CN101239919B - Method for synthesizing aromatic diamines monomer - Google Patents
Method for synthesizing aromatic diamines monomer Download PDFInfo
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- CN101239919B CN101239919B CN2008100873816A CN200810087381A CN101239919B CN 101239919 B CN101239919 B CN 101239919B CN 2008100873816 A CN2008100873816 A CN 2008100873816A CN 200810087381 A CN200810087381 A CN 200810087381A CN 101239919 B CN101239919 B CN 101239919B
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000000178 monomer Substances 0.000 title claims abstract description 18
- 150000004984 aromatic diamines Chemical class 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 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 claims abstract description 42
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012452 mother liquor Substances 0.000 claims abstract description 24
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 40
- 239000012065 filter cake Substances 0.000 claims description 37
- -1 aromatic nitro compound Chemical class 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000001953 recrystallisation Methods 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- ZPBYCSQKDDZPGO-UHFFFAOYSA-N 2-phenyl-4-propylphenol Chemical compound CCCC1=CC=C(O)C(C=2C=CC=CC=2)=C1 ZPBYCSQKDDZPGO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims description 3
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 claims description 3
- 210000000988 bone and bone Anatomy 0.000 claims description 3
- VCRYGHPVKURQMM-UHFFFAOYSA-N methane;platinum Chemical compound C.[Pt] VCRYGHPVKURQMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 claims description 2
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 claims description 2
- JHOPNNNTBHXSHY-UHFFFAOYSA-N 2-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1O JHOPNNNTBHXSHY-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000010517 secondary reaction Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 14
- 238000009833 condensation Methods 0.000 abstract description 11
- 230000005494 condensation Effects 0.000 abstract description 11
- 238000002425 crystallisation Methods 0.000 abstract description 10
- 230000008025 crystallization Effects 0.000 abstract description 10
- 230000035484 reaction time Effects 0.000 abstract description 9
- 238000001308 synthesis method Methods 0.000 abstract 2
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 28
- 150000002828 nitro derivatives Chemical class 0.000 description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 17
- 239000004642 Polyimide Substances 0.000 description 14
- 150000004985 diamines Chemical class 0.000 description 14
- 229920001721 polyimide Polymers 0.000 description 14
- 239000001294 propane Substances 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 13
- 230000002829 reductive effect Effects 0.000 description 10
- 239000002699 waste material Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000006482 condensation reaction Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000010828 elution Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- ZVDYLUNNDJVEOC-UHFFFAOYSA-N 1-(4-nitrophenoxy)-4-propylbenzene Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 ZVDYLUNNDJVEOC-UHFFFAOYSA-N 0.000 description 3
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical class [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
Abstract
The invention relates to a synthesis method of aromatic diamine monomers, in which object products are obtained by condensation and reduction. In the condensation process, a phase transfer catalyst is added, the mother liquor is recycled, proton polarity solvent crystallization is used to improve the purity of nitryl coumpounds, and the yield is above 98.0%. With the hydrazine hydrate reduction method, the hydrazine hydrate feeding manner and feeding time are controlled, the reaction condition is gentle, so that the product purity is more than 99% and the yield is more than 90%. The synthesis method of the invention shortens the reaction time, improves the reaction yield and product purity, reduces entironment pollution, and has application value on industrialisation.
Description
Technical field
The present invention relates to a kind of synthetic method of diamines monomer, relate in particular to diamines monomer synthetic of aromatic series polyether key, sec.-propyl and benzene ring side chain.
Background technology
Polyimide has obtained the abundant concern of countries in the world as high-performance high temperature-resistant polymer material, developed country such as the U.S. and Japan is active day by day to the research of polyimide in the world in recent years, they not only pay attention to the Application and Development of polyimide novel material, and pay much attention to the research and development of polyimide monomer (mainly being aromatic series dianhydride and aromatic diamine), guiding polyimide constantly towards variation, functionalization, development becomes more meticulous; And domestic very deficient aspect the polyimide monomer, only only limit to several dianhydrides and diamine monomer, seriously hindered the development of domestic polyimide novel material.The monomer diamines is the important monomer of synthesis of polyimides (PI).By in monomer two amine molecules, introducing ehter bond, sec.-propyl and benzene ring side chain etc., can make original insoluble PI be dissolved in N, organic solvents commonly used such as dinethylformamide, tetrahydrofuran (THF), N-Methyl pyrrolidone, increase the transparency of PI, reduce the dielectric properties of PI, and can make PI have lower second-order transition temperature, thereby improve the polyimide processing characteristics.
The method of synthon diamines is to carry out condensation reaction earlier to prepare aromatic nitro compound, then nitro-compound is reduced into amine.Prepare the method that nitro-compound adopts condensation, yet the time of traditional condensation reaction is generally all long, about 15～20h; The effect of phase-transfer catalyst, the reactions such as salt that are exactly catalyzer elder generation and aqueous phase generate intermediate compound, and this then intermediate compound can change organic phase over to and the reactant effect generates product.Utilize phase-transfer catalyst that the very slow reaction that maybe can not carry out of many speed of response is under general condition carried out smoothly, and speed of reaction also improve greatly.Simultaneously, the reaction conditions gentleness of phase transfer catalysis process, easy and simple to handle, side reaction is few, the selectivity height.Nitroreduction is the common method of preparation monomer diamines, mainly contains shortening method, metallic reducing method, hydrazine hydrate reduction method etc.Produce arylamine with the shortening technology, the transformation efficiency height, quality is good, the three wastes are few, is a kind of process for cleanly preparing, but hydrogenation technique catalyzer cost height at present, and the requirement height to equipment has limited its industrial applications; The metallic reducing method uses cheap reducing metal as reductive agent, save production cost, bring high benefit, widely use in early days, but because it produces a large amount of three-waste pollutions, the aftertreatment difficulty limits it to a certain extent and uses, and this method is eliminated gradually in the medium-sized and small enterprises of large-lot producer and coproduction.The product purity height of hydrazine hydrate reduction method preparation, and the by product of reaction is few, purifies for separation and has brought convenience, and along with the continuous decline of hydrazine hydrate price, the hydrazine hydrate reduction legal system is equipped with aromatic diamines, will have very big development prospect.
US3687663 reported by condensation, reductive method and prepared aromatic diamines, and in condensation reaction, the reaction times is 18h, and the solution entry is to obtain nitro-compound, N, dinethylformamide recrystallization; In the reduction reaction, the solution entry obtains the product diamines; This kind synthesis technique, the reaction times is oversize, and solution entry meeting causes the waste of a large amount of solvents, N, the polarity of dinethylformamide is very big, and is all very big to the solubleness of a lot of organic compound, come the crystallization meeting to make a lot of impurity with it, do not reach the purpose of purification also along with the nitro-compound dissolving.
JP03090052, JP2001002747 have reported preparation 2, condensation, the reductive operational path of two [3-phenyl-4-(4-amino-benzene oxygen) phenyl] propane of 2-.Wherein condensation reaction needs 20h, and overlong time, temperature of reaction are 100 ℃～250 ℃, and temperature is too high, to the corresponding raising that requires of equipment.
EP198480 has reported the preparation method of two (3-amino-benzene oxygen) compounds of aromatic series, adopts condensation, reducing process.Reaction needed 10h in the condensation course, the reaction solution entry obtains nitro-compound, purifies with benzene; This method reaction times is long, and the solution entry causes a large amount of solvent wastes, and benzene is used in aftertreatment, and benzene has certain toxicity.
Yu Xinhai (insulating material, 2002, NO.4) adopt condensation, reductive method to prepare 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, this method has been used the phase-transfer catalyst crown ether, makes the reaction times shorten; Yet elutriation obtains after the nitro thing through purifying, and makes to contain impurity in the nitro thing, can have influence on the purity and the yield of the second step reduzate; Use the hydrazine hydrate reduction legal system to be equipped with the corresponding diamine based compound, though purity is higher, adds hydrazine hydrate and still need react 8h afterwards, the reaction times is long; Reacting the later stage with the whole entry of reaction solution, thereby nitro-compound is separated out, this method has caused the waste of a large amount of solvents.
JP07233124 has reported the preparation method of aryl oxide dinitro compound, has added the phase-transfer catalyst quaternary ammonium salt in the condensation course, but its reaction still needs 10h, and yield only reaches 87.4%; Reaction solution entry in the last handling process causes the waste of solvent, is not suitable for suitability for industrialized production; And do not mention the synthetic route of corresponding diamine based compound in this patent.
JP420233403 has reported 2, the preparation method of two [4-(4-nitrophenoxy) phenyl] propane of 2-, and its condensation time is 10h, and the later stage is used recrystallizing methanol; The reaction times of this method is long, and methyl alcohol has certain toxicity, and human body is had certain injury; Simultaneously, this patent does not relate to the synthetic method of derived product diamino compound.
CN101037393 has reported 2, two [4-(4-amino-benzene oxygen) phenyl] propane and 4 of 2-, the preparation method of 4 '-two (4-amino-phenoxy group) phenyl ether, this method is that the coupling technique with iron powder reducing method and hydrazine hydrate reduction method prepares arylamine, with the most nitro-compound of lower-cost iron powder reducing, more unreduced nitro-compound is adopted hydrazine hydrate reduction earlier; Difficult the obtaining of the pairing nitro-compound of the arylamine that relates in the literary composition do not propose corresponding synthetic route.
CN03132010.4 has reported 2, the preparation method of 2 '-two [4-(4-amino-benzene oxygen) phenyl] propane, and the method for use elutriation has caused the waste of solvent in its aftertreatment, has increased cost; CN 1907952A has reported 2, and the preparation method of two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-does not use phase-transfer catalyst in the condensation course, and the reaction times is long, and the later stage does not purify.
US4064107 has reported the route of synthetic 4,4 '-two (4-amino-phenoxy group) phenyl ether, and the synthetic method for preparing the monomer diamines of this kind is the metallic reducing method, the yield that obtains product is 80.8%, the melting range broad of product, purity is not high, purifies for separation and makes troubles.And the metal mud drum that this kind method produces wraps up in a certain amount of product, brings environmental pollution, brought inconvenience to industrialization.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of preparation technology, and quantity of three wastes is few, and product is easily separated, purity height, the method for preparing aromatic diamines monomer that cost is low.
Technical scheme of the present invention is: the method for a kind of synthetic aroma family diamines monomer, and concrete steps are as follows:
A. the preparation of aromatic nitro compound (condensation reaction)
A, in the container that mechanical stirrer, thermometer, prolong are housed, add aromatic dihydroxy compound, to halogen oil of mirbane, aprotic polar solvent, phase-transfer catalyst, salt forming agent, dewatering agent, nitrogen protection is stirred down; Heat temperature raising to reflux state reacts 2h～4h, after reaction finishes dewatering agent is steamed, and continues reaction 2h～4h, and cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively;
B, aftertreatment
Above-mentioned steps gained filter cake is added in the entry, and pickling to pH value is 6～7, filters, and recrystallization obtains the aromatic nitro compound crystal, oven dry;
Reaction scheme is as follows:
Wherein R is :-O-,-CO-,-C (CH
3)
2-,-C (CF
3)
2-; X is :-H ,-C
6H
5R1 is Cl, Br, F;
B. the preparation of aromatic diamine (hydrazine hydrate reduction method)
A, in the container that mechanical stirrer, thermometer, prolong are housed, add catalyzer and solvent, be warming up to 120 ℃～160 ℃, reflux, keep 2h～4h under the reflux temperature;
B, reduce the temperature to 85 ℃, add the prepared aromatic nitro compound of steps A, temperature is controlled between 60 ℃～80 ℃, under the nitrogen protection, begins to drip hydrazine hydrate, the rate of addition of control hydrazine hydrate; Treat that hydrazine hydrate dropwises, continue isothermal reaction 4～6h; Be warming up to 85～95 ℃, heat filtering, mother liquor leaves standstill, and has crystal to separate out;
Reaction scheme is as follows:
Wherein R is :-O-,-CO-,-C (CH
3)
2-,-C (CF
3)
2-; X is :-H ,-C
6H
5
C, aftertreatment
The crystal of separating out in the mother liquor is filtered, use the alcohol flushing crystal, oven dry promptly obtains purpose product aromatic diamines.
The prepared aromatic diamine monomer of the present invention contains following structural formula:
Wherein R is :-O-,-CO-,-C (CH
3)
2-,-C (CF
3)
2-;
X is :-H ,-C
6H
5
Above-mentioned aromatic dihydroxy compound structural formula is:
Wherein R is :-O-,-CO-,-C (CH
3)
2-,-C (CF
3)
2-; X is :-H ,-C
6H
5Preferred 2, two (3-phenyl-4-hydroxy phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) HFC-236fa, 4 of 2-, 4 '-dihydroxy diphenyl ether or 4,4 '-dihydroxy benzophenone; Described phase-transfer catalyst is hexaoxacyclooctadecane-6-6 or polyoxyethylene glycol PEG600; Described aprotic polar solvent is N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or tetrahydrofuran (THF); Salt forming agent is Anhydrous potassium carbonate, saleratus, yellow soda ash or sodium bicarbonate; Described is parachloronitrobenzene, p-Nitrobromobenzene or p-fluoronitrobenzene to halogen oil of mirbane; Dewatering agent is toluene or dimethylbenzene.
Wherein the add-on of halogen oil of mirbane is 2.0～2.5 times of molar weights of aromatic dihydroxy compound; The add-on of phase-transfer catalyst is 0.15～0.35 times of molar weight of aromatic dihydroxy compound; The add-on of salt forming agent is 2.1～2.3 times of molar weights of aromatic dihydroxy compound; The add-on of aprotic polar solvent is a benchmark with the mole number of aromatic dihydroxy compound, and every mole adds 500～1000ml; The add-on of dewatering agent is a benchmark with the mole number of aromatic dihydroxy compound, and every mole adds 100～500ml.
Be heated to 130 ℃～170 ℃ when heat temperature raising is to reflux state in the steps A.In the steps A in the post-treating method functional quality percentage concentration be that 1%～5% hydrochloric acid carries out pickling; Adopt the mother liquor recycling method to carry out secondary reaction in the post-treating method; Use proton polar solvent ethylene glycol monomethyl ether, ethylene glycol or ethanol to carry out recrystallization.
Catalyzer described in the step B is gac/FeCl
36H
2O, palladium charcoal, platinum charcoal or bone nickel; Preferred catalyst is gac/FeCl
36H
2O, gac and FeCl
36H
2The mass ratio of O is 6: 1～10: 1; Solvent described in the step B is N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE or ethylene glycol monomethyl ether.
Wherein the add-on of the solvent described in the step B is a benchmark with the mole number of aromatic nitro compound, and every mole adds 1000～3000ml; The add-on of catalyzer and the mass ratio of aromatic nitro compound are 1: 1.3～1: 1.6; The add-on of hydrazine hydrate and the mol ratio of nitro-compound are 5: 1～10: 1.
The mass percentage concentration of used hydrazine hydrate is 50～80% among the present invention; The feed way of hydrazine hydrate adopts and drips reinforced mode, and the rate of addition of hydrazine hydrate is controlled at 20ml/h～40ml/h; The hydrazine hydrate reduction temperature of reaction is 60 ℃～100 ℃.
Filtrate collection with the A step later stage among the present invention gets up, and as solvent, uses when being used for the identical nitro-compound of next time preparation; The filter cake main component that filters out for the first time in the B step is a catalyzer, with its oven dry, reclaims next time and uses, because activity of such catalysts is limited, but its twice of reuse at most; The filtrate that filters out for the second time in the B step mainly is solvent, and also having some be the intermediate product of complete reaction, uses when can be used for preparing next time identical diamines.
Beneficial effect:
In traditional condensation reaction technology, added phase-transfer catalyst, the adding of phase-transfer catalyst can make organic-inorganic better combination mutually, reaction is carried out more fully, improved the efficient of reaction, shorten the time of reaction greatly, reaction times is 4～8h, simultaneously temperature of reaction is decided to be 130 ℃～170 ℃; The reaction later stage uses proton polar solvent to carry out the purity that recrystallization has improved nitro-compound; Adopt the method for mother liquor recycling use, improved the yield of reaction, reduced cost, reduced pollution environment; In the hydrazine hydrate reduction technology, the add-on of control catalyst and the add-on of hydrazine hydrate; The feed way of controlling hydrazine hydrate simultaneously adopts and drips reinforced mode, and the rate of addition of hydrazine hydrate is controlled at 20ml/h～40ml/h, has improved the utilization ratio of hydrazine hydrate, makes that reaction is more complete, and the purity of diamines can reach more than 99%
1, cost is low: the adding of phase-transfer catalyst is shortened the time of reaction greatly in the condensation reaction, and general bibliographical information 10h～20h only need 4h～8h now, and raw material reaction is complete; Recycling of solvent reduced a large amount of costs.
2, purity height: use ethylene glycol monomethyl ether, ethylene glycol, ethanol etc. to carry out recrystallization in the condensation reaction, improved the purity of nitro-compound; With hydrazine hydrate reduction method nitro compound reducing, the purity of product can reach more than 99.0% (the amine value).
3, yield height: the adding of phase-transfer catalyst in the condensation reaction, make organic-inorganic better combination mutually, react more complete, yield can reach more than 99.0%; The hydrazine hydrate reduction yield can reach 90.0%.
4, technological process is convenient: the hydrazine hydrate reduction legal system is equipped with diamines (general bibliographical information shortening method), and is lower to the requirement of device, need not high pressure-temperature, and operating process is easy, has certain application value.
5, the three wastes are few, and are easily separated: the foreign matter content in the two step products is few, and the solvent reclaim under reduced pressure, and three-waste pollution is reduced.
Embodiment
To help to understand the present invention by following example, but not limit content of the present invention.
Embodiment 1
In the there-necked flask of 500ml, add 2, two (3-phenyl-4-hydroxy phenyl) propane 19.0g, the p-Nitrophenyl chloride 16.5g of 2-, hexaoxacyclooctadecane-6-6,4g, salt of wormwood 15.2g, N-Methyl pyrrolidone 80g, toluene 70.5g, nitrogen protection is stirred down; Be warming up to 153.4 ℃ of backflows, the 3h that anhydrates that refluxes.After dividing water to finish toluene is steamed, continue reaction 2h and finish, cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively.The filtrate secondary circulation is used; Filter cake adds in the entry, is that 1% salt acid elution to pH value is 6.3 with mass percentage concentration, filters, and spent glycol monomethyl ether recrystallization obtains yellow 2, two [3-phenyl-4-(4-nitrophenoxy) phenyl] the propane crystal 3 1.2g of 2-, oven dry.Yield 98.4%.
In four-hole boiling flask, add gac 15, FeCl
36H
2O1.5g, ethylene glycol monomethyl ether 120g stirs and is warming up to 115.1 ℃ of backflows, back flow reaction 3h.Be cooled to 85 ℃, step gained nitro-compound 25.4g in the adding, 70 ℃ drip hydrazine hydrate 20g, and rate of addition is 35ml/h.After 70 ℃ of constant temperature continue reaction 6h down, heat up, 85 ℃ of following heat filterings are collected mother liquor, filter cake second stage employ, mother liquor crystallization, filter, use the washing with alcohol filter cake, get white crystal, oven dry, get 2, and two [3-phenyl-4-(4-amino-benzene oxygen) phenyl] the propane 20.6g of 2-(purity: 99.8%), yield 90.8%.
Embodiment 2
In the there-necked flask of 500ml, add 2, two (3-phenyl-4-hydroxy phenyl) the propane 19.0g of 2-, p-Nitrophenyl chloride 16.5g, hexaoxacyclooctadecane-6-64g, salt of wormwood 15.2g, N-Methyl pyrrolidone 80g, toluene 70.5g, nitrogen protection is stirred down; Be warming up to 153.4 ℃ of backflows, the 3h that anhydrates that refluxes.After dividing water to finish toluene is steamed, continue reaction 2h and finish, cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively.The filtrate secondary circulation is used; Filter cake adds in the entry, is that 1% salt acid elution to pH value is 6.7 with mass percentage concentration, filters, and spent glycol monomethyl ether recrystallization obtains yellow 2, two [3-phenyl-4-(4-nitrophenoxy) phenyl] the propane crystal 3 1.2g of 2-, oven dry.Yield 98.4%.
In four-hole boiling flask, add gac 9g, FeCl
36H
2O1.5g, ethylene glycol monomethyl ether 120g stirs and is warming up to 120.1 ℃ of backflows, back flow reaction 3h.Be cooled to 85 ℃, step gained nitro-compound 25.4g in the adding, 70 ℃ drip hydrazine hydrate 20g, and rate of addition is 35ml/h.After 70 ℃ of constant temperature continue reaction 6h down, heat up, 85 ℃ of following heat filterings are collected mother liquor, filter cake second stage employ, mother liquor crystallization, filter, use the washing with alcohol filter cake, get white crystal, oven dry, get 2, and two [3-phenyl-4-(4-amino-benzene oxygen) phenyl] the propane 20.2g of 2-(purity: 99.6%), yield 90.0%.
Embodiment 3
In the there-necked flask of 500ml, add 2, two (4-hydroxy phenyl) propane 22.8g of 2-, to nitro bromobenzene 31.5g, polyoxyethylene glycol PEG6006.5g, saleratus 30.4g, N,N-dimethylacetamide 80g, toluene 70.5g, nitrogen protection is stirred down; Be warming up to 143.5 ℃ of backflows, the 3h that anhydrates that refluxes.After dividing water to finish toluene is steamed, continue reaction 1h and finish, cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively.The filtrate secondary circulation is used; Filter cake adds in the entry, is that 2% salt acid elution to pH value is 6.4 with mass percentage concentration, filters, and the spent glycol recrystallization obtains yellow 2,2 '-two [4-(4-nitro phenoxyl) phenyl] propane crystal 4 6.5g, oven dry.Yield 99.0%.
In four-hole boiling flask, add palladium catalyst charcoal 12.2g, N, dinethylformamide 100g stirs and is warming up to 141.6 ℃ of backflows, back flow reaction 2.5h.Be cooled to 80 ℃, step gained nitro-compound 23.5g in the adding, 80 ℃ drip hydrazine hydrate 20g, and rate of addition is 25ml/h.After 70 ℃ of constant temperature continue reaction 4h down, heat up, 90 ℃ of following heat filterings are collected mother liquor, filter cake second stage employ, mother liquor crystallization filters, and uses the washing with alcohol filter cake, gets white crystal, the oven dry, 2,2 '-two [4-(4-amino-benzene oxygen) phenyl] propane 18.6g (purity: 99.7%), yield 90.6%.
Embodiment 4
In the there-necked flask of 500ml, add 4,4 '-dihydroxy diphenyl ether 25.3g, p-Nitrophenyl chloride 35.0g, hexaoxacyclooctadecane-6-65.2g, yellow soda ash 36.3g, N, dinethylformamide 90g, toluene 80g, nitrogen protection is stirred down; Be warming up to 132.5 ℃ of backflows, the 4h that anhydrates that refluxes.After dividing water to finish toluene is steamed, continue reaction 3h and finish, cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively.The filtrate secondary circulation is used; Filter cake adds in the entry, is that 2% salt acid elution to pH value is 7.0 with mass percentage concentration, filters, and uses ethyl alcohol recrystallization, obtains yellow 4,4 '-two (4-nitro-phenoxy group) phenyl ether crystal 5 4.7g, oven dry.Yield 98.6%.
Add catalyzer platinum charcoal 3.3g in four-hole boiling flask, N,N-dimethylacetamide 200g stirs and is warming up to 152.3 ℃ of backflows, back flow reaction 2h.Be cooled to 85 ℃, step gained nitro-compound 22.2g in the adding, 70 ℃ drip hydrazine hydrate 25g, and rate of addition is 30ml/h.After 70 ℃ of constant temperature continue reaction 5h down, heat up, 85 ℃ of following heat filterings are collected mother liquor, filter cake second stage employ, mother liquor crystallization filters, and uses the washing with alcohol filter cake, gets white crystal, the oven dry, 4,4 '-two (4-amino-phenoxy group) phenyl ether 17.4g (purity: 99.6%), yield 90.3%.
Embodiment 5
In the there-necked flask of 500ml, add 2, two (4-hydroxy phenyl) HFC-236fa 33.6g of 2-, to nitro bromobenzene 34.66g, polyoxyethylene glycol PEG6005.3g, salt of wormwood 30.4g, N,N-dimethylacetamide 80g, toluene 70.5g, nitrogen protection is stirred down; Be warming up to 143.5 ℃ of backflows, the 2h that anhydrates that refluxes.After dividing water to finish toluene is steamed, continue reaction 4h and finish, cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively.The filtrate secondary circulation is used; Filter cake adds in the entry, is that 1% salt acid elution to pH value is 6.7 with mass percentage concentration, filters, and spent glycol monomethyl ether recrystallization obtains yellow 2,2 '-two [4-(4-nitrophenoxy) phenyl] HFC-236fa crystal 5 6.64g, oven dry.Yield 98.0%.
In four-hole boiling flask, add gac 7.5g, FeCl
36H
2O0.75g, ethylene glycol monomethyl ether 100g stirs and is warming up to 117.5 ℃ of backflows, back flow reaction 2.5h.Be cooled to 80 ℃, step gained nitro-compound 28.9g in the adding, 80 ℃ drip hydrazine hydrate 30g, and rate of addition is 35ml/h.After 70 ℃ of constant temperature continue reaction 4h down, heat up, 90 ℃ of following heat filterings are collected mother liquor, filter cake second stage employ, mother liquor crystallization, filter, use the washing with alcohol filter cake, get white crystal, oven dry, 2,2 '-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa 47.02g (purity: 99.8%), yield 90.6%.
Embodiment 6
In the there-necked flask of 500ml, add 4,4 '-dihydroxy benzophenone 21.4g, p-Nitrophenyl chloride 36.24g, hexaoxacyclooctadecane-6-66.5g, salt of wormwood 30.4g, N,N-dimethylacetamide 80g, dimethylbenzene 70.5g, nitrogen protection is stirred down; Be warming up to 143.5 ℃ of backflows, the 2h that anhydrates that refluxes.After dividing water to finish dimethylbenzene is steamed, continue reaction 4h and finish, cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively.The filtrate secondary circulation is used; Filter cake adds in the entry, is that 1% salt acid elution to pH value is 6.0 with mass percentage concentration, filters, and the spent glycol recrystallization obtains yellow 4,4 '-two (4-nitro-phenoxy group) benzophenone crystal 4 5.01g, oven dry, yield 98.7%.
In four-hole boiling flask, add gac 7.5g, FeCl
36H
2O0.75g, ethylene glycol monomethyl ether 100g stirs and is warming up to 115.9 ℃ of backflows, back flow reaction 2.5h.Be cooled to 80 ℃, step gained nitro-compound 22.8g in the adding, 80 ℃ drip hydrazine hydrate 20g, and rate of addition is 25ml/h.After 70 ℃ of constant temperature continue reaction 4h down, heat up, 90 ℃ of following heat filterings are collected mother liquor, filter cake second stage employ, mother liquor crystallization filters, and uses the washing with alcohol filter cake, gets white crystal, the oven dry, 4,4 '-two (4-amino-phenoxy group) benzophenone 35.86g (purity: 99.4%), yield 90.0%.
Embodiment 7
In the there-necked flask of 500ml, add 2, two (3-phenyl-4-hydroxy phenyl) propane 38.0g of 2-, to nitro bromobenzene 33.1g, polyoxyethylene glycol PEG6006g, saleratus 30.4g, N, dinethylformamide 150g, toluene 80g, nitrogen protection is stirred down; Be warming up to 131.4 ℃ of backflows, the 4h that anhydrates that refluxes.After dividing water to finish toluene is steamed, continue reaction 4h and finish, cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively.The filtrate secondary circulation is used; Filter cake adds in the entry, is that 1% salt acid elution to pH value is 6.1 with mass percentage concentration, filters, and spent glycol monomethyl ether recrystallization obtains yellow 2, two [3-phenyl-4-(4-nitrophenoxy) phenyl] the propane crystal 6 2.6g of 2-, oven dry.Yield 98.7%.
In four-hole boiling flask, add gac 30g, FeCl
36H
2O3.0g, ethylene glycol monomethyl ether 200g stirs and is warming up to 119.3 ℃ of backflows, back flow reaction 2h.Be cooled to 85 ℃, step gained nitro-compound 50.8g in the adding, 75 ℃ drip hydrazine hydrate 50.0g, and rate of addition is 40ml/h.After 75 ℃ of constant temperature continue reaction 5h down, heat up, 85 ℃ of following heat filterings are collected mother liquor, filter cake second stage employ, mother liquor crystallization, filter, use the washing with alcohol filter cake, get white crystal, oven dry, get 2, and two [3-phenyl-4-(4-amino-benzene oxygen) phenyl] the propane 41g of 2-(purity: 99.7%), yield 90.3%.
Embodiment 8
In the there-necked flask of 500ml, add 2, two (4-hydroxy phenyl) the propane 45.6g of 2-, p-Nitrophenyl chloride 66.5g, hexaoxacyclooctadecane-6-68.2g, sodium bicarbonate 60.8g, N methyl-2-pyrrolidone 160g, dimethylbenzene 150g, nitrogen protection is stirred down; Be warming up to 145.7 ℃ of backflows, the 3h that anhydrates that refluxes.After dividing water to finish dimethylbenzene is steamed, continue reaction 2h and finish, cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively.The filtrate secondary circulation is used; Filter cake adds in the entry, is that 3% salt acid elution to pH value is 6.9 with mass percentage concentration, filters, and uses ethyl alcohol recrystallization, obtains yellow 2,2 '-two [4-(4-nitro phenoxyl) phenyl] propane crystal 90.5g, oven dry.Yield 99.0%.
In four-hole boiling flask, add catalyzer bone nickel 5.3g, N, dinethylformamide 100g stirs and is warming up to 145.6 ℃ of backflows, back flow reaction 2.5h.Be cooled to 80 ℃, step gained nitro-compound 23.5g in the adding, 80 ℃ drip hydrazine hydrate 25.5g, and rate of addition is 35ml/h.After 70 ℃ of constant temperature continue reaction 4h down, heat up, 90 ℃ of following heat filterings are collected mother liquor, filter cake second stage employ, mother liquor crystallization filters, and uses the washing with alcohol filter cake, gets white crystal, the oven dry, 2,2 '-two [4-(4-amino-benzene oxygen) phenyl] propane 18.6g (purity: 99.7%), yield 90.6%.
Claims (9)
1. the synthetic method of an aromatic diamines monomer, concrete steps are as follows:
A. the preparation of aromatic nitro compound
A, in the container that mechanical stirrer, thermometer, prolong are housed, add aromatic dihydroxy compound, to halogen oil of mirbane, aprotic polar solvent, phase-transfer catalyst, salt forming agent, dewatering agent, nitrogen protection is stirred down; Heat temperature raising to reflux state reacts 2h～4h, after reaction finishes dewatering agent is steamed, and continues reaction 2h～4h, and cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively; Wherein the aromatic dihydroxy compound structural formula is:
Wherein R is :-O-,-CO-,-C (CH
3)
2-,-C (CF
3)
2-; X is :-H ,-C
6H
5Described phase-transfer catalyst is hexaoxacyclooctadecane-6-6 or polyoxyethylene glycol PEG600; The add-on of phase-transfer catalyst is 0.15～0.35 times of molar weight of aromatic dihydroxy compound; Wherein said salt forming agent is Anhydrous potassium carbonate, saleratus, yellow soda ash or sodium bicarbonate; Described is parachloronitrobenzene, p-Nitrobromobenzene or p-fluoronitrobenzene to halogen oil of mirbane; Dewatering agent is toluene or dimethylbenzene;
B, aftertreatment
The filter cake of above-mentioned steps gained is added in the entry, and pickling to pH value is 6～7, filters, and recrystallization obtains the aromatic nitro compound crystal, oven dry;
B. the preparation of aromatic diamine
A, in the container that mechanical stirrer, thermometer, prolong are housed, add catalyzer and solvent, be warming up to 120 ℃～160 ℃, reflux, keep 2h～4h under the reflux temperature;
B, reduce the temperature to 85 ℃, add the prepared aromatic nitro compound of steps A, temperature is controlled between 60 ℃～80 ℃, under the nitrogen protection, begin to drip hydrazine hydrate, the rate of addition of control hydrazine hydrate, treat that hydrazine hydrate dropwises, continue isothermal reaction 4～6h; Be warming up to 85～95 ℃, heat filtering, mother liquor leaves standstill, and has crystal to separate out;
C, aftertreatment
The crystal of separating out in the mother liquor is filtered, use the alcohol flushing crystal, oven dry promptly obtains purpose product aromatic diamines monomer; Its structural formula is:
Wherein R is :-O-,-CO-,-C (CH
3)
2-,-C (CF
3)
2-; X is :-H ,-C
6H
5
2. the method for claim 1, it is characterized in that described aromatic dihydroxy compound is 2, two (3-phenyl-4-hydroxy phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) HFC-236fa, 4 of 2-, 4 '-dihydroxy diphenyl ether or 4,4 '-dihydroxy benzophenone; Described aprotic polar solvent is N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or tetrahydrofuran (THF).
3. the method for claim 1 is characterized in that described add-on to halogen oil of mirbane is 2.0～2.5 times of molar weights of aromatic dihydroxy compound; The add-on of salt forming agent is 2.1～2.3 times of molar weights of aromatic dihydroxy compound; The add-on of aprotic polar solvent is a benchmark with the mole number of aromatic dihydroxy compound, and every mole adds 500～1000ml; The add-on of dewatering agent is a benchmark with the mole number of aromatic dihydroxy compound, and every mole adds 100～500ml.
4. the method for claim 1 is characterized in that in the steps A heat temperature raising to 130 ℃～170 ℃.
5. the method for claim 1 is characterized in that in the steps A that pickling functional quality percentage concentration in the last handling process is that 1%～5% hydrochloric acid carries out; Adopt the mother liquor recycling method to carry out secondary reaction in the post-treating method; Use proton polar solvent ethylene glycol monomethyl ether, ethylene glycol or ethanol to carry out recrystallization.
6. the method for claim 1 is characterized in that the catalyzer described in the step B is gac/FeCl
36H
2O, palladium charcoal, platinum charcoal or bone nickel; Solvent described in the step B is N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE or ethylene glycol monomethyl ether.
7. method as claimed in claim 6 is characterized in that described catalyzer is gac/FeCl
36H
2During O, gac and FeCl
36H
2The mass ratio of O is 6: 1～10: 1.
8. the method for claim 1, the add-on that it is characterized in that the solvent described in the step (B) is a benchmark with the mole number of aromatic nitro compound, every mole adds 1000～3000ml; The add-on of catalyzer and the mass ratio of aromatic nitro compound are 1: 1.3～1: 1.6; The add-on of hydrazine hydrate and the mol ratio of aromatic nitro compound are 5: 1～10: 1.
9. the method for claim 1, the mass percentage concentration that it is characterized in that described hydrazine hydrate is 50～80%; The feed way of hydrazine hydrate adopts and drips reinforced mode, and the rate of addition of hydrazine hydrate is controlled at 20ml/h～40ml/h.
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| CN105001092B (en) * | 2015-07-06 | 2017-01-11 | 广西科技大学 | Method for preparing 2,2-di(4-(4-aminophenoxy)phenyl)hexafluoropropane and intermediate body thereof at low temperature |
| CN105037166B (en) * | 2015-07-06 | 2017-07-14 | 广西科技大学 | The preparation method of 2,2 2 (4 (4 amino-benzene oxygen) phenyl) HFC-236fas and its intermediate |
| CN107428704A (en) * | 2015-10-06 | 2017-12-01 | Gsp作物科学有限公司 | The method for preparing Fluoxastrobin |
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| CN113666347A (en) * | 2021-08-26 | 2021-11-19 | 陕西大美化工科技有限公司 | Regeneration treatment method of hydrazine hydrate hydrochloride |
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