UHFFFAOYSA-N methyl n-[4-(methoxycarbonylamino)phenyl]carbamate Chemical compound COC(=O)NC1=CC=C(NC(=O)OC)C=C1 ASJZPQFCFNYJJX-UHFFFAOYSA-N 0.000 description 1
- GLRSKDCBNNEWJE-UHFFFAOYSA-N methyl n-[5-(methoxycarbonylamino)pentyl]carbamate Chemical compound COC(=O)NCCCCCNC(=O)OC GLRSKDCBNNEWJE-UHFFFAOYSA-N 0.000 description 1
- DXZCANUBKZARPR-UHFFFAOYSA-N methyl n-[6-(methoxycarbonylamino)hexyl]carbamate Chemical compound COC(=O)NCCCCCCNC(=O)OC DXZCANUBKZARPR-UHFFFAOYSA-N 0.000 description 1
- AIGWBKGHHIAEAL-UHFFFAOYSA-N methyl n-[6-(methoxycarbonylamino)naphthalen-2-yl]carbamate Chemical compound C1=C(NC(=O)OC)C=CC2=CC(NC(=O)OC)=CC=C21 AIGWBKGHHIAEAL-UHFFFAOYSA-N 0.000 description 1
- XVLYQGJYLGKYEP-UHFFFAOYSA-N methyl n-[8-(methoxycarbonylamino)octyl]carbamate Chemical compound COC(=O)NCCCCCCCCNC(=O)OC XVLYQGJYLGKYEP-UHFFFAOYSA-N 0.000 description 1
- ANSHHIKPNXMKCF-UHFFFAOYSA-N methyl n-[[2-[(methoxycarbonylamino)methyl]-5-bicyclo[2.2.1]heptanyl]methyl]carbamate Chemical compound C1C2C(CNC(=O)OC)CC1C(CNC(=O)OC)C2 ANSHHIKPNXMKCF-UHFFFAOYSA-N 0.000 description 1
- PDDBZYGARMONMK-UHFFFAOYSA-N methyl n-[[3-[(methoxycarbonylamino)methyl]-5-bicyclo[2.2.1]heptanyl]methyl]carbamate Chemical compound C1C(CNC(=O)OC)C2C(CNC(=O)OC)CC1C2 PDDBZYGARMONMK-UHFFFAOYSA-N 0.000 description 1
- QUHOPNFCBASGGD-UHFFFAOYSA-N methyl n-[[3-[(methoxycarbonylamino)methyl]cyclohexyl]methyl]carbamate Chemical group COC(=O)NCC1CCCC(CNC(=O)OC)C1 QUHOPNFCBASGGD-UHFFFAOYSA-N 0.000 description 1
- XICVVDVFIUYMLD-UHFFFAOYSA-N methyl n-[[4-[(methoxycarbonylamino)methyl]cyclohexyl]methyl]carbamate Chemical compound COC(=O)NCC1CCC(CNC(=O)OC)CC1 XICVVDVFIUYMLD-UHFFFAOYSA-N 0.000 description 1
- FMFPRSAHOQBOCK-UHFFFAOYSA-N methyl n-[[4-[(methoxycarbonylamino)methyl]phenyl]methyl]carbamate Chemical compound COC(=O)NCC1=CC=C(CNC(=O)OC)C=C1 FMFPRSAHOQBOCK-UHFFFAOYSA-N 0.000 description 1
- CDSSYNXBUGMMSV-UHFFFAOYSA-N methyl n-benzhydrylcarbamate Chemical compound C=1C=CC=CC=1C(NC(=O)OC)C1=CC=CC=C1 CDSSYNXBUGMMSV-UHFFFAOYSA-N 0.000 description 1
- OXNAJPQXTZANJL-UHFFFAOYSA-N methyl n-hexylcarbamate Chemical compound CCCCCCNC(=O)OC OXNAJPQXTZANJL-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- APRJFNLVTJWEPP-UHFFFAOYSA-M n,n-diethylcarbamate Chemical compound CCN(CC)C([O-])=O APRJFNLVTJWEPP-UHFFFAOYSA-M 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- LTKHEOQACXOQFD-UHFFFAOYSA-N phenyl n-(dicyclohexylmethyl)carbamate Chemical compound C=1C=CC=CC=1OC(=O)NC(C1CCCCC1)C1CCCCC1 LTKHEOQACXOQFD-UHFFFAOYSA-N 0.000 description 1
- VOQWIAQVTYSSPY-UHFFFAOYSA-N phenyl n-[1,6-bis(phenoxycarbonylamino)hexan-3-yl]carbamate Chemical compound C=1C=CC=CC=1OC(=O)NCCCC(NC(=O)OC=1C=CC=CC=1)CCNC(=O)OC1=CC=CC=C1 VOQWIAQVTYSSPY-UHFFFAOYSA-N 0.000 description 1
- PVYDCVJTVNXZRB-UHFFFAOYSA-N phenyl n-[12-(phenoxycarbonylamino)dodecyl]carbamate Chemical compound C=1C=CC=CC=1OC(=O)NCCCCCCCCCCCCNC(=O)OC1=CC=CC=C1 PVYDCVJTVNXZRB-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KKVSYFFZJJRQPA-UHFFFAOYSA-N propyl n-(4-propylphenyl)carbamate Chemical compound CCCOC(=O)NC1=CC=C(CCC)C=C1 KKVSYFFZJJRQPA-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910002029 synthetic silica gel Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
Definitions
- the present invention relates to a solid catalyst containing at least one metal compound selected from the group consisting of alkali metal compounds and alkaline earth metal compounds, and silica.
- the present invention also relates to a method for producing an isocyanate compound in the presence of the solid catalyst.
- Isocyanate compounds are useful compounds that are widely used, for example, as raw materials for production of urethane, pharmaceuticals and agricultural chemicals.
- an isocyanate compound is industrially produced from a reaction between an amine and phosgene (for example, see Patent Document 1).
- a method for producing an isocyanate compound without using phosgene for example, a method is known in which a trihaloacetamide compound is detrihalomethanated in the presence of a catalyst such as a halogen salt of an alkali metal or a halogen salt of an alkaline earth metal (for example, see Patent Document 2).
- a catalyst such as a halogen salt of an alkali metal or a halogen salt of an alkaline earth metal
- heterogeneous catalyst calcium oxide, magnesium oxide, barium oxide, magnesium metal or the like is used, and an isocyanate compound is produced by pyrolyzing toluene diethyl carbamate as a carbamate compound (see, for example, Patent Document 3), Sodium carbonate, calcium carbonate or the like is used as a heterogeneous catalyst, and isopropyl N- (m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl) carbamate, N- (m-vinyl- ⁇ , ⁇ -dimethylbenzyl) carbamic acid It is known to produce an isocyanate compound by thermally decomposing a carbamate compound such as isopropyl (see, for example, Patent Document 5 and Patent Document 6).
- a catalyst for example, in the periodic table Contains oxide sintered bodies of at least one element selected from transition metal elements of Group Ib or Group VIII, lanthanoid group elements and actinoid group elements, or alkali metal elements and / or alkaline earth metal elements It is known to produce an isocyanate compound using an oxide sintered body (see, for example, Patent Document 7 and Patent Document 8).
- an isocyanate compound production catalyst has been developed in which at least one metal compound selected from the group consisting of an alkali metal compound and an alkaline earth metal compound is supported on a silica carrier (for example, Patent Document 9). reference).
- JP-A-11-310566 International Publication No. 2011/049023 JP 54-88201 A JP 2004-262892 A JP 2003-012632 A JP 2004-018507 A JP-A-5-186414 JP-A-5-186415 International Publication No. 2012/111750
- Patent Document 1 is highly toxic phosgene and a large amount of hydrogen chloride is produced as a by-product
- the production method of Patent Document 2 is a method of producing a halide such as chloroform as a by-product. Since the production method of No. 3 requires thermal decomposition under severe temperature conditions, side reactions are likely to occur, and the production method of Patent Document 4 exists in a state where the tin catalyst is uniformly dissolved. The fact that the catalyst is mixed into the product and the catalyst recovery operation becomes complicated, and the production methods of Patent Documents 5 to 8 are not sufficient in terms of the activity of the reaction of the carbamate compound and the selectivity of the isocyanate compound. It could not be said that the production method was suitable for production.
- Patent Document 9 At least one metal compound selected from the group consisting of an alkali metal compound and an alkaline earth metal compound was supported on a carrier.
- Catalysts for producing isocyanate compounds have been developed, but proposals for catalysts with higher reproducibility and selectivity have been demanded in order to make the production method more suitable for actual production.
- an object of the present invention to provide a catalyst that can produce an isocyanate compound with high selectivity and high yield and can be easily separated from a product with good reproducibility. To do. Furthermore, another object of the present invention is to provide a method for producing an isocyanate compound using such a catalyst.
- the yield and selectivity would be improved by increasing the number of times of contact between the metal and the substrate by increasing the content of the aforementioned metal compound or increasing the specific surface area of the catalyst.
- a solid catalyst capable of controlling the atomic ratio of metal atoms to silicon atoms on the catalyst surface and the specific surface area of the catalyst within the ranges described below, finding catalyst preparation conditions, and providing an excellent catalyst with good reproducibility. The manufacturing method has been completed.
- the present invention is as follows.
- the present invention 1 relates to a solid catalyst containing at least one metal compound selected from the group consisting of an alkali metal compound and an alkaline earth metal compound, and silica, and simultaneously satisfying the following two conditions.
- the ratio of the number of atoms of a metal atom in the metal compound and a silicon atom in the silica (hereinafter sometimes referred to as an atomic ratio, expressed as M / Si) measured with an X-ray photoelectron analyzer. 0.5-20.
- the specific surface area of the solid catalyst measured by a nitrogen gas adsorption method is 0.01 m 2 / g to 50 m 2 / g.
- the present invention 2 relates to the solid catalyst according to the present invention 1, which simultaneously satisfies the following two conditions.
- M / Si is 0.8-10.
- the surface area of the solid catalyst measured by a nitrogen gas adsorption method is 0.1 m 2 / g to 10 m 2 / g.
- the present invention 3 relates to the solid catalyst according to the present invention 1 or 2, wherein the alkali metal compound is a sodium compound or a cesium compound.
- the present invention 4 relates to the solid catalyst according to any one of the present inventions 1 to 3, wherein the alkaline earth metal compound is a magnesium compound or a calcium compound.
- the present invention 5 relates to the solid catalyst according to any one of the present inventions 1 to 4, wherein the silica is porous silica.
- the present invention 6 relates to the solid catalyst according to any one of the present inventions 1 to 5, wherein the silica is amorphous silica.
- the present invention 7 relates to the solid catalyst according to any one of the present inventions 1 to 6, wherein the silica has a median pore diameter measured by a mercury intrusion method of 0.1 ⁇ m to 10 ⁇ m.
- Invention 8 is prepared by adsorbing the metal compound on silica baked at 700 ° C. to 1200 ° C. for 1 to 20 hours and then baking at 300 ° C. to 1200 ° C. for 1 to 40 hours.
- the solid catalyst according to any one of 1 to 7.
- Invention 9 is prepared by adsorbing the metal compound on silica baked at 800 ° C. to 1100 ° C. for 1 to 10 hours and then baking at 500 ° C. to 1000 ° C. for 1 to 20 hours.
- the solid catalyst according to any one of 1 to 7.
- the present invention 10 relates to a method for producing an isocyanate compound, in which an isocyanate compound is produced from a carbamate compound in the presence of the solid catalyst according to any one of the present inventions 1 to 9.
- the carbamate compound is represented by the following general formula (1):
- n and R 1 have the same meanings as described above, and relates to the production method according to the tenth aspect of the present invention.
- This invention 12 is related with the manufacturing method of this invention 11 whose n is 2 in the said General formula (1) and (2).
- the present invention 13 relates to the production method according to any one of the present inventions 10 to 12, wherein a reaction temperature at the time of producing the isocyanate compound from the carbamate compound is 300 ° C. to 500 ° C.
- the present invention 14 relates to the production method according to any one of the present inventions 10 to 13, wherein the reaction pressure when producing the isocyanate compound from the carbamate compound is an absolute pressure of 0.1 kPa to 101.33 kPa.
- the present invention 15 relates to the production method according to any one of the present inventions 10 to 14, wherein the reaction for producing the isocyanate compound from the carbamate compound is performed in a gas phase.
- the present invention 16 relates to the production method according to any one of the present inventions 10 to 14, wherein the reaction for producing the isocyanate compound from the carbamate compound is performed in a liquid phase.
- the present invention 17 relates to the use of the solid catalyst according to any one of the present inventions 1 to 9 for the production of an isocyanate compound.
- the solid catalyst of the present invention the atomic ratio (M / Si) of the metal atom of the metal compound in the solid catalyst containing the predetermined metal compound and silica to the silicon atom in the silica, and nitrogen of the solid catalyst
- an isocyanate compound can be produced with high selectivity and high yield.
- such a solid catalyst can be produced with good reproducibility, and further, a method for producing an isocyanate compound using such a solid catalyst can be provided.
- the solid catalyst of the present invention is a catalyst preferably used for the production of an isocyanate compound, which contains at least one metal compound selected from the group consisting of an alkali metal compound and an alkaline earth metal compound, and silica.
- the solid catalyst of the present invention can be used in combination with other catalysts. Therefore, in the solid catalyst of the present invention, the metal compound and silica are different from the solid catalyst containing the metal compound and silica. What mixed physically the solid catalyst containing a different inorganic compound is also contained.
- the atomic ratio (M / Si) between the metal atom in the metal compound and the silicon atom in silica on the surface is 0.5 to 20, which is more preferable from the viewpoint of selectivity and yield. Is 0.7 to 10, more preferably 0.8 to 10, and particularly preferably 1 to 6.
- excellent selectivity is achieved by keeping the ratio of the number of metal atoms in the metal compound on the catalyst surface (which is thought to contribute mainly to the catalytic reaction) and the number of silicon atoms in silica within a certain range. And yields can be achieved.
- the atomic ratio (M / Si) on the surface of the above-mentioned solid catalyst is a value measured with an X-ray photoelectron analyzer (ESCA).
- the solid catalyst of the present invention has a specific surface area measured by the nitrogen gas adsorption method of 0.01 m 2 / g to 50 m 2 / g, and more preferably 0.1 m 2 from the viewpoint of selectivity and yield.
- Silica has pores, but the pores are broadly divided into three types: micropores, mesopores, and macropores.
- Micropores are pores with a diameter of less than 2 nm, mesopores with a diameter of 2 nm to 50 nm, and macropores with a diameter of more than 50 nm (see, for example, Carbon, 2008, 850-857.).
- Micropores and mesopores give the catalyst many reaction points, but on the other hand, the reaction substrate is strongly bound to the part, and even if the reaction is completed, the product does not desorb from it, or an unintended reaction Is considered to progress.
- silica is treated by a predetermined method described later, and the above-mentioned disadvantages are overcome by reducing the micropores and mesopores by controlling the specific surface area of the solid catalyst within a certain range. It is considered a thing.
- solid catalyst of the present invention in addition to silica, for example, activated carbon; metal oxides such as alumina, silica alumina, zirconia, and titania; composite metal oxides such as titania silica, titania zirconia, zirconia silica, and hydrotalcite Clay minerals such as kaolin, smectite, bentonite, chlorite, illite; metallosilicates such as zeolite; metal oxide precursors such as silica sol and alumina sol can be used, and alkali metal compounds and alkaline earth metals
- a solid catalyst containing at least one metal compound selected from the group consisting of compounds can also achieve excellent selectivity and yield.
- metal oxides and composite metal oxides are preferable, and alumina and silica alumina are more preferable.
- the silica used in the present invention is preferably amorphous silica.
- amorphous silica any of synthetic amorphous silica produced by a dry method or a wet method can be used.
- amorphous silica can be used for (2) pre-calcination step and (3) adsorption step in the catalyst preparation step, which will be described later, as it is, for example, a commercial product containing moisture.
- silica gel can also be used suitably.
- porous silica can be used as silica.
- Porous silica can also be used after sieving so as to be applicable to the apparatus.
- the particle diameter of the silica used in the present invention is not particularly limited, but is usually 0.5 mm to 10 mm.
- the median pore diameter of the silica measured by the mercury intrusion method is usually 8 nm to 300 ⁇ m, preferably 10 nm to 50 ⁇ m, more preferably 50 nm to 20 ⁇ m, and further preferably 0.1 ⁇ m to 10 ⁇ m.
- the pore diameter of silica can be measured by either the nitrogen gas adsorption method or the mercury intrusion method.
- the pore volume and specific surface area of the above-mentioned porous silica can be measured by any of the nitrogen gas adsorption method and the mercury intrusion method.
- the pore volume and specific surface area can be measured by the nitrogen gas adsorption method when the pore diameter of the porous silica is 0.4 nm to 200 nm, and can be measured by the mercury intrusion method when the pore diameter is 3.6 nm to 400 ⁇ m.
- measurement can be performed by either the nitrogen gas adsorption method or the mercury intrusion method.
- the porous silica preferably has a pore volume measured by mercury porosimetry from 0.01 mL / g to 2 mL / g, more preferably from 0.1 mL / g to 1 in terms of reaction activity and selectivity. 0.5 mL / g, more preferably 0.3 mL / g to 1 mL / g.
- the specific surface area of the porous silica measured by the mercury intrusion method is preferably 0.01 m 2 / g to 100 m 2 / g, more preferably 0.1 m 2 / g to 80 m 2 / g, Preferably, it is 0.3 m 2 / g to 50 m 2 / g.
- the pore volume of the porous silica measured by the nitrogen gas adsorption method is preferably 0.0001 mL / g to 1 mL / g, more preferably 0.0002 mL / g to 0.8 mL / g, Preferably, it is 0.0004 mL / g to 0.5 mL / g.
- the specific surface area of the porous silica measured by the nitrogen gas adsorption method is preferably 0.01 m 2 / g to 1000 m 2 / g, more preferably 0.01 m 2 / g to 100 m 2 / g. More preferred is 0.01 m 2 / g to 50 m 2 / g, and particularly preferred is 0.1 m 2 / g to 10 m 2 / g.
- any of the silicas described above may be used alone or in combination of two or more.
- At least one metal compound selected from the group consisting of alkali metal compounds and alkaline earth metal compounds is used.
- the alkali metal in the metal compound include lithium, sodium, potassium, rubidium, and cesium.
- the alkaline earth metal in the metal compound include beryllium, magnesium, calcium, strontium, barium and the like.
- sodium, cesium, magnesium, and calcium are preferable (that is, the alkali metal compound is preferably a sodium compound and a cesium compound, and the alkaline earth metal compound is preferably a magnesium compound and a calcium compound).
- it is calcium.
- the metal compound is not particularly limited as long as it is a compound of an alkali metal or alkaline earth metal with a predetermined element.
- Examples of the metal compound include metal oxides and composite oxides with silica. .
- an alkali metal compound or an alkaline earth metal compound is adsorbed on silica and calcined.
- the metal compound used in this adsorption step include alkali metal or alkaline earth metal inorganic acid salts such as nitrates, carbonates, hydrogen carbonates and silicates; alkalis such as fluorides and chlorides.
- the alkali metal compound and the alkaline earth metal compound may be hydrates.
- the total content of the metal compounds described above with respect to the total mass of the solid catalyst is preferably 0.01% by mass to 50% by mass in terms of each metal atom, More preferably, it is 0.05% by mass to 30% by mass, and still more preferably 0.1% by mass to 20% by mass.
- the content of the metal compound in the solid catalyst can be measured using, for example, fluorescent X-ray elemental analysis (XRF) or ICP-AES method.
- the particle size of the solid catalyst of the present invention is usually 1 mm to 10 mm, preferably 1 mm to 5 mm.
- the solid catalyst of the present invention for example, adsorbs at least one metal compound selected from the group consisting of an alkali metal compound and an alkaline earth metal compound on silica calcined at 700 ° C. to 1200 ° C. for 1 to 20 hours, It can be prepared by firing the fired silica adsorbing the metal compound at 300 ° C. to 1200 ° C. for 1 to 40 hours. More specifically, it is prepared by the following procedure, for example.
- Synthesis step silica is synthesized.
- Pre-firing step The obtained silica is fired to reduce micropores and mesopores.
- Adsorption process A metal compound is adsorbed on silica by an impregnation method or the like.
- Drying step the obtained solid is dried as necessary.
- Firing step The solid after drying is fired as necessary. Among these five steps, the important steps (2) and (5) will be described.
- the temperature in the baking treatment needs to be as high as 700 ° C. to 1200 ° C., and is preferably 800 ° C. to 1100 ° C., more preferably 900 ° C. to 1000 ° C. from the viewpoint of selectivity and yield.
- the specific surface area measured by the nitrogen gas adsorption method of the solid catalyst of the present invention obtained by reducing the micropores and mesopores in the silica and subsequent steps is controlled within the aforementioned range. Can do.
- the substrate is preferably easily detached from the solid catalyst of the present invention after the reaction, and reactions other than the target reaction are reduced.
- the specific surface area of silica is in a predetermined range at the stage of the synthesis step (1) before the pre-baking step (2), and will be described later without performing this step (2) (3) to (5). By passing through this process, the range of the specific surface area of the solid catalyst defined in the present invention may be achieved.
- this step (2) may be omitted.
- the approximate range of the specific surface area of silica at the stage of step (1), in which step (2) may be omitted, is determined by conducting a reasonable degree of test expected by those skilled in the art. The contractor can easily grasp.
- the time for firing the silica before the metal compound is adsorbed on the silica is 1 to 20 hours, more preferably 1 to 10 hours within the above temperature range.
- the specific surface area measured by the nitrogen gas adsorption method of the solid catalyst of this invention can be controlled to the above-mentioned range.
- the silica used in the pre-baking step (2) may be fired after sieving or the like so that the particle size is adjusted to 1 mm to 10 mm, more preferably 1 mm to 5 mm. desirable.
- Firing step After pre-firing the silica in step (2), the metal compound is adsorbed onto silica in step (3) described below, and the obtained solid is dried in step (4) as necessary, and further It is necessary to fire. Firing conditions can be appropriately adjusted depending on the type, form, content, dry state, etc. of an inorganic compound such as a metal compound and silica (such as silica and activated carbon described above).
- an inorganic compound such as a metal compound and silica (such as silica and activated carbon described above).
- the firing temperature is preferably 300 ° C to 1200 ° C, more preferably 500 ° C to 1000 ° C, and still more preferably 500 ° C to 800 ° C.
- the firing time is not particularly limited as long as the firing is sufficiently performed, but is preferably 1 hour to 40 hours, and more preferably 1 hour to 20 hours.
- the atomic ratio M / Si of the metal atom in the metal compound and the silicon atom in silica on the surface of the solid catalyst is controlled within the aforementioned range, and the necessary catalytic activity (reaction rate, reaction yield and selection) Improvement etc.) can be obtained.
- Silica can be synthesized according to a conventionally known method, and a commercially available product can be used as described above. Here, an example of a method for synthesizing silica will be described. Silica can be synthesized by mixing tetraethyl orthosilicate and nitric acid in a mixed solvent of water and polyethylene glycol, and drying after stirring and washing.
- the amount of water used here is preferably 0.1 mL to 3 mL, more preferably 0.5 mL to 2 mL with respect to 1 mL of tetraethyl orthosilicate.
- the polyethylene glycol to be used is preferably 0.01 mL to 0.2 mL, more preferably 0.02 mL to 0.1 mL with respect to 1 mL of tetraethyl orthosilicate. By setting it as this range, solidification of a reaction liquid can be prevented, maintaining favorable stirring property.
- the nitric acid used is, for example, preferably 0.01 mL to 0.1 mL, more preferably 0.02 mL to 0.08 mL with respect to 1 mL of tetraethyl orthosilicate when the concentration is 60%.
- the drying time after the silica gel synthesis is preferably 5 to 100 hours, more preferably 10 to 80 hours.
- the drying temperature is preferably 90 ° C to 150 ° C, more preferably 100 ° C to 120 ° C. By setting it as this range, the solvent in a silica gel can be reduced to the quantity which does not affect the next process within the above-mentioned time.
- baking may be performed at a temperature of about 600 ° C. in order to remove the residue of the material used for the synthesis of silica such as polyethylene glycol.
- the silica is pre-fired in the above-described step (2).
- This silica is impregnated with a metal compound.
- the metal compound used is an inorganic salt of an alkali metal or alkaline earth metal.
- a solid in which the metal compound is adsorbed on silica can be obtained by drying and filtering, drying or filtering.
- a method for drying and filtering a general method can be employed.
- a method of impregnating silica with a metal compound a usual method for preparing a solid catalyst can be used, and for example, a pore filling method, an evaporation to dryness method, an equilibrium adsorption method, an incipient wetness method, and the like can be applied.
- the solid obtained in the adsorption step is usually preferably dried for the purpose of removing the solvent used.
- the drying temperature during the production of the solid catalyst according to the present invention is preferably 50 ° C. to 150 ° C., more preferably 80 ° C. to 120 ° C.
- the drying time is preferably 6 hours to 36 hours, more preferably 12 hours to 24 hours. By setting it as this range, the solvent in the solid can be reduced to an amount that does not affect the next step.
- the solid catalyst thus obtained is obtained by calcining the solid thus obtained in the calcining step (5) described above.
- an alkali metal inorganic acid salt or the like is used in the adsorption step (3), it is considered that the inorganic acid salt or the like is oxidized by baking to become a metal oxide or a composite oxide with silica. It is done.
- the solid catalyst of the present invention described above can be used as a catalyst for various reactions, and is particularly useful as a catalyst for a reaction for producing an isocyanate compound from a carbamate compound.
- the method for producing an isocyanate compound of the present invention (hereinafter, also simply referred to as “the production method of the present invention”) is carried out by reacting a carbamate compound in the presence of the solid catalyst of the present invention.
- the production method of the present invention is preferably carried out by a pyrolysis reaction.
- a compound having at least one urethane bond (—NHCO 2 —) in the molecule is preferably used.
- R 1 represents a hydrocarbon group which may have a substituent.
- the hydrocarbon group include carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, and octadecyl.
- R 2 represents a hydrocarbon group which may have a substituent.
- the hydrocarbon group include carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, and octadecyl.
- An alkenyl group having 2 to 20 carbon atoms such as a propenyl group, a butenyl group or a pentenyl group;
- a cycloalkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cyclooctyl group, a dimethylcyclohexyl group, an isophorone group, a norbornane group, a decalin group, an adamantane group;
- Examples thereof include aryl groups containing 1 to 3 aromatic rings such as phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group, anthryl group and trimethylphenyl group. These groups include various isomers.
- examples of the substituent in the hydrocarbon group which may have the substituent include a hydroxyl group, a halogen atom, a cyano group, an amino group, and an alkylamino group.
- n is an integer of 1 to 4, which are those determined by the valency number corresponding R 1,
- R 1 is a monovalent radical (e.g., cyclohexyl)
- n is 1
- R 1 is a divalent group (for example, cyclohexylene group)
- n is 2.
- an alkyl group is exemplified as an example of the hydrocarbon group in R 1.
- the hydrocarbon group is a divalent group (alkylene) corresponding to the alkyl group. Group).
- n is 3, it is a corresponding trivalent group (alkanetriyl group).
- alkanetriyl group alkanetriyl group
- n is preferably 2 from the viewpoint of the usefulness of the isocyanate compound obtained by the production method of the present invention as various production raw materials.
- the carbamate compound used in the production method of the present invention is preferably a compound represented by the general formula (1) described above. Examples thereof include an aliphatic carbamate compound, an alicyclic carbamate compound, and an aromatic compound. Group carbamate compounds and the like.
- the aliphatic carbamate compound used in the production method of the present invention includes, for example, in the general formula (1), R 1 may have a substituent, an alkyl group having 1 to 20 carbon atoms, a carbon atom An alkenyl group having 2 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms, and R 2 may have a substituent and has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.
- Examples of the aliphatic carbamate compound used in the production method of the present invention include methylhexyl carbamate, methyl octyl carbamate, methyl dodecyl carbamate, methyl octadecyl carbamate, 1,4-bis (methoxycarbonylamino) butane, 1,4-bis.
- the alicyclic carbamate compound used in the production method of the present invention is, for example, a cycloalkyl group having 3 to 20 carbon atoms, in which R 1 in the general formula (1) may have a substituent.
- R 2 is a carbamate compound which may have a substituent and is an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- Examples of the alicyclic carbamate compound used in the production method of the present invention include 1,3- or 1,4-bis (methoxycarbonylamino) cyclohexane, 1,3- or 1,4-bis (ethoxycarbonylamino).
- R 1 is an aryl group containing an aromatic ring having 6 to 18 carbon atoms, which may have a substituent, and R 2 is substituted.
- Examples of the aromatic carbamate compound used in the production method of the present invention include 1,3- or 1,4-bis (methoxycarbonylaminomethyl) benzene, 1,3- or 1,4-bis (ethoxycarbonylaminomethyl).
- the corresponding isocyanate compound is produced from the carbamate compound represented by the general formula (1) described above.
- the isocyanate compound is preferably a compound represented by the following general formula (2). is there.
- R 1 and n have the same meanings as R 1 and n in the general formula (1).
- n is 2 or more
- a compound in which one,... (N ⁇ 1) carbamate groups are isocyanated may be obtained as an intermediate.
- isophorone dimethyl carbamate (1- (methoxycarbonylamino) -3,3,5-trimethyl-5- (methoxycarbonylaminomethyl) -cyclohexane) is used, in addition to the diisocyanate compound, Two types of monoisocyanate may be obtained.
- the solid catalyst of the present invention has a suitable reactivity by setting the metal atom / silicon atom atomic ratio between the metal compound and silica on the catalyst surface within a predetermined range, and the ratio of the catalyst measured by the nitrogen gas adsorption method. By keeping the surface area in a certain range, the reaction product is moderately easily desorbed.
- the isocyanate compound is produced by reacting a carbamate compound in the presence of the catalyst.
- the carbamate compound of the general formula (1) is reacted in the presence of the catalyst to produce the isocyanate compound of the general formula (2).
- the reaction form at this time is not particularly limited and may be either a gas phase reaction or a liquid phase reaction, but a gas phase reaction is desirable.
- a method used for a solid catalyst reaction such as a fixed bed method, a fluidized bed method, and a suspension bed method can be applied.
- a fixed bed system is preferably used.
- the gas phase fixed bed system preferably employed in the production method of the present invention includes, for example, a raw material tank (1), a substrate supply pump (2), a tubular reactor (3) filled with a catalyst, and a reactor shown in FIG. Heat source (tubular electric furnace, etc.) (4), product heat exchanger (6), receiver (7) for collecting condensed product isocyanate compound, alcohol (when producing isocyanate compound from carbamate compound)
- symbol in FIG. 1 is demonstrated in the Example mentioned later.
- the solid catalyst of the present invention is preferably used in an amount of 0.01 mL to 10 mL, more preferably 0.02 mL to 5 mL with respect to the substrate supply rate of 1 mL / h in the gas phase fixed bed system.
- the reaction may be performed with an inert gas such as nitrogen, or the reaction may be performed without using an inert gas. Or you may carry out under reduced pressure.
- an inert gas such as nitrogen
- these catalysts are preferably in the range of 0.1 to 100 parts by mass, for example, with respect to 100 parts by mass of the carbamate compound. Preferably, it is used in the range of 0.5 to 50 parts by mass.
- the reaction of the carbamate compound may be performed, for example, by heating the carbamate compound and the solid catalyst together with an inert solvent.
- the manufacturing method of this invention by the reactive distillation system which isolate
- the inert solvent is not particularly limited as long as it is inert with respect to the carbamate compound and the isocyanate compound to be formed. However, in order to carry out the reaction efficiently, it has a boiling point higher than that of the carbamate compound.
- a solvent is preferred. Examples of such a solvent include esters such as dioctyl phthalate, didecyl phthalate and didodecyl phthalate, or dibenzyl toluene, triphenylmethane, phenylnaphthalene, biphenyl, terphenyl, diethylbiphenyl, triethylbiphenyl, and the like. And aromatic hydrocarbons such as 1,3,5-triisopropylbenzene, aliphatic hydrocarbons, and the like. These solvents may be used alone or in combination of two or more. The amount used can be appropriately adjusted depending on the reaction apparatus and form.
- the inert solvent is preferably used in an amount of 0.1 to 150 mL, more preferably 1 to 50 mL, with respect to 1 mL of the carbamate compound. By setting it as this range, solidification of a reaction liquid can be prevented, maintaining favorable stirring property.
- the solid catalyst is preferably used in an amount of 0.01 mL to 10 mL, more preferably 0.02 mL to 5 mL with respect to the supply rate of 1 mL / h of the carbamate compound. By setting it as this range, an isocyanate compound can be obtained at an industrially suitable reaction rate.
- the reaction temperature of the carbamate compound is, for example, 80 ° C. to 600 ° C., preferably 200 ° C. to 500 ° C., and more preferably 300 ° C. to 500 ° C.
- a practical reaction (particularly thermal decomposition) rate can be obtained, and undesirable side reactions such as polymerization of isocyanate compounds can be suppressed.
- the reaction pressure is preferably a pressure at which the generated isocyanate compound and alcohol compound can be vaporized with respect to the above reaction temperature.
- the absolute pressure is 0.1 kPa to 101.33 kPa, and more preferably the absolute pressure is 0.5 kPa to 30 kPa.
- the aforementioned solid catalyst is preferably in the range of 0.1 to 100 parts by mass, more preferably 0 to 100 parts by mass of the carbamate compound. Used in the range of 5 to 50 parts by mass.
- the amount used is usually 1 to 30 mL per 1 g of the carbamate compound.
- the amount is preferably 1 to 10 mL.
- reaction pressure and temperature are as described above.
- the reaction time is appropriately adjusted depending on the amount of catalyst, temperature, substrate concentration and pressure, and is usually 0.5 to 10 hours, preferably 1 to 5 hours.
- the reaction may be carried out with an inert gas such as nitrogen, or the reaction may be carried out without using an inert gas. You may carry out under pressure or pressure reduction.
- the isocyanate compound obtained by the production method of the present invention is isolated and purified from the solution after the reaction by general operations such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography, and the like. Can do.
- the obtained isocyanate compound can be made into a high-purity isocyanate compound by further refining.
- the solid catalyst after completion of the reaction of the carbamate compound, can be easily recovered from the residual liquid of the reaction solution by a known separation method such as filtration or centrifugation, and the recovered solid catalyst can be used as it is or as a solvent. It can be reused after being reactivated by a known method such as washing or baking.
- the fired product was pulverized in a mortar and sieved to a particle size ranging from 1 mm to 2 mm to obtain 25 g of porous and amorphous silica gel.
- the median pore diameter of this silica gel was 7.5 ⁇ m as measured by mercury porosimetry (measurement device: fully automated pore distribution measurement device Pole Master 60-GT manufactured by Quanta Chrome Co.).
- the specific surface area of the solid catalyst measured by the nitrogen gas adsorption method is 0.3 m 2 / g, and the atomic ratio of calcium atoms to silicon atoms on the surface of the solid catalyst (Ca / Si) was 5.8.
- silica gel median pore diameter is measured by mercury porosimetry, and the measurement conditions are as follows.
- Quanta Chrome Co., Ltd. is a measuring device using the mercury intrusion method.
- measurement conditions of the mercury intrusion method measurement was performed while increasing the pressure from about 7 kPa to 414 MPa at room temperature.
- the mercury surface tension value was 480 dyn / cm, and the contact angle value was 140 °.
- the total catalyst Ca / Si ratio indicates the atomic ratio of calcium atoms to silicon atoms in the solid catalyst, and is a value calculated from the mass of the mixed silica gel and calcium nitrate.
- the Ca / Si ratio of the entire solid catalyst after preparation of the solid catalyst can be measured by fluorescent X-ray elemental analysis (XRF) or the like.
- the specific surface area of the solid catalyst represents the specific surface area of the solid catalyst after calcium is adsorbed and calcined (step (5) in catalyst preparation described above), and is measured by a nitrogen gas adsorption method.
- the measurement conditions are as follows.
- This measurement was performed by a physical adsorption method (nitrogen adsorption method) using a BET type powder specific surface area measuring device.
- “BELSORP-miniII” manufactured by Nippon Bell Co., Ltd. was used, nitrogen was used as the adsorption gas, and BET multipoint measurement was performed. Specifically, the powder sample is heated and deaerated under vacuum at a temperature of 150 ° C., then cooled to liquid nitrogen temperature to adsorb nitrogen gas, and the adsorption / desorption isotherm is measured. Calculated.
- the surface Ca / Si ratio indicates the atomic ratio of calcium atoms to silicon atoms on the surface of the solid catalyst and is analyzed by an X-ray photoelectron analyzer.
- the measurement conditions are as follows.
- a glass tube (3) having a diameter of 10 mm and a length of 42 cm is used as a reactor. 4) was installed.
- the lower part of the reactor is branched into two lines, each receiving a receiver (room temperature) (7) and (13) for obtaining an isocyanate compound, and a product heat exchanger (6) and ( 12), via a receiver for methanol acquisition (cooled with cold ethanol) (9) and (15) (in front of which there are heat exchangers (8) and (14) for methanol condensation, respectively)
- Both lines were connected to a vacuum pump (17) and the vacuum lines were connected. Switching between the two lines was performed by opening only one of the valves (5 and 10, and 11 and 16) (closing the other line).
- Isophorone dimethyl carbamate (1- (methoxycarbonylamino) -3,3,5-trimethyl-5- (methoxycarbonylaminomethyl) -cyclohexane) heated and melted at about 150 ° C. was added at 4 mL / h with a syringe pump (2). To the glass tube (3).
- Examples 2 to 6 Comparative Examples 1 to 5 (isophorone dimethyl carbamate (1- (methoxycarbonylamino) -3,3,5-trimethyl-5- (methoxycarbonylaminomethyl) using various Ca / SiO 2 ) -Production of isophorone diisocyanate by thermal decomposition of cyclohexane)] Isophorone diisocyanate was synthesized in the same manner as in Example 1 except that various conditions were changed as shown in Table 3 below.
- FIG. 2 shows a graph of Table 4 (Comparative Example 1 is not shown).
- the atomic ratio Ca / Si between the calcium atom and the silicon atom on the surface of the solid catalyst is 0.5-20, and the specific surface area of the solid catalyst is 0.01 m 2 / g-50 m 2 / g.
- the yield of the diisocyanate compound is 85% or more and the conversion rate of the dicarbamate compound is 100%.
- the solid catalyst does not satisfy any of the above-mentioned conditions (Comparative Examples 1 to 5), the yield and the conversion rate decrease.
- the fired product was pulverized in a mortar and sieved to a particle size range of 2 mm to 4 mm to obtain 55 g of porous and amorphous silica gel.
- the median pore diameter of this silica gel was 7.5 ⁇ m as measured by mercury porosimetry (measurement device: fully automated pore distribution measurement device Pole Master 60-GT manufactured by Quanta Chrome Co.).
- the obtained solid catalyst contained 0.84% by mass of sodium compound in terms of sodium atoms with respect to the entire solid catalyst. It was. That is, the atomic ratio (Na / Si) of sodium atoms to silicon atoms in the entire solid catalyst is 0.022.
- the specific surface area of the solid catalyst measured by the nitrogen gas adsorption method is 0.51 m 2 / g, and the atomic ratio (Na / Si) of sodium atoms to silicon atoms on the catalyst surface measured by an X-ray photoelectron analyzer is 0.5.
- Example 12 Except that the temperature of the catalyst layer was 365 ° C. and 3 mL of the solid catalyst (Na / SiO 2 : particle size 1.1 to 2.2 mm) obtained in Production Example 12 was used as the catalyst, the same as Example 1 was performed. Isophorone diisocyanate was produced.
- the yield of isophorone diisocyanate was 83% (selectivity 84%), and the yield of monoisocyanate was 17%.
- the fired product was pulverized in a mortar and sieved to a particle size range of 2 mm to 4 mm to obtain 55 g of porous and amorphous silica gel.
- the median pore diameter of this silica gel was 7.5 ⁇ m as measured by mercury porosimetry (measurement device: fully automated pore distribution measurement device Pole Master 60-GT manufactured by Quanta Chrome Co.).
- the specific surface area of the solid catalyst measured by the nitrogen gas adsorption method was 0.58 m 2 / g, and the atomic ratio of magnesium atoms to silicon atoms on the solid catalyst surface (Mg / Si) measured with an X-ray photoelectron analyzer was 1.9.
- the temperature of the catalyst layer was 365 ° C., and the same procedure as in Example 1 was performed except that 3 mL of the solid catalyst (Mg / SiO 2 : particle size 1.1 to 2.2 mm) obtained in Production Example 13 was used as the catalyst. Isophorone diisocyanate was produced.
- the yield of isophorone diisocyanate was 85% (selectivity 85%), and the yield of monoisocyanate was 12%.
- the atomic ratio M / Si of sodium atoms or magnesium atoms to silicon atoms on the surface of the solid catalyst is 0.5 to 20, and the specific surface area of the solid catalyst is 0.01 m 2 / g to 50 m 2. / G, it is understood that the yield of the diisocyanate compound is 83% or more when both conditions are satisfied.
- a part of the fired product was pulverized in a mortar and sieved to a particle size in the range of 1 mm to 2 mm to obtain 8.0 g of porous and amorphous silica gel.
- the median pore diameter of this silica gel was 6.1 ⁇ m as measured by a mercury intrusion method (measuring device: fully automated pore distribution measuring device Pole Master 60-GT manufactured by Quanta Chrome Co.).
- the temperature of the catalyst layer was 365 ° C., 3 mL of the solid catalyst (Ca / SiO 2 : particle size 1 to 2 mm) obtained in Production Example 14 was used as the catalyst, and 1,3-bis (methoxycarbonylaminomethyl) as the carbamate compound. ) 1,3-bis (isocyanatomethyl) cyclohexane was produced in the same manner as in Example 1 except that cyclohexane was used.
- a portion of the fired product was pulverized in a mortar and sieved to a particle size range of 1 mm to 2 mm to obtain 9 g of porous and amorphous silica gel.
- This silica gel had a median pore diameter of 1.0 ⁇ m as measured by a mercury intrusion method (measuring device: fully automated pore distribution measuring device Pole Master 60-GT manufactured by Quanta Chrome Co.).
- the temperature of the catalyst layer was 375 ° C., 3 mL of the solid catalyst (Ca / SiO 2 : particle size 1 to 2 mm) obtained in Production Example 15 was used as the catalyst, and 2,4-bis (methoxycarbonylamino) as the carbamate compound.
- Tolylene-2,4-diisocyanate was produced in the same manner as in Example 1 except that toluene was used.
- a solid catalyst useful as a heterogeneous catalyst for producing an isocyanate compound for example, can be produced with high selectivity and high yield and can be easily separated from the product.
- such a solid catalyst can be produced with good reproducibility, and further, a method for producing an isocyanate compound using such a solid catalyst can be provided.
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Abstract
Description
本発明1は、アルカリ金属化合物及びアルカリ土類金属化合物からなる群より選ばれた少なくとも1種の金属化合物、及びシリカを含んでおり、以下の2つの条件を同時に満たす固体触媒に関する。
(1)X線光電子分析装置で測定した、前記金属化合物における金属原子と前記シリカにおける珪素原子との原子の数の比(以下、原子比と称することがあり、M/Siと表す。)が0.5~20である。
(2)窒素ガス吸着法により測定した前記固体触媒の比表面積が0.01m2/g~50m2/gである。
(3)M/Siが0.8~10である。
(4)窒素ガス吸着法により測定した前記固体触媒の表面積が0.1m2/g~10m2/gである。
(B)固体触媒の調製方法
(C)イソシアネート化合物の製造方法
本発明の固体触媒は、アルカリ金属化合物及びアルカリ土類金属化合物からなる群より選ばれた少なくとも1種の金属化合物、及びシリカを含む、好適にはイソシアネート化合物の製造に用いられる触媒である。本発明の固体触媒は他の触媒と組み合わせて使用することができ、それゆえ本発明の固体触媒には、前記の金属化合物とシリカとを含む固体触媒に対し、前記の金属化合物とシリカとは異なる無機化合物とを含む固体触媒を物理的に混合したものも含まれる。
次に、本発明の固体触媒の製造方法について説明する。本発明の固体触媒は、例えば、700℃~1200℃で1~20時間焼成したシリカに、アルカリ金属化合物及びアルカリ土類金属化合物からなる群より選ばれた少なくとも1種の金属化合物を吸着させ、当該金属化合物を吸着させた焼成シリカを300℃~1200℃で1~40時間焼成することにより調製することができる。より具体的には、例えば以下のような手順で調製する。
(2)前焼成工程;得られたシリカを焼成し、ミクロ孔とメゾ孔を低減する。
(3)吸着工程;含浸法等により、金属化合物をシリカに吸着させる。
(4)乾燥工程;得られた固体を必要に応じて乾燥する。
(5)焼成工程;必要に応じて乾燥した後の固体を焼成する。
これら5工程の中で、重要な(2)及び(5)の工程から説明する。
本発明の固体触媒を調製する際に使用するシリカは、金属化合物を吸着させる前に、前述のミクロ孔とメゾ孔を低減する目的で焼成処理する必要がある。
工程(2)でシリカを前焼成した後、後述する工程(3)において金属化合物をシリカに吸着させ、得られた固体を必要に応じて工程(4)で乾燥後、更に焼成する必要がある。焼成条件は、金属化合物、シリカ等の無機化合物(前述のシリカや活性炭など)の種類、形態、含有量又は乾燥状態等によって適宜、調整することができる。
シリカは従来公知の方法に従って合成することができ、また上述の通り市販品も使用することができるが、ここではシリカの合成法の一例を説明する。水とポリエチレングリコールの混合溶媒に対しオルトケイ酸テトラエチルと硝酸を混合し、撹拌及び洗浄後に乾燥することでシリカを合成することができる。
工程(1)でシリカを合成した後、上述の工程(2)にてシリカを前焼成する。そして、このシリカに金属化合物を含浸させる。使用される金属化合物は、前述の通り、アルカリ金属やアルカリ土類金属の無機酸塩などである。
前記の吸着工程で得られた固体は通常、使用した溶媒の除去を目的として、乾燥することが好ましい。本発明による固体触媒製造時の乾燥温度は、好ましくは、50℃~150℃、更に好ましくは80℃~120℃である。乾燥時間は、好ましくは、6時間~36時間、更に好ましくは12時間~24時間である。この範囲とすることで、固体中の溶媒を次工程に影響のない量まで低減することができる。
以上説明した本発明の固体触媒は、各種の反応の触媒として使用しうるが、特にカルバメート化合物よりイソシアネート化合物を製造する反応の触媒として有用である。本発明のイソシアネート化合物の製造方法(以下、単に「本発明の製造方法」ともいう)は、本発明の固体触媒の存在下、カルバメート化合物を反応させることにより実施される。本発明の製造方法は、好ましくは熱分解反応により実施される。
当該炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、2-エチルヘキシル基、ノニル基、デシル基、ドデシル基、オクタデシル基等の炭素原子数1~20のアルキル基;
プロペニル基、ブテニル基、ペンテニル基等の炭素原子数2~20のアルケニル基;
メチリデン基、エチリデン基、プロピリデン基、ブチリデン基、ペンチリデン基、ヘキシリデン基等の炭素原子数1~20のアルキリデン基;
シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、メチルシクロヘキシル基、シクロオクチル基、メチルシクロヘキシルメチル基、ジメチルシクロヘキシル基、イソホロン基、ノルボルナン基、デカリン基、アダマンタン基、4,4’-メチレンビス(シクロヘキサン)基、2,4’-メチレンビス(シクロヘキサン)基等の炭素原子数3~20のシクロアルキル基;
1,4-シクロヘキシリデン基等の炭素原子数3~20のシクロアルキリデン基;
フェニル基、トリル基、キシリル基、ナフチル基、ビフェニル基、アントリル基、トリメチルフェニル基、4,4’-メチレンビスフェニレン基等の1~3個の芳香族環を含むアリール基等が挙げられる。なお、これらの基は、各種異性体を含む。
当該炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、2-エチルヘキシル基、ノニル基、デシル基、ドデシル基、オクタデシル基等の炭素原子数1~20のアルキル基;
プロペニル基、ブテニル基、ペンテニル基等の炭素原子数2~20のアルケニル基;
シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、メチルシクロヘキシル基、シクロオクチル基、ジメチルシクロヘキシル基、イソホロン基、ノルボルナン基、デカリン基、アダマンタン基等の炭素原子数3~20のシクロアルキル基;
フェニル基、トリル基、キシリル基、ナフチル基、ビフェニル基、アントリル基、トリメチルフェニル基等の1~3個の芳香族環を含むアリール基等が挙げられる。なお、これらの基は、各種異性体を含む。
反応時間は、触媒量、温度、基質の濃度及び圧力等によって適宜調節されるが、通常0.5~10時間、好ましくは1~5時間である。
水144.0g、ポリエチレングリコール(PEG、和光純薬工業株式会社製、平均分子量20,000)9.6gをポリエチレン容器の中で混合、攪拌し、均一溶液にした。これにオルトケイ酸テトラエチル(TEOS)120mL、60%硝酸水溶液(和光純薬工業株式会社製)8.4mLを加え、容器を密閉し室温(20℃~30℃)で1時間激しく攪拌した。
各種条件を、以下の表1、表2に示すとおりに変更した以外は製造例1と同様にして、各種Ca/SiO2固体触媒を調製した。
・装置名:PHI社製 Quantum2000
・X線源:単色化Al-Kα、出力15kV-20W(X線発生面積100μmφ)
・帯電中和:電子銃(20μA)、イオン銃(30V)併用
・分光系:パルスエネルギー187.85eV@ワイドスペクトル、46.95eV@ナロースペクトル(全元素)
・測定領域:スポット照射(照射面積<340μmφ)
・取り出し角:45°(表面より)
各種条件を、以下の表3に示すとおりに変更した以外は、実施例1と同様にして、ジイソシアン酸イソホロンを合成した。
水144.0g、ポリエチレングリコール(PEG、和光純薬工業株式会社製、平均分子量20,000)9.6gをポリエチレン容器の中で混合、攪拌し、均一溶液にした。これにオルトケイ酸テトラエチル(TEOS)120mL、60%硝酸水溶液(和光純薬工業株式会社製)8.4mLを加え、容器を密閉し室温(20℃~30℃)で1時間激しく攪拌した。
水144.0g、ポリエチレングリコール(PEG、和光純薬工業株式会社製、平均分子量20,000)9.6gをポリエチレン容器の中で混合、攪拌し、均一溶液にした。これにオルトケイ酸テトラエチル(TEOS)120mL、60%硝酸水溶液(和光純薬工業株式会社製)8.4mLを加え、容器を密閉し室温(20℃~30℃)で1時間激しく攪拌した。
水60g、ポリエチレングリコール(PEG、和光純薬工業株式会社製、平均分子量20,000)3.6gをポリエチレン容器の中で混合、攪拌し、均一溶液にした。これにオルトケイ酸テトラエチル(TEOS)60mL、60%硝酸水溶液(和光純薬工業株式会社製)4.2mLを加え、容器を密閉し室温(20℃~30℃)で1時間激しく攪拌した。
水120g、ポリエチレングリコール(PEG、和光純薬工業株式会社製、平均分子量20,000)9.6gをポリエチレン容器の中で混合、攪拌し、均一溶液にした。これにオルトケイ酸テトラエチル(TEOS)120mL、60%硝酸水溶液(和光純薬工業株式会社製)8.5mLを加え、容器を密閉し室温(20℃~30℃)で1時間激しく攪拌した。
1 原料タンク
2 基質供給ポンプ
3 触媒を充填した管状反応器
3a 気化層(石英充填)
3b 触媒層
4 反応器を加熱する熱源(管状電気炉)
5 弁
6 生成物熱交換器
7 凝縮した生成物のイソシアネート化合物を回収する受器
8 アルコール凝縮のための熱交換器
9 アルコール取得のための受器
10 弁
11 弁
12 生成物熱交換器
13 凝縮した生成物のイソシアネート化合物を回収する受器
14 アルコール凝縮のための熱交換器
15 アルコール取得のための受器
16 弁
17 真空ポンプ
Claims (17)
- アルカリ金属化合物及びアルカリ土類金属化合物からなる群より選ばれた少なくとも1種の金属化合物、及びシリカを含む、以下の2つの条件を同時に満たす固体触媒:
(1)X線光電子分析装置で測定した、前記金属化合物における金属原子と前記シリカにおける珪素原子との原子比(M/Si)が0.5~20である。
(2)窒素ガス吸着法により測定した前記固体触媒の比表面積が0.01m2/g~50m2/gである。 - 以下の2つの条件を同時に満たす、請求項1に記載の固体触媒:
(3)M/Siが0.8~10である。
(4)窒素ガス吸着法により測定した前記固体触媒の比表面積が0.1m2/g~10m2/gである。 - 前記アルカリ金属化合物がナトリウム化合物又はセシウム化合物である、請求項1又は2に記載の固体触媒。
- 前記アルカリ土類金属化合物がマグネシウム化合物又はカルシウム化合物である、請求項1~3のいずれか一項に記載の固体触媒。
- 前記シリカが多孔質シリカである、請求項1~4のいずれか一項に記載の固体触媒。
- 前記シリカが非晶質シリカである、請求項1~5のいずれか一項に記載の固体触媒。
- 前記シリカの、水銀圧入法で測定したメジアン細孔直径が0.1μm~10μmである、請求項1~6のいずれか一項に記載の固体触媒。
- 700℃~1200℃で1~20時間焼成したシリカに、前記金属化合物を吸着させた後、300℃~1200℃で1~40時間焼成したことにより調製された、請求項1~7のいずれか一項に記載の固体触媒。
- 800℃~1100℃で1~10時間焼成したシリカに、前記金属化合物を吸着させた後、500℃~1000℃で1~20時間焼成したことにより調製された、請求項1~7のいずれか一項に記載の固体触媒。
- 請求項1~9のいずれか一項に記載の固体触媒の存在下、カルバメート化合物よりイソシアネート化合物を製造する、イソシアネート化合物の製造方法。
- 前記一般式(1)及び(2)における、nが2である、請求項11に記載の製造方法。
- 前記カルバメート化合物より前記イソシアネート化合物を製造する際の反応温度が、300℃~500℃である、請求項10~12のいずれか一項に記載の製造方法。
- 前記カルバメート化合物より前記イソシアネート化合物を製造する際の反応圧力が、絶対圧0.1kPa~101.33kPaである、請求項10~13のいずれか一項に記載の製造方法。
- 前記カルバメート化合物より前記イソシアネート化合物を製造する際の反応を気相で行う、請求項10~14のいずれか一項に記載の製造方法。
- 前記カルバメート化合物より前記イソシアネート化合物を製造する際の反応を液相で行う、請求項10~14のいずれか一項に記載の製造方法。
- イソシアネート化合物の製造のための、請求項1~9のいずれか一項に記載の固体触媒の使用。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63183553A (ja) * | 1986-11-03 | 1988-07-28 | アメリカン・サイアナミド・カンパニー | メチルカルバメートのリモネンへの付加によるシクロヘキシルモノーおよびジーウレタンの製造法 |
JPH05186414A (ja) * | 1992-01-10 | 1993-07-27 | Nippon Shokubai Co Ltd | イソシアナート類の製造方法 |
JPH05186415A (ja) * | 1992-01-10 | 1993-07-27 | Nippon Shokubai Co Ltd | イソシアナート類の製造方法 |
JP2008029949A (ja) * | 2006-07-28 | 2008-02-14 | Gunma Prefecture | 選択的な炭素鎖延長反応用触媒、同触媒の製法およびそれを用いた炭化水素類の製造方法 |
WO2012111750A1 (ja) * | 2011-02-17 | 2012-08-23 | 宇部興産株式会社 | イソシアネート化合物製造用触媒及び当該触媒を用いたイソシアネート化合物の製造方法 |
WO2013008891A1 (ja) * | 2011-07-13 | 2013-01-17 | 宇部興産株式会社 | イソシアネート化合物の製造方法 |
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2014
- 2014-05-22 CN CN201480029670.4A patent/CN105263618B/zh not_active Expired - Fee Related
- 2014-05-22 JP JP2015518293A patent/JP6372484B2/ja not_active Expired - Fee Related
- 2014-05-22 WO PCT/JP2014/063619 patent/WO2014189120A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63183553A (ja) * | 1986-11-03 | 1988-07-28 | アメリカン・サイアナミド・カンパニー | メチルカルバメートのリモネンへの付加によるシクロヘキシルモノーおよびジーウレタンの製造法 |
JPH05186414A (ja) * | 1992-01-10 | 1993-07-27 | Nippon Shokubai Co Ltd | イソシアナート類の製造方法 |
JPH05186415A (ja) * | 1992-01-10 | 1993-07-27 | Nippon Shokubai Co Ltd | イソシアナート類の製造方法 |
JP2008029949A (ja) * | 2006-07-28 | 2008-02-14 | Gunma Prefecture | 選択的な炭素鎖延長反応用触媒、同触媒の製法およびそれを用いた炭化水素類の製造方法 |
WO2012111750A1 (ja) * | 2011-02-17 | 2012-08-23 | 宇部興産株式会社 | イソシアネート化合物製造用触媒及び当該触媒を用いたイソシアネート化合物の製造方法 |
WO2013008891A1 (ja) * | 2011-07-13 | 2013-01-17 | 宇部興産株式会社 | イソシアネート化合物の製造方法 |
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JP6372484B2 (ja) | 2018-08-15 |
JPWO2014189120A1 (ja) | 2017-02-23 |
CN105263618A (zh) | 2016-01-20 |
CN105263618B (zh) | 2018-02-16 |
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