CN115057785A - Purification method of 2,4, 6-triaminotoluene - Google Patents
Purification method of 2,4, 6-triaminotoluene Download PDFInfo
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Abstract
The application relates to the technical field of chemical engineering and materials, and provides a method for purifying 2,4, 6-triaminotoluene, which comprises the following steps: in an oxygen-free atmosphere, adding a specific hydrated organic solvent into a first container to dissolve a 2,4, 6-triaminotoluene crude product at a target dissolving temperature, then transferring the crude product into a second container, cooling the second container to a target cooling temperature, separating out a crystallization product, and then carrying out decoloration filter membrane and drying to obtain a final product. According to the method provided by the application, in the purification process, the inert gas atmosphere is used for protection in the whole process, so that the 2,4, 6-triaminotoluene is prevented from deteriorating due to oxidation in the purification process; the target dissolution temperature and the target cooling temperature set by the application are determined based on the solubility of the specific hydrated organic solvent for dissolving the 2,4, 6-triaminotoluene at different temperatures, and the yield and the purity of the 2,4, 6-triaminotoluene are improved. The method is simple to operate, low in solvent price, green, safe, high in purification efficiency and beneficial to industrial popularization.
Description
Technical Field
The embodiment of the application relates to the technical field of chemical engineering and materials, and particularly relates to a purification method of 2,4, 6-triaminotoluene.
Background
2,4, 6-triaminotoluene (TAT) has great application potential as a trifunctional aromatic polyamine, can be used as a precursor raw material of a plurality of high value-added chemical products, for example, can be used for synthesizing novel adhesive toluene triisocyanate, insensitive explosive 1,3, 5-triamino-2, 4, 6-trinitrobenzene (TATB) and the like, and can also be used for constructing novel porous polymer materials.
Pure TAT samples are white to pale yellow crystals with a melting point of 117 ℃ and an initial decomposition temperature of around 192 ℃. However, 2,4, 6-triaminotoluene (TAT) is usually obtained from trinitrotoluene by hydrogenation, and is therefore mixed with water as a by-product; on the other hand, it is a dark product because of its high reactivity and easy oxidation. In order to obtain high-purity TAT products, the crude TAT products need to be purified. However, TAT belongs to a novel chemical product, and a purification process method thereof is not reported, so that a simple, efficient, low-pollution and low-cost purification method is urgently needed in the field for purifying TAT.
Disclosure of Invention
The embodiment of the application aims to provide a method for purifying 2,4, 6-triaminotoluene, aims to solve the problem of the lack of the method for purifying 2,4, 6-triaminotoluene, and provides a method for purifying 2,4, 6-triaminotoluene, which is simple, efficient, low in pollution and low in cost.
The embodiment of the application provides a method for purifying 2,4, 6-triaminotoluene, which comprises the following steps:
adding a solvent and a crude product of 2,4, 6-triaminotoluene in a preset mass ratio into a first container to obtain a crude product mixture; conducting an oxygen removal operation on the first container and the second container, and conducting inert gas atmosphere replacement on the first container and the second container;
heating the temperature of the crude product mixture in the first container to a target dissolution temperature, and slowly stirring; passing the crude product mixture through a decolorizing filter membrane to obtain a crude product filtrate, wherein the decolorizing filter membrane is used for filtering and decolorizing the crude product mixture; transferring the crude product filtrate into the second container, cooling to a target cooling temperature, and slowly stirring to separate out a crystallized product;
filtering to obtain the crystallized product, and drying the crystallized product to obtain a final product, wherein the final product is 2,4, 6-triaminotoluene, the yield of the final product is more than 80%, and the purity of the final product is more than 99.0%.
Optionally, the method comprises at least one of the following features:
(1) the first container and the second container are totally-enclosed reaction kettles with jackets;
(2) the preset mass ratio of the crude 2,4, 6-triaminotoluene to the solvent is (1:10) - (1: 150);
(3) the solvent is a mixed solution formed by an organic solvent and water, the organic solvent is at least one of toluene, acetone, dioxane, ethyl acetate, ethanol, acetonitrile, methanol and N, N-dimethylformamide, and the mass ratio of the organic solvent to the water is (100:1) - (5: 1);
(4) the inert gas is nitrogen or argon.
Optionally, the first container and the second container are subjected to an oxygen removal operation, specifically comprising the following steps:
introducing high-pressure inert gas into the first container and the second container, so that the pressure in the first container and the pressure in the second container are both in a preset pressure range;
stirring in the first and second vessels for a first stirring period followed by depressurizing the pressure in the first and second vessels to atmospheric pressure;
and repeating the steps of introducing the high-pressure inert gas, stirring and releasing the pressure to the normal pressure for the first preset times.
Optionally, the first container and the second container are subjected to inert gas atmosphere replacement, and the specific steps are as follows:
introducing high-pressure inert gas into the first container and the second container to enable the pressure in the first container and the pressure in the second container to be within the preset pressure range;
stirring in the first and second vessels for the first stirring duration, followed by depressurizing the pressure in the first and second vessels to atmospheric pressure;
and repeating the steps of introducing the high-pressure inert gas, stirring and releasing the pressure to the normal pressure for the first preset times.
Optionally, raising the temperature of the crude mixture in the first vessel to a target dissolution temperature and slowly stirring; passing the crude product mixture through a decolorizing filter membrane to obtain a crude product filtrate, wherein the decolorizing filter membrane is used for filtering and decolorizing the crude product mixture; transferring the crude product filtrate into the second container, cooling to a target cooling temperature, and slowly stirring to separate out a crystallized product, wherein the specific steps are as follows:
raising the temperature of the crude mixture in the first vessel to the target dissolution temperature;
stirring the crude product mixture at a preset stirring speed within a second stirring time period;
carrying out quick filtration and color removal on the crude product mixture by using a decolorizing filter membrane while the crude product mixture is hot to obtain crude product filtrate;
transferring the crude product filtrate into the second container, and cooling the second container to the target cooling temperature;
and stirring the crude filtrate at the preset stirring speed within a third stirring time length to separate out the crystallized product.
Optionally, filtering to obtain the crystalline product, and drying the crystalline product to obtain a final product comprising:
passing the crude product filtrate through a decolorizing filter membrane by a positive pressure filter to obtain the crystallized product;
and (3) conveying the crystallized product into a vacuum drier, and drying at a drying temperature and a drying pressure to obtain the final product.
Optionally, the method comprises at least one of the following features:
(1) the preset pressure range is 0.4-1.0 MPa;
(2) the first stirring time is 10 min;
(3) the first preset number of times is 3.
Optionally, the method comprises at least one of the following features:
(1) the target dissolution temperature is 80-90 ℃;
(2) the second stirring time is 30-45 min;
(3) the preset stirring speed is 30 revolutions per minute;
(4) the target cooling temperature is 0-20 ℃;
(5) the third stirring time is 45-60 min.
Optionally, the method comprises at least one of the following features:
(1) the drying temperature is 40-60 ℃;
(2) the drying pressure is below-0.01 MPa.
Has the advantages that:
the application provides a 2,4, 6-triaminotoluene's purification method, in the oxygen-free atmosphere, add specific hydrated organic solvent and dissolve 2,4, 6-triaminotoluene crude product under the target solution temperature in first container, carry out in the second container after the hot filtration decoloration through the decoloration filter membrane, later cool down the second container to the target cooling temperature, filter and dry after the crystallization product is separated out, obtain the final product, have the following effect:
(1) according to the method, in the purification process, the inert gas atmosphere is used for protection in the whole process, so that the 2,4, 6-triaminotoluene is prevented from deteriorating due to oxidation in the purification process.
(2) The target dissolving temperature and the target cooling temperature are determined based on the solubility of the specific hydrated organic solvent for dissolving the 2,4, 6-triaminotoluene at different temperatures, and the yield and the purity of the 2,4, 6-triaminotoluene are improved.
(3) The method provided by the application is simple to operate, low in solvent price, green, safe, high in purification efficiency and beneficial to industrial popularization.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the description of the embodiments of the present application will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a flow chart of a process for purifying 2,4, 6-triaminotoluene as set forth in the examples herein;
FIG. 2 is a NMR spectrum of a final product of example one of the present application;
FIG. 3 is a NMR spectrum of a final product of example one of the present application;
FIG. 4 is an infrared spectrum of the final product of example one of the present application;
FIG. 5 is a high resolution mass spectrum of the final product of example one of the present application;
FIG. 6 is a high performance liquid chromatogram of the final product of example one of the present application;
FIG. 7 is a high performance liquid chromatogram of the final product of example two of the present application;
FIG. 8 is a high performance liquid chromatogram of the final product of example III of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some, but not all, embodiments of the present application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The specific experimental procedures or conditions are not noted in the examples and can be performed according to the procedures or conditions of the conventional experimental procedures described in the prior art in the field. The reagents and other instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
2,4, 6-triaminotoluene (TAT) is usually obtained by hydrogenation of trinitrotoluene and is mixed with byproduct water; on the other hand, it is a dark product because of its high reactivity and easy oxidation. In order to obtain high-purity TAT products, the crude TAT products need to be purified. However, TAT belongs to a novel chemical product, and a purification process method thereof has not been reported in the related art, so a simple, efficient, low-pollution and low-cost purification method is urgently needed in the field for purifying TAT.
In view of the above, the present application provides a method for purifying 2,4, 6-triaminotoluene, and fig. 1 shows a flow chart of the method for purifying 2,4, 6-triaminotoluene, as shown in fig. 1, the method for purifying 2,4, 6-triaminotoluene specifically comprises the following steps:
s101, adding a solvent and a crude product of 2,4, 6-triaminotoluene into a first container according to a preset mass ratio, and carrying out oxygen removal operation and atmosphere replacement.
In specific implementation, a solvent and a crude product of 2,4, 6-triaminotoluene are added into a first container according to a preset mass ratio, wherein the solvent is a specific hydrated organic solvent determined based on the solubility of the 2,4, 6-triaminotoluene in the solvent. And performing oxygen removal operation on the first container and the second container, and performing inert gas atmosphere replacement on the first container and the second container.
In some embodiments, the first vessel and the second vessel are jacketed, fully enclosed reaction vessels.
In some embodiments, the predetermined mass ratio of the crude 2,4, 6-triaminotoluene to the solvent is (1:10) - (1: 150).
In some embodiments, the solvent is a mixed solution of an organic solvent and water, the organic solvent is at least one of toluene, acetone, dioxane, ethyl acetate, ethanol, methanol and N, N-dimethylformamide, and the mass ratio of the organic solvent to the water is (100:1) to (5: 1).
In some embodiments, the inert gas is nitrogen or argon.
Wherein the oxygen removal operation is specifically to introduce high-pressure inert gas into the first container and the second container, so that the pressure in the first container and the pressure in the second container are both in a preset pressure range; stirring in the first and second vessels for a first stirring period, followed by depressurizing the pressure in the first and second vessels to atmospheric pressure; and repeating the steps of introducing the high-pressure inert gas, stirring and releasing the pressure to the normal pressure for the first preset times.
The atmosphere replacement is to introduce high-pressure inert gas into the first container and the second container, so that the pressure in the first container and the pressure in the second container are both in the preset pressure range; stirring in the first and second vessels for the first stirring duration, followed by depressurizing the pressure in the first and second vessels to atmospheric pressure; and repeating the steps of introducing the high-pressure inert gas, stirring and releasing the pressure to the normal pressure for the first preset times.
In some embodiments, the predetermined pressure range is 0.4 to 1.0 MPa.
In some embodiments, the first stirring time period is 10 min.
In some embodiments, the first preset number of times is 3.
In the prior art, 2,4, 6-triaminotoluene (TAT for short) is usually obtained by hydrogenation of trinitrotoluene, and therefore is mixed with byproduct water, so that in the embodiment of the present application, the ratio of the specific hydrated organic solvent to water is controlled, so that when the specific hydrated organic solvent is used for dissolving the crude 2,4, 6-triaminotoluene, the specific hydrated organic solvent does not separate from water and simultaneously ensures that the crude 2,4, 6-triaminotoluene in the crude 2,4, 6-triaminotoluene has a relatively high solubility in the solvent. Meanwhile, because the 2,4, 6-triaminotoluene has high reaction activity and is easy to oxidize and deteriorate, a fully-closed reaction kettle is selected as the first container and the second container, oxygen in the first container and the second container is removed through oxygen removal operation, and the atmosphere replacement is carried out in the inert gas atmosphere, so that the whole purification process is carried out in the inert gas atmosphere, and the 2,4, 6-triaminotoluene obtained through purification is prevented from being oxidized and deteriorated.
S102, heating the mixture in a first container to a target dissolving temperature, slowly stirring the mixture, and passing the mixture through a decolorizing filter membrane while the mixture is hot to obtain a crude product filtrate.
In specific implementation, the temperature of the crude product mixture in the first container is raised to the target dissolution temperature; stirring the crude product mixture at a preset stirring speed within a second stirring time period;
and filtering and decolorizing the crude product mixture by using a decolorizing filter membrane while the crude product mixture is hot, and filtering out insoluble impurities in the mixture to obtain a crude product filtrate, wherein the target dissolving temperature is determined based on the solubility of the specific hydrated organic solvent for dissolving the 2,4, 6-triaminotoluene at different temperatures, and the solvent has higher solubility for the 2,4, 6-triaminotoluene at the target dissolving temperature and can fully dissolve the 2,4, 6-triaminotoluene within the second stirring time.
In some embodiments, the target dissolution temperature is 80-90 ℃.
In some embodiments, the second stirring period is 30-45 min.
In some embodiments, the preset agitation rate is 30 rpm.
And S103, transferring the crude product filtrate into a second container, cooling the second container to a target cooling temperature, and slowly stirring to separate out a crystallized product.
In specific implementation, the second container is cooled to the target cooling temperature; and stirring the crude filtrate at the preset stirring speed within a third stirring time length to separate out the crystallized product.
In some embodiments, the target cooling temperature is 0-20 ℃;
in some embodiments, the third stirring period is 45-60 min.
Based on the understanding of the physicochemical characteristics of 2,4, 6-triaminotoluene, the crystallization kinetics are skillfully utilized through temperature difference and time difference, and a crystallization product is obtained. Through the solubility difference of the selected solvent to the 2,4, 6-triaminotoluene at different temperatures, 2,4, 6-triaminotoluene crystals are separated out from a supersaturated state when the 2,4, 6-triaminotoluene is cooled to a target cooling temperature from a target dissolving temperature under the preset stirring time length.
S104, filtering to obtain a crystallized product, and drying the crystallized product to obtain a final product.
Filtering the crude filtrate by a positive pressure filter (a decolorizing filter membrane) to obtain the crystallized product; and (3) conveying the crystallized product into a vacuum drier, and drying at a drying temperature and a drying pressure to obtain the final product.
In some embodiments, the drying temperature is 40-60 ℃;
in some embodiments, the drying pressure is-0.01 MPa or less.
Wherein the final product is 2,4, 6-triaminotoluene, the yield of the final product (based on the crude product of the 2,4, 6-triaminotoluene) is more than 80 percent, and the purity of the final product is more than 99.0 percent.
In order to make the present application more clearly understood by those skilled in the art, a method for extracting high-purity trinitrotoluene from retired ammunition as described herein will now be described in detail by way of the following examples.
Example one
S101, adding a solvent and a crude product of 2,4, 6-triaminotoluene into a first container according to a preset mass ratio, and carrying out oxygen removal operation and atmosphere replacement.
In specific implementation, the first container and the second container are fully-closed reaction kettles with jackets, 1kg of toluene and 0.1kg of water are added into the first container as a solvent (the mass ratio of the toluene to the water is 10:1), and 5g of crude 2,4, 6-triaminotoluene is rapidly added into the solvent in the reaction kettles to obtain a crude product mixture. And (3) introducing high-pressure nitrogen into the reaction kettle (the first container and the second container) to ensure that the pressure in the kettle reaches 0.4MPa, continuously stirring for 10 minutes, discharging to normal pressure, and repeating for 3 times to judge that the deoxygenation operation of the reaction kettle is finished. And introducing high-pressure nitrogen into the reaction kettle again to ensure that the pressure in the reaction kettle reaches 0.4MPa, continuously stirring for 10 minutes, discharging to normal pressure, and repeating for 3 times to finish the replacement of the nitrogen atmosphere.
S102, heating the mixture in a first container to a target dissolving temperature, slowly stirring the mixture, and passing the mixture through a decolorizing filter membrane while the mixture is hot to obtain a crude product filtrate.
Heating the reaction kettle to 90 ℃, stirring for 45 minutes at the stirring speed of 30 revolutions per minute, dissolving the crude 2,4, 6-triaminotoluene, passing through a decolorizing filter membrane while the crude product is hot, filtering to remove insoluble impurities in the solution, and decolorizing to obtain crude product filtrate.
And S103, transferring the crude product filtrate into a second container, cooling the second container to a target cooling temperature, and slowly stirring to separate out a crystallized product.
And (3) cooling the temperature of the reaction kettle to 0 ℃, continuously stirring for 45 minutes at a stirring speed of 30 revolutions per minute, and fully crystallizing and separating out the supersaturated 2,4, 6-triaminotoluene solution in the stirring time due to the temperature reduction to obtain a crystallized product.
S104, filtering to obtain a crystallized product, and drying the crystallized product to obtain a final product.
Filtering the crude product filtrate by a positive pressure filter (a decolorizing filter membrane) to obtain a wet crystallized product, and absorbing most of water in the wet crystallized product by a suction filter to obtain a crystallized product; and (3) placing the crystallized product in a vacuum drier for heat preservation and drying at the drying temperature of 40 ℃ and the drying pressure of lower than-0.01 MPa to obtain a final product, wherein the yield of the final product (based on the crude product of the 2,4, 6-triaminotoluene) is 80 percent, and the purity of the final product is 99.41 percent.
Fig. 2 shows the nmr hydrogen spectrum of the final product of this example, as shown in fig. 2, 1 H-NMR(400MHz,CDCl 3 ) Delta (ppm) 5.31 (singlet, integral 2, CH), 4.20 (singlet, integral 6, NH) 2 ) 1.69 (singlet, integral 3, CH) 3 ) The benzene ring hydrogen, amino hydrogen and methyl hydrogen in the 2,4, 6-triaminotoluene are matched with the structure of the 2,4, 6-triaminotoluene.
Fig. 3 shows the nmr carbon spectrum of the final product of this example, as shown in fig. 3, 13 C-NMR (101MHz, DMSO-D6) delta (ppm) structures of 146.85,146.33,94.91,92.05,9.86 and 2,4, 6-triaminotolueneThe two are identical and respectively represent the 2-position carbon or the 6-position carbon, the 4-position carbon, the 1-position carbon, the 3-position carbon or the 5-position carbon and the methyl carbon in the 2,4, 6-triaminotoluene.
FIG. 4 shows the IR spectrum of the final product of this example, as shown in FIG. 4, IR (KBr, cm-1):3338(s),3224(m),2963(s),2920(m),2854(m),1615(s),1590(m),1513(s),1464(m),1267(s),1222(w),1172(w),1068(m),818(w),704(w), wherein the two peaks 3338.18 and 3224.82 in the IR spectrum are indicative of the presence of amino groups, consistent with the structure of 2,4, 6-triaminotoluene.
FIG. 5 shows the high resolution mass spectrum of the final product of this example, as shown in FIG. 5, HR-MS (EI): M/z 138.102630[ M-H] - (found C 7 H 12 N 3 Required 138.102574) where peak 138 characterizes the composition of the final product as C 7 H 12 N 3 Removing the protons emitted in electrospray mode of mass spectrometry, the composition of the final product being C 7 H 11 N 3 The structure of the amino acid is identical with that of 2,4, 6-triaminotoluene.
Fig. 6 shows a high performance liquid chromatogram of the final product of this example, and as shown in fig. 6, the purity of the final product of this example was 99.41%.
Example two
S101, adding a solvent and a crude product of 2,4, 6-triaminotoluene into a first container according to a preset mass ratio, and carrying out oxygen removal operation and atmosphere replacement.
In specific implementation, the first container and the second container are fully-closed reaction kettles with jackets, 1.3kg of ethyl acetate and 0.04kg of water are added into the first container as a solvent (the mass ratio of the ethyl acetate to the water is 32.5:1), and 50g of crude 2,4, 6-triaminotoluene is rapidly added into the solvent in the reaction kettle to obtain a crude product mixture. And (3) introducing high-pressure nitrogen into the reaction kettle (the first container and the second container) to ensure that the pressure in the kettle reaches 1.0MPa, continuously stirring for 10 minutes, discharging to normal pressure, and repeating for 3 times to judge that the deoxygenation operation of the reaction kettle is finished. And introducing high-pressure nitrogen into the reaction kettle again to ensure that the pressure in the reaction kettle reaches 1.0MPa, continuously stirring for 10 minutes, discharging to normal pressure, repeating for 3 times, and finishing the replacement of the nitrogen atmosphere.
S102, heating the mixture in a first container to a target dissolving temperature, slowly stirring the mixture, and passing the mixture through a decoloring filter membrane while the mixture is hot to obtain a crude product filtrate.
Heating the reaction kettle to 90 ℃, stirring at the stirring speed of 30 revolutions per minute for 30 minutes, dissolving the crude 2,4, 6-triaminotoluene, passing through a decolorizing filter membrane while the crude product is hot, filtering to remove insoluble impurities in the solution, and decolorizing to obtain crude product filtrate.
And S103, transferring the crude product filtrate into a second container, cooling the second container to a target cooling temperature, and slowly stirring to separate out a crystallized product.
And (3) cooling the temperature of the reaction kettle to 20 ℃, continuously stirring at a stirring speed of 30 revolutions per minute for 60 minutes, and fully crystallizing and separating out the supersaturated 2,4, 6-triaminotoluene solution in the stirring time due to the temperature reduction to obtain a crystallized product.
S104, filtering to obtain a crystallized product, and drying the crystallized product to obtain a final product.
Filtering the crude product filtrate by a positive pressure filter (a decolorizing filter membrane) to obtain a wet crystallized product, and absorbing most of water in the wet crystallized product by a suction filter to obtain a crystallized product; the crystalline product was dried under vacuum at 60 ℃ and a drying pressure of less than-0.01 MPa in a vacuum desiccator to give the final product in 75% yield (based on crude 2,4, 6-triaminotoluene) and 99.33% purity.
Fig. 7 shows the high performance liquid chromatogram of the final product of this example, and as shown in fig. 7, the purity of the final product of this example is 99.33%.
EXAMPLE III
S101, adding a solvent and a crude product of 2,4, 6-triaminotoluene into a first container according to a preset mass ratio, and carrying out oxygen removal operation and atmosphere replacement.
In specific implementation, the first container and the second container are fully-closed reaction kettles with jackets, 1kg of dioxane and 0.2kg of water are added into the first container as a solvent (the mass ratio of dioxane to water is 5:1), and 800g of crude 2,4, 6-triaminotoluene is rapidly added into the solvent in the reaction kettles to obtain a crude product mixture. And (3) introducing high-pressure nitrogen into the reaction kettle, enabling the pressure in the kettle to reach 0.8MPa, continuously stirring for 10 minutes, discharging to normal pressure, and repeating for 3 times to finish the deoxidization operation of the reaction kettle. And introducing high-pressure nitrogen into the reaction kettle again to ensure that the pressure in the reaction kettle reaches 0.8MPa, continuously stirring for 10 minutes, discharging to normal pressure, and repeating for 3 times to finish the replacement of the nitrogen atmosphere.
S102, heating the mixture in a first container to a target dissolving temperature, slowly stirring the mixture, and passing the mixture through a decoloring filter membrane while the mixture is hot to obtain a crude product filtrate.
Heating the reaction kettle to 90 ℃, stirring for 35 minutes at a stirring speed of 30 revolutions per minute, dissolving the crude 2,4, 6-triaminotoluene, passing through a decolorizing filter membrane while the crude 2,4, 6-triaminotoluene is hot, filtering to remove insoluble impurities in the solution, and decolorizing to obtain crude filtrate.
And S103, transferring the crude product filtrate into a second container, cooling the second container to a target cooling temperature, and slowly stirring to separate out a crystallized product.
And (3) cooling the temperature of the reaction kettle to 20 ℃, continuously stirring at a stirring speed of 30 revolutions per minute for 60 minutes, and fully crystallizing and separating out the supersaturated 2,4, 6-triaminotoluene solution in the stirring time due to the temperature reduction to obtain a crystallized product.
S104, filtering to obtain a crystallized product, and drying the crystallized product to obtain a final product.
Filtering the crude product filtrate by a positive pressure filter (a decolorizing filter membrane) to obtain a wet crystallized product, and absorbing most of water in the wet crystallized product by a suction filter to obtain a crystallized product; the crystallized product was dried under vacuum at 60 ℃ under a pressure of less than-0.01 MPa in a vacuum desiccator to give a final product having a yield of 78% and a purity of 99.13% (based on crude 2,4, 6-triaminotoluene).
Fig. 8 shows a high performance liquid chromatogram of the final product of this example, and as shown in fig. 8, the purity of the final product of this example was 99.13%.
Example four
S101, adding a solvent and a crude product of 2,4, 6-triaminotoluene into a first container according to a preset mass ratio, and carrying out oxygen removal operation and atmosphere replacement.
In specific implementation, the first container and the second container are fully-closed reaction kettles with clamping sleeves, 1kg of acetonitrile and 0.15kg of water are added into the first container as a solvent (the mass ratio of the acetonitrile to the water is 100:15), and 60g of crude 2,4, 6-triaminotoluene is rapidly added into the solvent in the reaction kettles to obtain a crude mixture. And (3) introducing high-pressure nitrogen into the reaction kettle, keeping the pressure in the reaction kettle to be 0.8MPa, continuously stirring for 10 minutes, discharging to normal pressure, and repeating for 3 times to finish the deoxidization operation of the reaction kettle. And introducing high-pressure nitrogen into the reaction kettle again to ensure that the pressure in the reaction kettle reaches 0.8MPa, continuously stirring for 10 minutes, discharging to normal pressure, and repeating for 3 times to finish the replacement of the nitrogen atmosphere.
S102, heating the mixture in a first container to a target dissolving temperature, slowly stirring the mixture, and passing the mixture through a decoloring filter membrane while the mixture is hot to obtain a crude product filtrate.
Heating the reaction kettle to 90 ℃, stirring at the stirring speed of 30 r/min for 35 minutes, dissolving the crude 2,4, 6-triaminotoluene, filtering with a decolorizing filter membrane while the crude product is hot, removing insoluble impurities in the solution by filtration, and decolorizing to obtain crude filtrate.
And S103, transferring the crude product filtrate into a second container, cooling the second container to a target cooling temperature, and slowly stirring to separate out a crystallized product.
And (3) cooling the temperature of the reaction kettle to 20 ℃, continuously stirring at a stirring speed of 30 revolutions per minute for 60 minutes, and fully crystallizing and separating out the supersaturated 2,4, 6-triaminotoluene solution in the stirring time due to the temperature reduction to obtain a crystallized product.
S104, filtering to obtain a crystallized product, and drying the crystallized product to obtain a final product.
Filtering the crude product filtrate by a positive pressure filter (a decolorizing filter membrane) to obtain a wet crystallized product, and absorbing most of water in the wet crystallized product by a suction filter to obtain a crystallized product; the crystallized product was dried under vacuum at 60 ℃ under a pressure of less than-0.01 MPa in a vacuum drier under conditions of temperature and pressure to give a final product having a yield of 85% and a purity of 99.13% (based on crude 2,4, 6-triaminotoluene).
EXAMPLE five
S101, adding a solvent and a crude product of 2,4, 6-triaminotoluene into a first container according to a preset mass ratio, and carrying out oxygen removal operation and atmosphere replacement.
In specific implementation, the first container and the second container are fully-closed reaction kettles with jackets, 1kg of ethanol and 0.05kg of water are added into the first container as a solvent (the mass ratio of the ethanol to the water is 20:1), and 20g of crude 2,4, 6-triaminotoluene is rapidly added into the solvent in the reaction kettles to obtain a crude product mixture. And (3) introducing high-pressure nitrogen into the reaction kettle, keeping the pressure in the reaction kettle to be 0.8MPa, continuously stirring for 10 minutes, discharging to normal pressure, and repeating for 3 times to finish the deoxidization operation of the reaction kettle. And introducing high-pressure nitrogen into the reaction kettle again to ensure that the pressure in the reaction kettle reaches 0.8MPa, continuously stirring for 10 minutes, discharging to normal pressure, and repeating for 3 times to finish the replacement of the nitrogen atmosphere.
S102, heating the mixture in a first container to a target dissolving temperature, slowly stirring the mixture, and passing the mixture through a decolorizing filter membrane while the mixture is hot to obtain a crude product filtrate.
Heating the reaction kettle to 90 ℃, stirring at the stirring speed of 30 r/min for 35 minutes, dissolving the crude 2,4, 6-triaminotoluene, filtering with a decolorizing filter membrane while the crude product is hot, removing insoluble impurities in the solution by filtration, and decolorizing to obtain crude filtrate.
And S103, transferring the crude product filtrate into a second container, cooling the second container to a target cooling temperature, and slowly stirring to separate out a crystallized product.
And (3) cooling the temperature of the reaction kettle to 20 ℃, continuously stirring at a stirring speed of 30 revolutions per minute for 60 minutes, and fully crystallizing and separating out the supersaturated 2,4, 6-triaminotoluene solution in the stirring time due to the temperature reduction to obtain a crystallized product.
S104, filtering to obtain a crystallized product, and drying the crystallized product to obtain a final product.
Filtering the crude product filtrate by a positive pressure filter (a decolorizing filter membrane) to obtain a wet crystallized product, and absorbing most of water in the wet crystallized product by a suction filter to obtain a crystallized product; and (3) placing the crystallized product in a vacuum drier for heat preservation and drying at the drying temperature of 60 ℃ and the drying pressure of lower than-0.01 MPa to obtain a final product, wherein the yield of the final product (based on the crude product of the 2,4, 6-triaminotoluene) is 82 percent, and the purity of the final product is 99.0 percent.
According to the purification method of 2,4, 6-triaminotoluene provided by the embodiment of the application, in an oxygen-free atmosphere, a specific hydrated organic solvent is added into a first container to dissolve a crude product of 2,4, 6-triaminotoluene at a target dissolution temperature, then the crude product is transferred into a second container, the second container is cooled to a target cooling temperature, a crystallized product is separated out, and then the crystallized product is subjected to decoloration filter membrane and drying to obtain a final product, so that the purification method of 2,4, 6-triaminotoluene has the following effects:
(1) according to the method, in the purification process, the nitrogen atmosphere is used for protection in the whole process, so that the 2,4, 6-triaminotoluene is prevented from deteriorating due to oxidation in the purification process.
(2) The target dissolving temperature and the target cooling temperature are determined based on the solubility of the specific hydrated organic solvent for dissolving the 2,4, 6-triaminotoluene at different temperatures, and the yield and the purity of the 2,4, 6-triaminotoluene are improved.
(3) The method provided by the application is simple to operate, low in solvent price, green, safe, high in purification efficiency and beneficial to industrial popularization.
It should be noted that, in the present specification, the embodiments are all described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments may be referred to each other.
The technical solutions provided by the present application are described in detail above, and the principles and embodiments of the present application are described herein by using specific examples, which are only used to help understanding the present application, and the content of the present description should not be construed as limiting the present application. While various modifications of the illustrative embodiments and applications will be apparent to those skilled in the art based upon this disclosure, it is not necessary or necessary to exhaustively enumerate all embodiments, and all obvious variations and modifications can be resorted to, falling within the scope of the disclosure.
Claims (9)
1. A method for purifying 2,4, 6-triaminotoluene is characterized by comprising the following steps:
adding a solvent and a crude product of 2,4, 6-triaminotoluene in a preset mass ratio into a first container to obtain a crude product mixture; conducting an oxygen removal operation on the first container and the second container, and conducting inert gas atmosphere replacement on the first container and the second container;
heating the temperature of the crude product mixture in the first container to a target dissolution temperature, and slowly stirring; passing the crude product mixture through a decolorizing filter membrane to obtain a crude product filtrate, wherein the decolorizing filter membrane is used for filtering and decolorizing the crude product mixture; transferring the crude product filtrate into the second container, cooling to a target cooling temperature, and slowly stirring to separate out a crystallized product;
filtering to obtain the crystallized product, and drying the crystallized product to obtain a final product, wherein the final product is 2,4, 6-triaminotoluene, the yield of the final product is more than 80%, and the purity of the final product is more than 99.0%.
2. The method of claim 1, wherein the method comprises at least one of the following features:
(1) the first container and the second container are totally-enclosed reaction kettles with jackets;
(2) the preset mass ratio of the crude 2,4, 6-triaminotoluene to the solvent is (1:10) - (1: 150);
(3) the solvent is a mixed solution formed by an organic solvent and water, the organic solvent is at least one of toluene, acetone, dioxane, ethyl acetate, ethanol, acetonitrile, methanol and N, N-dimethylformamide, and the mass ratio of the organic solvent to the water is (100:1) - (5: 1);
(4) the inert gas is nitrogen or argon.
3. The method for purifying 2,4, 6-triaminotoluene as claimed in claim 1, wherein the first container and the second container are subjected to oxygen removal operation, and the steps are as follows:
introducing high-pressure inert gas into the first container and the second container, so that the pressure in the first container and the pressure in the second container are both in a preset pressure range;
stirring in the first and second vessels for a first stirring period followed by depressurizing the pressure in the first and second vessels to atmospheric pressure;
and repeating the steps of introducing the high-pressure inert gas, stirring and releasing the pressure to the normal pressure for a first preset time.
4. The method for purifying 2,4, 6-triaminotoluene as claimed in claim 1, wherein the first container and the second container are replaced by inert gas atmosphere, and the method comprises the following steps:
introducing high-pressure inert gas into the first container and the second container to enable the pressure in the first container and the pressure in the second container to be within the preset pressure range;
stirring in the first and second vessels for the first stirring duration, followed by depressurizing the pressure in the first and second vessels to atmospheric pressure;
and repeating the steps of introducing the high-pressure inert gas, stirring and releasing the pressure to the normal pressure for the first preset times.
5. The method for purifying 2,4, 6-triaminotoluene as claimed in claim 1, wherein the temperature of the crude mixture in the first container is raised to the target dissolution temperature, and slowly stirred; passing the crude product mixture through a decolorizing filter membrane to obtain a crude product filtrate, wherein the decolorizing filter membrane is used for filtering and decolorizing the crude product mixture; transferring the crude product filtrate into the second container, cooling to a target cooling temperature, and slowly stirring to separate out a crystallized product, wherein the specific steps are as follows:
raising the temperature of the crude mixture in the first vessel to the target dissolution temperature;
stirring the crude product mixture at a preset stirring speed within a second stirring time period;
passing the crude product mixture through a decolorizing filter membrane while the crude product mixture is hot, and rapidly filtering and decolorizing to obtain a crude product filtrate;
transferring the crude product filtrate into the second container, and cooling the second container to the target cooling temperature;
and stirring the crude filtrate at the preset stirring speed within a third stirring time length to separate out the crystallized product.
6. The method of claim 5, wherein the crystalline product is obtained by filtration and dried to obtain a final product comprising:
passing the crude product filtrate through a decolorizing filter membrane by a positive pressure filter to obtain the crystallized product;
and (3) feeding the crystallized product into a vacuum drier, and drying at a drying temperature and a drying pressure to obtain the final product.
7. A method according to any one of claims 3 to 4, wherein the method comprises at least one of the following features:
(1) the preset pressure range is 0.4-1.0 MPa;
(2) the first stirring time is 10 min;
(3) the first preset number of times is 3.
8. The method of claim 5, wherein the method comprises at least one of the following features:
(1) the target dissolution temperature is 80-90 ℃;
(2) the second stirring time is 30-45 min;
(3) the preset stirring speed is 30 revolutions per minute;
(4) the target cooling temperature is 0-20 ℃;
(5) the third stirring time is 45-60 min.
9. The method of claim 6, wherein the method comprises at least one of the following features:
(1) the drying temperature is 40-60 ℃;
(2) the drying pressure is below-0.01 MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB589716A (en) * | 1945-03-28 | 1947-06-27 | Andrew Mclean | Improvements in or relating to the production of triamino-monocyclic aromatic hydrocarbons |
| US2461498A (en) * | 1943-12-08 | 1949-02-08 | Edwal Lab Inc | Preparation of symmetrical triaminobenzene compounds |
| US2684383A (en) * | 1951-03-28 | 1954-07-20 | Ringwood Chemical Corp | Preparation of symmetrical triaminobenzene compounds |
-
2022
- 2022-07-22 CN CN202210861417.1A patent/CN115057785A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2461498A (en) * | 1943-12-08 | 1949-02-08 | Edwal Lab Inc | Preparation of symmetrical triaminobenzene compounds |
| GB589716A (en) * | 1945-03-28 | 1947-06-27 | Andrew Mclean | Improvements in or relating to the production of triamino-monocyclic aromatic hydrocarbons |
| US2684383A (en) * | 1951-03-28 | 1954-07-20 | Ringwood Chemical Corp | Preparation of symmetrical triaminobenzene compounds |
Non-Patent Citations (1)
| Title |
|---|
| 陆嫣 刘伟 主编: "《有机化学实验》", vol. 1, 电子科技大学出版社, pages: 38 - 39 * |
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