CN102372639A - Method for preparing 4-aminodiphenyamine - Google Patents
Method for preparing 4-aminodiphenyamine Download PDFInfo
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- CN102372639A CN102372639A CN2010102599368A CN201010259936A CN102372639A CN 102372639 A CN102372639 A CN 102372639A CN 2010102599368 A CN2010102599368 A CN 2010102599368A CN 201010259936 A CN201010259936 A CN 201010259936A CN 102372639 A CN102372639 A CN 102372639A
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- mirbane
- oil
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- water
- transfer catalyst
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- 238000000034 method Methods 0.000 title claims abstract description 31
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005406 washing Methods 0.000 claims abstract description 46
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 26
- 239000012074 organic phase Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 23
- 239000011707 mineral Substances 0.000 claims description 23
- -1 polyoxyethylene Polymers 0.000 claims description 18
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 16
- 238000009833 condensation Methods 0.000 claims description 15
- 230000005494 condensation Effects 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 150000001412 amines Chemical group 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 3
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 claims description 2
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 2
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 claims description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 230000006837 decompression Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims 1
- XXYMSQQCBUKFHE-UHFFFAOYSA-N 4-nitro-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC1=CC=CC=C1 XXYMSQQCBUKFHE-UHFFFAOYSA-N 0.000 abstract description 12
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 150000007529 inorganic bases Chemical class 0.000 abstract 2
- 238000007796 conventional method Methods 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 16
- MQKPEUAOJLJUMD-UHFFFAOYSA-N phenol;piperazine Chemical compound C1C[NH2+]CCN1.[O-]C1=CC=CC=C1 MQKPEUAOJLJUMD-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229920000767 polyaniline Polymers 0.000 description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 9
- 238000009835 boiling Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 description 1
- GNGCALKASVBYMT-UHFFFAOYSA-N 2-nitroso-n-phenylaniline Chemical compound O=NC1=CC=CC=C1NC1=CC=CC=C1 GNGCALKASVBYMT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KSGUUTWSWMLVHG-UHFFFAOYSA-N N.OOO Chemical compound N.OOO KSGUUTWSWMLVHG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of fine chemical organic synthesis, and relates to a new method for preparing 4-aminodiphenyamine (RT base) by aniline and nitrobenzene. According to the present invention, the nitrobenzene and the aniline are mainly adopted as raw materials; a solid inorganic base and a phase transfer catalyst are added to synthesize 4-nitrodiphenylamine and 4-nitrosodiphenylamine; then water and an acid are added to carry out washing; the phase transfer catalyst and the inorganic base are recovered from the water phase, and are recycled; the organic phase is directly subjected to hydrogenation to prepare the RT base. Compared to the conventional method, the method of the present invention has characteristics of simple preparation process, high yield, high product purity, and the like.
Description
Technical field: the invention belongs to technical field of organic synthesis; Being specifically related to a kind of is raw material with aniline and oil of mirbane; With the method for the synthetic 4-aminodiphenylamine of phase-transfer catalyst catalysis, the 4-aminodiphenylamine is a kind of midbody that is used to prepare rubber antioxidant usually.
Background technology: the method for producing the 4-aminodiphenylamine is gone up in industry at present to be had: pentanoic method, aniline process, formylaniline method, oil of mirbane method.First three technology all has shortcomings such as technical process length, a large amount of reluctant waste water; And the oil of mirbane method that developed recently gets up is to be that raw material carries out condensation reaction and prepares 4 nitrodiphenyl amine, 4-nitrosodiphenylamine with aniline and oil of mirbane, then hydrogenation system 4-aminodiphenylamine (referring to US51147063, US5253737; US5331099; US5453541, US5552531, US5633407).
The outstanding advantage of oil of mirbane method is not have the three wastes, but technical difficulty is higher, and production control is relatively more difficult.Its synthesis technique mainly concentrates on the selection of alkali in the condensation process, and in US5633407, it is mineral alkali or organic bases that condensation course adopts alkali, like basic metal; Alkalimetal hydride, oxyhydroxide, alkoxide etc.; Also four replace ammoniums phase-transfer catalyst or halides, select separately 1-18 carbon atom alkyl, aryl or aralkyl, like tetra-alkyl ammonium hydroxide; Quaternary alkylammonium halides, aryl trialkyl oxyhydroxide, aryl trialkyl ammonium oxyhydroxide; Alkyl replaces two ammonium oxyhydroxide, also can adopt other phase-transfer catalyst, like alkylammonium salt, crown ether etc.
CN1307556A mentions normally tetraalkylammonium hydroxide of used catalyzer, like tetramethylammonium hydroxide, and hydroxide tetrapropylammonium, benzyltrimethyl ammonium hydroxide, tetrabutylammonium hydroxide, phenyltrimethylammonium hydroxide, preferred tetramethylammonium hydroxide.
CN1733587A; US6395933 mentions except can using above quaternary ammonium hydroxide, also can use the for example salt of alkoxide, acetate, carbonate, supercarbonate, halogenide, resol, phosphoric acid salt, hydrophosphate, hypochlorite, borate, boric acid hydrogen salt, boric acid dihydric salt, sulfide, silicate, silicic acid hydrogen salt, silicic acid dihydric salt and silicic acid three hydrogen salts and so on.And preferably adopt sylvite, like KCl, KF, KBr etc.
CN1253428C, CN1202073C, CN1187316C, CN1185207C, a kind of improved oil of mirbane synthesis technique of proposition; Adopt and add the synthetic 4 nitrodiphenyl amine of composite catalyst, 4-nitrosodiphenylamine, the aqueous solution that its composite catalyst adopts tetraalkylphosphoniuhydroxide hydroxide amine, alkali metal hydroxide and tetraalkyl amine salt to form.
It is catalyzer that above synthesis technique all adopts tetraalkylammonium hydroxide, and this catalyzer costs an arm and a leg, and this catalyzer is difficult to reclaiming, thereby wastes raw material, and increases production cost.And consumption is all bigger, and the mol ratio of itself and oil of mirbane is at 0.7: 1~4: 1,, preferred 0.9~1.5: 1.Moreover catalyzer need be dissolved in a large amount of water, and reaction efficiency is low.The 3rd, need dehydration in advance before this catalyst reaction, high to the control moisture requirement, when promptly reacting the ratio of water and alkali is not less than 4: 1 and is not less than 0.6: 1 (CN1307556A) during the reaction end, complex process is difficult to effective control.The 4th, adopt this catalyzer, be prone to by product such as reaction generation 2-nitrodiphenylamine and 2-nitrosodiphenylamine on the oil of mirbane ortho position, impure many in the product, thus reducing product purity, quality product can be under some influence.
In order to improve reaction efficiency; Also moisture content is to the influence of reaction result in the reaction process, and CN1285566C mentions a kind of Zeolite support that is loaded with base material that is used for oil of mirbane and aniline condensation, and tetramethylphosphonihydroxide hydroxide amine is loaded on the ZSM-5 zeolite; Be used for the reaction of oil of mirbane and aniline condensation; But the interpolation of zeolite makes relatively difficulty of solution separating, and the control of moisture is also relatively stricter in the zeolite, and the industriallization operation easier is higher.
Summary of the invention: the improvement that the main p-nitrophenyl law technology of the object of the invention carries out, by aniline and oil of mirbane in the presence of mineral alkali, phase-transfer catalyst and solvent, at 60-150 ℃; Condensation reaction 2-24h gets product 4 nitrodiphenyl amine, 4-nitrosodiphenylamine, adds water and acid elution then; The water that contains mineral alkali and phase-transfer catalyst can reuse; Organic phase adopts catalyzer to carry out hydrogenation, 60 ℃-150 ℃ of hydrogenation temperatures, hydrogenation time 0.5h-5h.
The present invention mainly is that its principal feature is to the improvement of traditional oil of mirbane method synthesis technique:
(1). the phase-transfer catalyst of interpolation and mineral alkali are directly to add with the solid form, rather than the existence that big water gaging will be arranged of above patent requirement.Phase-transfer catalyst and mineral alkali directly add with the solid mode, have avoided the existence of a large amount of waters, have improved reaction efficiency, and have avoided in the condensation course the control of moisture content, and be simple to operate.
(2). wash after the condensation, can effectively avoid the poisoning effect of condensation catalyst, also can effectively avoid the resolution problem of condensation catalyst in the hydrogenation operation to hydrogenation catalyst.
(3). the mode of secondary washing is adopted in washing, uses water washing earlier, dissolves wherein most mineral alkali and phase-transfer catalyst; Next adds acid elution; Wash out mineral alkali residual in the solution and phase-transfer catalyst, can effectively avoid the traditional technology once washing, organic phase and water are difficult to isolating problem; Twice washing, efficient is higher.
(4). have only water, aniline, phenol piperazine, mutual-amido two polyaniline in the product of the present invention's preparation, product separation is simpler, and purity is higher.
The inventive method is compared with traditional method, and it is simple to have preparation technology, and is easy to operate, and reaction efficiency is high, characteristics such as good product purity.
The alkali that can supply select for use in the condensation course is generally mineral alkali, and like basic metal, alkalimetal hydride, alkali metal hydroxide, for reactive, preferably one or more choose mineral alkali such as NaOH, KOH, LiOH, Ca (OH) in following group
2, NaH, CaH
2, preferred again NaOH, KOH, preferred again KOH.The mol ratio of alkali and oil of mirbane is 0.2: 1~2: 1, and preferred mol ratio is 0.5: 1~1.5: 1.
The phase-transfer catalyst that can supply select for use is the one or more combination thing in quaternary amine, quaternary amine alkali, quaternary alkylphosphonium salt, polyoxyethylene glycol, polyoxyethylene glycol dialkyl ether, pyridine, the cyclic crown ether class etc.Preferred quaternary amine, polyoxyethylene glycol (PEG) 400-20000, crown ether, the preferred benzyltriethylammoinium chloride of quaternary amine, DTAC, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, OTAC, benzyl trimethyl ammonium chloride, benzyl tributyl ammonium chloride, tetramethyl ammonium chloride, tetrabutylammonium chloride (AF-4), Tetrabutyl amonium bromide (BF-4), Trimethyllaurylammonium bromide, TTAB, cetyl trimethylammonium bromide (B-16), octadecyl trimethylammonium bromide, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, benzyl tributyl brometo de amonio, 4 bromide.Preferred again Tetrabutyl amonium bromide, 4 bromide, tetraethylammonium bromide, cetyl trimethylammonium bromide, OTAC.
The mass ratio of phase-transfer catalyst and oil of mirbane is 0.005: 1~0.3: 1, preferred 0.01: 1~0.1: 1.
The solvent that can supply select for use has aniline, oil of mirbane, N, N-N-methyl-2-2-pyrrolidone N-, the trimethyl carbinol, propyl carbinol, ethanol, methyl alcohol, acetonitrile, toluene, benzene, acetone etc.But the present invention is not limited to above-mentioned organic solvent, for reactive, preferentially uses oil of mirbane and aniline, preferably selects aniline for use.
The mass ratio of solvent and oil of mirbane is 0.5: 1~10: 1 a scope, preferred 1: 1~5: 1.
Setting-up point is preferably 60-150 ℃, and preferred 80-130 ℃, if temperature of reaction is low, speed of reaction is just slow, and temperature surpasses 150 ℃, product 4 nitrodiphenyl amine, 4-nitrosodiphenylamine poor selectivity.Reaction times is preferably 2~24h, preferred 4~12h.
Solution washs layering after the condensation, and the water that contains mineral alkali and phase-transfer catalyst can reuse, and the direct hydrogenation of organic phase gets the product mutual-amido two polyaniline.
Washing is washing at twice, at first adds water washing, and the mass ratio of the add-on of water and raw material oil of mirbane is 0.5: 1~2: 1,30 ℃-100 ℃ of water washing temperature, preferred 50-80 ℃, washing time 10~60min..Washing finishes the back layering, and water reclaims alkali and phase-transfer catalyst, recycled.
Residual mineral alkali and phase-transfer catalyst are washed out in organic addition acid solution washing, and the interpolation of acid is so that influence is not good to hydrogenation catalyst, and general mineral acid all can add, preferred hydrochloric acid, nitric acid, carbonic acid (logical CO
2Washing), considers preferably logical CO from the angle of mineral alkali and phase-transfer catalyst recycling
2Washing, the mass ratio of the add-on of water and raw material oil of mirbane is 0.5: 1~2: 1 during washing,, 30 ℃-100 ℃ of wash temperatures, preferred 50-90 ℃, washing time 0.5h-2h, the aqueous solution after the washing adds Ca (OH)
2Form ZG 301, temperature of reaction 20-100 ℃, preferred 30-60 ℃, filter, the water that contains mineral alkali and phase-transfer catalyst can repeat to obtain to utilize.
Washing also can be adopted the mode of once adding the acid solution washing, and the mass ratio of the add-on of acid solution and raw material oil of mirbane is 0.5: 1~2: 1.
The direct hydrogenation of organic phase after the washing, the catalyzer that can supply select for use have noble metal catalyst and hydrogenation nickel catalyst, and hydrogenation nickel catalyst such as skeletal nickel catalyst, hydrogenation temperature be at 60-150 ℃, hydrogenation time 0.5-5h, hydrogen dividing potential drop 1.0MPa-3.0MPa.
Embodiment: the present invention is able to specify through following examples, but the present invention is not limited to these.
Embodiment 1. is oil of mirbane 50mL, aniline 200mL, and KOH 20g, Tetrabutyl amonium bromide 1.5g adds 500mL and is equipped with in the four-hole boiling flask of reflux condensate device and whisking appliance, and at 110 ℃, vacuum tightness is stirring reaction 7h under the 15KPa condition.
In condensated liquid, add water 50mL, at 80 ℃ of agitator treating 30min, leave standstill, layering, water 47g, wherein contain KOH 12g, Tetrabutyl amonium bromide 1.41g.With the organic addition water 50mL after the washing, at 80 ℃ of logical CO
2Gas 60min, the pH value of solution value is 8, leave standstill, layering, water 68g, add Ca (OH) at 40 ℃
29.7g isothermal reaction 1h filters, aqueous phase contains KOH 6g, Tetrabutyl amonium bromide 0.03g.
Organic phase contains 0.86% oil of mirbane, 52.3% aniline, 17.42% 4 nitrodiphenyl amine, 7.80% 4-nitrosodiphenylamine, phenol piperazine 1.23%, nitrogen benzide 15.30%.
Organic phase after the washing is added the 0.5L autoclave, hydrogen dividing potential drop 2.0MPa, 130 ℃ of temperature, skeletal nickel catalyst 6g, hydrogenation 1.5h contains 22.34% mutual-amido two polyaniline in the solution, phenol piperazine 1.92%, 68.12% aniline.
Embodiment 2. is with logical CO among the embodiment 1
2The scrubbing water sample, a 47g mixes with washing first time appearance, joins 500mL and is equipped with in the four-hole boiling flask of reflux condensate device and whisking appliance; Add 200mL aniline, underpressure distillation steams moisture in the solution; Add the 0.075g Tetrabutyl amonium bromide, 2g KOH adds basic benzene 50mL; At 110 ℃, vacuum tightness is stirring reaction 7h under the 15KPa condition
In condensated liquid, add water 50mL, at 80 ℃ of agitator treating 30min, leave standstill, layering, water 46g, wherein contain KOH 13g, Tetrabutyl amonium bromide 1.42g.With the organic addition water 50mL after the washing, at 80 ℃ of logical CO
2Gas 60min, the pH value of solution value is 8, leave standstill, layering, water 67g.Add Ca (OH) at 40 ℃
210.0g isothermal reaction 1h filters, aqueous phase contains KOH 6g, Tetrabutyl amonium bromide 0.03g.
Organic phase contains 0.53% oil of mirbane, 51.1% aniline, 17.85% 4 nitrodiphenyl amine, 7.62% 4-nitrosodiphenylamine, phenol piperazine 1.51%, nitrogen benzide 16.52%.
Organic phase after the washing is added the 0.5L autoclave, hydrogen dividing potential drop 2.0MPa, 130 ℃ of temperature, skeletal nickel catalyst 6g, hydrogenation 1.5h contains 23.16% mutual-amido two polyaniline in the solution, phenol piperazine 2.72%, 67.04% aniline.
Embodiment 3. is oil of mirbane 60mL, aniline 200mL, and KOH 20g, Tetrabutyl amonium bromide 1.5g adds 500mL and is equipped with in the four-hole boiling flask of reflux condensate device and whisking appliance, and at 110 ℃, vacuum tightness is stirring reaction 7h under the 15KPa condition.
In condensated liquid, add water 70mL, at 70 ℃ of agitator treating 30min, leave standstill, layering, water 62g, wherein contain KOH 13g, Tetrabutyl amonium bromide 1.43g.With the organic addition water 70mL after the washing, at 70 ℃ of logical CO
2Gas 40min, the pH value of solution value is 8, leave standstill, layering, water 85g.
Organic phase contains 1.32% oil of mirbane, 52.7% aniline, 17.37% 4 nitrodiphenyl amine, 7.70% 4-nitrosodiphenylamine, phenol piperazine 1.03%, nitrogen benzide 15.13%.
Organic phase after the washing is added the 0.5L autoclave, hydrogen dividing potential drop 2.5MPa, 140 ℃ of temperature, skeletal nickel catalyst 5g, hydrogenation 1h contains 23.24% mutual-amido two polyaniline in the solution, phenol piperazine 3.12%, 66.17% aniline.
Embodiment 4. is oil of mirbane 50mL, aniline 200mL, and KOH 20g, Tetrabutyl amonium bromide 1.5g adds 500mL and is equipped with in the four-hole boiling flask of reflux condensate device and whisking appliance, and at 110 ℃, vacuum tightness is stirring reaction 7h under the 15KPa condition.
In condensated liquid, add water 100mL, at 80 ℃ of logical CO
2Gas 60min leaves standstill, layering, water 112g, add Ca (OH) at 40 ℃
226g, isothermal reaction 1h filters, and aqueous phase contains KOH 19g, Tetrabutyl amonium bromide 1.45g.
Organic phase contains 0.37% oil of mirbane, 53.4% aniline, 17.12% 4 nitrodiphenyl amine, 7.85% 4-nitrosodiphenylamine, phenol piperazine 1.43%, nitrogen benzide 15.21%.
Organic phase after the washing is added the 0.5L autoclave, hydrogen dividing potential drop 3.0MPa, 140 ℃ of temperature, skeletal nickel catalyst 4g, hydrogenation 1.5h contains 22.72% basic pentanoic in the solution, phenol piperazine 2.62%, 67.46% aniline.
Embodiment 5. is oil of mirbane 70mL, aniline 250mL, and phase-transfer catalyst Tetrabutyl amonium bromide 2.5g, KOH 40g adds 500mL and is equipped with in the four-hole boiling flask of reflux condensate device and whisking appliance, and at 110 ℃, vacuum tightness is stirring reaction 7h under the 15KPa condition,
In condensated liquid, add water 50mL, at 40 ℃ of agitator treating 60min, leave standstill, layering, water 42g, wherein contain KOH 19g, Tetrabutyl amonium bromide 2.3g.With the organic addition water 50mL after the washing, at 40 ℃ of logical CO
2Gas 120min, the pH value of solution value is 8, leave standstill, layering, water 72g, add Ca (OH) at 40 ℃
226.4g isothermal reaction 1h filters, aqueous phase contains KOH 19g, Tetrabutyl amonium bromide 0.07g.
Organic phase contains 0.16% oil of mirbane, 50.7% aniline, 15.46% 4 nitrodiphenyl amine, 11.80% 4-nitrosodiphenylamine, phenol piperazine 1.20%, nitrogen benzide 16.10%.
Organic phase after the washing is added the 0.5L autoclave, hydrogen dividing potential drop 2.0MPa, 120 ℃ of temperature, skeletal nickel catalyst 6g, hydrogenation 2.5h contains 23.78% mutual-amido two polyaniline in the solution, phenol piperazine 2.42%, 66.36% aniline.
Embodiment 6. is oil of mirbane 50mL, aniline 200mL, and KOH 20g, tetraethylammonium bromide 1.5g adds 500mL and is equipped with in the four-hole boiling flask of reflux condensate device and whisking appliance, and at 110 ℃, vacuum tightness is stirring reaction 7h under the 15KPa condition.
In condensated liquid, add water 50mL, at 70 ℃ of agitator treating 30min, leave standstill, layering, water 52g, wherein contain KOH 12g, tetraethylammonium bromide 1.40g.With the organic addition water 50mL after the washing, at 70 ℃ of logical CO
2Gas 60min, the pH value of solution value is 8, leave standstill, layering, water 65g.
Organic phase contains 3.32% oil of mirbane, 55.2% aniline, 12.45% 4 nitrodiphenyl amine, 6.78% 4-nitrosodiphenylamine, phenol piperazine 1.17%, nitrogen benzide 16.25%.
Organic phase after the washing is added the 0.5L autoclave, hydrogen dividing potential drop 2.0MPa, 130 ℃ of temperature, skeletal nickel catalyst 6g, hydrogenation 1.5h contains 16.68% mutual-amido two polyaniline in the solution, phenol piperazine 3.12%, 72.17% aniline.
Embodiment 7. is oil of mirbane 50mL, aniline 200mL, and KOH 20g, cetyl trimethylammonium bromide 1.5g adds 500mL and is equipped with in the four-hole boiling flask of reflux condensate device and whisking appliance, and at 110 ℃, vacuum tightness is stirring reaction 7h under the 15KPa condition.
In condensated liquid, add water 50mL, at 80 ℃ of agitator treating 30min, leave standstill, layering, water 50g, wherein contain KOH 12g, cetyl trimethylammonium bromide 1.42g.With the organic addition water 50mL after the washing, at 80 ℃ of logical CO
2Gas 60min, the pH value of solution value is 8, leave standstill, layering, water 67g.
Organic phase contains 2.24% oil of mirbane, 56.23% aniline, 12.67% 4 nitrodiphenyl amine, 7.26% 4-nitrosodiphenylamine, phenol piperazine 1.23%, nitrogen benzide 15.54%.
Organic phase after the washing is added the 0.5L autoclave, hydrogen dividing potential drop 2.0MPa, 130 ℃ of temperature, skeletal nickel catalyst 6g, hydrogenation 1.5h contains 17.28% mutual-amido two polyaniline in the solution, phenol piperazine 2.67%, 72.23% aniline.
Can know from above embodiment, adopt the present invention's technology preparation mutual-amido two polyaniline to compare traditional technology and have the following advantages:
1). not to separate organic phase and water again behind the hydrogenation that adopts of traditional technology; But, condensation washs after finishing; Organic phase and water layering can effectively be avoided the poisoning effect of condensation catalyst to hydrogenation catalyst like this, also can avoid adding the decomposition of hydrogen system to condensation catalyst.
2). the mode of twice washing is adopted in washing, uses water washing earlier, dissolves wherein most mineral alkali and phase-transfer catalyst; Next adds acid elution; Wash out mineral alkali residual in the solution and phase-transfer catalyst, can effectively avoid the traditional technology once washing, organic phase and water are difficult to isolating problem; Twice washing, efficient is higher.
3). the consumption of condensation catalyst obviously reduces, and the phase-transfer catalyst consumption that the present invention adopts has only about 10% of traditional technology tetraalkylammonium hydroxide, and its rate of decomposition is also low than traditional technology, has only about 0.5%.
4). the solution behind the hydrogenation has only water, aniline, phenol piperazine, four kinds of products of mutual-amido two polyaniline, and product separation is simpler, and product purity is higher.
Claims (10)
1. a method for preparing the 4-aminodiphenylamine is a raw material by aniline, oil of mirbane, in the presence of mineral alkali, phase-transfer catalyst and solvent; Synthetic 4-aminodiphenylamine; It is characterized in that mineral alkali and phase-transfer catalyst are directly joined in oil of mirbane and aniline and the solvent system with the solid form, wherein mineral alkali and oil of mirbane mol ratio are 0.2: 1~2: 1, and the mass ratio of phase-transfer catalyst and oil of mirbane is 0.005: 1~0.3: 1; At 60-150 ℃, decompression stirring reaction 2-24h; Adding and oil of mirbane mass ratio are 0.5: 1~2: 1 water then; At 30-100 ℃ of washing 10-60min, standing demix, it is 0.5: 1~2: 1 acid solution that organic phase adds with the oil of mirbane mass ratio again; At 30-100 ℃; Washing 0.5-2h, water reclaims phase-transfer catalyst and mineral alkali, and is reusable; Organic phase in the presence of hydrogenation catalyst in 60-150 ℃, pressure 1.0-3.0MPa, direct hydrogenation 0.5-5h, product 4-aminodiphenylamine.
2. method according to claim 1 is characterized in that the mineral alkali that condensation reaction is selected for use is selected from NaOH in basic metal, alkalimetal hydride, the alkali metal hydroxide, KOH, LiOH, Ca (OH)
2, NaH, CaH
2One or several.
3. the method used according to claim 1 is characterized in that mineral alkali and oil of mirbane mol ratio are 0.5: 1~1.5: 1.
4. method according to claim 1 is characterized in that phase-transfer catalyst is that one or more choose the catalyzer in following group, quaternary amine, quaternary amine alkali, quaternary alkylphosphonium salt, polyoxyethylene glycol, polyoxyethylene glycol dialkyl ether, pyridine, cyclic crown ether.
5. method according to claim 4 is characterized in that the phase-transfer catalyst quaternary amine is one or several mixtures in benzyltriethylammoinium chloride, DTAC, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, OTAC, benzyl trimethyl ammonium chloride, benzyl tributyl ammonium chloride, tetramethyl ammonium chloride, tetrabutylammonium chloride, etamon chloride, Tetrabutyl amonium bromide, tetraethylammonium bromide, 4 bromide, Trimethyllaurylammonium bromide, TTAB, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, the benzyl tributyl brometo de amonio.
6. method according to claim 1, the mass ratio that it is characterized in that phase-transfer catalyst and oil of mirbane is 0.01: 1~0.1: 1.
7. method according to claim 1 is characterized in that solvent is a kind of in aniline, oil of mirbane, N, N-N-methyl-2-2-pyrrolidone N-, the trimethyl carbinol, propyl carbinol, ethanol, methyl alcohol, acetonitrile, toluene, benzene, the acetone etc.
8. method according to claim 1 is characterized in that setting-up point is 80-130 ℃, reaction times 4-12h, and solution is used water washing earlier after the condensation, uses acid elution again.The water washing temperature is at 50-80 ℃.
9. method according to claim 8 is characterized in that the acid of adopting is hydrochloric acid, nitric acid, phosphoric acid, a kind of in the carbonic acid.
10. according to claim 1 or 9 described methods, it is characterized in that carbonic acid is with logical CO
2Mode wash, the mass ratio of the add-on of water and raw material oil of mirbane is 0.5: 1~2: 1 during washing, wash temperature 50-90 ℃, washing time 0.5h-2h, the aqueous solution behind the acid elution adds Ca (OH)
2Form ZG 301, temperature of reaction is 30-60 ℃, filters, and contains the water recycling of mineral alkali and phase-transfer catalyst.
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CN109734606A (en) * | 2019-02-27 | 2019-05-10 | 青岛科技大学 | A method of extending arylamine kind antioxidant and prepares the spent hydroprocessing catalyst service life |
CN109734606B (en) * | 2019-02-27 | 2021-09-03 | 青岛科技大学 | Method for prolonging service life of hydrogenation catalyst for preparing arylamine antioxidant |
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CN112439454B (en) * | 2019-09-05 | 2023-04-07 | 中国石油化工股份有限公司 | RT base condensation catalyst and preparation method thereof |
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