CN108892620B - Preparation method of 4, 4' -triaminotriphenylmethane - Google Patents
Preparation method of 4, 4' -triaminotriphenylmethane Download PDFInfo
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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Abstract
The invention provides a preparation method of 4, 4 '-triaminotriphenylmethane, which comprises seven steps of preparation of sodium polysulfide solution, preparation of paraaminobenzaldehyde, preparation of crude product, primary salting-out, primary refining, secondary salting-out and secondary refining, and the 4, 4' -triaminotriphenylmethane with purity of more than 99% and iron ion content of below 20ppm is obtained. Compared with the existing route, the method has the advantages of simple process route and greatly reduced three wastes.
Description
Technical Field
The invention relates to the technical field of adhesive preparation, and particularly relates to a preparation method of high-purity 4, 4' -triaminotriphenylmethane.
Background
4, 4' -triaminotriphenylmethane, also known as a paracanthrin leuco group, is one of triaminotriphenylmethane dyes, and is mainly used as a main raw material for manufacturing rubber and metal adhesives, namely, Licona rubber.
There are currently two major routes to 4, 4', 4 "-triaminotriphenylmethane:
one such process is reported in U2258724 from the former Soviet Union patent by reducing parafuchsin with zinc powder in the presence of hydrochloric acid or acetic acid to give 4, 4' -triaminotriphenylmethane. The method firstly obtains dye parafuchsin, and then reduces the parafuchsin to obtain a target product, so that the operation steps are complicated, the reaction is not easy to control, the yield of the dye parafuchsin is not high, and the price of a reducing agent is high (zinc and hydrochloric acid or sodium hydrosulfite are carried out in an alcohol solution). From a technical-economic point of view, this process is of no industrial value.
The other method is disclosed by Chinese patent CN106977408, which provides an industrial preparation route of 4, 4' -triaminotriphenylmethane, wherein p-nitrotoluene is used as a starting material, sodium polysulfide is used for oxidation reduction to prepare p-aminobenzaldehyde, and the p-aminobenzaldehyde is condensed with aniline under the catalysis of hydrochloric acid to obtain a crude product, wherein the content of the crude product after refining is about 93 percent, and the melting point is 192 ℃. The route is convenient for industrialized operation, but the amount of three wastes is large, the content of the prepared product is low, and the requirement of customers cannot be met.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of 4, 4' -triaminotriphenylmethane. The technical scheme of the invention is as follows:
a preparation method of 4, 4' -triaminotriphenylmethane comprises the following steps:
1) preparation of sodium polysulfide solution: heating the sodium hydroxide solution to 90-100 ℃, adding sulfur in batches, and then stirring for 3-5 hours while keeping the temperature; the reaction equation is shown in formula [1 ]:
6NaOH+5S→Na2S+Na2S2+Na2S2O3+3H2O [1]；
2) preparation of p-aminobenzaldehyde: heating a mixed solution of p-nitrotoluene and ethanol to reflux, dropwise adding a sodium polysulfide solution in batches, controlling the dropwise adding time to be 3-4 hours, after the dropwise adding is finished, preserving heat for 3-5 hours under reflux, concentrating to be dry, and respectively collecting a p-aminobenzaldehyde concentrate and ethanol; the reaction equation is shown in formula [2 ]:
3) preparation of a crude product: adding aniline into the p-aminobenzaldehyde concentrate, adding hydrochloric acid and a phase transfer catalyst when the p-aminobenzaldehyde concentrate is completely dissolved in aniline, heating to 100-105 ℃, reacting for 8-12 hours, neutralizing to be alkaline after the reaction is finished, concentrating in vacuum, and respectively collecting a 4, 4' -triaminotriphenylmethane crude product and aniline; the reaction equation is shown in formula [3 ]:
4) primary salting out: adding hydrochloric acid and water into the crude 4, 4 '-triaminotriphenylmethane, heating to 60-70 ℃, adding sodium chloride in batches after all the sodium chloride is dissolved, keeping the temperature at 60-70 ℃ and stirring for 2 hours after the sodium chloride is added, fully salting out the sodium chloride, cooling to 30-35 ℃, and filtering to obtain a crude hydrochloride of 4, 4' -triaminotriphenylmethane;
5) primary refining: uniformly mixing a hydrochloride crude product of 4, 4' -triaminotriphenylmethane, water and activated carbon, heating to 60-80 ℃, keeping the temperature and stirring for 1-3 hours, thermally filtering to remove the activated carbon and insoluble substances, neutralizing filtrate with ammonia water to be alkaline, heating to 80-100 ℃, stirring for 1-3 hours to fully convert the crystals, then cooling to 20-30 ℃, and filtering to obtain a primary refined product;
6) secondary salting out: uniformly mixing the primary refined product and hydrochloric acid, heating to 60-80 ℃, adding sodium chloride in batches when the crude product is completely dissolved, keeping the temperature at 60-80 ℃ and stirring for 2 hours after the addition is finished, fully salting out, then cooling to 15-25 ℃, and filtering to obtain a pure hydrochloride product of 4, 4' -triaminotriphenylmethane;
7) secondary refining: uniformly mixing a pure hydrochloride product of 4, 4' -triaminotriphenylmethane, deionized water, activated carbon and a metal complexing agent, heating to 60-80 ℃, keeping the temperature, stirring for 1-3 hours, filtering, neutralizing filtrate with ammonia water to be alkaline, heating to 80-100 ℃, stirring for 1-3 hours, fully crystallizing, cooling to room temperature, and filtering to obtain a secondary refined product.
Further, in the step 1), the concentration of the sodium hydroxide solution is 30-35%, and the molar ratio of the sulfur to the sodium hydroxide is (0.5-1) to 1.
Furthermore, in the step 2), the dosage of the p-nitrotoluene is calculated by the molar ratio of the p-nitrotoluene to the sulfur of 1: 1-2, and the dosage of the ethanol is 2-5 times of the dosage of the p-nitrotoluene.
Furthermore, in the step 3), the molar ratio of the aniline to the p-nitrotoluene is (6-12) to 1, the molar ratio of the hydrochloric acid to the p-nitrotoluene is (3-4) to 1, and the dosage of the phase transfer catalyst is 1-10% of the dosage of the p-nitrotoluene.
Further, the phase transfer catalyst includes quaternary ammonium salts or polyethers.
Furthermore, the molar ratio of the hydrochloric acid to the p-nitrotoluene in the step 4) is (2-3) to 1, the amount of water is 3-5 times of the amount of the p-nitrotoluene, and the amount of sodium chloride is 1-1.5 times of the amount of the p-nitrotoluene.
Furthermore, the water dosage in the step 5) is 8-12 times of the weight input amount of the p-nitrotoluene, and the active carbon dosage is 5-20% of the weight input amount of the p-nitrotoluene.
Further, in the step 6), the concentration of the hydrochloric acid is 11%, the molar ratio of the hydrochloric acid to the primary refined product is (4-6) to 1, and the dosage of the sodium chloride is 1-1.5 times of the dosage of the primary refined product by weight.
Further, in the step 7), the using amount of the deionized water is 8-12 times of the feeding amount of the primary refined product, the using amount of the activated carbon is 5-20% of the feeding amount of the primary refined product, and the using amount of the metal complexing agent is 0.5-5% of the feeding amount of the primary refined product.
Further, the deionized water is distilled water or reverse osmosis water.
Further, the metal complexing agent comprises ethylenediaminetetraacetic acid or disodium ethylenediaminetetraacetate.
The content of the secondary refined product is more than 99 percent through liquid spectrum detection, the content of metal ions is below 20ppm, and particularly the content of iron ions can be well controlled below 20 ppm.
The invention has the advantages that: compared with the existing route, the 4, 4 ' -triaminotriphenylmethane preparation route provided by the invention has the advantages of simple process route and greatly reduced three wastes, and the 4, 4 ' -triaminotriphenylmethane fluorene prepared by the invention has good chromaticity, the purity is more than 99%, the iron ion content can be controlled below 20ppm, the requirement of customers can be met, and the 4, 4 ' -triaminotriphenylmethane fluorene is mainly used for export abroad.
Detailed Description
In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
Adding 44g of sodium hydroxide and 90g of water into a 250ml flask, heating the solution to 90-100 ℃, stirring for 10min at the temperature, and then batching 26g of sulfur powder for 30 min. After the addition is finished, stirring for 3 hours at 90-100 ℃ to obtain dark yellow transparent liquid for later use.
A1000 ml flask was charged with 70g of p-nitrotoluene and 246g of ethanol and heated to a strong reflux. Under the strong reflux state (the temperature is about 84 ℃), the prepared sodium polysulfide solution is slowly dripped, and the charging time is 3 hours. After the addition of the sodium polysulfide solution was completed, the mixture was stirred under strong reflux for 3 hours. And after the heat preservation reaction is finished, distilling to remove the ethanol, and stopping heating when the distillation temperature reaches 105-110 ℃, wherein the material is a very viscous paste.
558g of aniline was added to the 1000ml flask, and stirring was continued until the aniline solution in which p-aminobenzaldehyde was completely dissolved, 189g of 33% hydrochloric acid and 7g of tetrabutylammonium bromide were added, the feed solution was heated to 100 to 105 ℃, and stirred at 100 to 105 ℃ for 12 hours, and 76g of solid sodium hydroxide was added, and the feed solution was made alkaline, and then excess aniline was removed by high vacuum distillation using an oil pump.
After the distillation is finished, 161g of 33% hydrochloric acid and 244g of water are added into the flask, the flask is heated to 60 ℃ to completely dissolve the hydrochloric acid, 86g of refined salt is added in batches at 60 ℃ for 5-10 minutes, the mixture is kept at the temperature of 60 ℃ and stirred for 2 hours, after the addition, the temperature is reduced to 30-35 ℃, yellow filter cakes are obtained by filtration, and the filter cakes are washed by saturated salt water.
Adding the yellow filter cake and 590g of water in the previous step into a 1000ml flask, heating the mixture to 60 ℃, adding 7g of activated carbon at 60 ℃, stirring the mixture for 2 hours at 60 ℃, thermally filtering the mixture to remove the activated carbon and insoluble substances to obtain dark red transparent liquid, adding ammonia water to neutralize the pH value of the feed liquid to 9-11, heating the solution to 85 ℃, and stirring the solution for 1 hour at 85 ℃. Cooling to 20-30 ℃ with water, filtering, washing with water to neutrality, and drying to obtain 70.1g of the product, wherein the yield is 48.5%, and the content is 96.0%.
70.1g of crude product and 402g of 11% diluted hydrochloric acid are added into a 1000ml four-neck flask, when the temperature is heated to 60 ℃, the crude product is completely dissolved, 71g of refined salt is added at the time, the mixture is fully stirred for 2 hours, the mixture is cooled to 20-25 ℃ by water, the mixture is filtered to obtain off-white solid, and a filter cake is washed by saturated salt water.
Adding the obtained off-white solid into a four-neck flask, adding 720g of deionized water and 0.7g of ethylenediamine tetraacetic acid, heating the materials to 60 ℃, adding 7g of activated carbon at 60 ℃, stirring for 2 hours at 60 ℃, filtering to remove the activated carbon to obtain dark red transparent liquid, adding ammonia water to neutralize the liquid to show alkalinity, heating to 85 ℃, and stirring for 1 hour at 85 ℃. The mixture was cooled to room temperature with cold water, filtered and washed with water to neutrality, and dried to yield 65g of product. The content was 99.3%, the total yield was 45%, and the iron ion content was 6.3 ppm.
Example 2
Adding 44g of sodium hydroxide and 82g of water into a 250ml flask, heating the solution to 90-100 ℃, stirring for 10min at the temperature, and then batching 20g of sulfur powder for 30 min. After the addition is finished, stirring for 4 hours at 90-100 ℃ to obtain dark yellow transparent liquid for later use.
A1000 ml flask was charged with 70g of p-nitrotoluene and 175g of ethanol and heated to a strong reflux. Under the strong reflux state (the temperature is about 84 ℃), the prepared sodium polysulfide solution is slowly dripped, and the charging time is 4 hours. After the addition of the sodium polysulfide solution was complete, the mixture was stirred under strong reflux for 4 hours. And after the heat preservation reaction is finished, distilling to remove the ethanol, and stopping heating when the distillation temperature reaches 105-110 ℃, wherein the material is a very viscous paste.
Next, 418g of aniline was added to the above 1000ml flask, and stirring was continued until the aniline solution in which p-aminobenzaldehyde was completely dissolved, and then 166g of 33% hydrochloric acid and 3.5g of methyl ammonium bromide were added, and the solution was heated to 100 to 105 ℃, stirred at 100 to 105 ℃ for 10 hours, and then 66g of sodium hydroxide as a solid was added, and the solution was made alkaline, and then excess aniline was removed by high vacuum distillation using an oil pump.
After the distillation is finished, 110g of 33% hydrochloric acid and 280g of water are added into a flask, the flask is heated to 65 ℃ to be completely dissolved, 70g of refined salt is added in batches at 65 ℃ for 5-10 minutes, the mixture is kept at the temperature of 65 ℃ and stirred for 2 hours, after the addition, the temperature is reduced to 30-35 ℃, yellow filter cakes are obtained by filtration, and the filter cakes are washed by saturated salt water.
Adding the yellow filter cake and 700g of water in the previous step into a 1000ml flask, heating the mixture to 70 ℃, adding 10.5g of activated carbon at 70 ℃, stirring the mixture for 1 hour at 70 ℃, thermally filtering the mixture to remove the activated carbon and insoluble substances to obtain dark red transparent liquid, adding ammonia water to neutralize the pH value of the feed liquid to 9-11, heating the solution to 90 ℃, and stirring the solution for 2 hours at 90 ℃. The mixture is cooled to room temperature by cold water, filtered, washed to be neutral by water and dried to obtain 58g of product, the yield is 40.1 percent, and the content is 97.5 percent.
Adding 58g of crude product and 270g of 11% diluted hydrochloric acid into a 1000ml four-neck flask, heating to 70 ℃, completely dissolving the crude product, adding 70g of refined salt, fully stirring for 2 hours, cooling to 15-20 ℃ with water, filtering to obtain an off-white solid, and washing a filter cake with saturated salt water.
Adding the obtained off-white solid into a four-neck flask, adding 470g of deionized water and 1.7g of ethylenediamine tetraacetic acid, heating the materials to 70 ℃, adding 9g of activated carbon at 70 ℃, stirring for 2 hours at 70 ℃, filtering to remove the activated carbon to obtain dark red transparent liquid, adding ammonia water to neutralize the liquid to show alkalinity, heating to 90 ℃, and stirring for 2 hours at 90 ℃. The mixture was cooled to room temperature with cold water, filtered and washed with water to neutrality, and dried to obtain 50g of product. The content is 99.4%, the total yield is 34.6%, and the iron ion content is 10.2 ppm.
Example 3
44g of sodium hydroxide and 102g of water are added into a 250ml flask, the solution is heated to 90-100 ℃, 32g of sulfur is added in batches after stirring for 10min at the temperature, and the adding time is 30 min. After the addition is finished, stirring for 5 hours at 90-100 ℃ to obtain dark yellow transparent liquid for later use.
A1000 ml flask was charged with 70g of p-nitrotoluene and 350g of ethanol and heated to a strong reflux. Under the strong reflux state (the temperature is about 84 ℃), the prepared sodium polysulfide solution is slowly dripped, and the charging time is 3 hours. After the addition of the sodium polysulfide solution was completed, the mixture was stirred under strong reflux for 5 hours. And after the heat preservation reaction is finished, distilling to remove the ethanol, and stopping heating when the distillation temperature reaches 105-110 ℃, wherein the material is a very viscous paste.
279g of aniline was added to the 1000ml flask, and stirring was continued until the aniline solution in which p-aminobenzaldehyde was completely dissolved, 221g of 33% hydrochloric acid and 7g of polyethylene glycol-800 were added, the solution was heated to 100 to 105 ℃, stirred at 100 to 105 ℃ for 8 hours, 88g of solid sodium hydroxide was added, the solution was significantly alkaline, and excess aniline was removed by high vacuum distillation using an oil pump.
After distillation, 166g of hydrochloric acid and 350g of water are added into a flask, the flask is heated to 70 ℃ to be completely dissolved, 105g of refined salt is added in batches at 70 ℃ for 5-10 minutes, the mixture is stirred at 70 ℃ for 2 hours under heat preservation, after the addition, the temperature is reduced to 30-35 ℃, yellow filter cake is obtained through filtration, and the filter cake is washed by saturated salt water.
Adding the yellow filter cake and 800g of water in the previous step into a 1000ml flask, heating the mixture to 80 ℃, adding 14g of activated carbon at 80 ℃, stirring the mixture for 3 hours at 80 ℃, thermally filtering the mixture to remove the activated carbon and insoluble substances to obtain dark red transparent liquid, adding ammonia water to neutralize the liquid to obtain a pH value of 9-11, heating the liquid to 95 ℃, and stirring the liquid for 3 hours at 95 ℃. The mixture is cooled to room temperature by cold water, filtered, washed to be neutral by water and dried to obtain 65g of product, the yield is 45 percent, and the content is 97.2 percent.
Adding 65g of crude product and 448g of 11% diluted hydrochloric acid into a 1000ml four-neck flask, heating to 80 ℃, completely dissolving the crude product, adding 97g of refined salt, fully stirring for 2 hours, cooling to 15-20 ℃ with water, filtering to obtain an off-white solid, and washing a filter cake with saturated salt water.
Adding the obtained off-white solid into a four-neck flask, adding 780g of deionized water and 3.2g of disodium ethylenediamine tetraacetic acid, heating the materials to 80 ℃, adding 13g of activated carbon at 80 ℃, stirring the materials for 2 hours at 80 ℃, thermally filtering the materials to remove the activated carbon to obtain dark red transparent liquid, adding ammonia water to neutralize the liquid to show alkalinity, heating the liquid to 95 ℃, and stirring the liquid for 2 hours at 95 ℃. The solution was cooled to room temperature with cold water, filtered and washed with water to neutrality, and dried to obtain 55g of product, 99.5% in content, 38.1% in total yield, and 5.4ppm in iron ion content.
In conclusion, the 4, 4' -triaminotriphenylmethane fluorene prepared by the specific embodiment of the invention has good chroma, the purity is more than 99 percent, and the iron ion content can be controlled below 20 ppm.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (8)
1. A preparation method of 4, 4' -triaminotriphenylmethane is characterized by comprising the following steps:
1) preparation of sodium polysulfide solution: heating the sodium hydroxide solution to 90-100 ℃, adding sulfur in batches, and then stirring for 3-5 hours while keeping the temperature;
2) preparation of p-aminobenzaldehyde: heating a mixed solution of p-nitrotoluene and ethanol to reflux, dropwise adding a sodium polysulfide solution in batches, controlling the dropwise adding time to be 3-4 hours, after the dropwise adding is finished, preserving heat for 3-5 hours under reflux, concentrating to be dry, and respectively collecting a p-aminobenzaldehyde concentrate and ethanol;
3) preparation of a crude product: adding aniline into the p-aminobenzaldehyde concentrate, adding hydrochloric acid and a phase transfer catalyst when the p-aminobenzaldehyde concentrate is completely dissolved in aniline, wherein the molar ratio of aniline to p-nitrotoluene is (6-12) to 1, the molar ratio of hydrochloric acid to p-nitrotoluene is (3-4) to 1, and the dosage of the phase transfer catalyst is 1-10% of the dosage of p-nitrotoluene; heating to 100-105 ℃, reacting for 8-12 hours, neutralizing to be alkaline after the reaction is finished, concentrating in vacuum, and respectively collecting a 4, 4' -triaminotriphenylmethane crude product and aniline; the phase transfer catalyst comprises quaternary ammonium salt or polyether;
4) primary salting out: adding hydrochloric acid and water into the crude 4, 4 '-triaminotriphenylmethane, heating to 60-70 ℃, adding sodium chloride in batches after all the sodium chloride is dissolved, keeping the temperature at 60-70 ℃ and stirring for 2 hours after the sodium chloride is added, fully salting out the sodium chloride, cooling to 30-35 ℃, and filtering to obtain a crude hydrochloride of 4, 4' -triaminotriphenylmethane;
5) primary refining: uniformly mixing a hydrochloride crude product of 4, 4' -triaminotriphenylmethane, water and activated carbon, heating to 60-80 ℃, keeping the temperature and stirring for 1-3 hours, thermally filtering to remove the activated carbon and insoluble substances, neutralizing filtrate with ammonia water to be alkaline, heating to 80-100 ℃, stirring for 1-3 hours to fully convert the crystals, then cooling to 20-30 ℃, and filtering to obtain a primary refined product;
6) secondary salting out: uniformly mixing the primary refined product and hydrochloric acid, heating to 60-80 ℃, adding sodium chloride in batches when the crude product is completely dissolved, keeping the temperature at 60-80 ℃ and stirring for 2 hours after the addition is finished, fully salting out, then cooling to 15-25 ℃, and filtering to obtain a pure hydrochloride product of 4, 4' -triaminotriphenylmethane;
7) secondary refining: uniformly mixing a pure hydrochloride product of 4, 4' -triaminotriphenylmethane, deionized water, activated carbon and a metal complexing agent, heating to 60-80 ℃, keeping the temperature, stirring for 1-3 hours, filtering, neutralizing filtrate with ammonia water to be alkaline, heating to 80-100 ℃, stirring for 1-3 hours, fully crystallizing, cooling to room temperature, and filtering to obtain a secondary refined product.
2. The method for preparing 4, 4' -triaminotriphenylmethane according to claim 1, wherein the concentration of the sodium hydroxide solution in the step 1) is 30-35%, and the molar ratio of the sulfur to the sodium hydroxide is (0.5-1) to 1.
3. The method for preparing 4, 4' -triaminotriphenylmethane as claimed in claim 1, wherein the amount of p-nitrotoluene used in step 2) is 2-5 times the amount of p-nitrotoluene used in the molar ratio of p-nitrotoluene to sulfur is 1: 1-2.
4. The method for preparing 4, 4' -triaminotriphenylmethane as claimed in claim 1, wherein the molar ratio of hydrochloric acid to p-nitrotoluene in step 4) is (2-3) to 1, the amount of water is 3-5 times of the amount of p-nitrotoluene, and the amount of sodium chloride is 1-1.5 times of the amount of p-nitrotoluene.
5. The method for preparing 4, 4' -triaminotriphenylmethane as claimed in claim 1, wherein the amount of water used in step 5) is 8-12 times of the amount of p-nitrotoluene charged by weight, and the amount of activated carbon is 5-20% of the amount of p-nitrotoluene charged by weight.
6. The method for preparing 4, 4' -triaminotriphenylmethane according to claim 1, wherein the hydrochloric acid concentration in the step 6) is 11%, the molar ratio of the hydrochloric acid to the primary refined product is (4-6): 1, and the sodium chloride dosage is 1-1.5 times of the dosage of the primary refined product.
7. The method for preparing 4, 4' -triaminotriphenylmethane as claimed in claim 1, wherein the amount of deionized water in step 7) is 8-12 times of the amount of the primary refined product, the amount of the activated carbon is 5-20% of the amount of the primary refined product, and the amount of the metal complexing agent is 0.5-5% of the amount of the primary refined product.
8. The method of claim 1 or 7, wherein the metal complexing agent comprises ethylenediaminetetraacetic acid or disodium salt of ethylenediaminetetraacetic acid.
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