CN115650864B - Method for synthesizing diaminodiphenyl ether by continuous method - Google Patents
Method for synthesizing diaminodiphenyl ether by continuous method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 41
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 238000011437 continuous method Methods 0.000 title claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 28
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 24
- 239000011591 potassium Substances 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 15
- 238000005576 amination reaction Methods 0.000 claims abstract description 14
- 239000001103 potassium chloride Substances 0.000 claims abstract description 14
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 239000012043 crude product Substances 0.000 claims abstract description 5
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000006266 etherification reaction Methods 0.000 claims description 16
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 235000012438 extruded product Nutrition 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 3
- 238000012824 chemical production Methods 0.000 abstract 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 18
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 150000003842 bromide salts Chemical class 0.000 description 4
- -1 polymaleimide Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- YAWIAFUBXXPJMQ-UHFFFAOYSA-N 1-bromo-4-(4-bromophenoxy)benzene Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1 YAWIAFUBXXPJMQ-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- YOCIQNIEQYCORH-UHFFFAOYSA-M chembl2028361 Chemical compound [Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=CC=C1 YOCIQNIEQYCORH-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- CURNJKLCYZZBNJ-UHFFFAOYSA-M sodium;4-nitrophenolate Chemical compound [Na+].[O-]C1=CC=C([N+]([O-])=O)C=C1 CURNJKLCYZZBNJ-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- GMMAPXRGRVJYJY-UHFFFAOYSA-J tetrasodium 4-acetamido-5-hydroxy-6-[[7-sulfonato-4-[(4-sulfonatophenyl)diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].OC1=C2C(NC(=O)C)=CC=C(S([O-])(=O)=O)C2=CC(S([O-])(=O)=O)=C1N=NC(C1=CC(=CC=C11)S([O-])(=O)=O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 GMMAPXRGRVJYJY-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for synthesizing diaminodiphenyl ether by a continuous method in the field of chemical production, which takes 100 parts by weight of hydroquinone and 130-170 parts by weight of 25wt% ammonia water as raw materials, and enters a fixed bed filled with ammonium molybdate-aluminum silicate catalyst for continuous liquid phase amination reaction after stirring and dissolving, then 3-7wt% of silicon dioxide supported potassium catalyst is added, the temperature is raised to 190-210 ℃ to obtain a crude product of 4,4' -diaminodiphenyl ether, and finally the crude product of 4,4' -diaminodiphenyl ether is purified to obtain a finished product of 4,4' -diaminodiphenyl ether. According to the invention, the porous silicon dioxide powder is added into the potassium chloride for soaking and roasting to obtain the silicon dioxide supported potassium catalyst, so that the water generated in the reaction process can not easily dissolve the potassium chloride, the potassium chloride is continuously lost, and the catalyst efficiency is reduced. The invention has high reaction yield and small corrosion to equipment. Provides an industrial new idea for continuously synthesizing the diaminodiphenyl ether.
Description
Technical Field
The invention relates to the technical field of chemical product production, in particular to a synthesis method of diaminodiphenyl ether.
Background
Diaminodiphenyl ether refers to 4,4' -diaminodiphenyl ether, the alias name is 4,4' -oxydiphenylamine, and the english name is 4,4' -Oxydianiline, abbreviated to ODA. ODA with CAS number 101-80-4 is a white or pale yellow crystal with density of 1.315g/ml (20deg.C), melting point 191.5 deg.C, and can be separated from ethanol to obtain crystals, which are insoluble in water and soluble in hydrochloric acid.
ODA is an intermediate with high added value. The application comprises the following steps: first, one of important monomers used for producing high temperature resistant resins such as special engineering plastic polyimide, polymaleimide, polyamide-imide, polyetherimide, polyester imide, polyaramide and the like, wherein the most outstanding performance of the resin is high temperature resistance, and the resin can be continuously used at 260 ℃ and the intermittent use temperature can reach 480 ℃. Has good insulativity, higher strength, outstanding wear resistance and chemical stability, excellent self-lubricating property and radiation protection performance. Can be made into films, molded products, wire paint, glass fiber reinforced layer products and the like, and can be widely applied to the fields of electronic and electric appliance industry (insulation of inner and outer layers of heat-resistant cables, interlayer insulation of transformers, and gasket of motors) such as aerospace, navigation, atomic energy, new energy and the like. Secondly, the epoxy resin, polyurethane and other synthetic polymer materials, cross-linking agent and curing agent have high thermal deformation temperature, good thermal stability, excellent chemical resistance and water resistance. Thirdly, the method is used for replacing benzidine to produce azo dyes, reactive dyes, perfume and other fields. At present, diaminodiphenyl ether is used as a raw material to develop direct dyes with different color scales such as scarlet, brilliant red, sha Gong, yellow brown, green, gray, blue, brilliant orange, black and the like, and the direct dyes can be used for dyeing fabrics such as silk, wool, cotton, hemp and the like, and are superior to benzidine dyes in terms of color fastness, exhaustion rate and the like.
Patent CN107162919B, CN102391136A, CN111072503A, CN106496047A discloses that the traditional production route of diaminodiphenyl ether is a condensation-reduction method, in which paranitrochlorobenzene and paranitrophenol (or sodium paranitrophenolate) are condensed under the action of a polar solvent and a catalyst to obtain dinitrodiphenyl ether, then the dinitrodiphenyl ether is subjected to reduction reaction to obtain a crude diaminodiphenyl ether product, and finally the diaminodiphenyl ether product is obtained through refining treatment. The method for synthesizing ODA by reduction reaction mainly comprises the following steps: (1) an iron powder reduction method; (2) stannous chloride-hydrochloric acid reduction; (3) alkali sulfide reduction method; (4) hydrazine hydrate reduction method; (5) Zinc powder-ammonium chloride reduction method. Wherein, the first three methods generate a great amount of three wastes; the method 4 has the defect of strong corrosiveness and high toxicity of hydrazine hydrate. The reaction equation is as follows:
there is also a new process at present, including the diphenyl ether nitrosation-hydrogenation process and the diphenyl ether amination process. Chinese patent CN10918051a discloses a method for synthesizing 4,4' -diaminodiphenyl ether, comprising the steps of: first, nitrosation reaction: adding sodium nitrite and diphenyl ether into the water phase, slowly dropwise adding hydrochloric acid at the temperature of 0-5 ℃ until the reaction is finished, separating out crystals, filtering, and drying in vacuum to obtain 4,4' -dinitroso diphenyl ether, wherein the reaction process is as follows: second, reduction reaction: adding the obtained solid into an autoclave, taking alcohol as a solvent, adding a catalyst, pressurizing hydrogen to 0.5-4MPa, heating and stirring to 70-120 ℃, and preserving heat for 2-6 hours to obtain the 4,4' -diaminodiphenyl ether.
Patent CN114085158A is a synthetic method of 4,4' -diaminodiphenyl ether, which comprises: the 4,4' -diaminodiphenyl ether is synthesized by taking diphenyl ether, hydrogen peroxide, ammonia water and bromide as starting materials through one-step reaction in the presence of a solvent, a catalyst and a ligand. The invention solves the technical problems of high temperature and high pressure, poor selectivity and low yield of the reaction condition in the existing synthesis process of 4,4' -diaminodiphenyl ether; the Mannich alkali ligand has strong electricity supply and large steric hindrance, and can coordinate with copper salt to obviously improve the catalysis effect of copper salt; the adopted bromide salt can lead the diphenyl ether to carry out oxidation bromination reaction to generate a 4,4' -dibromodiphenyl ether intermediate; the synthesis process can be completed at room temperature, and has the advantages of mild reaction conditions, good selectivity, simple post-treatment and purification, high yield and good product quality.
The prior art has the following defects: the existing condensation-reduction process and the synthesis of diaminodiphenyl ether by adopting diphenyl ether, hydrogen peroxide, ammonia water and bromide salt respectively have the problems of high temperature, high pressure and low yield, and the diphenyl ether is expensive, so that the cost is high, and in addition, the serious problem of bromide salt corrosion equipment exists.
Disclosure of Invention
The invention aims to provide a method for synthesizing diaminodiphenyl ether by a continuous method, which has the advantages of low production cost, high yield and small corrosion to equipment.
The purpose of the invention is realized in the following way: (1) amination: 100 parts by weight of hydroquinone and 130-170 parts by weight of 25wt% ammonia water are taken as raw materials, and the raw materials are stirred and dissolved and then enter a fixed bed filled with an ammonium molybdate-aluminum silicate catalyst for continuous liquid phase amination reaction, wherein the mass airspeed is 1+/-0.1 h -1 The reaction temperature is 90-100 ℃, the reaction pressure is 0.5-0.7MPa, and the para-aminophenol reaction liquid is obtained;
the reaction formula is as follows:
；
(2) Etherification: adding 3-7wt% of silicon dioxide supported potassium catalyst into the para-aminophenol reaction liquid, and heating to 190-210 ℃ for etherification and dehydration to obtain a crude product of 4,4' -diaminodiphenyl ether;
the reaction formula is as follows:
；
(3) Purifying: cooling, crystallizing and centrifugally separating the product to obtain the finished product of the 4,4' -diaminodiphenyl ether.
In the ammonium molybdate-aluminum silicate catalyst in the step (1), the molar ratio of ammonium molybdate to aluminum silicate is 1:1.
further, the silica supported potassium catalyst in the step (2) contains porous silica and potassium chloride, and the molar ratio of the porous silica to the potassium chloride is 5:1.
the silica supported potassium catalyst is prepared by the following method:
(1) Adding porous silicon dioxide powder into potassium chloride aqueous solution for soaking, and performing ultrasonic dispersion for 1-2h;
(2) Then put into a pressure-resistant reaction kettle for sealing, and then heated to 220+/-10 ℃ and kept at constant temperature for 5-6 hours; cooling to room temperature, and drying the solid obtained by filtering in an oven; the drying temperature in the oven is 100 ℃, and the drying time is 3 hours;
(3) Adding 5wt% polyvinyl alcohol as binder into the dried solid, and extruding to form a cylinder with the diameter of 2-3mm and the length of 3-6 mm; and (3) transferring the extruded product into a muffle furnace air atmosphere at 600+/-50 ℃ to bake for 6-8h, so as to obtain the silicon dioxide supported potassium catalyst.
Compared with the prior art, the invention has the beneficial effects that: the invention does not adopt nitrophenol or nitrochlorobenzene raw material and hydrogenation reduction process, and does not adopt diphenyl ether and bromide salt. The corresponding phenolic hydroxyl compound has low price, and the synthesis method has low cost and great economic significance. According to the invention, the porous silicon dioxide powder is added into potassium chloride for soaking and roasting to obtain the silicon dioxide supported potassium catalyst, and through high-temperature roasting, the electron interaction between oxygen in the porous silicon dioxide and supported potassium is enhanced, so that the electron binding energy of potassium ions is improved, and the etherification activity of potassium ions with high electron binding energy is higher. Meanwhile, the porous structure can ensure that water generated in the reaction process can not easily dissolve potassium chloride in the porous structure, so that the potassium chloride is not easy to run off, and the catalyst efficiency is not easy to be reduced. Silica provides a weakly acidic center at a molar ratio of porous silica to potassium chloride of 5: in the case of 1, the etherification reaction can be efficiently and smoothly performed. Thus, in the present invention, the porous silica contributes not only to the etherification reaction in terms of physical structure but also to the etherification reaction in terms of chemical function. Finally, the quality technical index of the finished product is as follows: the white crystal powder has a melting point of more than or equal to 187 ℃, a purity of more than or equal to 99.5% and a yield of more than or equal to 95%. The reaction yield is high, and the corrosion to equipment is small. Provides an industrial new idea for continuously synthesizing the diaminodiphenyl ether.
Detailed Description
Features and exemplary embodiments of various aspects of the present invention will be described in detail below, and in order to make the objects, technical solutions, and advantages of the present invention more apparent, the present invention will be further described with reference to the following embodiments, and any solution obtained by performing equivalent substitution and conventional reasoning on the technical features of the technical solution of the present invention will fall within the protection scope of the present invention.
Example 1:
stirring and dissolving 100 parts by weight of hydroquinone and 150 parts by weight of 25wt% ammonia water, then putting the mixture into a fixed bed filled with an ammonium molybdate-aluminum silicate catalyst, and carrying out continuous catalytic liquid phase amination reaction, wherein the mass airspeed is 1+/-0.1 h -1 The amination reaction temperature is 90 ℃, the reaction pressure is 0.5-0.7MPa, and the para-aminophenol reaction liquid is obtained.
Adding 5wt% of silicon dioxide supported potassium catalyst into the para-aminophenol reaction solution obtained in the last step,
heating to the etherification temperature of 200 ℃ to obtain the crude product of the 4,4' -diaminodiphenyl ether. And cooling, crystallizing and centrifugally separating the product to obtain a white crystal 4,4' -diaminodiphenyl ether finished product. Sampling and testing: the melting point is more than or equal to 189.6 ℃, the purity is more than or equal to 99.87%, and the yield is 95.96%.
Wherein, in the ammonium molybdate-aluminum silicate catalyst, the molar ratio of the ammonium molybdate to the aluminum silicate is 1:1.
In the silicon dioxide supported potassium catalyst, the molar ratio of silicon dioxide to potassium chloride is 5:1, the preparation method of the silica supported potassium catalyst comprises the following steps:
the silica was impregnated with an aqueous potassium chloride solution and dispersed by ultrasonic sound for 1 hour. Sealing in pressure-resistant reaction kettle, heating to 220 deg.C, and maintaining the temperature for 5 hr. Cooling to room temperature, filtering to obtain a solid, and drying the solid in a baking oven at 100 ℃ for 3 hours; and adding 5wt% polyvinyl alcohol into the dried solid as a binder, extruding and forming a cylinder with the diameter of 2-3mm and the length of 3-6mm, and transferring the extruded and formed product into a muffle furnace air atmosphere for roasting at 600 ℃ for 8 hours to obtain the silicon dioxide supported potassium catalyst.
Example 1-1: using 100 parts by weight of hydroquinone and 130 parts by weight of 25% ammonia water as raw materials, the process was the same as in example 1.
Examples 1-2: using 100 parts by weight of hydroquinone and 140 parts by weight of 25% ammonia water as raw materials, the process was the same as in example 1.
Examples 1-3: using 100 parts by weight of hydroquinone and 160 parts by weight of 25% ammonia water as raw materials, the process was the same as in example 1.
Examples 1 to 4: using 100 parts by weight of hydroquinone and 170 parts by weight of 25% ammonia water as raw materials, the process was the same as in example 1.
Comparative example 1-a: using 100 parts by weight of hydroquinone and 120 parts by weight of 25% ammonia water as raw materials, the process was the same as in example 1.
Comparative example 1-b: using 100 parts by weight of hydroquinone and 180 parts by weight of 25wt% ammonia water as raw materials, the process was the same as in example 1.
TABLE 1 influence of raw Material ratio on ODA quality and yield
According to the comparison results in Table 1, the higher the weight parts of hydroquinone and ammonia water, the higher the melting point, purity and yield are, and the lower the melting point, purity and yield are, preferably 1:1.3 to 1.7 weight parts, more preferably 1:1.5.
Example 2-1: the procedure of example 1 was followed except that the "amination reaction temperature was changed to 90 ℃.
Example 2-2: the procedure of example 1 was followed except that the amination reaction temperature was changed to 100 ℃.
Comparative example 2-a: the procedure of example 1 was followed except that the "amination reaction temperature was 85 ℃.
Comparative example 2-b: the procedure of example 1 was followed except that the amination reaction temperature was changed to 105 ℃.
TABLE 2 comparison of the influence of amination temperature on ODA quality and yield
According to the comparison results in Table 2, the higher the amination temperature, the higher the melting point, purity and yield are, the higher the melting point, the lower the purity and the yield are, preferably from 90 to 100℃and more preferably 95 ℃.
Example 3-1: example 1 was repeated except that the catalyst was changed to "3 wt% of the silica-supported potassium catalyst was added".
Example 3-2: example 1 was repeated except that the catalyst was changed to "4 wt% of the silica-supported potassium catalyst was added".
Examples 3-3: example 1 was repeated except that the catalyst was changed to "6 wt% of the silica-supported potassium catalyst was added".
Examples 3-4: example 1 was repeated except that the catalyst was changed to "7 wt% of the silica-supported potassium catalyst was added".
Comparative example 3-a: example 1 was repeated except that "2 wt% of the silica-supported potassium catalyst was added" was used instead.
Comparative example 3-b: example 1 was repeated except that the catalyst was changed to "8 wt% of the silica-supported potassium catalyst was added".
TABLE 3 influence of etherification catalyst quantity on ODA quality and yield Table
According to the comparison result in Table 3, the more the amount of the etherification catalyst is, the melting point, purity and yield are increased and then decreased, preferably 3 to 7% by weight, more preferably 5% by weight.
Example 4-1: the procedure of example 1 is followed except that the temperature is increased to 190℃instead of the "etherification temperature".
Example 4-2: the procedure of example 1 is followed except that the temperature is increased to 195 ℃.
Examples 4-3: the procedure of example 1 was followed except that the temperature was increased to 205℃for the etherification.
Examples 4-4: the procedure of example 1 is followed except that the temperature is increased to 210℃instead of the "etherification temperature".
Comparative example 4-a: the procedure of example 1 is followed except that the temperature is increased to 185 ℃.
Comparative example 4-b: the procedure of example 1 is followed except that the temperature is increased to 215 ℃.
TABLE 4 influence of etherification temperature on ODA quality and yield
According to the comparison results in Table 4, the higher the etherification temperature, the higher the melting point, purity and yield are, the higher the melting point, the lower the purity and the yield are, preferably 190 to 210℃and more preferably 200 ℃.
The invention is not limited to the above embodiments, and based on the technical solution disclosed in the invention, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the invention.
Claims (6)
1. A method for synthesizing diaminodiphenyl ether by a continuous method, which is characterized by comprising the following steps:
(1) Amination: 100 parts by weight of hydroquinone and 130-170 parts by weight of 25wt% ammonia water are taken as raw materials, and the raw materials are stirred and dissolved and then enter a fixed bed filled with an ammonium molybdate-aluminum silicate catalyst for continuous liquid phase amination reaction, wherein the mass airspeed is 1+/-0.1 h -1 The reaction temperature is 90-100 ℃, the reaction pressure is 0.5-0.7MPa, and the para-aminophenol reaction liquid is obtained;
the reaction formula is as follows:
；
(2) Etherification: adding 3-7wt% of silicon dioxide supported potassium catalyst into the para-aminophenol reaction liquid, and heating to 190-210 ℃ for etherification and dehydration to obtain a crude product of 4,4' -diaminodiphenyl ether;
the reaction formula is as follows:
；
(3) Purifying: cooling, crystallizing and centrifugally separating the product to obtain the finished product of the 4,4' -diaminodiphenyl ether.
2. The method for synthesizing diaminodiphenyl ether by the continuous process according to claim 1, wherein in the ammonium molybdate-aluminum silicate catalyst in the step (1), the molar ratio of ammonium molybdate to aluminum silicate is 1:1.
3. the method for synthesizing diaminodiphenyl ether by continuous process according to claim 1, wherein the silica supported potassium catalyst in step (2) contains porous silica and potassium chloride in a molar ratio of 5:1.
4. the method for synthesizing diaminodiphenyl ether by the continuous process according to claim 3, wherein the silica-supported potassium catalyst is prepared by:
(1) Adding porous silicon dioxide powder into potassium chloride aqueous solution for soaking, and performing ultrasonic dispersion for 1-2h;
(2) Then put into a pressure-resistant reaction kettle for sealing, and then heated to 220+/-10 ℃ and kept at constant temperature for 5-6 hours; cooling to room temperature, and drying the solid obtained by filtering in an oven;
(3) And adding 5wt% polyvinyl alcohol as a binder into the dried solid, and transferring the extruded product into a muffle furnace air atmosphere at 600+/-50 ℃ to bake for 6-8h to obtain the silica supported potassium catalyst.
5. The method for synthesizing diaminodiphenyl ether by continuous process according to claim 4, wherein in the step (3) of preparing the silica-supported potassium catalyst, a cylinder having a diameter of 2 to 3mm and a length of 3 to 6mm is extrusion-molded.
6. The method for synthesizing diaminodiphenyl ether by continuous process according to claim 4, wherein in the step (2) of preparing the silica-supported potassium catalyst, the drying temperature in the oven is 100℃and the drying time is 3 hours.
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| US9461254B2 (en) * | 2012-01-03 | 2016-10-04 | Universal Display Corporation | Organic electroluminescent materials and devices |
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| WO1992012118A1 (en) * | 1991-01-10 | 1992-07-23 | E.I. Du Pont De Nemours And Company | Preparation of aromatic diamines from amino phenols or dihydroxyaromatics and bromoaniline |
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