CN114671770A - Production method of 4,4' -diaminodiphenyl ether - Google Patents
Production method of 4,4' -diaminodiphenyl ether Download PDFInfo
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- 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 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 60
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002425 crystallisation Methods 0.000 claims abstract description 27
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 13
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- MWAGUKZCDDRDCS-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenoxy)benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 MWAGUKZCDDRDCS-UHFFFAOYSA-N 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007868 Raney catalyst Substances 0.000 claims description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- -1 aromatic nitro compound Chemical class 0.000 abstract description 16
- 239000012535 impurity Substances 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 7
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 abstract description 5
- GWJGGKXYMWOPID-UHFFFAOYSA-N benzene;hydroxylamine Chemical compound ON.C1=CC=CC=C1 GWJGGKXYMWOPID-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- 239000012442 inert solvent Substances 0.000 abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 230000000717 retained effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- Organic Chemistry (AREA)
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Abstract
The invention discloses a method for producing 4,4' -diaminodiphenyl ether, which relates to the technical field of aromatic nitro compound hydrogenation synthesis; according to the production method of 4,4' -diaminodiphenyl ether, firstly, a method of vacuumizing and evaporating the solvent is adopted to discharge trace oxygen dissolved in the solvent, so that the problem that residual oxygen in the solvent cannot be replaced by using nitrogen only is solved, the oxidization of hydroxylamine benzene and azobenzene in the nitro hydrogenation process is inhibited, and the problems of deepening of the color of the product and increase of the impurity amount are avoided; secondly, a specific inert poor solvent is adopted for crystallization, so that on one hand, side reaction of the amino compound and the solvent can be prevented, on the other hand, the inert solvent can crystallize and separate out the product from the reaction solvent, but impurities generated in the reaction are retained in the solvent, and the purity of the product is improved; in addition, the addition of the reducing agent can prevent the amino from being oxidized by extremely trace oxygen free radicals in the solvent and the nitrogen to influence the color of the product, so as to ensure the color stability of the amino compound.
Description
Technical Field
The invention relates to the technical field of aromatic nitro compound hydrogenation synthesis, in particular to a production method of 4,4' -diaminodiphenyl ether.
Background
4,4 '-diaminodiphenyl ether is widely applied in the fields of rubber, tires, plastics, fibers and the like, but amino groups of the product are easily oxidized in the synthesis process, so that the chromaticity of the product is poor, and the reaction mechanism of the hydrogenation of the 4, 4' -dinitrodiphenyl ether serving as a raw material is divided into two types: one is nitro-nitroso-hydroxylamine-aniline; the other is azoxy-azo-hydrazo-aniline. For the majority of aromatic nitro compounds, the first hydrogenation route and the second side reaction route cause the coupling of azo compounds to generate side reaction impurities. Meanwhile, it can be known from the hydrogenation process that the presence of oxygen can cause the oxidation reaction of hydroxylamine benzene and azobenzene with strong reducibility to generate a series of oxidation products, which are the main reasons for the darkening of the color of the aromatic nitro compound in the hydrogenation process.
On the other hand, the existing hydrogenation preparation process has two post-treatment processes, one is separation distillation, the obtained crude product is sublimated and then is crushed to obtain a granular product; secondly, adding acid into the crude product to form salt, decoloring, adding alkali to adjust the pH value to be neutral, and recrystallizing, but the sublimation operation not only consumes large energy, but also the prepared product is massive and needs to be crushed again, and the method of adding acid to form salt and adjust alkali can generate a large amount of waste salt, and the two treatment methods have the problems of poor chromaticity, low purity and low yield, and do not accord with the current trend of green development.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide a method for producing 4, 4' -diaminodiphenyl ether.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for producing 4, 4' -diaminodiphenyl ether comprises the following steps:
adding 4, 4' -dinitrodiphenyl ether, a catalyst and a hydrogenation solvent into an autoclave, stirring and mixing uniformly, evaporating part of the hydrogenation solvent by adopting a low-temperature vacuumizing mode, replacing the autoclave with nitrogen for 3-5 times, then filling hydrogen into the autoclave, wherein the hydrogenation pressure is 0.4-1.2 MPa, and reacting for 4-6 hours at 50-90 ℃ to obtain a reaction solution;
the hydrogenation solvent is one or two of methanol, ethanol, toluene, ethylbenzene, N-dimethylformamide and N, N-dimethylacetamide;
the catalyst is Pt/C, Pd/C and Raney nickel;
wherein the mass ratio of the 4, 4' -dinitrodiphenyl ether, the catalyst and the hydrogenation solvent is 100: 0.5-2: 500-600 parts;
secondly, adding a reducing agent and a crystallization solvent subjected to deoxidization treatment into a crystallizer, removing air by adopting nitrogen, filtering the reaction liquid obtained in the step one, then crystallizing the reaction liquid in the crystallizer for 10-15 hours at the crystallization temperature of 45-60 ℃, filtering the reaction liquid after crystallization is finished, and washing a filter cake to obtain 4, 4' -diaminodiphenyl ether;
The reducing agent is sodium thiosulfate, zinc powder or hydroxylamine hydrochloride;
the crystallization solvent is deionized water, ethylene glycol or chlorobenzene;
wherein the mass of the crystallization solvent subjected to the deoxidization treatment is 0.5-2 times of that of the hydrogenation solvent, and the mass of the reducing agent is 0.1-1% of that of the hydrogenation solvent.
Preferably, the evaporation amount of the hydrogenation solvent is 0.1-0.2 of the addition amount.
Preferably, the hydrogenation solvent is prepared from toluene and N, N-dimethylformamide according to a mass ratio of 4: 1 are mixed to obtain the product.
Preferably, the hydrogenation pressure is 1.0 MPa.
Preferably, the reducing agent is hydroxylamine hydrochloride.
Preferably, the mass of the crystallization solvent subjected to oxygen removal treatment is 0.8 times the mass of the hydrogenation solvent.
Preferably, the mass of the reducing agent is 0.5% of the mass of the hydrogenation solvent.
Preferably, the crystallization solvent is ethylene glycol.
Preferably, the reagent used in washing the filter cake in the step (II) is deionized water.
Compared with the prior art, the invention has the following advantages:
according to the production method of 4, 4' -diaminodiphenyl ether, firstly, a method of vacuumizing and evaporating the solvent is adopted to discharge trace oxygen dissolved in the solvent, so that the problem that residual oxygen in the solvent cannot be replaced by using nitrogen only is solved, the oxidization of hydroxylamine benzene and azobenzene in the nitro hydrogenation process is inhibited, and the problems of deepening of the color of the product and increase of the impurity amount are avoided; secondly, a specific inert poor solvent is adopted for crystallization, so that on one hand, side reaction of the amino compound and the solvent can be prevented, on the other hand, the inert solvent can crystallize and separate out the product from the reaction solvent, but impurities generated in the reaction are retained in the solvent, and the purity of the product is improved; in addition, the addition of the reducing agent can prevent the amino from being oxidized by extremely trace oxygen free radicals in the solvent and the nitrogen to influence the color of the product, so as to ensure the color stability of the amino compound.
The method for producing 4,4 '-diaminodiphenyl ether shortens the four steps of hydrogenation-sublimation (decoloration and impurity removal) -recrystallization or the five steps of hydrogenation-acid addition-salifying decoloration-neutralization-recrystallization of the traditional process into two steps of hydrogenation-crystallization, effectively solves a series of problems of product coke coupling, yield reduction, large waste salt amount, high energy consumption and the like caused by sublimation, and prepares the 4, 4' -diaminodiphenyl ether product with controllable degree of outstanding color and high purity.
Drawings
FIG. 1 is a liquid chromatogram of 4, 4' -diaminodiphenyl ether;
FIG. 2 is an appearance diagram of 4, 4' -diaminodiphenyl ether;
FIG. 3 is an appearance diagram of purchased 4, 4' -diaminodiphenyl ether;
FIG. 4 is a liquid chromatogram of commercially available 4, 4' -diaminodiphenyl ether.
Detailed Description
The invention aims to provide a method for producing 4, 4' -diaminodiphenyl ether, which is realized by the following technical scheme:
the production process of 4, 4' -diamino diphenyl ether has the reaction equation:
the hydrogenation reaction mechanism of the aromatic nitro compound is divided into two types: one is nitro-nitroso-hydroxylamine-aniline; the other is azoxyazohydridoaniline. For most aromatic nitro compounds, the first hydrogenation route is used, and the second hydrogenation route is used as a side reaction route, which causes the coupling of azo compounds to generate side reaction impurities. Meanwhile, it can also be known from the hydrogenation reaction process that the presence of oxygen can cause the oxidation reaction of hydroxylamine benzene and azobenzene with strong reducibility to generate a series of oxidation products, which are the main reasons for the darkening of the color of the aromatic nitro compound in the hydrogenation process, and the reaction mechanism is as follows:
According to the production method of 4, 4' -diaminodiphenyl ether, firstly, a method of vacuumizing and evaporating the solvent is adopted to discharge trace oxygen dissolved in the solvent, so that the problem that residual oxygen in the solvent cannot be replaced by using nitrogen only is solved, the oxidization of hydroxylamine benzene and azobenzene in the nitro hydrogenation process is inhibited, and the problems of deepening of the color of the product and increase of the impurity amount are avoided; secondly, a specific inert poor solvent is adopted for crystallization, so that on one hand, side reaction of the amino compound and the solvent can be prevented, on the other hand, the inert solvent can crystallize and separate out the product from the reaction solvent, but impurities generated in the reaction are retained in the solvent, and the purity of the product is improved; in addition, the addition of the reducing agent can prevent the amino from being oxidized by extremely trace oxygen free radicals in the solvent and the nitrogen to influence the color of the product so as to ensure the color stability of the amino compound
The invention is further described with reference to specific examples.
Example 1
A method for producing 4, 4' -diaminodiphenyl ether comprises the following steps:
adding 1kg of 4, 4' -dinitrodiphenyl ether, 5g of catalyst Pt/C and 5kg of methanol into a high-pressure kettle, stirring and mixing uniformly, evaporating 500g of methanol by adopting a low-temperature vacuumizing mode, replacing the high-pressure kettle with nitrogen for 3 times, then filling hydrogen into the high-pressure kettle, controlling the hydrogenation pressure to be 0.4MPa, and reacting for 6 hours at 50 ℃ to obtain a reaction solution;
Adding 5g of sodium thiosulfate and 2.5kg of deionized water subjected to oxygen removal treatment into a crystallizer, removing air by adopting nitrogen, filtering the reaction solution obtained in the step I, then crystallizing the reaction solution in the crystallizer for 10 hours at the crystallization temperature of 45 ℃, filtering the reaction solution after crystallization is finished, and washing a filter cake by using deionized water to obtain 738g of white granular product 4, 4' -diaminodiphenyl ether, wherein the purity of the product is 99.72%, and the particle size is about 60 meshes.
Example 2
A method for producing 4, 4' -diaminodiphenyl ether comprises the following steps:
adding 1kg of 4, 4' -dinitrodiphenyl ether, 20g of catalyst Pd/C and 6kg of toluene into an autoclave, stirring and mixing uniformly, evaporating 1kg of hydrogenation solvent by adopting a low-temperature vacuum pumping mode, replacing the autoclave with nitrogen for 5 times, then filling hydrogen into the autoclave, wherein the hydrogenation pressure is 1.2MPa, and reacting for 4 hours at 90 ℃ to obtain reaction liquid;
adding 60g of zinc powder and 12kg of deoxygenated ethylene glycol into a crystallizer, removing air by adopting nitrogen, filtering the reaction solution obtained in the step I, then crystallizing the reaction solution in the crystallizer for 15 hours at the crystallization temperature of 60 ℃, filtering the reaction solution after crystallization, washing a filter cake to obtain 742g of white granular product 4, 4' -diaminodiphenyl ether, wherein the yield is 96.48 percent, the product purity is 99.80 percent, and the particle size is about 150 meshes.
Example 3
A method for producing 4, 4' -diaminodiphenyl ether comprises the following steps:
adding 1kg of 4, 4' -dinitrodiphenyl ether, 10g of catalyst Raney nickel and 5.4kg of hydrogenation solvent N, N-dimethylacetamide into an autoclave, stirring and mixing uniformly, evaporating 0.8kg of hydrogenation solvent by adopting a low-temperature vacuumizing mode, replacing the autoclave with nitrogen for 4 times, then filling hydrogen into the autoclave at the hydrogenation pressure of 0.6MPa, and reacting for 4.5 hours at 65 ℃ to obtain reaction liquid;
secondly, 21.6g of hydroxylamine hydrochloride and 4.32kg of chlorobenzene subjected to oxygen removal treatment are added into a crystallizer, air is removed by adopting nitrogen, then the reaction solution obtained in the step I is filtered and then enters the crystallizer for crystallization for 12 hours, the crystallization temperature is 55 ℃, after crystallization is finished, filtration is carried out, and a filter cake is washed, thus obtaining 750g of white granular product 4, 4' -diaminodiphenyl ether, the yield is 97.53%, the product purity is 99.82%, and the particle size is about 80 meshes.
Example 4
A method for producing 4, 4' -diaminodiphenyl ether comprises the following steps:
adding 1kg of 4, 4' -dinitrodiphenyl ether, 8g of catalyst Pt/C and 5.8kg of hydrogenation solvent into an autoclave, stirring and mixing uniformly, evaporating 0.6kg of hydrogenation solvent by adopting a low-temperature vacuumizing mode, replacing the autoclave with nitrogen for 5 times, then filling hydrogen into the autoclave, wherein the hydrogenation pressure is 1.2MPa, and reacting for 5.5 hours at 80 ℃ to obtain reaction liquid;
The hydrogenation solvent is prepared from ethanol and toluene according to a mass ratio of 1: 1, preparing a composition;
adding 45g of zinc powder and 3.5kg of deoxygenated ethylene glycol into a crystallizer, removing air by adopting nitrogen, filtering the reaction solution obtained in the step I, then crystallizing the reaction solution in the crystallizer for 14 hours at the crystallization temperature of 48 ℃, filtering the reaction solution after the crystallization is finished, and washing a filter cake to obtain 754g of white granular product 4, 4' -diaminodiphenyl ether, wherein the yield is 98.05%, the product purity is 99.76%, and the particle size is about 100 meshes.
Example 5
A method for producing 4, 4' -diaminodiphenyl ether comprises the following steps:
adding 1kg of 4, 4' -dinitrodiphenyl ether, 15g of catalyst Pt/C and 5.5kg of hydrogenation solvent into a high-pressure kettle, stirring and mixing uniformly, evaporating 550g of hydrogenation solvent by adopting a low-temperature vacuumizing mode, replacing 5 times by using nitrogen in the high-pressure kettle, then filling hydrogen into the high-pressure kettle, and reacting for 5 hours at 60 ℃ under the hydrogenation pressure of 1.0MPa to obtain reaction liquid;
the hydrogenation solvent is prepared from toluene and N, N-dimethylformamide according to a mass ratio of 4: 1, mixing to obtain;
② adding 27.5g of hydroxylamine hydrochloride and 4.4kg of oxygen-removed ethylene glycol into a crystallizer, and adopting nitrogen to remove air, then filtering the reaction solution obtained in the step I, then crystallizing in the crystallizer for 13 hours at 55 ℃, filtering, washing filter cake to obtain 758g of white granular product 4,4 ' -diaminodiphenyl ether, wherein the yield is 98.57%, as shown in the liquid chromatogram of figure 1, the product purity is 99.94%, the particle size is about 90 meshes, the product appearance is as shown in figure 2, the appearance of the purchased 4,4 ' -diaminodiphenyl ether is as shown in figure 3, and the liquid chromatogram is as shown in figure 4, so that the 4,4 ' -diaminodiphenyl ether product obtained by the preparation method has good crystal form, white color, while the purchased product has poor crystal form, black color and only 99.54% purity.
Claims (9)
1. A production method of 4,4' -diaminodiphenyl ether is characterized in that: the method comprises the following steps:
adding 4,4' -dinitrodiphenyl ether, a catalyst and a hydrogenation solvent into an autoclave, stirring and mixing uniformly, evaporating part of the hydrogenation solvent by adopting a low-temperature vacuumizing mode, replacing the autoclave with nitrogen for 3-5 times, then filling hydrogen into the autoclave, wherein the hydrogenation pressure is 0.4-1.2 MPa, and reacting for 4-6 hours at 50-90 ℃ to obtain a reaction solution;
the hydrogenation solvent is one or two of methanol, ethanol, toluene, ethylbenzene, N-dimethylformamide and N, N-dimethylacetamide;
the catalyst is Pt/C, Pd/C and Raney nickel;
wherein the mass ratio of the 4,4' -dinitrodiphenyl ether, the catalyst and the hydrogenation solvent is 100: 0.5-2: 500-600 parts;
secondly, adding a reducing agent and a crystallization solvent subjected to deoxidization treatment into a crystallizer, removing air by adopting nitrogen, filtering the reaction liquid obtained in the step one, then crystallizing the reaction liquid in the crystallizer for 10-15 hours at the crystallization temperature of 45-60 ℃, filtering the reaction liquid after crystallization is finished, and washing a filter cake to obtain 4,4' -diaminodiphenyl ether;
the reducing agent is sodium thiosulfate, zinc powder or hydroxylamine hydrochloride;
the crystallization solvent is deionized water, ethylene glycol or chlorobenzene;
Wherein the mass of the crystallization solvent subjected to the deoxidization treatment is 0.5-2 times of that of the hydrogenation solvent, and the mass of the reducing agent is 0.1-1% of that of the hydrogenation solvent.
2. The process for producing 4,4' -diaminodiphenyl ether according to claim 1, characterized in that: the evaporation amount of the hydrogenation solvent is 0.1-0.2 of the addition amount.
3. The process for producing 4,4' -diaminodiphenyl ether according to claim 1, characterized in that: the hydrogenation solvent is prepared from toluene and N, N-dimethylformamide according to a mass ratio of 4: 1 are mixed to obtain the product.
4. The process for producing 4,4' -diaminodiphenyl ether according to claim 1, characterized in that: the hydrogenation pressure was 1.0 MPa.
5. The process for producing 4,4' -diaminodiphenyl ether according to claim 1, characterized in that: the reducing agent is hydroxylamine hydrochloride.
6. The process for producing 4,4' -diaminodiphenyl ether according to claim 1, characterized in that: the mass of the crystallization solvent subjected to the oxygen removal treatment is 0.8 times that of the hydrogenation solvent.
7. The process for producing 4,4' -diaminodiphenyl ether according to claim 1, characterized in that: the mass of the reducing agent was 0.5% of the mass of the hydrogenation solvent.
8. The process for producing 4,4' -diaminodiphenyl ether according to claim 1, characterized in that: the crystallization solvent is ethylene glycol.
9. The process for producing 4,4' -diaminodiphenyl ether according to claim 1, characterized in that: and step two, a reagent used for washing the filter cake is deionized water.
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| PCT/CN2022/117517 WO2023098203A1 (en) | 2021-12-04 | 2022-09-07 | Production method for 4,4'-diaminodiphenyl ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023098203A1 (en) * | 2021-12-04 | 2023-06-08 | 青岛科技大学 | Production method for 4,4'-diaminodiphenyl ether |
| CN116444353A (en) * | 2023-06-14 | 2023-07-18 | 山东奥友化学有限责任公司 | Preparation method of 4,4' -dichloro-2-hydroxydiphenyl ether |
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| CN117030919A (en) * | 2023-10-09 | 2023-11-10 | 山东欧亚高分子材料有限公司 | Gas chromatography detection method for 4,4' -diaminodiphenyl ether content |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1038005A (en) * | 1964-04-22 | 1966-08-03 | Ici Ltd | Purification of p-aminophenol |
| JPH06239813A (en) * | 1993-02-05 | 1994-08-30 | Tokuyama Soda Co Ltd | Purification of halogenoaminonophenol |
| CN101357892A (en) * | 2007-08-02 | 2009-02-04 | 上海焦化有限公司 | Preparation method of 4,4'-aminodiphenylamine |
| CN105348432A (en) * | 2015-11-13 | 2016-02-24 | 同济大学 | Polymer type sulfonium salt photo-acid generator, and preparation method and application thereof |
| CN106366229A (en) * | 2016-09-06 | 2017-02-01 | 常州大学 | Synthetic method of polycyclic branched polymer |
| CN106496047A (en) * | 2016-10-31 | 2017-03-15 | 南通汇顺化工有限公司 | The method that one kind prepares 4,4 ' diaminodiphenyl ethers |
| CN108752541A (en) * | 2018-04-27 | 2018-11-06 | 同济大学 | There is weary oxygen, temperature dual responsiveness Amphipathilic block polymer and preparation method thereof with what azo bond made connecting key |
| CN110639553A (en) * | 2019-10-21 | 2020-01-03 | 西安凯立新材料股份有限公司 | Iron-cobalt composite carbon-copper catalyst and method for continuously producing 4, 4-diaminodiphenyl ether |
| CN111072503A (en) * | 2019-12-28 | 2020-04-28 | 南通汇顺化工有限公司 | Method for preparing 3, 4' -diaminodiphenyl ether |
| CN112062683A (en) * | 2020-09-24 | 2020-12-11 | 青岛科技大学 | Synthesis method of 4, 4-aminodiphenyl ether |
| CN113087631A (en) * | 2021-02-25 | 2021-07-09 | 万达集团股份有限公司 | Preparation method of 4, 4' -diaminodiphenyl ether |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188814A (en) * | 2017-07-13 | 2017-09-22 | 山东冠森高分子材料科技股份有限公司 | Diaminodiphenyl ether technique is produced in closing oxygen-free environment note hydrogen reduction |
| CN108276297A (en) * | 2017-12-29 | 2018-07-13 | 上海固创化工新材料有限公司 | A kind of preparation method of 4,4 '-diaminodiphenyl ethers |
| CN110105227A (en) * | 2019-06-06 | 2019-08-09 | 山东铭博检测技术有限公司 | A kind of technique synthesizing 4,4 ' diaminodiphenyl ethers |
| CN114671770A (en) * | 2021-12-04 | 2022-06-28 | 青岛科技大学 | Production method of 4,4' -diaminodiphenyl ether |
-
2021
- 2021-12-04 CN CN202111467910.7A patent/CN114671770A/en active Pending
-
2022
- 2022-09-07 WO PCT/CN2022/117517 patent/WO2023098203A1/en unknown
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1038005A (en) * | 1964-04-22 | 1966-08-03 | Ici Ltd | Purification of p-aminophenol |
| JPH06239813A (en) * | 1993-02-05 | 1994-08-30 | Tokuyama Soda Co Ltd | Purification of halogenoaminonophenol |
| CN101357892A (en) * | 2007-08-02 | 2009-02-04 | 上海焦化有限公司 | Preparation method of 4,4'-aminodiphenylamine |
| CN105348432A (en) * | 2015-11-13 | 2016-02-24 | 同济大学 | Polymer type sulfonium salt photo-acid generator, and preparation method and application thereof |
| CN106366229A (en) * | 2016-09-06 | 2017-02-01 | 常州大学 | Synthetic method of polycyclic branched polymer |
| CN106496047A (en) * | 2016-10-31 | 2017-03-15 | 南通汇顺化工有限公司 | The method that one kind prepares 4,4 ' diaminodiphenyl ethers |
| CN108752541A (en) * | 2018-04-27 | 2018-11-06 | 同济大学 | There is weary oxygen, temperature dual responsiveness Amphipathilic block polymer and preparation method thereof with what azo bond made connecting key |
| CN110639553A (en) * | 2019-10-21 | 2020-01-03 | 西安凯立新材料股份有限公司 | Iron-cobalt composite carbon-copper catalyst and method for continuously producing 4, 4-diaminodiphenyl ether |
| CN111072503A (en) * | 2019-12-28 | 2020-04-28 | 南通汇顺化工有限公司 | Method for preparing 3, 4' -diaminodiphenyl ether |
| CN112062683A (en) * | 2020-09-24 | 2020-12-11 | 青岛科技大学 | Synthesis method of 4, 4-aminodiphenyl ether |
| CN113087631A (en) * | 2021-02-25 | 2021-07-09 | 万达集团股份有限公司 | Preparation method of 4, 4' -diaminodiphenyl ether |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023098203A1 (en) * | 2021-12-04 | 2023-06-08 | 青岛科技大学 | Production method for 4,4'-diaminodiphenyl ether |
| CN116444353A (en) * | 2023-06-14 | 2023-07-18 | 山东奥友化学有限责任公司 | Preparation method of 4,4' -dichloro-2-hydroxydiphenyl ether |
| CN116444353B (en) * | 2023-06-14 | 2023-09-08 | 山东奥友化学有限责任公司 | Preparation method of 4,4' -dichloro-2-hydroxydiphenyl ether |
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| WO2023098203A1 (en) | 2023-06-08 |
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