CN114315590A - Method for purifying 4,4' -dinitrodiphenyl ether - Google Patents
Method for purifying 4,4' -dinitrodiphenyl ether Download PDFInfo
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- CN114315590A CN114315590A CN202111682094.1A CN202111682094A CN114315590A CN 114315590 A CN114315590 A CN 114315590A CN 202111682094 A CN202111682094 A CN 202111682094A CN 114315590 A CN114315590 A CN 114315590A
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- 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 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 40
- 238000000605 extraction Methods 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000008025 crystallization Effects 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 20
- 239000003463 adsorbent Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000004966 Carbon aerogel Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000003883 substance clean up Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005992 Sodium p-nitrophenolate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- CURNJKLCYZZBNJ-UHFFFAOYSA-M sodium;4-nitrophenolate Chemical compound [Na+].[O-]C1=CC=C([N+]([O-])=O)C=C1 CURNJKLCYZZBNJ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-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
- -1 3 ' Natural products 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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Classifications
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for purifying 4,4' -dinitrodiphenyl ether, and relates to the technical field of compound purification. Mixing a 4,4' -dinitrodiphenyl ether crude product, an adsorbent and water, and carrying out first solid-liquid separation after adsorption to obtain a liquid component; mixing the liquid component with acid, sequentially performing extraction, cooling crystallization and second solid-liquid separation, washing the obtained solid component with water, and drying to obtain a refined 4,4' -dinitrodiphenyl ether product; the temperature of the adsorption, the first solid-liquid separation and the extraction is independently more than or equal to 145 ℃; the initial temperature of the cooling crystallization is the temperature of the extraction, and the termination temperature is 85-120 ℃; and the temperature of the second solid-liquid separation is 85-120 ℃. The purification method provided by the invention is simple to operate, and the obtained refined 4,4' -dinitrodiphenyl ether has high purity, high yield and low metal ion content, and can be used for preparing semiconductor materials; and the energy consumption is low, and the cost is low.
Description
Technical Field
The invention relates to the technical field of compound purification, in particular to a method for purifying 4,4' -dinitrodiphenyl ether.
Background
4,4' -dinitrodiphenyl ether (DEDPE, the structural formula is shown as formula I) is an important intermediate for synthesizing semiconductor materials, the DEDPE is hydrogenated and imidized to obtain polyimide materials, the polyimide materials are widely applied to the aspects of insulation, passivation, stress buffering and ray blocking of semiconductor devices, and the prepared semiconductor materials can be used in various fields of electronics, photovoltaic power generation, aviation, aerospace and the like. When the DEDPE is applied to the synthesis of semiconductor materials, the DEDPE is required to have the characteristics of low concentration (less than or equal to 1ppm) of single metal ions and high purity (more than or equal to 99.9%).
Chinese patent CN110041205A discloses a purification process of 4,4' -dinitrodiphenyl ether, which comprises the following steps: (1) putting crude 4,4' -dinitrodiphenyl ether to be purified into a material dissolving kettle, adding an organic solvent which is 1.2-1.5 times of the weight of the crude 4,4' -dinitrodiphenyl ether, stirring and dissolving, then adding active carbon with the mass of 0.2-0.4% of the crude 4,4' -dinitrodiphenyl ether, filtering out partial impurities from the mixed materials in the material dissolving kettle through a plate and frame filter, and then putting the mixed materials into a centrifuge for centrifugal filtration; (2) sending the mixed material after centrifugal filtration into a vacuum distillation tower for multistage distillation treatment, and then cooling and crystallizing to obtain 4,4' -dinitrodiphenyl ether crystal; (3) putting 4,4' -dinitrodiphenyl ether crystals into a storage kettle, keeping the vacuum degree of the storage kettle at-0.09 MPa, adding a mixed solvent of methanol and toluene into the storage kettle, mixing, uniformly stirring at 50-70 ℃, adding a mixture of argil, alumina and sepiolite into the storage kettle, stirring at 50-60 rpm for 10-15 min, and adding the mixed solution into a centrifuge for centrifugal treatment; (4) sequentially subjecting the mixed solution subjected to the centrifugal treatment to ion exchange by ion exchange resin according to the sequence of strong acid cation → strong base anion → strong acid cation → strong base anion; (5) and (3) carrying out reduced pressure distillation on the mixed solution after the ion exchange treatment to obtain the 4,4 '-dinitrodiphenyl ether, wherein the purity of the purified 4,4' -dinitrodiphenyl ether reaches more than 99.8 percent. However, the above purification method requires operations of activated carbon adsorption, coarse filtration with a plate and frame filter, fine filtration with a centrifuge, multistage distillation for removing organic solvents, cooling crystallization, removal of suspended particles and colloids with a mixture of clay, alumina and sepiolite, multistage ion exchange and reduced pressure distillation, and the purification method is complicated.
Disclosure of Invention
In view of the above, the present invention provides a method for purifying 4,4 '-dinitrodiphenyl ether, which is simple to operate and can obtain a refined product of 4,4' -dinitrodiphenyl ether with a purity of 99.93% or higher.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for purifying 4,4' -dinitrodiphenyl ether, which comprises the following steps:
mixing the 4,4' -dinitrodiphenyl ether crude product, an adsorbent and water, and carrying out first solid-liquid separation after adsorption to obtain a liquid component;
mixing the liquid component with acid, sequentially performing extraction, cooling crystallization and second solid-liquid separation, washing the obtained solid component with water, and drying to obtain a refined 4,4' -dinitrodiphenyl ether product;
the temperature of the adsorption, the first solid-liquid separation and the extraction is independently more than or equal to 145 ℃;
the initial temperature of the cooling crystallization is the temperature of the extraction, and the termination temperature is 85-120 ℃;
and the temperature of the second solid-liquid separation is 85-120 ℃.
Preferably, the adsorbent comprises one or more of carbon aerogel, activated carbon, diatomite and fumed silica.
Preferably, the mass ratio of the crude 4,4' -dinitrodiphenyl ether, the adsorbent and the water is 1: 0.003 to 0.03: 3 to 10.
Preferably, the adsorption temperature is 145-180 ℃ and the time is 0.5-4 h.
Preferably, the acid includes organic acids and inorganic acids.
Preferably, the mass ratio of the crude 4,4' -dinitrodiphenyl ether to the acid is 1: 0.0003 to 0.005.
Preferably, the extraction temperature is 145-180 ℃, and the extraction time is 0.5-3 h.
Preferably, the cooling rate of the cooling crystallization is 0.15-0.75 ℃/min.
Preferably, the water for washing is hot water, and the temperature of the hot water is 85-90 ℃.
Preferably, the drying temperature is 100-110 ℃.
The invention provides a method for purifying 4,4' -dinitrodiphenyl ether, which comprises the following steps: mixing the 4,4' -dinitrodiphenyl ether crude product, an adsorbent and water, and carrying out first solid-liquid separation after adsorption to obtain a liquid component; mixing the liquid component with acid, sequentially performing extraction, cooling crystallization and second solid-liquid separation, washing the obtained solid component with water, and drying to obtain a refined 4,4' -dinitrodiphenyl ether product; the temperature of the adsorption, the first solid-liquid separation and the extraction is independently more than or equal to 145 ℃; the initial temperature of the cooling crystallization is the temperature of the extraction, and the termination temperature is 85-120 ℃; and the temperature of the second solid-liquid separation is 85-120 ℃. The purification method provided by the invention is simple to operate, low in energy consumption, low in VOC (volatile organic compounds) generation and environment-friendly. The invention adopts the adsorbent to adsorb at the temperature of more than 145 ℃, solves the problem that the 4,4 '-dinitrodiphenyl ether is solid at the temperature of less than 145 ℃ and can not pass through the adsorbent, and can remove impurities such as macromolecular tar and the like in the crude product of the 4,4' -dinitrodiphenyl ether; the first solid-liquid separation can remove the adsorbent adsorbed with impurities at the temperature of more than or equal to 145 ℃; na, Fe, Cr and K wrapped in the crude 4,4 '-dinitrodiphenyl ether product can be dissolved in water by adopting acid for extraction, so that the concentration of Na, Fe, Cr and K in the 4,4' -dinitrodiphenyl ether product is obviously reduced; the p-nitrochlorobenzene impurities can be removed through cooling crystallization and second solid-liquid separation at 85-120 ℃; water-soluble impurities on the surface of the 4,4' -dinitrodiphenyl ether are removed by washing, and water in the 4,4' -dinitrodiphenyl ether is removed by drying, so that a high-purity refined 4,4' -dinitrodiphenyl ether product is obtained. After the crude 4,4' -dinitrodiphenyl ether is purified by the purification method provided by the invention, the purity of the obtained refined 4,4' -dinitrodiphenyl ether product is more than 99.93 percent, the yield is more than 98.5 percent, the content of single metal ions (Na, Fe, Cr and K) in the refined 4,4' -dinitrodiphenyl ether product is less than 1ppm, the content of Cl is less than 2ppm, and the obtained refined 4,4' -dinitrodiphenyl ether product meets the requirement of the semiconductor material on the purity of the metal ions of the raw 4,4' -dinitrodiphenyl ether material, and can be used for preparing the semiconductor material. In addition, the purification method provided by the invention takes water as a solvent, does not need to use an organic solvent, is environment-friendly and has low production cost.
Furthermore, the adsorbent and the acid adopted by the purification method provided by the invention have wide sources and low price.
Drawings
FIG. 1 is a high performance liquid chromatogram of a crude product of 4,4' -dinitrodiphenyl ether used in examples 1 to 3;
FIG. 2 is a high performance liquid chromatogram of a refined 4,4' -dinitrodiphenyl ether prepared in example 1;
FIG. 3 is a high performance liquid chromatogram of a refined 4,4' -dinitrodiphenyl ether prepared in example 2;
FIG. 4 is a high performance liquid chromatogram of a purified 4,4' -dinitrodiphenyl ether prepared in example 3.
Detailed Description
The invention provides a method for purifying 4,4' -dinitrodiphenyl ether, which comprises the following steps:
mixing the 4,4' -dinitrodiphenyl ether crude product, an adsorbent and water, and carrying out first solid-liquid separation after adsorption to obtain a liquid component;
mixing the liquid component with acid, sequentially performing extraction, cooling crystallization and second solid-liquid separation, washing the obtained solid component with water, and drying to obtain a refined 4,4' -dinitrodiphenyl ether product;
the temperature of the adsorption, the first solid-liquid separation and the extraction is independently more than or equal to 145 ℃;
the initial temperature of the cooling crystallization is the temperature of the extraction, and the termination temperature is 85-120 ℃;
and the temperature of the second solid-liquid separation is 85-120 ℃.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The method mixes the 4,4' -dinitrodiphenyl ether crude product, the adsorbent and water, and performs first solid-liquid separation after adsorption to obtain a liquid component.
In the present invention, the crude 4,4 '-dinitrodiphenyl ether is preferably obtained by self-production, and the preparation method of the crude 4,4' -dinitrodiphenyl ether preferably comprises the following steps: mixing p-nitrochlorobenzene, sodium p-nitrophenolate, nitrobenzene and a catalyst, and carrying out etherification reaction to obtain a crude product of the 4,4' -dinitrodiphenyl ether. In the present invention, the molar ratio of nitrochlorobenzene to sodium p-nitrophenolate is preferably 1: 0.94 to 1, more preferably 1: 0.96-0.98. In the present invention, the catalyst preferably comprises a potassium salt catalyst preferably comprising potassium chloride and/or potassium carbonate and/or a sodium salt catalyst preferably comprising sodium chloride and/or sodium carbonate; the mass ratio of the nitrochlorobenzene to the catalyst is preferably 1: 0.07 to 0.15, more preferably 1: 0.08 to 0.12. In the present invention, the ratio of the amount of the substance of p-nitrochlorobenzene to the volume of nitrobenzene (solvent) is preferably 1 mol: 300-500 mL, more preferably 1 mol: 350-450 mL. The mixing method of the present invention is not particularly limited, and the raw materials can be uniformly mixed by a mixing method known to those skilled in the art, specifically, stirring and mixing. In the invention, the temperature of the substitution reaction is preferably 220-235 ℃, more preferably 225-230 ℃, and the time of the substitution reaction is preferably 18-25 h, more preferably 20-22 h. After the etherification reaction is finished, the invention preferably also comprises the steps of concentrating the reaction liquid obtained by the substitution reaction to constant weight, adding water for crystallization, and performing centrifugal separation to obtain a crude product of the 4,4' -dinitrodiphenyl ether. The concentration method of the present invention is not particularly limited, and a concentration method known to those skilled in the art may be used, specifically, distillation under reduced pressure. The crystallization mode of the concentrated solution added into water is not particularly limited in the invention, and the crystallization mode known to those skilled in the art can be adopted.
In the invention, the adsorbent comprises one or more of carbon aerogel, activated carbon, diatomite and fumed silica. The water used in the present invention is not particularly limited, and water known to those skilled in the art may be used, specifically, one or more of pure water, deionized water and distilled water. In the present invention, the mass ratio of the crude 4,4' -dinitrodiphenyl ether, the adsorbent and the water is preferably 1: 0.003 to 0.03: 3-10, more preferably 1: 0.01-0.03: 5 to 10.
In the invention, the adsorption temperature is not less than 145 ℃, preferably 145-180 ℃, and more preferably 145-155 ℃; the adsorption time is preferably 0.5-4 h, and more preferably 0.5-2 h; the adsorption is preferably carried out under stirring conditions; the stirring speed and time are not specially limited, and normal adsorption can be ensured. The adsorbent has good heat resistance and strong adsorption capacity, and can adsorb at the temperature of over 145 ℃, so that the problem that 4,4 '-dinitrodiphenyl ether is solid at the temperature of below 145 ℃ and cannot pass through the adsorbent is solved, and impurities such as macromolecular tar and the like in the crude product of 4,4' -dinitrodiphenyl ether can be removed.
In the invention, the temperature of the first solid-liquid separation is more than or equal to 145 ℃, preferably 145-180 ℃, and more preferably 145-155 ℃; the first solid-liquid separation mode is not particularly limited, and a solid-liquid separation mode known to those skilled in the art can be adopted, specifically, filtration or centrifugal separation; the conditions of the centrifugal separation are not particularly limited, and the separation of the liquid component and the solid component can be realized; the purpose of the first solid-liquid separation is to remove the adsorbent adsorbed with impurities.
After the liquid component is obtained, the liquid component is mixed with acid, extraction, cooling crystallization and second solid-liquid separation are sequentially carried out, and the obtained solid component is washed with water and dried to obtain the refined 4,4' -dinitrodiphenyl ether.
In the present invention, the acid preferably includes organic acids and inorganic acids; the organic acid comprises one or more of citric acid, 3 ', 4,4' -diphenyl ether tetracarboxylic acid and 3,3 ', 4,4' -diphenyl tetracarboxylic acid; the inorganic acid comprises hydrochloric acid and/or sulfuric acid. In the present invention, the mass ratio of the crude 4,4' -dinitrodiphenyl ether to the acid is preferably 1: 0.0003 to 0.005, more preferably 0.001 to 0.003.
In the invention, the extraction temperature is not less than 145 ℃, preferably 145-180 ℃, and more preferably 145-155 ℃; the extraction time is preferably 0.5-3 h, and more preferably 0.5-2 h; the adsorption is preferably carried out under stirring conditions; the stirring speed and time are not specially limited, and the normal extraction can be ensured. The acid is adopted for extraction at the temperature of more than 145 ℃, and Na, Fe, Cr and K wrapped in the crude 4,4 '-dinitrodiphenyl ether product can be dissolved in water, so that the concentration of Na, Fe, Cr and K in the 4,4' -dinitrodiphenyl ether product is obviously reduced.
In the invention, the initial temperature of the cooling crystallization is the temperature of the extraction, and the termination temperature is 85-120 ℃; the cooling rate of the cooling crystallization is preferably 0.15-0.75 ℃/min, more preferably 0.2-0.6 ℃/min, and even more preferably 0.3-0.5 ℃/min.
In the invention, the temperature of the second solid-liquid separation is 85-120 ℃, preferably 85-110 ℃, and further preferably 90-100 ℃; the second solid-liquid separation mode is not particularly limited in the invention, and a solid-liquid separation mode known to those skilled in the art can be adopted, specifically, filtration or centrifugal separation; the conditions for the centrifugal separation are not particularly limited, and the separation of the liquid component and the solid component can be achieved. The melting point of the p-nitrochlorobenzene is 81-84 ℃, the p-nitrochlorobenzene is liquid at the temperature of more than 85 ℃, and the p-nitrochlorobenzene impurities can be removed by carrying out second solid-liquid separation and filtration at the temperature of 85-120 ℃.
In the invention, the water for washing is preferably hot water, and the temperature of the hot water is preferably 80-90 ℃, more preferably 85-90 ℃; the number of washing times is preferably 2-3; the purpose of the water washing is to remove water-soluble impurities from the surface of the solid component.
In the invention, the drying temperature is preferably 100-110 ℃, and more preferably 105-108 ℃; in the present invention, the drying time is not particularly limited, and the drying time may be set to a constant weight.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Putting p-nitrochlorobenzene (7.68kmol), p-sodium nitrophenolate (7.45kmol), potassium carbonate (121 kg) and 3000L nitrobenzene into a 6300L reaction kettle, heating to 225 ℃ for etherification reaction, performing reduced pressure distillation to recover nitrobenzene after 21h of reaction, transferring the residual materials in the kettle into 6000L of water for crystallization, and performing centrifugal separation to obtain a crude product of the 4,4' -dinitrodiphenyl ether (the purity is 98.95%). The inventive example uses the crude 4,4' -dinitrodiphenyl ether as a starting material.
Example 1
Under the condition of stirring, 600kg of crude 4,4' -dinitrodiphenyl ether (with the purity of 98.95 percent), 1800kg of pure water and 1.8kg of carbon aerogel are added into a 3000L glass lining reaction kettle to be mixed, the temperature is raised to 155 ℃, the mixture is subjected to heat preservation and adsorption for 0.5h, and the mixture is filtered while the mixture is hot to obtain a liquid component; adding 180g of 3,3 ', 4,4' -diphenyl ether tetracarboxylic acid into the liquid component, extracting at 155 ℃ for 0.5h under the condition of heat preservation, cooling the obtained extract to 120 ℃ at the speed of 0.15 ℃/min for crystallization, centrifuging while hot, adding hot pure water at 85 ℃ into the obtained solid component, washing for 2 times (300 kg of hot water each time), and then drying at 110 ℃ for 3h to obtain a refined 4,4' -dinitrodiphenyl ether product (pale yellow crystals, 591kg, the yield is 98.5%, and the purity is 99.93%).
Example 2
Under the condition of stirring, 600kg of crude 4,4' -dinitrodiphenyl ether (with the purity of 98.95 percent), 4200kg of pure water and 9kg of carbon aerogel are added into a 6300L glass lining reaction kettle to be mixed, the temperature is raised to 145 ℃, then the mixture is subjected to heat preservation and adsorption for 1.5h, and the hot mixture is filtered to obtain a liquid component; adding 1.5kg of 3,3 ', 4,4' -diphenyl ether tetracarboxylic acid into the liquid component, extracting at 155 ℃ for 1.5h under the condition of heat preservation, cooling the obtained extract to 90 ℃ at the speed of 0.5 ℃/min for crystallization, centrifuging while the extract is hot, adding 95 ℃ hot pure water into the obtained solid component, washing for 2 times (300 kg of hot water for each time), and then drying at 100 ℃ for 3h to obtain a refined 4,4' -dinitrodiphenyl ether (light yellow crystals, 594.6kg, the yield is 99.1%, and the purity is 99.96%).
Example 3
Under the condition of stirring, 500kg of crude 4,4' -dinitrodiphenyl ether (with the purity of 98.95 percent), 5000kg of pure water and 15kg of carbon aerogel are added into a 6300L glass lining reaction kettle to be mixed, the temperature is raised to 180 ℃, the mixture is subjected to heat preservation and adsorption for 4 hours, and the mixture is filtered while the mixture is hot to obtain a liquid component; adding 2.5kg of 3,3 ', 4,4' -diphenyl ether tetracarboxylic acid into the liquid component, extracting for 3h at 180 ℃, cooling the obtained extract to 105 ℃ at the speed of 0.75 ℃/min, crystallizing, centrifuging while hot, adding hot pure water at 95 ℃ into the obtained solid component, washing for 2 times (300 kg of hot water each time), and drying at 110 ℃ for 3h to obtain a refined product of 4,4' -dinitrodiphenyl ether (light yellow crystals, 493.5kg, yield 98.7%, purity 99.95%).
The contents of metal ions and Cl in the crude 4,4 '-dinitrodiphenyl ether used in the examples and the refined 4,4' -dinitrodiphenyl ether prepared in examples 1 to 3 are shown in table 1:
TABLE 14 ion content of crude 4,4 '-dinitrodiphenyl ether and of refined 4,4' -dinitrodiphenyl ether prepared in examples 1 to 3
As can be seen from Table 1, the contents of Na, Fe, Cr and K and the content of Cl in the refined 4,4 '-dinitrodiphenyl ether prepared by the invention are all less than 1ppm, and less than 2ppm, which indicates that the refined 4,4' -dinitrodiphenyl ether prepared by the invention has high purity.
The HPLC peak information of the crude 4,4 '-dinitrodiphenyl ether used in the examples and the refined 4,4' -dinitrodiphenyl ether prepared in examples 1 to 3 are shown in Table 2 and FIGS. 1 to 4. Fig. 1 is a high performance liquid chromatogram of a crude product of 4,4 '-dinitrodiphenyl ether used in examples 1 to 3, fig. 2 is a high performance liquid chromatogram of a refined product of 4,4' -dinitrodiphenyl ether prepared in example 1, fig. 3 is a high performance liquid chromatogram of a refined product of 4,4 '-dinitrodiphenyl ether prepared in example 2, and fig. 4 is a high performance liquid chromatogram of a refined product of 4,4' -dinitrodiphenyl ether prepared in example 3.
TABLE 24 HPLC peak information of crude 4,4 '-dinitrodiphenyl ether and refined 4,4' -dinitrodiphenyl ether prepared in examples 1 to 3
As can be seen from Table 2 and FIGS. 1 to 4, the purity of the refined 4,4' -dinitrodiphenyl ether prepared by the present invention is high.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for purifying 4,4' -dinitrodiphenyl ether is characterized by comprising the following steps:
mixing the 4,4' -dinitrodiphenyl ether crude product, an adsorbent and water, and carrying out first solid-liquid separation after adsorption to obtain a liquid component;
mixing the liquid component with acid, sequentially performing extraction, cooling crystallization and second solid-liquid separation, washing the obtained solid component with water, and drying to obtain a refined 4,4' -dinitrodiphenyl ether product;
the temperature of the adsorption, the first solid-liquid separation and the extraction is independently more than or equal to 145 ℃;
the initial temperature of the cooling crystallization is the temperature of the extraction, and the termination temperature is 85-120 ℃;
and the temperature of the second solid-liquid separation is 85-120 ℃.
2. The purification method according to claim 1, wherein the adsorbent comprises one or more of carbon aerogel, activated carbon, diatomaceous earth and fumed silica.
3. The purification method according to claim 1 or 2, wherein the mass ratio of the crude 4,4' -dinitrodiphenyl ether, the adsorbent and the water is 1: 0.003 to 0.03: 3 to 10.
4. The purification method according to claim 1, wherein the temperature of the adsorption is 145-180 ℃ and the time is 0.5-4 h.
5. The purification process of claim 1, wherein the acid comprises an organic acid and an inorganic acid.
6. The purification method according to claim 1 or 5, wherein the mass ratio of the crude 4,4' -dinitrodiphenyl ether to the acid is 1: 0.0003 to 0.005.
7. The purification method according to claim 1, wherein the temperature of the extraction is 145-180 ℃ and the time is 0.5-3 h.
8. The purification method according to claim 1, wherein the cooling rate of the cooling crystallization is 0.15-0.75 ℃/min.
9. The purification method according to claim 1, wherein the water for washing is hot water having a temperature of 85 to 90 ℃.
10. The purification method according to claim 1, wherein the drying temperature is 100 to 110 ℃.
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| CN107337605A (en) * | 2017-07-13 | 2017-11-10 | 山东冠森高分子材料科技股份有限公司 | Anhydrous condensation reaction produces 4,4 ＇ dinitro diphenyl ether processes |
| CN110041205A (en) * | 2019-04-26 | 2019-07-23 | 山东欧亚化工有限公司 | A kind of purifying technique of 4,4 '-dinitro diphenyl ether |
| CN112724021A (en) * | 2021-01-20 | 2021-04-30 | 泰兴中科艾德膜材料科技有限公司 | Preparation method of 4, 4' -dinitrodiphenyl ether |
| CN114507130A (en) * | 2022-02-09 | 2022-05-17 | 河北海力香料股份有限公司 | Purification method of 3,3',4,4' -biphenyltetracarboxylic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107337605A (en) * | 2017-07-13 | 2017-11-10 | 山东冠森高分子材料科技股份有限公司 | Anhydrous condensation reaction produces 4,4 ＇ dinitro diphenyl ether processes |
| CN110041205A (en) * | 2019-04-26 | 2019-07-23 | 山东欧亚化工有限公司 | A kind of purifying technique of 4,4 '-dinitro diphenyl ether |
| CN112724021A (en) * | 2021-01-20 | 2021-04-30 | 泰兴中科艾德膜材料科技有限公司 | Preparation method of 4, 4' -dinitrodiphenyl ether |
| CN114507130A (en) * | 2022-02-09 | 2022-05-17 | 河北海力香料股份有限公司 | Purification method of 3,3',4,4' -biphenyltetracarboxylic acid |
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