CN114315590B - Method for purifying 4,4' -dinitrodiphenyl ether - Google Patents
Method for purifying 4,4' -dinitrodiphenyl ether Download PDFInfo
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- CN114315590B CN114315590B CN202111682094.1A CN202111682094A CN114315590B CN 114315590 B CN114315590 B CN 114315590B CN 202111682094 A CN202111682094 A CN 202111682094A CN 114315590 B CN114315590 B CN 114315590B
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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 87
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000926 separation method Methods 0.000 claims abstract description 40
- 239000000047 product Substances 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 21
- 239000003463 adsorbent Substances 0.000 claims abstract description 20
- 238000000605 extraction Methods 0.000 claims abstract description 20
- 239000012043 crude product Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000000746 purification Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 13
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 10
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000004966 Carbon aerogel Substances 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000006266 etherification reaction Methods 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- CURNJKLCYZZBNJ-UHFFFAOYSA-M sodium;4-nitrophenolate Chemical compound [Na+].[O-]C1=CC=C([N+]([O-])=O)C=C1 CURNJKLCYZZBNJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000005992 Sodium p-nitrophenolate Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 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 10
- 239000012535 impurity Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000004821 distillation Methods 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000003860 storage Methods 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
- 239000011521 glass Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000126 substance 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
- 239000004113 Sepiolite Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- 239000005909 Kieselgur Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate 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
- 229910021485 fumed silica Inorganic materials 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
- 238000004519 manufacturing process Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- 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 crude product of 4,4' -dinitrodiphenyl ether, an adsorbent and water, and performing first solid-liquid separation after adsorption to obtain a liquid component; mixing the liquid component with acid, sequentially extracting, cooling and crystallizing, performing second solid-liquid separation, washing the obtained solid component with water, and drying to obtain a fine product of 4,4' -dinitrodiphenyl ether; the temperature of the adsorption, the first solid-liquid separation and the extraction is independently not less than 145 ℃; the initial temperature of the cooling crystallization is the extraction temperature, and the final temperature is 85-120 ℃; 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 4,4' -dinitrodiphenyl ether refined product 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
The 4,4' -dinitro diphenyl ether (DEDPE, the structural formula is shown as formula I) is an important intermediate for synthesizing a semiconductor material, the DEDPE is hydrogenated and imidized to obtain a polyimide material, the polyimide material is widely applied to the aspects of insulation, passivation, stress buffering and ray blocking of semiconductor devices, and the prepared semiconductor material can be used in various fields of electronics, photovoltaic power generation, aviation, aerospace and the like. When DEDPE is used for synthesizing semiconductor materials, the DEDPE is required to have the characteristics of low concentration of single metal ions (less than or equal to 1 ppm) and high purity (less than or equal to 99.9%).
Chinese patent CN110041205a discloses a process for purifying 4,4' -dinitrodiphenyl ether, comprising the steps of: (1) Adding crude 4,4' -dinitrodiphenyl ether to be purified into a chemical material kettle, adding an organic solvent with the weight 1.2-1.5 times that of the crude 4,4' -dinitrodiphenyl ether, stirring for dissolving, adding activated carbon with the mass 0.2-0.4% of that of the crude 4,4' -dinitrodiphenyl ether, filtering part of impurities from the mixed material in the chemical material kettle through a plate-frame filter, and then putting the mixed material into a centrifuge for centrifugal filtration; (2) Delivering the centrifugally filtered mixture into a vacuum distillation tower, performing multistage distillation treatment, and then cooling and crystallizing to obtain 4,4' -dinitrodiphenyl ether crystals; (3) Placing 4,4' -dinitrodiphenyl ether crystals into a storage kettle, keeping the vacuum degree of the storage kettle at-0.09 MPa, adding a methanol and toluene mixed solvent into the storage kettle, mixing uniformly at 50-70 ℃, adding a mixture of clay, aluminum oxide 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) The mixed solution after centrifugal treatment sequentially passes through ion exchange resin for ion exchange according to the sequence of strong acid cation, strong alkali anion, strong acid cation and strong alkali 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 is more than 99.8%. However, the above purification method requires operations such as adsorption by activated carbon, coarse filtration by a plate-and-frame filter, fine filtration by a centrifuge, removal of an organic solvent by multistage distillation, cooling crystallization, removal of suspended particles and colloid by using a mixture of clay, alumina and sepiolite, multistage ion exchange and distillation under reduced pressure, and is complicated and complicated.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for purifying 4,4 '-dinitrodiphenyl ether, which is simple to operate and can obtain a refined 4,4' -dinitrodiphenyl ether product with a purity of 99.93% or more.
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 crude product of 4,4' -dinitrodiphenyl ether, 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 extracting, cooling and crystallizing, performing second solid-liquid separation, washing the obtained solid component with water, and drying to obtain a fine product of 4,4' -dinitrodiphenyl ether;
the temperature of the adsorption, the first solid-liquid separation and the extraction is independently not less than 145 ℃;
the initial temperature of the cooling crystallization is the extraction temperature, and the final temperature is 85-120 ℃;
the temperature of the second solid-liquid separation is 85-120 ℃.
Preferably, the adsorbent comprises one or more of carbon aerogel, activated carbon, diatomaceous earth and fumed silica.
Preferably, the mass ratio of the crude 4,4' -dinitrodiphenyl ether to the adsorbent to the water is 1:0.003 to 0.03:3 to 10.
Preferably, the adsorption temperature is 145-180 ℃ and the adsorption 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 crude product of 4,4' -dinitrodiphenyl ether, 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 extracting, cooling and crystallizing, performing second solid-liquid separation, washing the obtained solid component with water, and drying to obtain a fine product of 4,4' -dinitrodiphenyl ether; the temperature of the adsorption, the first solid-liquid separation and the extraction is independently not less than 145 ℃; the initial temperature of the cooling crystallization is the extraction temperature, and the final temperature is 85-120 ℃; 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) and environment-friendly. The invention adopts the adsorbent to adsorb at the temperature of more than 145 ℃, solves the problem that 4,4 '-dinitrodiphenyl ether is solid at the temperature of less than 145 ℃ and can not pass through the adsorbent, and can remove macromolecular tar and other impurities in the crude product of the 4,4' -dinitrodiphenyl ether; the adsorbent adsorbed with impurities can be removed by the first solid-liquid separation under the condition of 145 ℃ or more; the Na, fe, cr and K wrapped in the crude 4,4 '-dinitrodiphenyl ether can be dissolved into water by adopting acid for extraction, so that the concentration of Na, fe, cr and K in the 4,4' -dinitrodiphenyl ether is obviously reduced; through cooling crystallization and second solid-liquid separation at the temperature of 85-120 ℃, p-nitrochlorobenzene impurities can be removed; water-soluble impurities on the surface of the 4,4' -dinitrodiphenyl ether are removed through water washing, and water in the 4,4' -dinitrodiphenyl ether is removed through drying, so that the high-purity 4,4' -dinitrodiphenyl ether refined product is obtained. After the 4,4' -dinitrodiphenyl ether crude product is purified by the purification method provided by the invention, the purity of the obtained 4,4' -dinitrodiphenyl ether refined product is more than 99.93%, the yield is more than 98.5%, the content of single metal ions (Na, fe, cr and K) in the 4,4' -dinitrodiphenyl ether refined product is less than 1ppm, the content of Cl is less than 2ppm, and the obtained 4,4' -dinitrodiphenyl ether refined product meets the requirement of semiconductor material synthesis on the purity of metal ions of the 4,4' -dinitrodiphenyl ether raw material, and can be used for preparing semiconductor materials. In addition, the purification method provided by the invention uses water as a solvent, does not need to use an organic solvent, is environment-friendly and has low production cost.
Furthermore, the purification method provided by the invention adopts a wide source of the adsorbent and the acid and has low cost.
Drawings
FIG. 1 is a high performance liquid chromatogram of crude 4,4' -dinitrodiphenyl ether employed in examples 1-3;
FIG. 2 is a high performance liquid chromatogram of a fine 4,4' -dinitrodiphenyl ether product prepared in example 1;
FIG. 3 is a high performance liquid chromatogram of a fine 4,4' -dinitrodiphenyl ether product prepared in example 2;
FIG. 4 is a high performance liquid chromatogram of a fine 4,4' -dinitrodiphenyl ether product prepared in example 3.
Detailed Description
The invention provides a method for purifying 4,4' -dinitrodiphenyl ether, which comprises the following steps:
mixing the crude product of 4,4' -dinitrodiphenyl ether, 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 extracting, cooling and crystallizing, performing second solid-liquid separation, washing the obtained solid component with water, and drying to obtain a fine product of 4,4' -dinitrodiphenyl ether;
the temperature of the adsorption, the first solid-liquid separation and the extraction is independently not less than 145 ℃;
the initial temperature of the cooling crystallization is the extraction temperature, and the final temperature is 85-120 ℃;
the temperature of the second solid-liquid separation is 85-120 ℃.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
The invention mixes the crude product of 4,4' -dinitrodiphenyl ether, adsorbent and water, and carries out first solid-liquid separation after adsorption to obtain liquid component.
In the invention, the crude 4,4 '-dinitrodiphenyl ether is preferably prepared by self-making, 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 4,4' -dinitrodiphenyl ether. In the present invention, the molar ratio of the nitrochlorobenzene to the sodium p-nitrophenolate is preferably 1:0.94 to 1, more preferably 1: 0.96-0.98. In the present invention, the catalyst preferably includes a potassium salt catalyst and/or a sodium salt catalyst, the potassium salt catalyst preferably includes potassium chloride and/or potassium carbonate, and the sodium salt catalyst preferably includes 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 1mol:300 to 500mL, more preferably 1mol: 350-450 mL. The mode of the mixing is not particularly limited, and the raw materials can be uniformly mixed by a mixing mode well known to those skilled in the art, and in particular, stirring and mixing can be adopted. In the present invention, the temperature of the substitution reaction is preferably 220 to 235 ℃, more preferably 225 to 230 ℃, and the time of the substitution reaction is preferably 18 to 25 hours, more preferably 20 to 22 hours. After the etherification reaction is completed, the invention preferably further comprises the steps of concentrating the reaction liquid obtained by the substitution reaction to constant weight, adding the reaction liquid into water for crystallization, and centrifugally separating to obtain a crude product of the 4,4' -dinitrodiphenyl ether. The concentration method of the present invention is not particularly limited, and any concentration method known to those skilled in the art, such as reduced pressure distillation, may be used. The method of adding the concentrate to water for crystallization is not particularly limited, and crystallization methods known to those skilled in the art may be employed.
In the invention, the adsorbent comprises one or more of carbon aerogel, activated carbon, diatomite and gas-phase silicon dioxide. The water is not particularly limited, and water known to those skilled in the art may be used, such as one or more of pure water, deionized water and distilled water. In the invention, the mass ratio of the crude product of the 4,4' -dinitrodiphenyl ether to the adsorbent to the water is preferably 1:0.003 to 0.03:3 to 10, more preferably 1:0.01 to 0.03:5 to 10.
In the invention, the adsorption temperature is more than or equal to 145 ℃, preferably 145-180 ℃, more preferably 145-155 ℃; the time of the adsorption is preferably 0.5 to 4 hours, more preferably 0.5 to 2 hours; the adsorption is preferably carried out under stirring conditions; the stirring speed and the stirring time are not particularly limited, and the normal adsorption can be ensured. The adsorbent adopted by the invention has good heat resistance and strong adsorption capacity, and the adsorbent can adsorb at more than 145 ℃, so that the problem that 4,4 '-dinitrodiphenyl ether is solid at the temperature of less than 145 ℃ and cannot pass through the adsorbent is solved, and the impurities such as macromolecular tar in the crude product of the 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 ℃, more preferably 145-155 ℃; the mode of the first solid-liquid separation is not particularly limited, and a solid-liquid separation mode well known to those skilled in the art, such as filtration or centrifugal separation, may be adopted; the invention has no special limitation on the conditions of centrifugal separation, and can realize separation of liquid components and solid components; 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 then dried, so that the 4,4' -dinitrodiphenyl ether refined product is obtained.
In the present invention, the acid preferably includes an organic acid and an inorganic acid; the organic acid comprises one or more of citric acid, 3', 4' -diphenyl ether tetracarboxylic acid and 3,3', 4' -diphenyl tetracarboxylic acid; the inorganic acid comprises hydrochloric acid and/or sulfuric acid. In the 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 more than or equal to 145 ℃, preferably 145-180 ℃, more preferably 145-155 ℃; the extraction time is preferably 0.5 to 3 hours, more preferably 0.5 to 2 hours; the adsorption is preferably carried out under stirring conditions; the invention has no special limitation on the stirring speed and time, and can ensure that the extraction is performed normally. The invention adopts the acid to extract at the temperature of more than 145 ℃, and can dissolve Na, fe, cr and K wrapped in the crude product of the 4,4 '-dinitrodiphenyl ether into water, thereby obviously reducing the concentration of the Na, fe, cr and K of the 4,4' -dinitrodiphenyl ether.
In the invention, the initial temperature of the cooling crystallization is the extraction temperature, and the end temperature is 85-120 ℃; the cooling rate of the cooling crystallization is preferably 0.15 to 0.75 ℃/min, more preferably 0.2 to 0.6 ℃/min, and even more preferably 0.3 to 0.5 ℃/min.
In the present invention, the temperature of the second solid-liquid separation is 85 to 120 ℃, preferably 85 to 110 ℃, and more preferably 90 to 100 ℃; the mode of the second solid-liquid separation is not particularly limited, and a solid-liquid separation mode well known to those skilled in the art, such as filtration or centrifugal separation, may be adopted; 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 ℃, and the p-nitrochlorobenzene is liquid at the temperature of more than 85 ℃, and the p-nitrochlorobenzene impurity can be removed by performing second solid-liquid separation and filtration under the condition of 85-120 ℃.
In the present invention, the water for washing is preferably hot water, and the temperature of the hot water is preferably 80 to 90 ℃, more preferably 85 to 90 ℃; the number of times of water washing is preferably 2-3 times; the purpose of the water washing is to remove water-soluble impurities from the surface of the solid component.
In the present invention, the drying temperature is preferably 100 to 110 ℃, more preferably 105 to 108 ℃; the drying time is not particularly limited, and the drying time is required to be constant.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Paranitrochlorobenzene (7.68 kmol), sodium paranitrophenolate (7.45 kmol), potassium carbonate 121kg and 3000L nitrobenzene are put into a 6300L reaction kettle, the temperature is raised to 225 ℃ for etherification, nitrobenzene is recovered by reduced pressure distillation after 21h of reaction, the residual materials in the kettle are transferred into 6000L water for crystallization, and centrifugal separation is carried out, thus obtaining a crude product of 4,4' -dinitrodiphenyl ether (the purity is 98.95%). The embodiment of the invention takes the crude product of the 4,4' -dinitrodiphenyl ether as a raw material.
Example 1
600kg of crude 4,4' -dinitrodiphenyl ether (purity is 98.95%) is added into a 3000L glass lining reaction kettle for mixing, 1800kg of pure water and 1.8kg of carbon aerogel are added into the kettle under the stirring condition, the temperature is raised to 155 ℃, the heat preservation and the adsorption are carried out for 0.5h, and the liquid component is obtained by filtering when the liquid component is hot; 180g of 3,3', 4' -diphenyl ether tetracarboxylic acid is added into the liquid component, then the mixture is extracted for 0.5h under the condition of heat preservation at 155 ℃, the obtained extract is cooled to 120 ℃ at the speed of 0.15 ℃/min for crystallization, centrifugal separation is carried out while the extract is hot, the obtained solid component is added with 85 ℃ hot pure water for washing 2 times (300 kg of hot water is used for each time), and then the solid component is dried for 3h at 110 ℃ to obtain the refined 4,4' -dinitrodiphenyl ether (light yellow crystallization, 591kg, the yield is 98.5%, and the purity is 99.93%).
Example 2
600kg of crude 4,4' -dinitrodiphenyl ether (purity is 98.95%) is added into a 6300L glass lining reaction kettle to be mixed, the temperature is raised to 145 ℃, the temperature is kept for 1.5h, and the mixture is filtered while the mixture is hot, so as to obtain a liquid component; adding 1.5kg of 3,3', 4' -diphenyl ether tetracarboxylic acid into the liquid component, extracting at 155 ℃ for 1.5h under heat preservation, cooling the obtained extract to 90 ℃ at the speed of 0.5 ℃/min for crystallization, centrifugally separating while the extract is hot, adding 95 ℃ hot pure water into the obtained solid component for washing 2 times (300 kg of hot water each time), and then drying at 100 ℃ for 3h to obtain a fine product of 4,4' -dinitrodiphenyl ether (light yellow crystallization, 594.6kg, yield of 99.1% and purity of 99.96%).
Example 3
Under the stirring condition, 500kg of crude 4,4' -dinitrodiphenyl ether (purity is 98.95%), 5000kg of pure water and 15kg of carbon aerogel are added into a 6300L glass lining reaction kettle to be mixed, heated to 180 ℃, and then subjected to heat preservation and adsorption for 4 hours, and filtered while the mixture is hot to obtain a liquid component; adding 2.5kg of 3,3', 4' -diphenyl ether tetracarboxylic acid into the liquid component, then carrying out heat preservation extraction for 3 hours at 180 ℃, cooling the obtained extract to 105 ℃ at the speed of 0.75 ℃/min for crystallization, centrifuging while the extract is hot, adding 95 ℃ hot pure water into the obtained solid component for washing 2 times (300 kg of hot water is used each time), and then drying for 3 hours at 110 ℃ to obtain a fine product of 4,4' -dinitrodiphenyl ether (light yellow crystallization, 493.5kg, yield is 98.7%, purity is 99.95%).
The contents of metal ions and Cl in the crude 4,4 '-dinitrodiphenyl ether product used in the examples and the refined 4,4' -dinitrodiphenyl ether products prepared in examples 1 to 3 are shown in Table 1:
table 1 ion content of crude 4,4 '-dinitrodiphenyl ether and refined 4,4' -dinitrodiphenyl ether products prepared in examples 1 to 3
As is clear from Table 1, the contents of Na, fe, cr and K in the 4,4 '-dinitrodiphenyl ether refined product prepared by the invention are all less than 1ppm, and the content of Cl is less than 2ppm, which indicates that the purity of the 4,4' -dinitrodiphenyl ether refined product prepared by the invention is high.
The information of the high performance liquid chromatography peaks of the crude 4,4 '-dinitrodiphenyl ether product adopted in the examples and the refined 4,4' -dinitrodiphenyl ether product prepared in the 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 4,4 '-dinitrodiphenyl ether product used in examples 1 to 3, fig. 2 is a high performance liquid chromatogram of a fine 4,4' -dinitrodiphenyl ether product prepared in example 1, fig. 3 is a high performance liquid chromatogram of a fine 4,4 '-dinitrodiphenyl ether product prepared in example 2, and fig. 4 is a high performance liquid chromatogram of a fine 4,4' -dinitrodiphenyl ether product prepared in example 3.
Table 2 high performance liquid chromatography peak information of crude 4,4 '-dinitrodiphenyl ether and refined 4,4' -dinitrodiphenyl ether prepared in examples 1 to 3
As is clear from Table 2 and FIGS. 1 to 4, the 4,4' -dinitrodiphenyl ether fine product prepared by the present invention has high purity.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (2)
1. A process for purifying 4,4' -dinitrodiphenyl ether, comprising the steps of:
mixing the crude product of 4,4' -dinitrodiphenyl ether, an adsorbent and water, and carrying out first solid-liquid separation after adsorption to obtain a liquid component; the adsorbent is carbon aerogel; the mass ratio of the crude product of the 4,4' -dinitrodiphenyl ether to the adsorbent to the water is 1: 0.003-0.03: 3-10; the adsorption temperature is 145-180 ℃ and the adsorption time is 0.5-4 hours; the temperature of the first solid-liquid separation is 145-180 ℃;
mixing the liquid component with acid, sequentially extracting, cooling and crystallizing, performing second solid-liquid separation, washing the obtained solid component with water, and drying to obtain a fine product of 4,4' -dinitrodiphenyl ether; the acid is 3,3', 4' -biphenyl ether tetracarboxylic acid; the mass ratio of the crude 4,4' -dinitrodiphenyl ether to the acid is 1:0.0003 to 0.005; the extraction temperature is 145-180 ℃ and the extraction time is 0.5-3 h; the initial temperature of the cooling crystallization is the extraction temperature, the end temperature is 85-120 ℃, and the cooling rate of the cooling crystallization is 0.15-0.75 ℃/min; the temperature of the second solid-liquid separation is 85-120 ℃; the water for washing is hot water, and the temperature of the hot water is 85-90 ℃ or 95 ℃;
the preparation method of the crude product of the 4,4' -dinitrodiphenyl ether 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 4,4' -dinitrodiphenyl ether; the catalyst is a potassium salt catalyst and/or a sodium salt catalyst, the potassium salt catalyst is potassium chloride and/or potassium carbonate, and the sodium salt catalyst is sodium chloride and/or sodium carbonate.
2. The purification method according to claim 1, wherein the drying temperature is 100-110 ℃.
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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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