CN116768763A - 一种脂环族氨基甲酸酯的制备方法及其应用 - Google Patents
一种脂环族氨基甲酸酯的制备方法及其应用 Download PDFInfo
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- CN116768763A CN116768763A CN202210216513.0A CN202210216513A CN116768763A CN 116768763 A CN116768763 A CN 116768763A CN 202210216513 A CN202210216513 A CN 202210216513A CN 116768763 A CN116768763 A CN 116768763A
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- combination
- alicyclic
- catalyst
- carbamate
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- 125000002723 alicyclic group Chemical group 0.000 title claims abstract description 37
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 125000003118 aryl group Chemical group 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 27
- -1 nitro, hydroxyl Chemical group 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 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 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000010924 continuous production Methods 0.000 abstract description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- RGNNZMMFGAYFJO-UHFFFAOYSA-N benzene;carbamic acid Chemical compound NC(O)=O.NC(O)=O.C1=CC=CC=C1 RGNNZMMFGAYFJO-UHFFFAOYSA-N 0.000 description 8
- 230000009615 deamination Effects 0.000 description 6
- 238000006481 deamination reaction Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- FSPRIMKLIVYESK-UHFFFAOYSA-N [3-(carbamoyloxymethyl)phenyl]methyl carbamate Chemical compound NC(=O)OCC1=CC=CC(COC(N)=O)=C1 FSPRIMKLIVYESK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000006840 diphenylmethane group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 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
- 238000009776 industrial production Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 150000003335 secondary amines Chemical class 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Classifications
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明提供了一种脂环族氨基甲酸酯的制备方法及其应用,所述制备方法包括以下步骤:将含芳香环氨基甲酸酯、催化剂和溶剂混合,之后通入氢气反应,得到所述脂环族氨基甲酸酯;所述催化剂包括载体以及负载于载体上的活性组分;所述活性组分包括Pt、Rh、Ru、Ir或Pd中任意一种或至少两种的组合。本发明提供的脂环族氨基甲酸酯的制备方法反应条件温和,操作简单,安全隐患小,脂环族氨基甲酸酯收率高,适用多种反应器,易于大规模连续生产,有良好工业应用前景。
Description
技术领域
本发明属于化工领域,具体涉及一种脂环族氨基甲酸酯的制备方法及其应用,尤其涉及一种收率高的脂环族氨基甲酸酯的制备方法及其应用。
背景技术
聚氨酯的生产工艺已经趋于成熟,其中最成熟的是异氰酸酯路线。脂肪族和脂环族二异氰酸酯(简称ADI)制备的聚氨酯材料具有优良的机械性能、突出的化学稳定性及优异的耐候性,广泛应用于高档涂料、高档合成革、弹性体、胶黏剂、火箭推进剂等领域。ADI与芳香族异氰酸酯中的MDI和TDI等相比,ADI系列大多数品种具有更优异的性能和更低的毒性。
脂环族二异氰酸酯属于ADI品种,其合成方法主要分为光气化法和非光气化法。光气法是工业上常用的生产方法,但该法制备异氰酸酯的过程中使用的光气为剧毒原料,反应中又会放出大量的氯化氢,容易造成设备腐蚀和环境污染,有较高危险性和难操作性。从绿色环保的角度出发,开发非光气法技术是有必要的。非光气法主要是氨基甲酸酯裂解法,氨基甲酸酯是热解合成异氰酸酯的关键前体;同时,作为合成聚氨酯的非异氰酸酯路线,氨基甲酸酯与多元醇酯交换可以直接合成聚氨酯。
目前技术路线中,无论是光气法还是非光气法,都需要先将含芳环二胺进行苯环加氢得到脂环二胺,然后通过非光气或光气法合成ADI。
为了抑制含芳环胺在苯环加氢过程中脱氨(或脱甲胺)副反应,往往需要对催化剂进行碱改性处理或添加碱金属盐、亚硝酸盐等促进剂或氨、有机胺等来抑制脱氨(或脱甲胺)副反应。然而碱的流失使得催化剂再生频率升高,增加了成本;工业装置中较大量氨气的引入会导致设备腐蚀,带来安全隐患;有机胺溶剂回收成本高;催化剂套用中不间断地添加新的促进剂,使得碱金属不断残留累积,催化剂性能受到损害。
CN110105223A将间苯二甲胺添加溶剂和助催化剂配制成混合溶液,通过固定床反应器中连续制备1,3-环己二甲胺,但是助催化剂含有硝酸盐或亚硝酸盐。
US3697449A1采用1-35wt%碱金属的醇盐或者氢氧化物的水溶液对固载钌催化剂进行改性,然后进行二氨基二苯基甲烷的加氢还原反应。
CN111804324A使用氨基锂对金属负载催化剂进行改性,用于催化二氨基二苯基甲烷加氢,避免了仲胺副产以及PACM-OH的大量增加,但是锂在使用过程中易流失,增加了产品后处理和催化剂再生成本。
鉴于含芳环胺直接苯环加氢合成脂环胺过程中使用碱改性或碱金属盐、亚硝酸盐、氨或有机胺带来的不利影响,以及光气法合成异氰酸酯及聚氨酯的环境和安全问题,因此开发一种绿色安全的脂环族氨基甲酸酯合成技术路线具有重要意义。
发明内容
针对现有技术的不足,本发明的目的在于提供一种脂环族氨基甲酸酯的制备方法及其应用,尤其提供一种收率高的脂环族氨基甲酸酯的制备方法及其应用。本发明提供的脂环族氨基甲酸酯的制备方法反应条件温和,操作简单,安全隐患小,脂环族氨基甲酸酯收率高,适用多种反应器,易于大规模连续生产,有良好工业应用前景。
为达到此发明目的,本发明采用以下技术方案:
一方面,本发明提供了一种脂环族氨基甲酸酯的制备方法,所述制备方法包括以下步骤:将含芳香环氨基甲酸酯、催化剂和溶剂混合,之后通入氢气反应,得到所述脂环族氨基甲酸酯。
所述催化剂包括载体以及负载于载体上的活性组分。
所述活性组分包括Pt、Rh、Ru、Ir或Pd中任意一种或至少两种的组合,例如Pt和Rh的组合、Rh和Ru的组合或Ir和Pd的组合等,但不限于以上所列举的组合,上述组合范围内其他未列举的组合同样适用。
上述制备方法规避了含芳环胺直接氢化存在胺脱氨缩合副产物的问题,以及焦油导致催化剂失活问题、催化剂组分流失问题;产物脂环族氨基甲酸酯是非光气法合成ADI的一种重要中间体,为ADI的合成提供了一种毒害小、安全的绿色生产工艺;同时通过选择特定催化剂能够有效提高产物的收率。
优选地,所述活性组分为Ru和Pd的组合、Rh和Ru的组合、Ru和Pt的组合、Ru和Ir的组合、Rh和Pt的组合、Ir和Pt的组合、Pd和Pt的组合或Ir和Pd的组合中任意一种,优选Ru和Pd的组合。
上述特定的活性组分进一步提高了产物的收率。
优选地,所述载体包括SiO2、Al2O3、ZrO2、TiO2、MgO、高岭土、膨润土、蒙脱土、ZSM-5、X型沸石、Y型沸石、B型沸石、丝光沸石、尖晶石、镁铝水滑石、活性炭、石墨烯、碳纳米管、g-C3N4(石墨相氮化碳)、h-BN(六方相氮化硼)或氮掺杂碳复合材料中任意一种或至少两种的组合,例如SiO2和Al2O3的组合、X型沸石和Y型沸石的组合或活性炭和石墨烯的组合等,但不限于以上所列举的组合,上述组合范围内其他未列举的组合同样适用。
优选地,所述催化剂还包括负载于载体上的助剂,所述助剂包括金属单质和/或金属单质氧化物。
优选地,所述金属单质包括Ni、Fe、Co、La或Ce中任意一种或至少两种的组合,例如Ni和Fe的组合、Co和La的组合或La和Ce的组合等,但不限于以上所列举的组合,上述组合范围内其他未列举的组合同样适用。
优选地,所述助剂为Ni、Fe、Co、La2O3、CeO2、NiO、Ni2O3、FeO、Fe2O3、Fe3O4、CoO、Co2O3、Co3O4中任意一种或至少两种的组合,优选Ni和Co的组合。
上述特定助剂的选择能够进一步提高反应的效果,提高产物的收率。
优选地,所述活性组分质量为催化剂总质量的0.1-10%。
优选地,所述助剂质量为催化剂总质量的0-10%,0表示催化剂不含助剂。
优选地,所述含芳香环氨基甲酸酯与催化剂的质量比为(30-100):0.1。
其中,活性组分质量可以是催化剂总质量的0.1%、0.2%、0.3%、0.5%、1%、2%、3%、4%、5%、6%、7%、8%、9%或10%等,助剂质量可以是催化剂总质量的0.1%、0.2%、0.3%、0.5%、1%、2%、3%、4%、5%、6%、7%、8%、9%或10%等,含芳香环氨基甲酸酯与催化剂的质量比可以是30:0.1、40:0.1、50:0.1、60:0.1、70:0.1、80:0.1、90:0.1或100:0.1等,但不限于以上所列举的数值,上述数值范围内其他未列举的数值同样适用。
优选地,所述溶剂包括甲醇、水、乙醇、正丙醇、异丙醇、正丁醇、2-丁醇、四氢呋喃、二甲基甲酰胺、二甲基亚砜、2-甲基四氢呋喃、1,4-二氧六环、乙酸乙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、甲基环己烷或环己烷中任意一种或至少两种的组合,例如甲醇和水的组合、乙醇和正丙醇的组合或碳酸二甲酯和碳酸二乙酯的组合等,但不限于以上所列举的组合,上述组合范围内其他未列举的组合同样适用,优选甲醇和水的组合、甲醇和乙醇的组合、乙醇和水的组合、四氢呋喃和水的组合、四氢呋喃和乙醇的组合或四氢呋喃和甲醇的组合中任意一种,进一步优选乙醇和水的组合。
上述特定溶剂能够有效提高反应的效果,同时采用优选的溶剂组合能够进一步提高产物的收率。
优选地,所述含芳香环氨基甲酸酯具有如下通式:
其中,R1选自C6-C30取代或未取代的含芳香环烃基、取代或未取代的芳基,所述取代的取代基选自硝基、羟基、烷巯基、芳巯基、磺酰基、羰基、卤原子、氰基、氨基、羧基、酯基、烷氧基或芳氧基中任意一种,所述芳基、芳香环独立地为选自苯环、联苯、萘或二苯甲烷中任意一种。
n选自1-5的整数,例如1、2、3、4或5。
R2选自C1-C8的直链或支链饱和烃基或C5-C10的饱和环烃基。
上述C6-C30分别表示组成中含有六个碳原子、七个碳原子、八个碳原子、九个碳原子……,以此类推,不再赘述,其余C1-C8、C5-C10同理。
优选地,R2选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、戊基、己基、庚基、辛基、异辛基、2-乙基己基、环戊基或环己基中任意一种。
需要说明的是,就含芳香环烃基而言,只要其烃基中含有1个及以上的苯环即可,也可以在该芳香族烃上键合脂肪族烃基等。这种情况下,含芳香环氨基甲酸酯中的氨基可直接键合于芳香族烃,也可以键合于芳香族烃上的脂肪族烃基,二者均可。
作为含芳香环氨基甲酸酯,其结构可以举出如式I-式Ⅸ(不局限于所举例子)所示:
但不局限于以上所列举的化合物,其中R2具有和上述相同的限定范围。
优选地,所述含芳香环氨基甲酸酯在溶剂中的质量分数为0.5-30%,例如0.5%、1%、3%、6%、9%、12%、15%、18%、21%、24%、27%或30%等,但不限于以上所列举的数值,上述数值范围内其他未列举的数值同样适用。
优选地,所述反应在反应器中进行,所述反应器为固定床、流化床或釜式反应器中任意一种。
优选地,所述反应器为固定床或流化床,所述反应的温度为0-180℃,反应的压力为0.1-10MPa,氢气与含芳香环氨基甲酸酯的摩尔比为(20-300):1,含芳香环氨基甲酸酯的液时空速为0.1-10h-1。
其中,反应的温度可以是0℃、20℃、40℃、60℃、80℃、100℃、120℃、140℃、160℃或180℃等,反应的压力可以是0.1MPa、0.2MPa、.3MPa、0.5MPa、1MPa、2MPa、3MPa、4MPa、5MPa、6MPa、7MPa、8MPa、9MPa或10MPa等,氢气与含芳香环氨基甲酸酯的摩尔比可以是20:1、40:1、60:1、80:1、100:1、120:1、140:1、160:1、180:1、200:1、220:1、240:1、260:1、280:1或300:1等,含芳香环氨基甲酸酯的液时空速可以是0.1h-1、0.2h-1、0.3h-1、0.5h-1、1h-1、2h-1、3h-1、4h-1、5h-1、6h-1、7h-1、8h-1、9h-1或10h-1等,但不限于以上所列举的数值,上述数值范围内其他未列举的数值同样适用。
优选地,所述反应器为釜式反应器,所述反应的温度为0-180℃,反应的压力为0.1-10MPa。
其中,反应的温度可以是0℃、20℃、40℃、60℃、80℃、100℃、120℃、140℃、160℃或180℃等,反应的压力可以是0.1MPa、0.2MPa、.3MPa、0.5MPa、1MPa、2MPa、3MPa、4MPa、5MPa、6MPa、7MPa、8MPa、9MPa或10MPa等,但不限于以上所列举的数值,上述数值范围内其他未列举的数值同样适用。
另一方面,本发明提供了如上所述的脂环族氨基甲酸酯的制备方法在聚氨酯制备中的应用。
与现有技术相比,本发明具有如下有益效果:
本发明提供了一种脂环族氨基甲酸酯的制备方法,所述制备方法规避了含芳环胺直接氢化存在胺脱氨缩合副产物的问题,以及焦油导致催化剂失活问题和催化剂组分流失问题;产物脂环族氨基甲酸酯是非光气法合成ADI的一种重要中间体,为ADI的合成提供了一种毒害小、安全的绿色生产工艺;同时通过选择特定催化剂能够有效提高产物的收率;并通过选择特定助剂、特定溶剂,进一步提高了产物的收率。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果,以下结合本发明的优选实施例来进一步说明本发明的技术方案,但本发明并非局限在实施例范围内。
实施例1
本实施例提供了一种脂环族氨基甲酸酯的制备方法,所述方法具体包括如下步骤:
称取0.5%Pd-0.5%Ru-0.1%Co-0.1%Ni/Al2O3 2g,装入长600mm,内径为10mm的固定床反应器中;反应溶剂乙醇和水(体积比1:1),对苯二氨基甲酸乙酯(式II结构式)在溶剂中的质量分数为5%,反应温度为30℃,反应压力为2.0MPa,H2:苯二氨基甲酸乙酯摩尔比=100:1,苯二氨基甲酸乙酯的液时空速为0.2h-1;反应稳定后取样分析,苯二氨基甲酸乙酯转化率99.5%,1,4-环己基二氨基甲酸乙酯收率99.3%。
实施例2
本实施例提供了一种脂环族氨基甲酸酯的制备方法,所述方法具体包括如下步骤:
称取3%Ru/SiO2 2g,装入长600mm,内径为10mm的固定床反应器中;反应溶剂乙醇,间苯二亚甲基二氨基甲酸甲酯(式I结构式)在溶剂中的质量分数为20%,反应温度为130℃,反应压力为2.0MPa,H2:苯二氨基甲酸乙酯摩尔比=100:1,苯二氨基甲酸乙酯的液时空速为0.5h-1;反应稳定后取样分析,间苯二亚甲基二氨基甲酸甲酯转化率99.6%,1,3-环己基二亚甲基氨基甲酸甲酯收率99.4%。
实施例3
本实施例提供了一种脂环族氨基甲酸酯的制备方法,所述方法具体包括如下步骤:
称取1%Ru/g-C3N4 2g,装入长600mm,内径为10mm的固定床反应器中;反应溶剂四氢呋喃,对苯二氨基甲酸乙酯(式II结构式)在溶剂中的质量分数为10%,反应温度为160℃,反应压力为5.0MPa,H2:苯二氨基甲酸乙酯摩尔比=200:1,苯二氨基甲酸乙酯的液时空速为2.0h-1;反应稳定后取样分析,苯二氨基甲酸乙酯转化率99.3%,1,4-环己基二氨基甲酸乙酯收率99.1%。
实施例4
本实施例提供了一种脂环族氨基甲酸酯的制备方法,所述方法具体包括如下步骤:
称取1%Ru/g-C3N4 0.6g,4-甲基苯氨基甲酸甲酯(式Ⅸ结构式)12g,溶剂甲醇228g,投入500mL不锈钢高压釜中,氮气置换釜内空气后,通入氢气,开启搅拌,控制反应温度60℃,反应压力3.0MPa,反应1h后,停止反应,取样分析,4-甲基苯氨基甲酸甲酯转化率99.6%,4-甲基环己基二氨基甲酸甲酯收率99.3%。
实施例5
本实施例提供了一种脂环族氨基甲酸酯的制备方法,步骤中除将催化剂替换成等量的0.5%Pd-0.5%Ru/Al2O3外,其余与实施例1一致。
最终苯二氨基甲酸乙酯转化率92.5%,1,4-环己基二氨基甲酸乙酯收率90.3%。
实施例6
本实施例提供了一种脂环族氨基甲酸酯的制备方法,步骤中除将催化剂替换成等量的0.5%Pd-0.5%Pt-0.1%Co-0.1%Ni/Al2O3外,其余与实施例1一致。
最终苯二氨基甲酸乙酯转化率93.4%,1,4-环己基二氨基甲酸乙酯收率90.5%。
实施例7
本实施例提供了一种脂环族氨基甲酸酯的制备方法,步骤中除将催化剂替换成等量的0.5%Rh-0.5%Ru-0.1%Co-0.1%Ni/Al2O3外,其余与实施例1一致。
最终苯二氨基甲酸乙酯转化率91.8%,1,4-环己基二氨基甲酸乙酯收率90.3%。
实施例8
本实施例提供了一种脂环族氨基甲酸酯的制备方法,步骤中除将催化剂替换成等量的0.5%Pd-0.5%Ru-0.1%Co-0.1%Fe/Al2O3外,其余与实施例1一致。
最终苯二氨基甲酸乙酯转化率94.5%,1,4-环己基二氨基甲酸乙酯收率93.6%。
实施例9
本实施例提供了一种脂环族氨基甲酸酯的制备方法,步骤中除将催化剂替换成等量的0.5%Pd-0.5%Ru-0.2%CeO2/Al2O3外,其余与实施例1一致。
最终苯二氨基甲酸乙酯转化率95.5%,1,4-环己基二氨基甲酸乙酯收率94.8%。
实施例10
本实施例提供了一种脂环族氨基甲酸酯的制备方法,步骤中除将溶剂替换成等量的甲醇外,其余与实施例1一致。
最终苯二氨基甲酸乙酯转化率88.9%,1,4-环己基二氨基甲酸乙酯收率88.3%。
实施例11
本实施例提供了一种脂环族氨基甲酸酯的制备方法,步骤中除将溶剂替换成等量的环己烷和甲醇混合溶剂(体积比1:1)外,其余与实施例1一致。
最终苯二氨基甲酸乙酯转化率93.5%,1,4-环己基二氨基甲酸乙酯收率92.5%。
以上结果显示,本发明提供的脂环族氨基甲酸酯的制备方法适用多种反应器,反应转化率高,收率高;比较实施例1、5-11可以发现,本发明通过采用特定活性组分、助剂和溶剂的组合进一步提高了反应的转化率和收率。
申请人声明,本发明通过上述实施例来说明本发明的脂环族氨基甲酸酯的制备方法及其应用,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。
Claims (10)
1.一种脂环族氨基甲酸酯的制备方法,其特征在于,所述制备方法包括以下步骤:将含芳香环氨基甲酸酯、催化剂和溶剂混合,之后通入氢气反应,得到所述脂环族氨基甲酸酯;
所述催化剂包括载体以及负载于载体上的活性组分;
所述活性组分包括Pt、Rh、Ru、Ir或Pd中任意一种或至少两种的组合。
2.根据权利要求1所述的脂环族氨基甲酸酯的制备方法,其特征在于,所述活性组分为Ru和Pd的组合、Rh和Ru的组合、Ru和Pt的组合、Ru和Ir的组合、Rh和Pt的组合、Ir和Pt的组合、Pd和Pt的组合或Ir和Pd的组合中任意一种,优选Ru和Pd的组合;
优选地,所述载体包括SiO2、Al2O3、ZrO2、TiO2、MgO、高岭土、膨润土、蒙脱土、ZSM-5、X型沸石、Y型沸石、B型沸石、丝光沸石、尖晶石、镁铝水滑石、活性炭、石墨烯、碳纳米管、g-C3N4、h-BN或氮掺杂碳复合材料中任意一种或至少两种的组合;
优选地,所述催化剂还包括负载于载体上的助剂,所述助剂包括金属单质和/或金属单质氧化物;
优选地,所述金属单质包括Ni、Fe、Co、La或Ce中任意一种或至少两种的组合;
优选地,所述助剂为Ni、Fe、Co、La2O3、CeO2、NiO、Ni2O3、FeO、Fe2O3、Fe3O4、CoO、Co2O3、Co3O4中任意一种或至少两种的组合,优选Ni和Co的组合。
3.根据权利要求2所述的脂环族氨基甲酸酯的制备方法,其特征在于,所述活性组分质量为催化剂总质量的0.1-10%;
优选地,所述助剂质量为催化剂总质量的0-10%,0表示催化剂不含助剂;
优选地,所述含芳香环氨基甲酸酯与催化剂的质量比为(30-100):0.1。
4.根据权利要求1-3中任一项所述的脂环族氨基甲酸酯的制备方法,其特征在于,所述溶剂包括甲醇、水、乙醇、正丙醇、异丙醇、正丁醇、2-丁醇、四氢呋喃、二甲基甲酰胺、二甲基亚砜、2-甲基四氢呋喃、1,4-二氧六环、乙酸乙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、甲基环己烷或环己烷中任意一种或至少两种的组合,优选甲醇和水的组合、甲醇和乙醇的组合、乙醇和水的组合、四氢呋喃和水的组合、四氢呋喃和乙醇的组合或四氢呋喃和甲醇的组合中任意一种,进一步优选乙醇和水的组合。
5.根据权利要求1-4中任一项所述的脂环族氨基甲酸酯的制备方法,其特征在于,所述含芳香环氨基甲酸酯具有如下通式:
其中,R1选自C6-C30取代或未取代的含芳香环烃基、取代或未取代的芳基,所述取代的取代基选自硝基、羟基、烷巯基、芳巯基、磺酰基、羰基、卤原子、氰基、氨基、羧基、酯基、烷氧基或芳氧基中任意一种,所述芳基、芳香环独立地为选自苯环、联苯、萘或二苯甲烷中任意一种;
n选自1-5的整数;
R2选自C1-C8的直链或支链饱和烃基或C5-C10的饱和环烃基;
优选地,R2选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、戊基、己基、庚基、辛基、异辛基、2-乙基己基、环戊基或环己基中任意一种。
6.根据权利要求1-5中任一项所述的脂环族氨基甲酸酯的制备方法,其特征在于,所述含芳香环氨基甲酸酯在溶剂中的质量分数为0.5-30%。
7.根据权利要求1-6中任一项所述的脂环族氨基甲酸酯的制备方法,其特征在于,所述反应在反应器中进行,所述反应器为固定床、流化床或釜式反应器中任意一种。
8.根据权利要求7所述的脂环族氨基甲酸酯的制备方法,其特征在于,所述反应器为固定床或流化床,所述反应的温度为0-180℃,反应的压力为0.1-10MPa,氢气与含芳香环氨基甲酸酯的摩尔比为(20-300):1,含芳香环氨基甲酸酯的液时空速为0.1-10h-1。
9.根据权利要求7所述的脂环族氨基甲酸酯的制备方法,其特征在于,所述反应器为釜式反应器,所述反应的温度为0-180℃,反应的压力为0.1-10MPa。
10.一种根据权利要求1-9中任一项所述的脂环族氨基甲酸酯的制备方法在聚氨酯制备中的应用。
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