CN103391813B - Isocyanate compound catalyst for producing and use the manufacture method of isocyanate compound of this catalyst - Google Patents
Isocyanate compound catalyst for producing and use the manufacture method of isocyanate compound of this catalyst Download PDFInfo
- Publication number
- CN103391813B CN103391813B CN201280009284.XA CN201280009284A CN103391813B CN 103391813 B CN103391813 B CN 103391813B CN 201280009284 A CN201280009284 A CN 201280009284A CN 103391813 B CN103391813 B CN 103391813B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- compound
- methyloxycarbonylamino
- isocyanate compound
- cyclohexane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000003054 catalyst Substances 0.000 title claims abstract description 160
- -1 Isocyanate compound Chemical class 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 69
- 239000012948 isocyanate Substances 0.000 title claims abstract description 62
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 64
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims abstract description 38
- 239000011575 calcium Substances 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- DUDXQIXWPJMPRQ-UHFFFAOYSA-N isocyanatomethylcyclohexane Chemical compound O=C=NCC1CCCCC1 DUDXQIXWPJMPRQ-UHFFFAOYSA-N 0.000 claims description 25
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 20
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229940043430 calcium compound Drugs 0.000 claims description 16
- 150000001674 calcium compounds Chemical class 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- RDZZSLRUHLWLAV-UHFFFAOYSA-N methyl n-(cyclohexylmethyl)carbamate Chemical compound COC(=O)NCC1CCCCC1 RDZZSLRUHLWLAV-UHFFFAOYSA-N 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 12
- OXNAJPQXTZANJL-UHFFFAOYSA-N methyl n-hexylcarbamate Chemical compound CCCCCCNC(=O)OC OXNAJPQXTZANJL-UHFFFAOYSA-N 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- IESROWBDLANHBQ-UHFFFAOYSA-N dimethylcarbamic acid;3,5,5-trimethylcyclohex-2-en-1-one Chemical compound CN(C)C(O)=O.CC1=CC(=O)CC(C)(C)C1 IESROWBDLANHBQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 abstract description 25
- 150000001339 alkali metal compounds Chemical class 0.000 abstract description 25
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 25
- 239000000969 carrier Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 description 41
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical class CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 31
- 238000010438 heat treatment Methods 0.000 description 30
- YAQPZDICKJDHTR-UHFFFAOYSA-N hexylcarbamic acid Chemical class CCCCCCNC(O)=O YAQPZDICKJDHTR-UHFFFAOYSA-N 0.000 description 30
- 238000004458 analytical method Methods 0.000 description 27
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 24
- 239000000376 reactant Substances 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 238000004811 liquid chromatography Methods 0.000 description 17
- 229910004298 SiO 2 Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000005297 pyrex Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 150000001340 alkali metals Chemical class 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 10
- 150000001342 alkaline earth metals Chemical class 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 9
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000006630 butoxycarbonylamino group Chemical group 0.000 description 6
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 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 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 4
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 150000002642 lithium compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 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 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229940072033 potash Drugs 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 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 3
- 238000009826 distribution Methods 0.000 description 3
- 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 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KBRSJPHSCOAFDR-UHFFFAOYSA-N 3-chloro-6-methyl-5,5-dioxo-11h-benzo[c][2,1]benzothiazepin-11-ol Chemical compound O=S1(=O)N(C)C2=CC=CC=C2C(O)C2=CC=C(Cl)C=C21 KBRSJPHSCOAFDR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-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
- 229910002651 NO3 Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 230000001476 alcoholic effect Effects 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
- 239000011324 bead Substances 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
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([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
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 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
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 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
- 239000000945 filler Substances 0.000 description 2
- 238000010574 gas phase reaction 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
- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 229910052749 magnesium Inorganic materials 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 239000000843 powder Substances 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
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 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
- 239000012974 tin catalyst Substances 0.000 description 2
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- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-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
- OLCIOXGQTLVZQT-UHFFFAOYSA-N 3-methylbutyl carbamate Chemical compound CC(C)CCOC(N)=O OLCIOXGQTLVZQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- RMYMMJJLFLNOAN-UHFFFAOYSA-N NC(=O)OCC.C(C)O[Si](OCC)(OCC)SSSSCCC.[Si] Chemical class NC(=O)OCC.C(C)O[Si](OCC)(OCC)SSSSCCC.[Si] RMYMMJJLFLNOAN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004647 alkyl sulfenyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 230000008901 benefit Effects 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
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-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
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [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 GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 description 1
- PILVIBLEOYWKLP-UHFFFAOYSA-N diethylcarbamic acid;toluene Chemical class CC1=CC=CC=C1.CCN(CC)C(O)=O PILVIBLEOYWKLP-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 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
- KXABTIOYSXLRSL-UHFFFAOYSA-N dodecyl(methyl)carbamic acid Chemical class CCCCCCCCCCCCN(C)C(O)=O KXABTIOYSXLRSL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 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
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- IMXBRVLCKXGWSS-UHFFFAOYSA-N methyl 2-cyclohexylacetate Chemical class COC(=O)CC1CCCCC1 IMXBRVLCKXGWSS-UHFFFAOYSA-N 0.000 description 1
- ONDKZBMQUACRQG-UHFFFAOYSA-N methyl n-[1,6-bis(methoxycarbonylamino)hexan-3-yl]carbamate Chemical compound COC(=O)NCCCC(NC(=O)OC)CCNC(=O)OC ONDKZBMQUACRQG-UHFFFAOYSA-N 0.000 description 1
- VLPBGAPTYGNIII-UHFFFAOYSA-N methyl n-[4-[4-(methoxycarbonylamino)phenyl]phenyl]carbamate Chemical group C1=CC(NC(=O)OC)=CC=C1C1=CC=C(NC(=O)OC)C=C1 VLPBGAPTYGNIII-UHFFFAOYSA-N 0.000 description 1
- ZWZIHLRSOOMEKT-UHFFFAOYSA-N methyl n-benzylcarbamate Chemical compound COC(=O)NCC1=CC=CC=C1 ZWZIHLRSOOMEKT-UHFFFAOYSA-N 0.000 description 1
- IZPAJCSXPWFEPU-UHFFFAOYSA-N methyl n-naphthalen-1-ylcarbamate Chemical compound C1=CC=C2C(NC(=O)OC)=CC=CC2=C1 IZPAJCSXPWFEPU-UHFFFAOYSA-N 0.000 description 1
- RRQZQNFQNFVZCU-UHFFFAOYSA-N methyl n-nonylcarbamate Chemical compound CCCCCCCCCNC(=O)OC RRQZQNFQNFVZCU-UHFFFAOYSA-N 0.000 description 1
- QXOUFQKDZIMOMU-UHFFFAOYSA-N methyl n-octylcarbamate Chemical compound CCCCCCCCNC(=O)OC QXOUFQKDZIMOMU-UHFFFAOYSA-N 0.000 description 1
- VBJIQWCGMYVMKK-UHFFFAOYSA-N methyl n-pentylcarbamate Chemical compound CCCCCNC(=O)OC VBJIQWCGMYVMKK-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RFPMGSKVEAUNMZ-UHFFFAOYSA-N pentylidene Chemical group [CH2+]CCC[CH-] RFPMGSKVEAUNMZ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
- B01J23/04—Alkali metals
-
- 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
- B01J35/643—Pore diameter less than 2 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
- B01J35/647—2-50 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of the isocyanate compound catalyst for producing and the manufacture method thereof that have alkali metal compound and/or alkali earth metallic compound at supported on carriers.In addition, the present invention relates to a kind of manufacture method of isocyanate compound, it is characterized in that, under the existence of described catalyst, make carbamate compounds thermal decomposition.
Description
Technical field
The present invention relates to a kind of the isocyanate compound catalyst for producing and the manufacture method thereof that have alkali metal compound and/or alkali earth metallic compound at supported on carriers.In addition, the present invention relates to a kind of manufacture method of isocyanate compound, it is characterized in that, under the existence of above-mentioned catalyst, make carbamate compounds thermal decomposition.
Background technology
Isocyanate compound has high response, is such as the raw material of polyurethane, pharmaceuticals, agricultural chemicals etc. and widely used useful compound.
Isocyanate compound industrially primarily of amines and phosgene reaction and manufacture (for example, referring to patent document 1).But, the strong toxicity of phosgene, trivial operations, and secondary can bear a large amount of hydrochloric acid, therefore there is the problem needing to worry corrosion of equipment etc.Therefore, the industrially preparing process of the isocyanate compound developing a kind of alternative the method is wished.
As the manufacture method of isocyanate compound not using phosgene, such as, there will be a known the method (for example, referring to patent document 2) making carbamate compounds thermal decomposition.But, because the reactivity of carbamate compounds is low, need to carry out thermal decomposition under the temperature conditions of harshness, therefore exist and produce side reaction and the low problem of the yield of the isocyanate compound obtained by thermal decomposition.Therefore, the scheme using various catalyst has been proposed.
Known following method: as 1 of above-mentioned catalyst, the two dodecyloxy-1 of 3-, 1, under the existence of the solid acid catalysts such as organotin catalysts and MCM-41, TS-1 such as 3,3-tetrabutyltin oxygen alkane, make 1,6-hexa-methylene dimethylcarbamate (1, two (methyloxycarbonylamino) hexane of 6-), the carbamate compounds thermal decomposition such as 1,3-two (Methoxycarbonylmethyl) cyclohexanes and manufacture the method (for example, referring to patent document 3) of isocyanate compound; Use dibutyl tin laurate as catalyst, make 1,6-hexa-methylene two (3-methyl butyl) carbamate (1, two (the 3-methylbutoxy group carbonylamino) hexane of 6-) etc. carbamate compounds thermal decomposition and manufacture the method (for example, referring to patent document 4) of isocyanate compound; Use dibutyl tin laurate as catalyst, make the carbamate compounds thermal decompositions such as the γ containing silicon-triethoxysilylpropyltetrasulfide urethanes and manufacture the method (for example, referring to patent document 5) of isocyanate compound; And, use stannous chloride as catalyst, make the carbamate compounds thermal decompositions such as two (4-butoxycarbonylamino group cyclohexyl) methane and manufacture the method (for example, referring to patent document 6) etc. of isocyanate compound.
The thermal decomposition of these tin catalysts known to carbamate compounds demonstrates good reaction achievement.But, because tin catalyst exists to solve homogeneously in state in reactant liquor, therefore there is catalyst component and be mixed into possibility in product, and indicate the toxicity of organotin catalysts.In addition, also exist and be used for catalyst recovery and the problem of the trivial operations re-used, being therefore difficult to is industrial preferred manufacture method.
On the other hand, as the method addressed these problems, also proposed and use heterogeneous system catalyst, make carbamate compounds thermal decomposition and manufacture the method for isocyanate compound.
Known following method: use calcium oxide, magnesia, barium monoxide, magnesium metal etc. as above-mentioned heterogeneous system catalyst, make the toluene diethylamino formic acid esters thermal decomposition as carbamate compounds, manufacture isocyanate compound (for example, referring to patent document 2); Use sodium carbonate, calcium carbonate etc. as heterogeneous system catalyst, make N-(m-isopropenyl-α, α-dimethylbenzyl) carbamic acid isopropyl ester, N-(m-vinyl-α, α-dimethylbenzyl) carbamic acid isopropyl ester thermal decomposition, and react while making isocyanates distillate outside reaction system, manufacture isocyanate compound (for example, referring to patent document 7 or patent document 8) etc.
On the other hand, solvent is not used as use heterogeneous system catalyst, and under gas phase condition, make carbamate and catalyst exposure, carry out thermal decomposition to manufacture the method for isocyanate compound, such as, known following method etc.: use and be selected from the transition metal of the Ib race in the periodic table of elements to VIII, the oxidate sintered body of the above element of at least one in lanthanide series and actinides, or the oxidate sintered body containing alkali metal and/or alkaline-earth metal element is as catalyst, manufacture isocyanates (such as, with reference to patent document 9 or patent document 10).Sinter under the catalyst of patent document 9 and 10 high temperature more than 1000 DEG C, almost there is no micropore, and surface area is minimum.
But, although these heterogeneous system catalyst have product and the segregative advantage of catalyst, the activity of the thermal decomposition for carbamate compounds and isocyanate compound selective in Shortcomings.Therefore, wish that exploitation is a kind of compared with above-mentioned catalyst, industrially can manufacture the catalyst of isocyanate compound with high selectivity and high yield.
At first technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 11-310566 publication
Patent document 2: Japanese Unexamined Patent Publication 54-88201 publication
Patent document 3: Japanese Unexamined Patent Publication 2004-262892 publication
Patent document 4: No. 2008/084824th, International Publication
Patent document 5: Japanese Unexamined Patent Publication 2008-1613 publication
Patent document 6: Japanese Unexamined Patent Publication 2006-36778 publication
Patent document 7: Japanese Unexamined Patent Publication 2003-012632 publication
Patent document 8: Japanese Unexamined Patent Publication 2004-018507 publication
Patent document 9: Japanese Unexamined Patent Publication 5-186414 publication
Patent document 10: Japanese Unexamined Patent Publication 5-186415 publication
Summary of the invention
The problem that invention will solve
The present invention is in view of the situation of above-mentioned prior art, its problem is, provide a kind of thermal decomposition rate of carbamate compounds fast, isocyanate compound can be manufactured with high selectivity with high yield, solve the problems such as the separation and recovery of catalyst is difficult and the catalyst be easily separated with product.In addition, its problem is, provides a kind of manufacture method using the isocyanate compound of this catalyst.
For solving the method for problem
The present inventor conducts in-depth research in view of the above problems, found that, by the isocyanate compound catalyst for producing at supported on carriers alkali metal compound and/or alkali earth metallic compound, can solve the problem, and complete the present invention thus.In addition, when manufacturing isocyanate compound making carbamate compounds thermal decomposition, be used in the above-mentioned catalyst that supported on carriers has alkali metal compound or alkali earth metallic compound, find the infant industry manufacture method that can manufacture isocyanate compound with high selectivity and high yield thus, thus complete the present invention.
The present invention is as described below.
1. an isocyanate compound catalyst for producing, it has alkali metal compound and/or alkali earth metallic compound at supported on carriers.
2. the catalyst according to above-mentioned 1, it have passed through and burns till at 400 ~ 800 DEG C.
3. the catalyst according to above-mentioned 1 or 2, wherein, alkali metal compound and/or alkali earth metallic compound are converted into alkali metal and/or alkaline-earth metal, then relative to catalyst, load has alkali metal compound and/or the alkali earth metallic compound of 0.05 ~ 30 quality %.
4. the catalyst according to above-mentioned 1 or 2, wherein, alkali metal compound and/or alkali earth metallic compound are converted into alkali metal and/or alkaline-earth metal, then relative to catalyst, load capacity has alkali metal compound and/or the alkali earth metallic compound of 0.1 ~ 20 quality %.
5. the catalyst according to any one of above-mentioned 1 ~ 4, wherein, carrier is silica.
6. the catalyst according to any one of above-mentioned 1 ~ 5, wherein, alkali metal compound and/or alkali earth metallic compound are lithium compound, calcium compound, strontium compound or barium compound.
7. the catalyst according to any one of above-mentioned 1 ~ 5, wherein, alkali metal compound and/or alkali earth metallic compound are lithium compound or calcium compound.
8. the catalyst according to any one of above-mentioned 1 ~ 7, is characterized in that, the mean pore footpath of carrier is 0.1nm ~ 20 μm.
9. a manufacture method for the catalyst according to any one of above-mentioned 1 ~ 8, wherein, makes alkali metal compound and/or alkali earth metallic compound be impregnated in carrier, and carries out drying.
10. a manufacture method for the catalyst according to any one of above-mentioned 1 ~ 8, wherein, makes alkali metal compound and/or alkali earth metallic compound be impregnated in carrier, carries out drying, then burn till.
The manufacture method of 11. catalyst according to above-mentioned 10, wherein, firing temperature is 400 ~ 800 DEG C.
12. 1 kinds of manufacture methods obtaining isocyanate compound, is characterized in that, under the existence of the catalyst described in above-mentioned 1 ~ 8, make carbamate compounds thermal decomposition.
13. manufacture methods according to above-mentioned 12, is characterized in that, the carbamate compounds of carbamate compounds represented by general formula (1),
[in formula, R
1and R
2can be identical or different, expression can have substituent alkyl, and n represents the integer of 1 ~ 4],
The isocyanate compound of isocyanate compound represented by general formula (2),
[in formula, n, R
1with above-mentioned synonym].
14. manufacture methods according to above-mentioned 12 or 13, it is characterized in that, the heat decomposition temperature of carbamate compounds is 80 ~ 500 DEG C.
15. manufacture methods according to any one of above-mentioned 12 ~ 14, it is characterized in that, the thermal decomposition pressure of carbamate compounds is 0.1 ~ 90kPa.
16. manufacture methods according to any one of above-mentioned 12 ~ 15, is characterized in that, carry out the thermal decomposition of carbamate compounds in the gas phase.
17. manufacture methods according to any one of above-mentioned 12 ~ 15, is characterized in that, carry out the thermal decomposition of carbamate compounds in the liquid phase.
Invention effect
According to the present invention, can provide a kind of and can manufacture isocyanate compound with high selectivity and high yield and product and catalyst is segregative, the manufacture heterogeneous system catalyst of isocyanate compound.
Detailed description of the invention
Below, the present invention is described in detail.
Catalyst of the present invention is the isocyanate compound catalyst for producing having alkali metal compound and/or alkali earth metallic compound at supported on carriers.Catalyst of the present invention comprises: the material of the different types of alkali metal compound of load and/or alkali earth metallic compound in same vehicle; Or by the material of the isocyanate compound catalyst for producing physical mixed of load on different carriers.
As the carrier used in the present invention, such as, silica, aluminium oxide, sial, zirconia, titanium oxide, active carbon etc. can be enumerated, in addition, the composite oxides such as titanium silicon (titaniasilica), titanium zirconium (titaniazirconia), zirconium silicon (zirconiasilica), hydrotalcite can also be enumerated; The clay minerals such as kaolin, montmorillonite, bentonite, chlorite, illite; The metal silicates etc. such as zeolite.As the carrier used in the present invention, be preferably silica, aluminium oxide, sial, and be particularly preferably silica.Also the presoma such as Ludox, Alumina gel can suitably be used.
The particle diameter of the carrier used in the present invention, is not particularly limited, and can suitably use.
The micropore diameter of the carrier used in the present invention, is not particularly limited, and can suitably use, such as, be 0.1nm ~ 20 μm.When using catalyst of the present invention in the gas phase, with regard to the micropore diameter of carrier used in the present invention, its mean pore footpath is preferably 50nm ~ 20 μm, is particularly preferably 100nm ~ 10 μm.Such as, pass through AppliedCatalysisA:General284(2005) method recorded in 247-251, namely, use tetraethyl orthosilicate to use polyethylene glycol as the sol-gal process of microcellular structure directed agents (template) as silicon source, the silica in the mean pore footpath had about 50nm ~ 20 μm can be manufactured.Mean pore footpath can be measured by mercury penetration method.
Catalyst of the present invention is such as at 300 DEG C ~ 1000 DEG C, is preferably 400 ~ 800 DEG C, is particularly preferably the catalyst burnt till at 500 ~ 600 DEG C.
With regard to the micropore diameter of catalyst of the present invention, its mean pore footpath is such as 0.1nm ~ 20 μm, is preferably 50nm ~ 20 μm, is particularly preferably 100nm ~ 10 μm.Mean pore footpath can be measured by mercury penetration method.
As the alkali metal of load on catalyst of the present invention or alkaline-earth metal, such as, lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium etc. can be enumerated, be preferably lithium, sodium, potassium, magnesium, calcium, strontium, barium, more preferably lithium, potassium, strontium, barium, most preferably is lithium or calcium.The alkali metal compound of catalyst institute of the present invention load or alkali earth metallic compound, can be one or more, such as, have: the inorganic acid salt of the alkali metal such as nitrate, carbonate, bicarbonate, silicate or alkaline-earth metal; The halide of the alkali metal such as fluoride, chloride or alkaline-earth metal; The hydroxide of alkali metal or alkaline-earth metal; The oxide of alkali metal or alkaline-earth metal; Or the acylate of the alkali metal such as acetate, oxalates or alkaline-earth metal.
With regard to catalyst of the present invention, alkali metal compound and/or alkali earth metallic compound are converted into the load capacity of alkali metal and/or alkaline-earth metal, then relative to catalyst, load has preferably 0.01 ~ 50 quality %, more preferably 0.05 ~ 30 quality %, the alkali metal compound most preferably being 0.1 ~ 20 quality % and/or alkali earth metallic compound.The load capacity of the alkali metal compound in catalyst and/or alkali earth metallic compound etc., such as, can use ICP-AES method etc. to measure.Such as, as pre-treatment, catalyst (heating) can be made to be dissolved in the aqueous solution of various acid (such as, nitric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid etc.), then to measure.Then, the titer (commercially available) of the amount of metal containing regulation can be used to carry out quantitatively as benchmark.
The manufacture method of isocyanate compound catalyst for producing of the present invention, by making supported on carriers alkali metal compound and/or alkali earth metallic compound and implementing.Alkali metal compound and/or alkali earth metallic compound, same as described above.Such as, by making alkali metal compound and/or alkali earth metallic compound be impregnated in carrier, and carry out drying and implement.Baking temperature, is preferably 50 ~ 150 DEG C, is particularly preferably 80 ~ 120 DEG C.Drying time, be preferably 6 ~ 36 hours, and be particularly preferably 12 ~ 24 hours.
Method in carrier is impregnated in as making alkali metal compound or alkali earth metallic compound, the usual way preparing solid catalyst can be used, such as, pore filling method, evaporation drying solidification method, Equilibrium Adsorption Method, Incipientwetness method etc. can be suitable for.
There is the material of alkali metal compound or alkali earth metallic compound at supported on carriers, can directly use, also can burn till further.Such as, when the nitrate of carrying alkali metal also burns till in atmosphere, firing temperature is such as 300 DEG C ~ 1000 DEG C, is preferably 400 ~ 800 DEG C, is particularly preferably 500 ~ 600 DEG C.Firing time is preferably 1 ~ 10 hour, more preferably 2 ~ 5 hours.The firing temperature preferably do not changed at the micropore diameter burning till front and back carrier and/or catalyst and/or firing time.
The manufacture method of isocyanate compound of the present invention, by under the existence of catalyst having alkali metal compound and/or alkali earth metallic compound at supported on carriers, makes carbamate compounds thermal decomposition and implements.
The carbamate compounds used in method of the present invention, is suitable for using and in molecule, has at least one amino-formate bond (-NHCO represented by general formula (1)
2-) compound,
[in formula, R
1and R
2can be identical or different, expression can have substituent alkyl, and n represents the integer of 1 ~ 4].
In above-mentioned general formula (1), R
1expression can have substituent alkyl, as alkyl, such as, can enumerate: the carbon numbers such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, 2-ethylhexyl, nonyl, decyl, dodecyl, octadecyl are the alkyl of 1 ~ 20; The carbon numbers such as acrylic, cyclobutenyl, pentenyl are the thiazolinyl of 2 ~ 20; The carbon numbers such as ethidine, propylidene base, fourth fork base, pentylidene base, oneself fork base are the alkylidene radical of 2 ~ 20; Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, methylcyclohexyl, ring octyl group, Dimethylcyclohexyl, isophorone base, norborny, naphthalane base (decalinyl), adamantyl, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexane) base, 2, the carbon numbers such as 4 '-di-2-ethylhexylphosphine oxide (cyclohexane) base, Isosorbide-5-Nitrae-cyclohexylidene are the cycloalkyl of 3 ~ 20; Phenyl, tolyl, xylyl, naphthyl, xenyl, anthryl, trimethylphenyl, 4, the aryl etc. comprising aromatic ring of 4 '-methylene diphenylene etc. 1 ~ 3 ring.It should be noted that, these groups comprise various isomers.
In above-mentioned general formula (1), R
2expression can have substituent alkyl, as alkyl, such as, can enumerate: the carbon numbers such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, 2-ethylhexyl, nonyl, decyl, dodecyl, octadecyl are the alkyl of 1 ~ 20; The carbon numbers such as acrylic, cyclobutenyl, pentenyl are the thiazolinyl of 2 ~ 20; The carbon numbers such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, methylcyclohexyl, ring octyl group, Dimethylcyclohexyl, isophorone base, norborny, naphthalane base, adamantyl are the cycloalkyl of 3 ~ 20; The aryl etc. comprising aromatic ring of 1 ~ 3 rings such as phenyl, tolyl, xylyl, naphthyl, xenyl, anthryl, trimethylphenyl.It should be noted that, these groups comprise various isomers.
In above-mentioned general formula (1), the above-mentioned substituting group can with substituent alkyl, such as, can enumerate: hydroxyl, halogen atom, cyano group, amino, alkyl amino, carboxyl, alkoxyl, aryloxy group, alkyl sulfenyl, artyl sulfo, (methyl) acryloxy etc.
In above-mentioned general formula (1), n is the integer of 1 ~ 4, but it is by corresponding to R
1bonding valence mumber and determine, such as, work as R
1when being 1 valency group (such as, cyclohexyl), n is 1; Work as R
1during for divalent group (such as, cyclohexylidene), n is 2.
The carbamate compounds used in method of the present invention, such as, can enumerate aliphatic urethane compound, alicyclic urethane compound, aromatic series urethane compound etc.
The aliphatic urethane compound used in method of the present invention is following carbamate compounds, that is, in above-mentioned general formula (1), and R
1for can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl, maybe can have the alkylidene radical that substituent carbon number is 1 ~ 20, R
2in order having, substituent carbon number is 1 ~ 20, preferred carbon number is the alkyl or phenyl of 1 ~ 6.As the aliphatic urethane compound used in method of the present invention, such as, can enumerate: methylhexyl carbamate, Methyl Octyl carbamate, methyl dodecylamino formic acid esters, methyl octadecyl carbamate, Isosorbide-5-Nitrae-bis-(methyloxycarbonylamino) butane, Isosorbide-5-Nitrae-bis-(ethoxycarbonylamino group) butane, Isosorbide-5-Nitrae-bis-(butoxycarbonylamino group) butane, two (methyloxycarbonylamino) pentane of 1,5-, two (methyloxycarbonylamino) hexane of 1,6-, two (ethoxycarbonylamino group) hexane of 1,6-, two (butoxycarbonylamino group) hexane of 1,6-, two (methyloxycarbonylamino) octane of 1,8-, two (butoxycarbonylamino group) octane of 1,8-, two (the phenoxycarbonylamino)-4-(phenoxycarbonylamino methyl of 1,8-) octane, two (methyloxycarbonylamino) nonane of 1,9-, two (butoxycarbonylamino group) nonane of 1,9-, two (the methyloxycarbonylamino)-decane of 1,10-, two (the butoxycarbonylamino group)-dodecane of 1,12-, two (the methyloxycarbonylamino)-dodecane of 1,12-, two (the phenoxycarbonylamino)-dodecane of 1,12-, 1,3,6-tri-(methyloxycarbonylamino) hexane, 1,3,6-tri-(phenoxycarbonylamino) hexane etc.
The alicyclic urethane compound used in method of the present invention is following carbamate compounds, that is, in above-mentioned general formula (1), and R
1for the cycloalkyl that substituent carbon number is 3 ~ 20 can be had, R
2for the alkyl or phenyl that substituent carbon number is 1 ~ 6 can be had.As the alicyclic urethane compound used in method of the present invention, such as, can enumerate: 1,3-or Isosorbide-5-Nitrae-bis-(methyloxycarbonylamino) cyclohexane, 1,3-or Isosorbide-5-Nitrae-bis-(ethoxycarbonylamino group) cyclohexane, 1,3-or Isosorbide-5-Nitrae-bis-(butoxycarbonylamino group) cyclohexane, 1,3-or Isosorbide-5-Nitrae-bis-(methyloxycarbonylamino methyl) cyclohexane, 1,3-or Isosorbide-5-Nitrae-bis-(ethoxycarbonylamino group methyl) cyclohexane, 1,3-or Isosorbide-5-Nitrae-bis-(Butyloxycarbonylaminomethyl) cyclohexane, 2,4 '-or 4,4 '-bis-(methyloxycarbonylamino) dicyclohexyl methyl hydride, 2,4 '-or 4,4 '-bis-(ethoxycarbonylamino group) dicyclohexyl methyl hydride, 2,4 '-or 4,4 '-bis-(butoxycarbonylamino group) dicyclohexyl methyl hydride, 2,4 '-or 4,4 '-bis-(phenoxycarbonylamino) dicyclohexyl methyl hydride, two (methyloxycarbonylamino methyl) two rings [2.2.1] heptane of 2,5-, 2,5-two (Butyloxycarbonylaminomethyl) two ring [2.2.1] heptane, two (methyloxycarbonylamino methyl) two rings [2.2.1] heptane of 2,6-, 2,6-two (Butyloxycarbonylaminomethyl) two ring [2.2.1] heptane, 1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane, 1-(butoxycarbonylamino group)-3,3,5-trimethyl-5-(Butyloxycarbonylaminomethyl)-cyclohexane, 3-(methyloxycarbonylamino methyl)-3,5,5-trimethyl-1-(methyloxycarbonylamino) cyclohexane, 4,4 '-bis-(methyloxycarbonylamino)-2,2 '-dicyclohexyl propane, 4,4 '-bis-(butoxycarbonylamino group)-2,2 '-dicyclohexyl propane etc.
With regard to the aromatic series urethane compound used in method of the present invention, R
1for can have substituting group and carbon number be 6 ~ 18 the aryl comprising aromatic ring, R
2for the alkyl or phenyl that substituent carbon number is 1 ~ 6 can be had.As the aromatic series urethane compound used in method of the present invention, such as, can enumerate: 1,3-or Isosorbide-5-Nitrae-bis-(methyloxycarbonylamino methyl) benzene, 1,3-or Isosorbide-5-Nitrae-bis-(ethoxycarbonylamino group methyl) benzene, 1,3-or Isosorbide-5-Nitrae-bis-(Butyloxycarbonylaminomethyl) benzene, 1,3-or Isosorbide-5-Nitrae-bis-(methyloxycarbonylamino) benzene, 1,3-or Isosorbide-5-Nitrae-bis-(butoxycarbonylamino group) benzene, 2,2 '-bis-(4-propoxy carbonylamino phenyl) propane, 2,4 '-or 4,4 '-bis-(methyloxycarbonylamino) diphenyl methane, 2,4 '-bis-(ethoxycarbonylamino group) diphenyl methane, 2,4 '-bis-(butoxycarbonylamino group) diphenyl methane, 4,4 '-bis-(phenoxycarbonylamino) diphenyl methane, two (methyloxycarbonylamino) naphthalene of 1,5-or 2,6-, two (butoxycarbonylamino group) naphthalene of 1,5-or 2,6-, 4,4 '-bis-(methyloxycarbonylamino) biphenyl, 4,4 '-bis-(butoxycarbonylamino group) biphenyl, two (methyloxycarbonylamino) toluene of 2,4-or 2,6-, two (ethoxycarbonylamino group) toluene of 2,4-or 2,6-, two (butoxycarbonylamino group) toluene of 2,4-or 2,6-etc.
In the method for the invention, isocyanate compound is by under the existence of above-mentioned catalyst, and carbamate compounds thermal decomposition is manufactured.Preferably under the existence of above-mentioned catalyst, make the carbamate compounds thermal decomposition of above-mentioned formula (1), thus manufacture the isocyanate compound of above-mentioned formula (2).Now, reactive mode is not particularly limited, any one in gas-phase reaction, liquid phase reactor.In addition, reactive mode can apply the mode that fixed bed mode, thermopnore mode, suspension bed mode etc. can be used for solid catalyst reaction.Particularly preferably use fixed bed mode or suspension bed mode.
During liquid phase reactor, preferably use liquid phase suspension bed mode further.In addition, during gas-phase reaction, gas phase fixed bed mode is preferably used further.
In the method for the invention, when using catalyst in the liquid phase, these catalyst relative to carbamate compounds, such as preferred with the scope of 0.1 ~ 100 quality %, preferably further to use with the scope of 0.5 ~ 50 quality %.
In the method for the invention, when using catalyst in the gas phase, these catalyst such as relative to the feed speed 1g/h of the carbamate as matrix, preferably with 0.01 ~ 5g, preferably further to use with the scope of 0.02 ~ 3g.
In the method for the invention, when using catalyst in the liquid phase, the thermal decomposition of carbamate compounds, such as, as long as make carbamate compounds with solid catalyst, carry out heating together with torpescence solvent, in addition, the reaction distillation mode be separated to outside system preferably by the isocyanate compound making to generate in this thermal decomposition, alcoholic compound is implemented.
In the method for the invention, when using catalyst in the gas phase, the material after catalyst particle being shaped to suitable size is filled in reaction tube, and can at inactive gas such as use nitrogen as diluent, or do not use inactive gas, under normal or reduced pressure, react under carbamate is with gas phase existent condition.
In the method for the invention, when using catalyst in the liquid phase, as long as torpescence solvent is torpescence relative to the isocyanate compound of carbamate compounds and generation, be just not particularly limited, in order to effectively implement thermal decomposition, preferred boiling point is higher than the solvent of carbamate compounds.As this solvent, can enumerate: the ester classes such as such as o-phthalic acid dibutyl ester, didecyl phthalate, phthalic acid two (dodecyl) ester, or, such as dibenzyl toluene, triphenyl methane, phenylnaphthalene, biphenyl, terphenyl, diethyl biphenyl, triethyl group biphenyl, 1, the fragrant family hydrocarbon such as 3,5-triisopropylbenzene or fatty family hydrocarbon etc.
In the method for the invention, when using catalyst in the liquid phase, such as, relative to carbamate compounds 1g, preferably use the torpescence solvent of 0.1 ~ 150g, preferably use the torpescence solvent of 1 ~ 50g further.
In the method for the invention, when using catalyst, the heat decomposition temperature of carbamate compounds, such as, be preferably 80 DEG C ~ 500 DEG C.
In the method for the invention, when using catalyst in the liquid phase, the heat decomposition temperature of carbamate compounds, such as, be preferably 80 DEG C ~ 350 DEG C, more preferably 100 DEG C ~ 300 DEG C.If heat decomposition temperature is the scope of 80 ~ 350 DEG C, then can obtain practical thermal decomposition rate, and the not preferred side reactions such as the polymerization of isocyanate compound can be suppressed.
In the method for the invention, when using catalyst in the gas phase, the heat decomposition temperature of carbamate compounds, such as, be preferably 250 DEG C ~ 500 DEG C, more preferably 300 DEG C ~ 450 DEG C.
In the method for the invention, when using catalyst in the liquid phase, thermal decomposition pressure is preferably relative to above-mentioned heat decomposition temperature, the pressure that the isocyanate compound generated and alcoholic compound can gasify, and consider from equipment aspect and effectiveness aspect, in actual use, thermal decomposition pressure is preferably 0.1 ~ 90kPa, more preferably 0.5 ~ 30kPa.
In the method for the invention, when using catalyst in the gas phase, thermal decomposition pressure is preferably relative to above-mentioned heat decomposition temperature, the pressure that carbamate can gasify, and consider from equipment aspect and effectiveness aspect, in actual use, thermal decomposition pressure is preferably 0.1 ~ 30kPa, more preferably 0.1 ~ 10kPa.
According to method of the present invention, isocyanate compound can be obtained with high selectivity and high yield.Then, by known process for purification such as distillations, more highly purified isocyanate compound can be obtained.
In addition, after the thermal decomposition of carbamate compounds terminates, with regard to using the situation of catalyst in the liquid phase, can by known separation methods such as filtration or centrifugations, easily from the raffinate of reactant liquor, reclaim solid catalyst, the solid catalyst of recovery, can directly re-use, or by solvent wash, the activate again of known method such as to burn till, then re-use.
With regard to using the situation of catalyst in the gas phase, due to reaction product and catalyst separation, therefore directly solid catalyst can be reclaimed, the solid catalyst reclaimed, can directly re-use, or by solvent wash, the activate again of known method such as to burn till, then re-use.
Embodiment
Next, enumerate embodiment and the present invention is specifically described, but scope of the present invention is not limited thereto.
[embodiment 1]
(Ca/SiO
2the preparation of catalyst)
Mix and blend calcium nitrate 4 hydrate 1.6g(6.7mmol in flask) and ion exchange water 13.0g, obtain calcium nitrate aqueous solution.SiO 2 powder (Silysia chemical company of Fuji CARiACTQ10, particle diameter is 20 ~ 150 μm, and micropore diameter is 10nm) 4.0g(66.6mmol is added in this calcium nitrate aqueous solution), at room temperature stir 1 hour.Then, evaporation drying, at 110 DEG C, drying 12 hours, burns till 2 hours in atmosphere, at 500 DEG C, obtains catalyst (Ca/SiO
2) 4.3g.Catalyst (the Ca/SiO of gained
2) in, calcium compound is scaled calcium, then relative to catalyst, load has the calcium compound of 6.2 quality %.
[embodiment 2]
(Li/SiO
2the preparation of catalyst)
Mix and blend lithium nitrate 0.46g(6.7mmol in flask) and ion exchange water 13.0g, obtain the lithium nitrate aqueous solution.SiO 2 powder (Silysia chemical company of Fuji CARiACTQ10, particle diameter is 20 ~ 150 μm, and micropore diameter is 10nm) 4.0g(66.6mmol is added in this lithium nitrate aqueous solution), at room temperature stir 1 hour.Then, evaporation drying, at 110 DEG C, drying 12 hours, burns till 2 hours in atmosphere, at 500 DEG C, obtains catalyst (Li/SiO
2) 4.0g.Catalyst (the Li/SiO of gained
2) in, lithium compound is scaled lithium, load has the lithium compound of 1.2 quality % relative to catalyst.
[embodiment 3]
(manufacture of the hexyl isocyanates implemented by the thermal decomposition of hexylamino formic acid esters)
Using 100ml flask as reactor, make its via Webster still (Claisen-type), for make isocyanates condensing cooling tube (20 DEG C of water flowings), for obtain isocyanates flask, be connected with vavuum pump for the collector (cooling with cold ethanol) obtaining methyl alcohol, link vacuum pipeline.To in the flask of reactor, add methylhexyl carbamate 10g(62.9mmol), the catalyst (Ca/SiO that prepared by embodiment 1
2) 0.2g, NeoSK-OIL1400(Zong Yan Tecnix Inc., principal component: dibenzyl toluene) 10g.Be decompressed to 6.0kPa, use oil bath to be heated to 180 DEG C.In intensification, beginning distillates.After 3.5 hours, the liquid in reactor distillates substantially, then terminates.Gas chromatography analysis is adopted to distillate composition, wherein containing hexyl isocyanates 20.6mmol, hexylamino formic acid esters 7.2mmol.In addition, hexyl isocyanates 1.6mmol, hexylamino formic acid esters 22.9mmol is contained in reactor.It is 68% that result obtains hexyl isocyanates 22.2mmol(selection rate, and yield is 35%), and to have reclaimed hexylamino formic acid esters 30.1mmol(conversion ratio be 52%).
[embodiment 4]
(manufacture of the hexyl isocyanates implemented by the thermal decomposition of hexylamino formic acid esters)
Use the catalyst (Li/SiO prepared by embodiment 2
2) 0.8g as catalyst, in addition, carry out the operation identical with embodiment 3.From heating starts after 3.7 hours, the liquid in reactor distillates substantially, then terminates.Gas chromatography analysis is adopted to distillate composition, containing hexyl isocyanates 20.0mmol, hexylamino formic acid esters 6.2mmol.In addition, hexyl isocyanates 0.8mmol, hexylamino formic acid esters 25.0mmol is contained in reactor.It is 66% that result obtains hexyl isocyanates 20.8mmol(selection rate, and yield is 33%), and to have reclaimed hexylamino formic acid esters 31.2mmol(conversion ratio be 50%).
[comparative example 1]
(manufacture of the hexyl isocyanates implemented by the thermal decomposition of hexylamino formic acid esters)
Use barium monoxide (BaO) 0.2g as catalyst, in addition, carry out the operation identical with embodiment 3.From heating starts after 3.5 hours, the liquid in reactor distillates substantially, then terminates.Gas chromatography analysis is adopted to distillate composition, wherein containing hexyl isocyanates 15.7mmol, hexylamino formic acid esters 4.2mmol.In addition, hexyl isocyanates 1.1mmol, hexylamino formic acid esters 26.1mmol is contained in reactor.It is 51% that result obtains hexyl isocyanates 16.8mmol(selection rate, and yield is 27%), and to have reclaimed hexylamino formic acid esters 30.3mmol(conversion ratio be 52%).
[comparative example 2]
(manufacture of the hexyl isocyanates implemented by the thermal decomposition of hexylamino formic acid esters)
Use barium monoxide (BaO) 0.4g as catalyst, in addition, carry out the operation identical with embodiment 3.From heating starts after 1.6 hours, the liquid in reactor distillates substantially, then terminates.Gas chromatography analysis is adopted to distillate composition, wherein containing hexyl isocyanates 16.1mmol, hexylamino formic acid esters 6.4mmol.In addition, hexyl isocyanates 0.7mmol, hexylamino formic acid esters 24.8mmol is contained in reactor.It is 53% that result obtains hexyl isocyanates 16.8mmol(selection rate, and yield is 27%), and to have reclaimed hexylamino formic acid esters 31.2mmol(conversion ratio be 50%).
[comparative example 3]
(manufacture of the hexyl isocyanates implemented by the thermal decomposition of hexylamino formic acid esters)
Use calcium oxide (CaO) 0.2g as catalyst, in addition, carry out the operation identical with embodiment 3.From heating starts after 4.1 hours, the liquid in reactor distillates substantially, then terminates.Gas chromatography analysis is adopted to distillate composition, wherein containing hexyl isocyanates 17.8mmol, hexylamino formic acid esters 9.4mmol.In addition, hexyl isocyanates 0.6mmol, hexylamino formic acid esters 19.1mmol is contained in reactor.It is 54% that result obtains hexyl isocyanates 18.4mmol(selection rate, and yield is 29%), and to have reclaimed hexylamino formic acid esters 28.5mmol(conversion ratio be 52%).
[comparative example 4]
(manufacture of the hexyl isocyanates implemented by the thermal decomposition of hexylamino formic acid esters)
Use calcium oxide (CaO) 0.4g as catalyst, in addition, carry out the operation identical with embodiment 3.From heating starts after 1.5 hours, the liquid in reactor distillates substantially, then terminates.Gas chromatography analysis is adopted to distillate composition, wherein containing hexyl isocyanates 9.6mmol, hexylamino formic acid esters 4.4mmol.In addition, hexyl isocyanates 0.7mmol, hexylamino formic acid esters 31.4mmol is contained in reactor.It is 38% that result obtains hexyl isocyanates 10.3mmol(selection rate, and yield is 16%), and to have reclaimed hexylamino formic acid esters 35.8mmol(conversion ratio be 43%).
[comparative example 5]
(manufacture of the hexyl isocyanates implemented by the thermal decomposition of hexylamino formic acid esters)
Use magnesia (MgO) 0.4g as catalyst, in addition, carry out the operation identical with embodiment 3.From heating starts after 1.6 hours, the liquid in reactor distillates substantially, then terminates.Gas chromatography analysis is adopted to distillate composition, wherein containing hexyl isocyanates 11.6mmol, hexylamino formic acid esters 5.0mmol.In addition, hexyl isocyanates 0.9mmol, hexylamino formic acid esters 36.1mmol is contained in reactor.It is 57% that result obtains hexyl isocyanates 12.5mmol(selection rate, and yield is 20%), and to have reclaimed hexylamino formic acid esters 41.1mmol(conversion ratio be 35%).
[comparative example 6]
(manufacture of the hexyl isocyanates implemented by the thermal decomposition of hexylamino formic acid esters)
Use potash (K
2cO
3) 0.2g as catalyst, in addition, carry out the operation identical with embodiment 3.From heating starts after 2.1 hours, the liquid in reactor distillates substantially, then terminates.Gas chromatography analysis is adopted to distillate composition, wherein containing hexyl isocyanates 3.8mmol, hexylamino formic acid esters 3.0mmol.In addition, hexyl isocyanates 0.3mmol, hexylamino formic acid esters 46.9mmol is contained in reactor.It is 31% that result obtains hexyl isocyanates 4.1mmol(selection rate, and yield is 6%), and to have reclaimed hexylamino formic acid esters 49.9mmol(conversion ratio be 21%).
[comparative example 7]
(manufacture of the hexyl isocyanates implemented by the thermal decomposition of hexylamino formic acid esters)
Use potash (K
2cO
3) 0.4g as catalyst, in addition, carry out the operation identical with embodiment 3.From heating starts after 1.8 hours, the liquid in reactor distillates substantially, then terminates.Gas chromatography analysis is adopted to distillate composition, wherein containing hexyl isocyanates 11.4mmol, hexylamino formic acid esters 10.4mmol.In addition, hexyl isocyanates 0.1mmol, hexylamino formic acid esters 19.9mmol is contained in reactor.It is 35% that result obtains hexyl isocyanates 11.5mmol(selection rate, and yield is 18%), and to have reclaimed hexylamino formic acid esters 30.3mmol(conversion ratio be 48%).
[comparative example 8]
(manufacture of the hexyl isocyanates implemented by the thermal decomposition of hexylamino formic acid esters)
Use sodium carbonate (Na
2cO
3) 0.8g as catalyst, in addition, carry out the operation identical with embodiment 3.From heating starts after 1.8 hours, the liquid in reactor distillates substantially, then terminates.Gas chromatography analysis is adopted to distillate composition, wherein containing hexyl isocyanates 1.4mmol, hexylamino formic acid esters 10.6mmol.In addition, hexyl isocyanates 0.2mmol, hexylamino formic acid esters 47.9mmol is contained in reactor.It is 36% that result obtains hexyl isocyanates 1.6mmol(selection rate, and yield is 3%), and to have reclaimed hexylamino formic acid esters 58.5mmol(conversion ratio be 7%).
Then, the result of embodiment 3 and 4 and comparative example 1 to comparative example 8 is shown in table 1.
[table 1]
[embodiment 5]
(manufacture of 1,3-two (isocyanatomethyl) cyclohexane implemented by the thermal decomposition of two (methyloxycarbonylamino methyl) cyclohexane of 1,3-)
Using the four-hole boiling flask of 500ml as reactor, via the dropping funel for adding carbamate wherein, thermometer, be filled with 4 Sulzer fillers (25mm Φ × 53mm) rectifying column, for condensing isocyanates cooling tube (70 DEG C of water flowings), for obtain isocyanates flask, be connected with vavuum pump for the collector (cooling with cold ethanol) obtaining methyl alcohol, link vacuum pipeline.To in the flask of reactor, add two (methyloxycarbonylamino methyl) the cyclohexane 10.0g(38.7mmol of 1,3-), the catalyst (Ca/SiO that prepared by embodiment 1
2) 0.8g, NeoSK-OIL1400(Zong Yan Tecnix Inc., principal component: dibenzyl toluene) 190g.Be decompressed to 1.33kPa, use oil bath to be heated to 240 DEG C.After 30 minutes, more slowly add two (methyloxycarbonylamino methyl) the cyclohexane 30g(116.1mmol of 1,3-by dropping funel).From heating starts after 5 hours, the liquid in reactor distillates substantially, then terminates.Liquid chromatography analysis is adopted to distillate composition, wherein containing 1,3-two (isocyanatomethyl) cyclohexane 111.7mmol, monoisocyanates 13.3mmol.In addition, 1,3-two (isocyanatomethyl) cyclohexane 14.5mmol, monoisocyanates 10.3mmol is contained in reactor.It is 82% that result obtains two (isocyanatomethyl) cyclohexane 126.2mmol(selection rate of 1,3-, and yield is 82%), and to obtain monoisocyanates 23.6mmol(yield be 12%).
[embodiment 6]
(by isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) thermal decomposition and the manufacture of the IPDI implemented)
Using the four-hole boiling flask of 500ml as reactor, via the dropping funel for adding carbamate wherein, thermometer, be filled with 4 Sulzer fillers (25mm Φ × 53mm) rectifying column, for condensing isocyanates cooling tube (70 DEG C of water flowings), for obtain isocyanates flask, be connected with vavuum pump for the collector (cooling with cold ethanol) obtaining methyl alcohol, link vacuum pipeline.To in the flask of reactor, add isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) 10.0g(34.9mmol), the catalyst (Ca/SiO that prepared by embodiment 1
2) 0.8g, NeoSK-OIL1400(Zong Yan Tecnix Inc., principal component: dibenzyl toluene) 190g.Be decompressed to 1.20kPa, use oil bath to be heated to 240 DEG C.After 30 minutes, more slowly add isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl by dropping funel)-cyclohexane) 30g(104.8mmol).From heating starts after 5 hours, the liquid in reactor distillates substantially, then terminates.Liquid chromatography analysis is adopted to distillate composition, wherein containing IPDI 85.0mmol, monoisocyanates 14.0mmol.In addition, IPDI 16.8mmol, monoisocyanates 10.1mmol is contained in reactor.It is 73% that result obtains IPDI 101.8mmol(selection rate, and yield is 73%), and to obtain monoisocyanates 25.1mmol(yield be 18%).
[comparative example 9]
(manufacture of 1,3-two (isocyanatomethyl) cyclohexane implemented by the thermal decomposition of two (methyloxycarbonylamino methyl) cyclohexane of 1,3-)
Use calcium oxide (CaO) 0.8g as catalyst, in addition, carry out the operation identical with embodiment 5.From heating starts after 4.6 hours, the liquid in reactor distillates substantially, then terminates.Liquid chromatography analysis is adopted to distillate composition, wherein containing 1,3-two (isocyanatomethyl) cyclohexane 106.2mmol, monoisocyanates 13.8mmol.In addition, 1,3-two (isocyanatomethyl) cyclohexane 10.3mmol, monoisocyanates 2.3mmol is contained in reactor.It is 75% that result obtains two (isocyanatomethyl) cyclohexane 116.5mmol(selection rate of 1,3-, and yield is 75%), and to obtain monoisocyanates 16.1mmol(yield be 10%).
[comparative example 10]
(manufacture of 1,3-two (isocyanatomethyl) cyclohexane implemented by the thermal decomposition of two (methyloxycarbonylamino methyl) cyclohexane of 1,3-)
Use potash (K
2cO
3) 0.8g as catalyst, in addition, carry out the operation identical with embodiment 5.From heating starts after 4.9 hours, the liquid in reactor distillates substantially, then terminates.Liquid chromatography analysis is adopted to distillate composition, wherein containing two (isocyanatomethyl) cyclohexane 0.9mmol of 1,3-.In addition, 1,3-two (isocyanatomethyl) cyclohexane 3.5mmol, monoisocyanates 0.1mmol is contained in reactor.It is 3% that result obtains two (isocyanatomethyl) cyclohexane 4.4mmol(selection rate of 1,3-, and yield is 3%), and to obtain monoisocyanates 0.1mmol(yield be 0.1%).
[comparative example 11]
(manufacture of 1,3-two (isocyanatomethyl) cyclohexane implemented by the thermal decomposition of two (methyloxycarbonylamino methyl) cyclohexane of 1,3-)
Use barium monoxide (BaO) 0.8g as catalyst, in addition, carry out the operation identical with embodiment 5.From heating starts after 5.0 hours, the liquid in reactor distillates substantially, then terminates.Liquid chromatography analysis is adopted to distillate composition, wherein containing 1,3-two (isocyanatomethyl) cyclohexane 81.8mmol, monoisocyanates 11.5mmol.In addition, 1,3-two (isocyanatomethyl) cyclohexane 12.8mmol, monoisocyanates 8.1mmol is contained in reactor.It is 61% that result obtains two (isocyanatomethyl) cyclohexane 94.6mmol(selection rate of 1,3-, and yield is 61%), and to obtain monoisocyanates 19.6mmol(yield be 13%).
[comparative example 12]
(by isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) thermal decomposition and the manufacture of the IPDI implemented)
Use barium monoxide (BaO) 0.8g as catalyst, in addition, carry out the operation identical with embodiment 6.From heating starts after 5.0 hours, the liquid in reactor distillates substantially, then terminates.Liquid chromatography analysis is adopted to distillate composition, wherein containing IPDI 54.0mmol, monoisocyanates 4.5mmol.In addition, IPDI 20.1mmol, monoisocyanates 0.7mmol is contained in reactor.It is 53% that result obtains IPDI 74.1mmol(selection rate, and yield is 53%), and to obtain monoisocyanates 5.2mmol(yield be 4%).
[comparative example 13]
(by isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) thermal decomposition and the manufacture of the IPDI implemented)
Use potash (K
2cO
3) 1.6g as catalyst, in addition, carry out the operation identical with embodiment 6.From heating starts after 3.0 hours, owing to not observing distillating of liquid in reactor, therefore stop heating.Containing IPDI 2.4mmol, monoisocyanates 0.2mmol in reactor.It is 2% that result obtains IPDI 2.4mmol(selection rate, and yield is 2%), and to obtain monoisocyanates 0.2mmol(yield be 0.1%).
Then, the result of embodiment 5 and 6 and comparative example 9 to comparative example 13 is shown in table 2.
[table 2]
[embodiment 7]
(Ca/SiO
2the preparation of catalyst)
In polyethylene can, mixing water 30.0g, polyethylene glycol (Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity is 20000) 1.8g, stir, and forms homogeneous solution.Add tetraethyl orthosilicate 30ml, 60% aqueous solution of nitric acid (Wako Pure Chemical Industries, Ltd.'s system) 2.9g wherein, airtight and vigorous stirring 1 hour.Then at 50 DEG C, leave standstill 12 hours, take out the gel generated, with purified water washing, then at 110 DEG C dry 12 hours, burn till 2 hours in atmosphere, at 600 DEG C, obtain silica dioxide gel 7.6g.The mean pore footpath of this silica dioxide gel adopting mercury penetration method (determinator: QuantaChromeCo. system full-automatic micropore distribution measurement device PoreMaster60-GT) to measure is 5.1 μm.Pulverized in mortar, and the size of particle is sized to the scope of 1mm ~ 2mm.Mix and blend calcium nitrate 4 hydrate 0.6g(2.5mmol in flask) and ion exchange water 1.5g, obtain calcium nitrate aqueous solution.Prepared silica dioxide gel 1.5g(25.0mmol is added in this calcium nitrate aqueous solution), at 110 DEG C, drying 12 hours, burns till 2 hours in atmosphere, at 500 DEG C, obtains catalyst (Ca/SiO
2) 1.7g.Catalyst (the Ca/SiO of gained
2) in, calcium compound is scaled calcium, then relative to catalyst, load has the calcium compound of 6.0 quality %.
[embodiment 8]
(manufacture of 1,3-two (isocyanatomethyl) cyclohexane implemented by the thermal decomposition of two (methyloxycarbonylamino methyl) cyclohexane of 1,3-)
Take diameter as 10mm, the length Pyrex glass tube that is 42cm is as reactor, and from outer setting electric furnace with the temperature making catalyst layer reach regulation, in reaction tube bottom via the collector (room temperature) for obtaining isocyanates, be connected with vavuum pump for the collector (cooling with cold ethanol) obtaining methyl alcohol, link vacuum pipeline.
Catalyst (the Ca/SiO prepared by embodiment 7 is filled in above-mentioned Pyrex glass tube
2) 1.0g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat 1,3-two (methyloxycarbonylamino methyl) cyclohexane of melting with the supply of the speed of 2.2g/h.Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 30 minutes, adopt liquid chromatography analysis Ethylene recov.As product, the yield (selection rate is 87%) with 87% obtains two (isocyanatomethyl) cyclohexane of 1,3-, and obtains monoisocyanates with the yield of 2%.
[embodiment 9]
(by isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) thermal decomposition and the manufacture of the IPDI implemented)
Catalyst (the Ca/SiO prepared by embodiment 7 is filled in above-mentioned Pyrex glass tube
2) 0.8g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3, the 5-trimethyl-5-(methyloxycarbonylamino methyl of melting with the supply of the speed of 2.1g/h)-cyclohexane).Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 30 minutes, adopt liquid chromatography analysis Ethylene recov.As product, the yield (selection rate is 98%) with 98% obtains IPDI, and obtains monoisocyanates with the yield of 2%.
[embodiment 10]
(manufacture of 1, the 6-hexamethylene diisocyanate implemented by the thermal decomposition of two (methyloxycarbonylamino) hexane of 1,6-)
Catalyst (the Ca/SiO prepared by embodiment 7 is filled in above-mentioned Pyrex glass tube
2) 0.3g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat 1,6-two (methyloxycarbonylamino) hexane of melting with the supply of the speed of 2.1g/h.Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 30 minutes, adopt liquid chromatography analysis Ethylene recov.As product, the yield (selection rate is 95%) with 95% obtains 1,6-hexamethylene diisocyanate, and obtains monoisocyanates with the yield of 2%.
[embodiment 11]
(Ca/SiO
2the preparation of catalyst)
In polyethylene can, mixing water 60.0g, polyethylene glycol (Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity is 20000) 4.0g, stir, and forms homogeneous solution.Add tetraethyl orthosilicate 50ml, 60% aqueous solution of nitric acid (Wako Pure Chemical Industries, Ltd.'s system) 4.8g wherein, airtight and vigorous stirring 1 hour.Then at 50 DEG C, leave standstill 12 hours, take out the gel generated, with purified water washing, then at 110 DEG C dry 12 hours, and burn till 2 hours in atmosphere, at 600 DEG C, obtain silica dioxide gel 12.9g.The mean pore footpath of this silica dioxide gel adopting mercury penetration method (determinator: QuantaChromeCo. system full-automatic micropore distribution measurement device PoreMaster60-GT) to measure is 1.9 μm.Pulverized in mortar, and the size of particle is sized to the scope of 1mm ~ 2mm.Mix and blend calcium nitrate 4 hydrate 0.8g(3.4mmol in flask) and ion exchange water 2.0g, obtain calcium nitrate aqueous solution.Prepared silica dioxide gel 2.0g(33.4mmol is added in this calcium nitrate aqueous solution), then at 110 DEG C dry 12 hours, burn till 2 hours in atmosphere, at 500 DEG C, obtain catalyst (Ca/SiO
2) 2.3g.Catalyst (the Ca/SiO of gained
2) in, calcium compound is scaled calcium, then relative to catalyst, load has the calcium compound of 6.2 quality %.
[embodiment 12]
(manufacture of 1,3-two (isocyanatomethyl) cyclohexane implemented by the thermal decomposition of two (methyloxycarbonylamino methyl) cyclohexane of 1,3-)
Take diameter as 10mm, the length Pyrex glass tube that is 42cm is as reactor, from outer setting electric furnace with the temperature making catalyst layer reach regulation, in reaction tube bottom via the collector (room temperature) for obtaining isocyanates, be connected with vavuum pump for the collector (cooling with cold ethanol) obtaining methyl alcohol, link vacuum pipeline.
Catalyst (the Ca/SiO prepared by embodiment 11 is filled in above-mentioned Pyrex glass tube
2) 0.9g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat 1,3-two (methyloxycarbonylamino methyl) cyclohexane of melting with the supply of the speed of 2.2g/h.Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 30 minutes, adopt liquid chromatography analysis Ethylene recov.As product, the yield (selection rate is 88%) with 88% obtains two (isocyanatomethyl) cyclohexane of 1,3-, and obtains monoisocyanates with the yield of 4%.
[embodiment 13]
(by isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) thermal decomposition and the manufacture of the IPDI implemented)
Catalyst (the Ca/SiO prepared by embodiment 11 is filled in above-mentioned Pyrex glass tube
2) 0.7g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3, the 5-trimethyl-5-(methyloxycarbonylamino methyl of melting with the supply of the speed of 2.1g/h)-cyclohexane).Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 30 minutes, adopt liquid chromatography analysis Ethylene recov.As product, the yield (selection rate is 95%) with 95% obtains IPDI, and obtains monoisocyanates with the yield of 5%.
[embodiment 14]
(1, the 6-hexamethylene diisocyanate implemented by the thermal decomposition of two (methyloxycarbonylamino) hexane of 1,6-)
Catalyst (the Ca/SiO prepared by embodiment 11 is filled in above-mentioned Pyrex glass tube
2) 0.7g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat 1,6-two (methyloxycarbonylamino) hexane of melting with the supply of the speed of 2.1g/h.Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 30 minutes, adopt liquid chromatography analysis Ethylene recov.As product, the yield (selection rate is 96%) with 96% obtains 1,6-hexamethylene diisocyanate, and obtains monoisocyanates with the yield of 3%.
[embodiment 15]
(Ca/SiO
2the modulation of catalyst)
Mixing water 240g, polyethylene glycol (Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity is 20000) 19.2g in polyethylene can, and stir, form homogeneous solution.Add tetraethyl orthosilicate 240ml, 60% aqueous solution of nitric acid (Wako Pure Chemical Industries, Ltd.'s system) 23.2g wherein, airtight and vigorous stirring 1 hour.Then at 50 DEG C, leave standstill 12 hours, take out the gel generated, with purified water washing, then at 110 DEG C dry 12 hours, and burn till 2 hours in atmosphere, at 600 DEG C, obtain silica dioxide gel 59.6g.The mean pore footpath of this silica dioxide gel measured by mercury penetration method (determinator: QuantaChromeCo. system full-automatic micropore distribution measurement device PoreMaster60-GT) is 1.6 μm.Pulverized in mortar, and the size of particle is sized to the scope of 1mm ~ 2mm.Mix and blend calcium nitrate 4 hydrate 17.7g(74.9mmol in flask) and ion exchange water 18.8g, obtain calcium nitrate aqueous solution.Prepared silica dioxide gel 15.0g(249.7mmol is added in this calcium nitrate aqueous solution), at 110 DEG C, drying 12 hours, burns till 2 hours in atmosphere, at 500 DEG C, obtains catalyst (Ca/SiO
2) 22.7g.Catalyst (the Ca/SiO of gained
2) in, calcium compound is scaled calcium, then relative to catalyst, load has the calcium compound of 16.0 quality %.
[embodiment 16]
(by isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) thermal decomposition and the manufacture of the IPDI implemented)
Catalyst (the Ca/SiO prepared by embodiment 15 is filled in above-mentioned Pyrex glass tube
2) 2.3g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3, the 5-trimethyl-5-(methyloxycarbonylamino methyl of melting with the supply of the speed of 4.2g/h)-cyclohexane).Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 15 minutes, adopt liquid chromatography analysis Ethylene recov.As product, the yield (selection rate is 95%) with 95% obtains IPDI, and obtains monoisocyanates with the yield of 1%.
[reference example 1]
(Ca/SiO
2the modulation of catalyst)
Mix and blend calcium nitrate 4 hydrate 0.8g(3.4mmol in flask) and ion exchange water 2.1g, obtain calcium nitrate aqueous solution.Silica beads (Silysia chemical company of Fuji CARiACTQ10 is added in this calcium nitrate aqueous solution, particle diameter is 1.2 ~ 2.4mm, micropore diameter is 10nm) 2.0g(33.3mmol), then at 110 DEG C dry 12 hours, burn till 2 hours in atmosphere, at 500 DEG C, obtain catalyst (Ca/SiO
2) 2.2g.
[reference example 2]
(manufacture of 1,3-two (isocyanatomethyl) cyclohexane implemented by the thermal decomposition of two (methyloxycarbonylamino methyl) cyclohexane of 1,3-)
Take diameter as 10mm, the length Pyrex glass tube that is 42cm is as reactor, and from outer setting electric furnace with the temperature making catalyst layer reach regulation, in reaction tube bottom via the collector (room temperature) for obtaining isocyanates, be connected with vavuum pump for the collector (cooling with cold ethanol) obtaining methyl alcohol, link vacuum pipeline.
Catalyst (the Ca/SiO prepared by reference example 1 is filled in above-mentioned Pyrex glass tube
2) 0.4g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat 1,3-two (methyloxycarbonylamino methyl) cyclohexane of melting with the supply of the speed of 3.2g/h.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 30 minutes, adopt liquid chromatography analysis Ethylene recov.Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.As product, the yield with 49% obtains two (isocyanatomethyl) cyclohexane of 1,3-, and obtains monoisocyanates with the yield of 12%.
[reference example 3]
(Ca/SiO
2the preparation of catalyst)
Mix and blend calcium nitrate 4 hydrate 1.2g(5.1mmol in flask) and ion exchange water 4.2g, obtain calcium nitrate aqueous solution.Silica beads (Silysia chemical company of Fuji CARiACTQ50 is added in this calcium nitrate aqueous solution, particle diameter is 1.2 ~ 2.4mm, micropore diameter is 50nm) 3.0g(49.9mmol), drying 12 hours at 110 DEG C, burn till 2 hours in atmosphere, at 500 DEG C, obtain catalyst (Ca/SiO
2) 3.3g.
[reference example 4]
(manufacture of 1,3-two (isocyanatomethyl) cyclohexane implemented by the thermal decomposition of two (methyloxycarbonylamino methyl) cyclohexane of 1,3-)
Take diameter as 10mm, the length Pyrex glass tube that is 42cm is as reactor, and from outer setting electric furnace with the temperature making catalyst layer reach regulation, in reaction tube bottom via the collector (room temperature) for obtaining isocyanates, be connected with vavuum pump for the collector (cooling with cold ethanol) obtaining methyl alcohol, link vacuum pipeline.
Catalyst (the Ca/SiO prepared by reference example 3 is filled in above-mentioned Pyrex glass tube
2) 0.3g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat 1,3-two (methyloxycarbonylamino methyl) cyclohexane of melting with the supply of the speed of 2.2g/h.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 30 minutes, adopt liquid chromatography analysis Ethylene recov.Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.As product, the yield with 64% obtains two (isocyanatomethyl) cyclohexane of 1,3-, and obtains monoisocyanates with the yield of 5%.
[reference example 5]
(by isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) thermal decomposition and the manufacture of the IPDI implemented)
Catalyst (the Ca/SiO prepared by reference example 3 is filled in above-mentioned Pyrex glass tube
2) 0.4g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3, the 5-trimethyl-5-(methyloxycarbonylamino methyl of melting with the supply of the speed of 3.1g/h)-cyclohexane).Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 30 minutes, adopt liquid chromatography analysis Ethylene recov.As product, obtain IPDI with the yield of 36%, and obtain monoisocyanates with the yield of 23%.
[reference example 6]
(manufacture of 1, the 6-hexamethylene diisocyanate implemented by the thermal decomposition of two (methyloxycarbonylamino) hexane of 1,6-)
Catalyst (the Ca/SiO prepared by reference example 3 is filled in above-mentioned Pyrex glass tube
2) 0.3g, be decompressed to 1.33kPa, and use syringe pump at 150 DEG C, to heat 1,6-two (methyloxycarbonylamino) hexane of melting with the supply of the speed of 2.1g/h.Carry out heating to make the temperature of catalyst layer to reach 350 DEG C with electric furnace.After the composition of reaction system and reactant liquor is stable, reclaim reactant liquor 30 minutes, adopt liquid chromatography analysis Ethylene recov.As product, the yield with 57% obtains 1,6-hexamethylene diisocyanate, and obtains monoisocyanates with the yield of 7%.
Next, the result of embodiment 8 to embodiment 10, embodiment 12 to embodiment 14, embodiment 16, reference example 2 and reference example 4 to reference example 6 is shown in table 3.
[table 3]
Claims (8)
1. an isocyanate compound catalyst for producing, its by use tetraethyl orthosilicate as silicon source and use that polyethylene glycol manufactures as the sol-gal process of microcellular structure directed agents, load calcium compound on silica supports that mean pore footpath is 100nm ~ 10 μm, and have passed through at 400 ~ 800 DEG C and burn till and obtain
1,3-two (isocyanatomethyl) cyclohexane, IPDI or hexa-methylene-1, the 6-vulcabond of described isocyanate compound represented by general formula (2),
In formula, R
1expression can have substituent alkyl, and n is 2.
2. catalyst according to claim 1, wherein, is converted into calcium by calcium compound, then relative to catalyst, load has the calcium compound of 0.05 ~ 30 quality %.
3. catalyst according to claim 1, wherein, is converted into calcium by calcium compound, then relative to catalyst, load has the calcium compound of 0.1 ~ 20 quality %.
4. the manufacture method of the catalyst according to any one of a claims 1 to 3, wherein, calcium compound is made to be impregnated in by using tetraethyl orthosilicate as silicon source and using that polyethylene glycol manufactures as the sol-gal process of microcellular structure directed agents, in silica supports that mean pore footpath is 100nm ~ 10 μm, carry out drying, then burn till at 400 ~ 800 DEG C.
5. the manufacture method of an isocyanate compound, it is characterized in that, under the existence of the catalyst according to any one of claims 1 to 3, make the carbamate compounds represented by general formula (1), namely 1,3-two (methyloxycarbonylamino methyl) cyclohexane, isophorone dimethylcarbamate or 1, the thermal decomposition of two (methyloxycarbonylamino) hexane of 6-is carried out under the condition of gas phase
In formula, R
1and R
2can be identical or different, expression can have substituent alkyl, and n is 2,
Described isocyanate compound represents with general formula according to claim 1 (2).
6. manufacture method according to claim 5, is characterized in that, the heat decomposition temperature of carbamate compounds is 80 ~ 500 DEG C.
7. manufacture method according to claim 5, is characterized in that, the thermal decomposition pressure of carbamate compounds is 0.1 ~ 90kPa.
8. manufacture method according to claim 6, is characterized in that, the thermal decomposition pressure of carbamate compounds is 0.1 ~ 90kPa.
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| JP2011-032421 | 2011-02-17 | ||
| JP2011032421 | 2011-02-17 | ||
| PCT/JP2012/053661 WO2012111750A1 (en) | 2011-02-17 | 2012-02-16 | Catalyst for isocyanate compound production and method for producing isocyanate compound using same |
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| CN103391813B true CN103391813B (en) | 2016-04-13 |
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| JP (2) | JP5928348B2 (en) |
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| CN103391813B (en) * | 2011-02-17 | 2016-04-13 | 宇部兴产株式会社 | Isocyanate compound catalyst for producing and use the manufacture method of isocyanate compound of this catalyst |
| WO2013008891A1 (en) * | 2011-07-13 | 2013-01-17 | 宇部興産株式会社 | Method for producing isocyanate compound |
| WO2014189120A1 (en) * | 2013-05-24 | 2014-11-27 | 宇部興産株式会社 | Solid catalyst, and method for producing isocyanate compound using said solid catalyst |
| EP3450424A1 (en) * | 2017-09-04 | 2019-03-06 | Covestro Deutschland AG | Method for making isocyanates |
| JP7229548B2 (en) * | 2020-06-24 | 2023-02-28 | 正晴 銅谷 | Method for producing 3-methylcycloalkenones |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788329A (en) * | 1986-11-03 | 1988-11-29 | American Cyanamid Company | Preparation of cyclohexyl mono- and diurethanes and isocyanates derived therefrom by addition of methylcarbamate to limonene, process and compositions |
| US5326903A (en) * | 1992-01-10 | 1994-07-05 | Nippon Shokubai Co., Ltd. | Process for preparing isocyanates using sintered oxides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5814818B2 (en) * | 1979-03-06 | 1983-03-22 | インスチット・オルガニ チエスコイ ヒミイイメニ エヌ・デ−・ゼリンスコゴ アカデミイ ナウク エスエスエスア−ル | Catalyst for carbonylation of aromatic nitro compounds |
| JPH08804B2 (en) * | 1992-01-10 | 1996-01-10 | 株式会社日本触媒 | Method for producing isocyanates |
| JPH07119190B2 (en) * | 1992-01-10 | 1995-12-20 | 株式会社日本触媒 | Method for producing isocyanates |
| EP0676391B1 (en) * | 1994-04-07 | 1998-10-14 | Bayer Ag | Process for the preparation of isocyanates or isocyanate mixtures |
| CN103391813B (en) * | 2011-02-17 | 2016-04-13 | 宇部兴产株式会社 | Isocyanate compound catalyst for producing and use the manufacture method of isocyanate compound of this catalyst |
-
2012
- 2012-02-16 CN CN201280009284.XA patent/CN103391813B/en not_active Expired - Fee Related
- 2012-02-16 WO PCT/JP2012/053661 patent/WO2012111750A1/en active Application Filing
- 2012-02-16 JP JP2012558008A patent/JP5928348B2/en not_active Expired - Fee Related
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2016
- 2016-02-12 JP JP2016025095A patent/JP2016135486A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788329A (en) * | 1986-11-03 | 1988-11-29 | American Cyanamid Company | Preparation of cyclohexyl mono- and diurethanes and isocyanates derived therefrom by addition of methylcarbamate to limonene, process and compositions |
| US5326903A (en) * | 1992-01-10 | 1994-07-05 | Nippon Shokubai Co., Ltd. | Process for preparing isocyanates using sintered oxides |
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| WO2012111750A1 (en) | 2012-08-23 |
| JPWO2012111750A1 (en) | 2014-07-07 |
| JP2016135486A (en) | 2016-07-28 |
| JP5928348B2 (en) | 2016-06-01 |
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