CN110041205A - A kind of purifying technique of 4,4 '-dinitro diphenyl ether - Google Patents
A kind of purifying technique of 4,4 '-dinitro diphenyl ether Download PDFInfo
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- CN110041205A CN110041205A CN201910344856.3A CN201910344856A CN110041205A CN 110041205 A CN110041205 A CN 110041205A CN 201910344856 A CN201910344856 A CN 201910344856A CN 110041205 A CN110041205 A CN 110041205A
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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Abstract
The present invention relates to the purification technique fields of fine chemistry industry organic material, especially one kind 4, the purifying technique of 4'- dinitro diphenyl ether, the following steps are included: (1) is by thick 4,4'- dinitro diphenyl ether is put into material kettle, then organic solvent and active carbon, the filtering of plate and frame filter, centrifuge carry out centrifugal filtration processing；(2) mixed material after centrifugal filtration is sent into row multistage distillation；(3) methanol and toluene Mixed Solvent mixing is added, adds the mixture of carclazyte, aluminium oxide and sepiolite；(4) mixed liquor is subjected to ion-exchange；(5) by ion-exchange, treated that mixed liquor is evaporated under reduced pressure to get 4,4'- dinitro diphenyl ether.The present invention can make 4, the 4'- dinitro diphenyl ether purity after purification up to 99.8% or more, and 4, the 4'- dinitro diphenyl ether product catalytic performance reaction speed that solution produces in the prior art is low, the low problem of conversion ratio.
Description
Technical field
The invention belongs to the purification technique fields of fine chemistry industry organic material, and in particular to a kind of 4,4 '-dinitro hexichol
The purifying technique of ether.
Background technique
4,4 '-dinitro diphenyl ethers are a kind of important fine chemical products, it is manufacture medicine and the useful centre of pesticide
Body, and 4,4 '-dinitro diphenyl ethers are widely used in 4,4 ' -- the production of diaminodiphenyl ether, and 4,4 ' -- diaminodiphenyl ether
It is the important monomer and high performance heat resistant for manufacturing the fire resistant resins such as new special engineering plastics polyimides and Nomex
The crosslinking agent of the polymer materials such as property epoxy resin, polyurethane, and be found through experiments that, 4, the purity of 4 '-dinitro diphenyl ethers
Higher, catalytic, reaction speed are higher, and corresponding 4, reduzate 4,4 ' -- the diamino two of 4 '-dinitro diphenyl ethers
The yield of phenylate is higher, and the existing purifying technique for being used for 4,4 '-dinitro diphenyl ethers, generally existing 4,4 '-dinitros
The low problem of the purity of diphenyl ether, 4, the 4 '-dinitro diphenyl ether product catalytic performances for causing production to obtain, reaction speed are relatively low,
It is difficult to meet the needs of production.
In consideration of it, it is necessary to provide a kind of purifying technique of 4,4 '-dinitro diphenyl ethers, to solve to exist in the prior art
The problem of.
Summary of the invention
The purpose of the present invention is to provide a kind of purifying techniques of 4,4 '-dinitro diphenyl ethers, and 4,4 '-after can making purification
Dinitro diphenyl ether purity up to 99.8% or more, urge by 4, the 4 '-dinitro diphenyl ether products for solving to produce in the prior art
It is low to change performance reaction speed, the low problem of conversion ratio.
The present invention is achieved by the following technical solutions:
A kind of purifying technique of 4,4 '-dinitro diphenyl ethers, comprising the following steps:
(1) by thick the 4 of processing to be purified, 4 '-dinitro diphenyl ethers are put into material kettle, are then added thick 4,4 '-two
The organic solvent of 1.2-1.5 times of itrodiphenyl ethers weight after stirring and dissolving, adds thick 4,4 '-dinitro diphenyl ether quality
Then it is miscellaneous to be filtered out part therein by plate and frame filter by the active carbon of 0.2%-0.4% for mixed material in material kettle
Matter places into and carries out centrifugal filtration processing in centrifuge；
(2) mixed material after centrifugal filtration is sent into vacuum (distilling) column, carries out multistage distillation processing, then cooling knot
Crystalline substance obtains the crystallization of 4,4 '-dinitro diphenyl ethers；
(3) by 4,4 '-dinitro diphenyl ethers crystallization be put into material storage kettle, and keep material storage kettle vacuum degree be-
0.09MPa, and methanol and toluene Mixed Solvent mixing are added into material storage kettle, it is stirred evenly at 50-70 DEG C, then to storing
The mixture of carclazyte, aluminium oxide and sepiolite is added in tank, and 10-15min is stirred with 50-60rpm speed, then by mixed liquor
It is added in centrifuge and carries out centrifugal treating；
(4) by the mixed liquor after centrifugal treating according to highly acidic cation → strong alkalinity anion → highly acidic cation →
The sequence of strong alkalinity anion passes sequentially through ion exchange resin and carries out ion-exchange；
(5) by ion-exchange, treated that mixed liquor is evaporated under reduced pressure to get 4,4 '-dinitro diphenyl ethers.
More preferred, the organic solvent in the step (1) is n,N-dimethylacetamide, dimethyl sulfoxide or 1,3-
Dimethyl-2-imidazolinone.
More preferred, the mesh number of the plate and frame filter cloth in the step (1) is 300-400 mesh.
More preferred, the multistage distillation in the step (2) is the molecular distillation of continuity three-level.
More preferred, the continuity three-level molecular distillation includes: that level-one distiller adjusts 165 DEG C -175 DEG C of temperature,
Vacuum degree is 350-450Pa；Secondary distillation device adjusts 180 DEG C -190 DEG C of temperature, vacuum degree 15-25Pa；Three-stage distillation device is adjusted
200 DEG C -210 DEG C of temperature, vacuum degree 2-4Pa.
More preferred, the volume ratio of methanol and toluene in the step (3) is 2-4:1.
More preferred, the mass ratio of carclazyte, aluminium oxide and sepiolite in the step (3) is 6:3:1.
More preferred, the highly acidic cation in the step (4) is highly acid acrylic acid type cation exchange resin,
Strong alkalinity anion is strong basicity acrylic acid type anion exchange resin.
More preferred, the pressure of the vacuum distillation in the step (5) is 4-6mmHg, and temperature is 65-75 DEG C.
Compared with prior art, the beneficial effects of the present invention are:
Purifying technique of the invention can effectively improve the purity of 4,4 '-dinitro diphenyl ethers, can make 4,4 '-dinitro hexichol
The purity of ether solves 4,4 '-caused by 4, the 4 '-dinitro diphenyl ether purity deficiencies extracted in the prior art up to 99.8 or more
The product catalytic performance reaction speed of dinitro diphenyl ether product is low, the low problem of conversion ratio；
Thick 4,4 '-dinitro diphenyl ethers are dissolved in organic solvent in addition, the present invention first passes through, and by the way that activity is added
Charcoal adsorbs impurity therein, suspended matter etc., then carries out coarse filtration by plate and frame filter, then using centrifuge
Smart filtering is carried out, thus to thick 4, the primary filtration of the impurity in 4 '-dinitro diphenyl ethers；
The present invention by using three-level molecular distillation mode, can to the organic solvent in thick 4,4 '-dinitro diphenyl ethers into
Row distills step by step, and can be carried away the impurity of thick 4,4 '-dinitro diphenyl ethers by organic solvent, to further increase
The purity of the 4,4 ' of the application-dinitro diphenyl ether；
The present invention passes through the collaboration of three by the mixture of addition carclazyte, aluminium oxide and sepiolite under vacuum conditions
Effect, can effectively remove 4, suspended particulate in 4 '-dinitro diphenyl ethers, and by above-mentioned processing step may remaining colloid into
The removal of one step, further increases of the invention 4, the purity of 4 '-dinitro diphenyl ethers；
The present invention by the mixed liquor after centrifugal treating according to highly acidic cation → strong alkalinity anion → highly acid sun from
Son → strong alkalinity anion sequence passes sequentially through ion exchange resin and carries out ion-exchange, can effectively adsorb 4,4 '-dinitro hexichol
The trace impurity of ether, so that of the invention 4 are further increased, the purity of 4 '-dinitro diphenyl ethers.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The 4 of the present embodiment, the purifying technique of 4 '-dinitro diphenyl ethers, comprising the following steps:
(1) by thick the 4 of the 1500kg of processing to be purified, 4 '-dinitro diphenyl ethers are put into material kettle, are then added
The organic solvent of 1950kg after stirring and dissolving, adds 4.5kg active carbon, mixed material in material kettle is then passed through sheet frame
Formula filter filters out partial impurities therein, places into and carries out centrifugal filtration processing in centrifuge；
(2) mixed material after centrifugal filtration is sent into vacuum (distilling) column, carries out multistage distillation processing, then cooling knot
Crystalline substance obtains the crystallization of 4,4 '-dinitro diphenyl ethers；
(3) by 4,4 '-dinitro diphenyl ethers crystallization be put into material storage kettle, and keep material storage kettle vacuum degree be-
0.09MPa, and methanol and toluene Mixed Solvent mixing are added into material storage kettle, it is stirred evenly at 50 DEG C, then to storage tank
The interior mixture that carclazyte, aluminium oxide and sepiolite is added, and 10min is stirred with 50rpm speed, then mixed liquor is added and is centrifuged
Centrifugal treating is carried out in machine；
(4) by the mixed liquor after centrifugal treating according to highly acidic cation → strong alkalinity anion → highly acidic cation →
The sequence of strong alkalinity anion passes sequentially through ion exchange resin and carries out ion-exchange；
(5) by ion-exchange, treated that mixed liquor is evaporated under reduced pressure to get 4,4 '-dinitro diphenyl ethers.
Wherein, the organic solvent in the step (1) is n,N-dimethylacetamide, dimethyl sulfoxide or 1,3- diformazan
Base -2- imidazolone.
Wherein, the mesh number of the plate and frame filter cloth in the step (1) is 300-400 mesh.
Wherein, the multistage distillation in the step (2) is the molecular distillation of continuity three-level.
Wherein, the continuity three-level molecular distillation includes: that level-one distiller adjusts 165 DEG C DEG C of temperature, and vacuum degree is
350Pa；Secondary distillation device adjusts 180 DEG C of temperature, vacuum degree 15Pa；Three-stage distillation device adjusts 200 DEG C of temperature, vacuum degree 2Pa.
Wherein, the volume ratio of the methanol in the step (3) and toluene is 2:1.
Wherein, the mass ratio of the carclazyte in the step (3), aluminium oxide and sepiolite is 6:3:1.
Wherein, the highly acidic cation in the step (4) is highly acid acrylic acid type cation exchange resin, strong basicity
Anion is strong basicity acrylic acid type anion exchange resin.
Wherein, the pressure of the vacuum distillation in the step (5) is 4mmHg, and temperature is 65 DEG C.
Embodiment 2
The 4 of the present embodiment, the purifying technique of 4 '-dinitro diphenyl ethers, comprising the following steps:
(1) by thick the 4 of the 1450kg of processing to be purified, 4 '-dinitro diphenyl ethers are put into material kettle, are then added
The organic solvent of 1900kg after stirring and dissolving, adds the active carbon of 5kg, mixed material in material kettle is then passed through sheet frame
Formula filter filters out partial impurities therein, places into and carries out centrifugal filtration processing in centrifuge；
(2) mixed material after centrifugal filtration is sent into vacuum (distilling) column, carries out multistage distillation processing, then cooling knot
Crystalline substance obtains the crystallization of 4,4 '-dinitro diphenyl ethers；
(3) by 4,4 '-dinitro diphenyl ethers crystallization be put into material storage kettle, and keep material storage kettle vacuum degree be-
0.09MPa, and methanol and toluene Mixed Solvent mixing are added into material storage kettle, it is stirred evenly at 70 DEG C, then to storage tank
The interior mixture that carclazyte, aluminium oxide and sepiolite is added, and 15min is stirred with 60rpm speed, then mixed liquor is added and is centrifuged
Centrifugal treating is carried out in machine；
(4) by the mixed liquor after centrifugal treating according to highly acidic cation → strong alkalinity anion → highly acidic cation →
The sequence of strong alkalinity anion passes sequentially through ion exchange resin and carries out ion-exchange；
(5) by ion-exchange, treated that mixed liquor is evaporated under reduced pressure to get 4,4 '-dinitro diphenyl ethers.
Wherein, the organic solvent in the step (1) is n,N-dimethylacetamide, dimethyl sulfoxide or 1,3- diformazan
Base -2- imidazolone.
Wherein, the mesh number of the plate and frame filter cloth in the step (1) is 300-400 mesh.
Wherein, the multistage distillation in the step (2) is the molecular distillation of continuity three-level.
Wherein, the continuity three-level molecular distillation includes: that level-one distiller adjusts 175 DEG C of temperature, and vacuum degree is
450Pa；Secondary distillation device adjusts 190 DEG C of temperature, vacuum degree 25Pa；Three-stage distillation device adjusts 210 DEG C of temperature, vacuum degree 4Pa.
Wherein, the volume ratio of the methanol in the step (3) and toluene is 4:1.
Wherein, the mass ratio of the carclazyte in the step (3), aluminium oxide and sepiolite is 6:3:1.
Wherein, the highly acidic cation in the step (4) is highly acid acrylic acid type cation exchange resin, strong basicity
Anion is strong basicity acrylic acid type anion exchange resin.
Wherein, the pressure of the vacuum distillation in the step (5) is 6mmHg, and temperature is 75 DEG C.
Embodiment 3
The 4 of the present embodiment, the purifying technique of 4 '-dinitro diphenyl ethers, comprising the following steps:
(1) by the 1550kg of processing to be purified thick 4,4 '-dinitro diphenyl ethers are put into material kettle, are then added
The organic solvent of 2100kg after stirring and dissolving, adds the active carbon of 5.5kg, mixed material in material kettle is then passed through plate
Frame filter filters out partial impurities therein, places into and carries out centrifugal filtration processing in centrifuge；
(2) mixed material after centrifugal filtration is sent into vacuum (distilling) column, carries out multistage distillation processing, then cooling knot
Crystalline substance obtains the crystallization of 4,4 '-dinitro diphenyl ethers；
(3) by 4,4 '-dinitro diphenyl ethers crystallization be put into material storage kettle, and keep material storage kettle vacuum degree be-
0.09MPa, and methanol and toluene Mixed Solvent mixing are added into material storage kettle, it is stirred evenly at 60 DEG C, then to storage tank
The interior mixture that carclazyte, aluminium oxide and sepiolite is added, and 13min is stirred with 55rpm speed, then mixed liquor is added and is centrifuged
Centrifugal treating is carried out in machine；
(4) by the mixed liquor after centrifugal treating according to highly acidic cation → strong alkalinity anion → highly acidic cation →
The sequence of strong alkalinity anion passes sequentially through ion exchange resin and carries out ion-exchange；
(5) by ion-exchange, treated that mixed liquor is evaporated under reduced pressure to get 4,4 '-dinitro diphenyl ethers.
Wherein, the organic solvent in the step (1) is n,N-dimethylacetamide, dimethyl sulfoxide or 1,3- diformazan
Base -2- imidazolone.
Wherein, the mesh number of the plate and frame filter cloth in the step (1) is 300-400 mesh.
Wherein, the multistage distillation in the step (2) is the molecular distillation of continuity three-level.
Wherein, the continuity three-level molecular distillation includes: that level-one distiller adjusts 170 DEG C of temperature, and vacuum degree is
400Pa；Secondary distillation device adjusts 185 DEG C of temperature, vacuum degree 20Pa；Three-stage distillation device adjusts 205 DEG C of temperature, vacuum degree 3Pa.
Wherein, the volume ratio of the methanol in the step (3) and toluene is 3:1.
Wherein, the mass ratio of the carclazyte in the step (3), aluminium oxide and sepiolite is 6:3:1.
Wherein, the highly acidic cation in the step (4) is highly acid acrylic acid type cation exchange resin, strong basicity
Anion is strong basicity acrylic acid type anion exchange resin.
Wherein, the pressure of the vacuum distillation in the step (5) is 5mmHg, and temperature is 70 DEG C.
Embodiment 4
The 4 of the present embodiment, the purifying technique of 4 '-dinitro diphenyl ethers, comprising the following steps:
(1) by thick the 4 of the 1400kg of processing to be purified, 4 '-dinitro diphenyl ethers are put into material kettle, are then added
The organic solvent of 1900kg after stirring and dissolving, adds the active carbon of thick 4,4 '-dinitro diphenyl ether quality 4.8kg, then will
Mixed material filters out partial impurities therein by plate and frame filter in material kettle, places into and carries out being centrifuged in centrifuge
Filter processing；
(2) mixed material after centrifugal filtration is sent into vacuum (distilling) column, carries out multistage distillation processing, then cooling knot
Crystalline substance obtains the crystallization of 4,4 '-dinitro diphenyl ethers；
(3) by 4,4 '-dinitro diphenyl ethers crystallization be put into material storage kettle, and keep material storage kettle vacuum degree be-
0.09MPa, and methanol and toluene Mixed Solvent mixing are added into material storage kettle, it is stirred evenly at 55 DEG C, then to storage tank
The interior mixture that carclazyte, aluminium oxide and sepiolite is added, and 11min is stirred with 53rpm speed, then mixed liquor is added and is centrifuged
Centrifugal treating is carried out in machine；
(4) by the mixed liquor after centrifugal treating according to highly acidic cation → strong alkalinity anion → highly acidic cation →
The sequence of strong alkalinity anion passes sequentially through ion exchange resin and carries out ion-exchange；
(5) by ion-exchange, treated that mixed liquor is evaporated under reduced pressure to get 4,4 '-dinitro diphenyl ethers.
Wherein, the organic solvent in the step (1) is n,N-dimethylacetamide, dimethyl sulfoxide or 1,3- diformazan
Base -2- imidazolone.
Wherein, the mesh number of the plate and frame filter cloth in the step (1) is 300-400 mesh.
Wherein, the multistage distillation in the step (2) is the molecular distillation of continuity three-level.
Wherein, the continuity three-level molecular distillation includes: that level-one distiller adjusts 168 DEG C of temperature, and vacuum degree is
380Pa；Secondary distillation device adjusts 182 DEG C of temperature, vacuum degree 18Pa；Three-stage distillation device adjusts 204 DEG C of temperature, and vacuum degree is
2.5Pa。
Wherein, the volume ratio of the methanol in the step (3) and toluene is 2.5:1.
Wherein, the mass ratio of the carclazyte in the step (3), aluminium oxide and sepiolite is 6:3:1.
Wherein, the highly acidic cation in the step (4) is highly acid acrylic acid type cation exchange resin, strong basicity
Anion is strong basicity acrylic acid type anion exchange resin.
Wherein, the pressure of the vacuum distillation in the step (5) is 4.5mmHg, and temperature is 68 DEG C.
Embodiment 5
The 4 of the present embodiment, the purifying technique of 4 '-dinitro diphenyl ethers, comprising the following steps:
(1) by the 1600kg of processing to be purified thick 4,4 '-dinitro diphenyl ethers are put into material kettle, are then added
The organic solvent of 2100kg after stirring and dissolving, adds the active carbon of 5.5kg, mixed material in material kettle is then passed through plate
Frame filter filters out partial impurities therein, places into and carries out centrifugal filtration processing in centrifuge；
(2) mixed material after centrifugal filtration is sent into vacuum (distilling) column, carries out multistage distillation processing, then cooling knot
Crystalline substance obtains the crystallization of 4,4 '-dinitro diphenyl ethers；
(3) by 4,4 '-dinitro diphenyl ethers crystallization be put into material storage kettle, and keep material storage kettle vacuum degree be-
0.09MPa, and methanol and toluene Mixed Solvent mixing are added into material storage kettle, it is stirred evenly at 50-70 DEG C, then to storing
The mixture of carclazyte, aluminium oxide and sepiolite is added in tank, and 10-15min is stirred with 50-60rpm speed, then by mixed liquor
It is added in centrifuge and carries out centrifugal treating；
(4) by the mixed liquor after centrifugal treating according to highly acidic cation → strong alkalinity anion → highly acidic cation →
The sequence of strong alkalinity anion passes sequentially through ion exchange resin and carries out ion-exchange；
(5) by ion-exchange, treated that mixed liquor is evaporated under reduced pressure to get 4,4 '-dinitro diphenyl ethers.
Wherein, the organic solvent in the step (1) is n,N-dimethylacetamide, dimethyl sulfoxide or 1,3- diformazan
Base -2- imidazolone.
Wherein, the mesh number of the plate and frame filter cloth in the step (1) is 300-400 mesh.
Wherein, the multistage distillation in the step (2) is the molecular distillation of continuity three-level.
Wherein, the continuity three-level molecular distillation includes: that level-one distiller adjusts 172 DEG C of temperature, and vacuum degree is
420Pa；Secondary distillation device adjusts 188 DEG C of temperature, vacuum degree 22Pa；Three-stage distillation device adjusts 208 DEG C of temperature, and vacuum degree is
3.5Pa。
Wherein, the volume ratio of the methanol in the step (3) and toluene is 3.5:1.
Wherein, the mass ratio of the carclazyte in the step (3), aluminium oxide and sepiolite is 6:3:1.
Wherein, the highly acidic cation in the step (4) is highly acid acrylic acid type cation exchange resin, strong basicity
Anion is strong basicity acrylic acid type anion exchange resin.
Wherein, the pressure of the vacuum distillation in the step (5) is 5.5mmHg, and temperature is 72 DEG C.
Comparative example 1
Multistage distillation processing in step (2) is changed to level-one distillation, i.e. distiller adjusts 165 DEG C -175 DEG C of temperature,
Vacuum degree is 350-450Pa.
Comparative example 2
Multistage distillation processing in step (2) is changed to level-one distillation, i.e. distiller adjusts 180 DEG C -190 DEG C of temperature,
Vacuum degree 15-25Pa.
Comparative example 3
Multistage distillation processing in step (2) is changed to level-one distillation, i.e. distiller adjusts 200 DEG C -210 DEG C of temperature,
Vacuum degree is 2-4Pa.
Comparative example 4
Carclazyte, aluminium oxide and sepiolite in step (3) is changed to carclazyte is used alone.
Comparative example 5
Step (4) is saved, other steps are constant.
Comparative example 6
By " highly acidic cation → strong alkalinity anion → highly acidic cation → strong alkalinity anion " in step (4)
Processing step should be " highly acidic cation → strong alkalinity anion ".
Experimental example
The method of embodiment 1-5 and comparative example 1-6 are made 4, the purity of 4 '-dinitro diphenyl ethers is measured, specifically
As a result shown in table 1.
Table 1
As shown in Table 1, the purity is high of 4,4 '-dinitro diphenyl ethers made from the method for 1-5 of the embodiment of the present invention, and by right
Ratio 1-6 is it is found that the present invention passes through three-level molecular distillation mode, carclazyte, aluminium oxide and sepiolite combine adsorption mode and ion-exchange
Processing can improve the purity of 4,4 '-dinitro diphenyl ethers.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. one kind 4, the purifying technique of 4'- dinitro diphenyl ether, which comprises the following steps:
(1) thick 4, the 4'- dinitro diphenyl ether of processing to be purified is put into material kettle, thick 4,4'- dinitro is then added
The organic solvent of 1.2-1.5 times of diphenyl ether weight after stirring and dissolving, adds thick 4,4'- dinitro diphenyl ether quality 0.2%-
Then mixed material in material kettle is filtered out partial impurities therein by plate and frame filter, then put by 0.4% active carbon
Enter and carries out centrifugal filtration processing in centrifuge；
(2) mixed material after centrifugal filtration is sent into vacuum (distilling) column, carries out multistage distillation processing, then crystallisation by cooling,
Obtain the crystallization of 4,4'- dinitro diphenyl ether；
(3) crystallization of 4,4'- dinitro diphenyl ether is put into material storage kettle, and keeping the vacuum degree of material storage kettle is -0.09MPa, and
Methanol and toluene Mixed Solvent mixing are added into material storage kettle, stirs evenly, is then added into storage tank white at 50-70 DEG C
The mixture of soil, aluminium oxide and sepiolite, and 10-15min is stirred with 50-60rpm speed, centrifuge then is added in mixed liquor
Middle carry out centrifugal treating；
(4) by the mixed liquor after centrifugal treating according to highly acidic cation → strong alkalinity anion → highly acidic cation → highly basic
Property anion sequence pass sequentially through ion exchange resin carry out ion-exchange；
(5) by ion-exchange, treated that mixed liquor is evaporated under reduced pressure to get 4,4'- dinitro diphenyl ether.
2. the purifying technique of 4,4'- dinitro diphenyl ether according to claim 1, which is characterized in that in the step (1)
Organic solvent be DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or 1,3- dimethyl-2-imidazolinone.
3. the purifying technique of 4,4'- dinitro diphenyl ether according to claim 1, which is characterized in that in the step (1)
Plate and frame filter cloth mesh number be 300-400 mesh.
4. the purifying technique of 4,4'- dinitro diphenyl ether according to claim 1, which is characterized in that in the step (2)
Multistage distillation be the molecular distillation of continuity three-level.
5. the purifying technique of 4,4'- dinitro diphenyl ether according to claim 4, which is characterized in that the continuity three
Grade molecular distillation includes: that level-one distiller adjusts 165 DEG C -175 DEG C of temperature, vacuum degree 350-450Pa；Secondary distillation device is adjusted
180 DEG C -190 DEG C of temperature, vacuum degree 15-25Pa；Three-stage distillation device adjusts 200 DEG C -210 DEG C of temperature, vacuum degree 2-4Pa.
6. the purifying technique of 4,4'- dinitro diphenyl ether according to claim 1, which is characterized in that in the step (3)
Methanol and toluene volume ratio be 2-4:1.
7. the purifying technique of 4,4'- dinitro diphenyl ether according to claim 1, which is characterized in that in the step (3)
Carclazyte, aluminium oxide and sepiolite mass ratio be 6:3:1.
8. the purifying technique of 4,4'- dinitro diphenyl ether according to claim 1, which is characterized in that in the step (4)
Highly acidic cation be highly acid acrylic acid type cation exchange resin, strong alkalinity anion be strong basicity acrylic acid series yin from
Sub-exchange resin.
9. the purifying technique of 4,4'- dinitro diphenyl ether according to claim 1, which is characterized in that in the step (5)
Vacuum distillation pressure be 4-6mmHg, temperature be 65-75 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114315590A (en) * | 2021-12-31 | 2022-04-12 | 河北海力香料股份有限公司 | Method for purifying 4,4' -dinitrodiphenyl ether |
| CN114591178A (en) * | 2022-03-17 | 2022-06-07 | 宁夏德昊科技产业有限公司 | ODA production process and production system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114315590A (en) * | 2021-12-31 | 2022-04-12 | 河北海力香料股份有限公司 | Method for purifying 4,4' -dinitrodiphenyl ether |
| CN114315590B (en) * | 2021-12-31 | 2023-10-31 | 河北海力恒远新材料股份有限公司 | Method for purifying 4,4' -dinitrodiphenyl ether |
| CN114605266A (en) * | 2022-03-09 | 2022-06-10 | 河北海力香料股份有限公司 | Refining method of 4,4' -dinitrodiphenyl ether |
| CN114591178A (en) * | 2022-03-17 | 2022-06-07 | 宁夏德昊科技产业有限公司 | ODA production process and production system |
| CN114591178B (en) * | 2022-03-17 | 2023-08-29 | 宁夏德昊科技产业有限公司 | ODA production process and production system |
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