CN108586206B - Method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) by one-pot method - Google Patents
Method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) by one-pot method Download PDFInfo
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- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
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- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
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Abstract
The invention relates to a method for preparing 4, 4 '-butylidene bis (6-tert-butyl-m-cresol) by a one-pot method, which takes 6-tert-butyl-m-cresol and n-butyl aldehyde as raw materials, methanol as a solvent and hydrochloric acid as a catalyst to prepare 4, 4' -butylidene bis (6-tert-butyl-m-cresol), after condensation reaction is finished, an aromatic hydrocarbon solvent and a mixed solvent consisting of the methanol solvent and the aromatic hydrocarbon solvent are added to ensure that a reaction mixture is completely dissolved and layered at the reflux temperature of the methanol, an acid water layer is separated out, an organic layer is heated to evaporate the rest methanol, and a crystal product is obtained by post-treatment. The invention solves the problem that a large amount of acid water needs to be neutralized in the production process, avoids using a large amount of alkali liquor, and simultaneously avoids the pollution problem of neutralized products caused by using the alkali liquor. The acid water separation process is beneficial to improving the melting point and the light transmittance index of the product, and the separated acid water can be partially or completely reused, so that the pollution control cost is reduced.
Description
Technical Field
The invention relates to a method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) by a one-pot method, belonging to the technical field of preparation of antioxidants for polyolefin and rubber.
Background
4, 4' -butylidene bis (6-tert-butyl-m-cresol) is used as antioxidant for polyolefin and rubber, and is prepared by reacting 6-tert-butyl-m-cresol with n-butyl aldehyde under the condition of acid catalyst. The acids used are mineral or organic acids, such as hydrochloric acid, the amount of acid used being particularly large.
In US 2970151, hydrochloric acid is used as a catalyst to form 4, 4' -butylidenebis (6-tert-butyl-m-cresol), the volatiles are distilled off after the reaction is completed in order to remove the acid, then benzene is added, and the excess acid is washed off with water. In example 2, heptane was added after the reaction was complete, and the product was filtered off, washed, dried and recrystallized from benzene solvent.
US 28318974 is an improvement on the process for the preparation of 4, 4' -alkylidene bisphenols by using an alcohol as the reaction solvent, washing the reaction mixture with a large amount of water after the reaction is completed, washing the reaction mixture with water several times until neutral or slightly acidic, adding a solvent (heptane), and filtering to obtain the product. This removal of acid not only requires the use of large amounts of water, but also the acid enclosed therein is not washed cleanly when the material is not completely dissolved.
In example 1 of US 2822404, 6-tert-butyl-m-cresol and paraldehyde are reacted with hydrochloric acid as catalyst, after the reaction is completed, sodium carbonate is added for neutralization, and then the crude product is recrystallized from a benzene-alcohol mixture.
In JP 2012-136548A, during the production of 4, 4' -butylidenebis (6-tert-butyl-m-cresol), the reaction of the materials is also neutralized with an aqueous solution of sodium hydroxide, and then the product is filtered to obtain a crude product, which is recrystallized from methanol.
6-tert-butyl metacresol and n-butyl aldehyde use hydrochloric acid as catalyst, react in methanol solution, if directly evaporate methanol and acid after the reaction is finished, it is the simplest method, but find in the course of actual operation, along with evaporating to dryness, the phenomenon that the material takes off suddenly is serious. Since strong acid has very high corrosion to equipment, if the acid is subjected to immediate neutralization treatment after the reaction is finished, a large amount of alkali is consumed, and a large amount of generated neutralized products are needed to be treated, and the method of neutralizing a large amount of acid is not beneficial to industrial application.
4, 4' -butylidenebis (6-tert-butyl-m-cresol) is dissolved in methanol, ethanol, ethyl acetate or acetone. It is known from US3761525 that it is insoluble in petroleum hydrocarbon solvents, and in the three-structured products of antioxidant production by reacting mixed phenol of 2-tert-butyl-p-cresol and 6-tert-butyl-m-cresol with n-butyraldehyde, most of the generated solid 4, 4' -butylidenebis (6-tert-butyl-m-cresol) can be removed by treating the reaction product with petroleum hydrocarbon solvents.
There are many examples in the literature of flushing the product with heptane, however, the product does not undergo recrystallization and washing with water, and the melting point and light transmittance of the product tend to be low.
Disclosure of Invention
The invention aims to provide a method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) by a one-pot method, which is used for solving the problem that a large amount of acid water needs to be neutralized in the production process, and the method avoids using a large amount of alkali liquor and simultaneously avoids the pollution problem of neutralized products caused by using the alkali liquor. The acid water separation process in the method is equivalent to one-time water washing in the recrystallization process, which is beneficial to improving the melting point and light transmittance indexes of the product, the separated acid water can be partially or completely reused, the pollution control cost is reduced, great economic benefits are achieved, and the acid water can be reused after absorbing industrial hydrogen chloride waste gas to a certain concentration, so that the method is beneficial to green and environment-friendly industrial application.
A one-pot method for preparing 4, 4 '-butylidene bis (6-tert-butyl-m-cresol) uses 6-tert-butyl-m-cresol and n-butyl aldehyde as raw materials, methanol as a solvent and hydrochloric acid as a catalyst, and in the method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol), after condensation reaction is completed, an aromatic hydrocarbon solvent and a mixed solvent consisting of the methanol solvent and the aromatic hydrocarbon solvent are added to enable a reaction mixture to be completely dissolved and layered at the reflux temperature of the methanol, an acid water layer is separated out, an organic layer is heated to evaporate the residual methanol, and then the residual methanol is subjected to post-treatment to obtain a crystalline product.
The post-treatment comprises neutralization, water washing, temperature reduction, suction filtration and vacuum drying of filter cakes to obtain a crystallized product.
The aromatic hydrocarbon solvent is used for product refining.
The reflux temperature of the methanol was 72-78 ℃.
The volume weight ratio of the using amount of the methanol solvent to the using amount of the reactant 6-tert-butyl-m-cresol is 0.5-1.5. Wherein the methanol solvent is used by volume, and the reactant 6-tert-butyl-m-cresol is used by weight. The volume to weight ratio is expressed in ml/g.
The aromatic hydrocarbon solvent is one or more of toluene, xylene, trimethylbenzene or petroleum aromatic hydrocarbon solvent oil.
The amount of the aromatic hydrocarbon solvent is larger than the total dissolved amount of the reaction materials under the condition that the reaction mixture is in the mixed solvent and the methanol flows back.
The amount of the aromatic hydrocarbon solvent used is an amount of the aromatic hydrocarbon solvent required to dissolve the whole amount of the reaction mixture at 100 ℃ at a temperature below the azeotropic point of the aromatic hydrocarbon solvent with water or at a temperature not generating the azeotropic point. The amount of the aromatic hydrocarbon solvent used at this time is an optimum amount.
The volume weight ratio of the using amount of the aromatic hydrocarbon solvent to the using amount of the reactant 6-tert-butyl-m-cresol is 2.5-10. Wherein the methanol solvent is used by volume, and the reactant 6-tert-butyl-m-cresol is used by weight. The volume to weight ratio is expressed in ml/g.
Adding 6-tert-butyl metacresol, methanol and concentrated hydrochloric acid, stirring, heating the material to 30-40 ℃, dropwise adding a mixture of methanol and n-butyl aldehyde, keeping the temperature for 30-60 minutes, keeping the temperature of the material at 72-78 ℃ under the condition of methanol reflux, stirring for 4 hours, adding an aromatic hydrocarbon solvent after the condensation reaction is finished, keeping the temperature and stirring to completely dissolve the material, stopping stirring, standing for layering, separating out acid water, neutralizing the material with an ammonia water reagent under the stirring of an organic phase to be neutral, heating the material under the stirring of the organic phase to evaporate volatile matters such as methanol and the like, washing with water, cooling, suction filtering, and drying a filter cake in vacuum to obtain a crystalline product.
The 4, 4' -butylidene bis (6-tert-butyl-m-cresol) product has greater solubility in aromatic hydrocarbon solvents at higher temperatures, such as 84 ℃ in toluene solvent, or 100 ℃ in aromatic hydrocarbon solvent oil with a boiling range of 140-200 ℃, and the feed ratio is higher when used as a recrystallization solvent. For example, 4' -butylidene bis (6-tert-butyl-m-cresol) product can be completely dissolved at 84 ℃ only when the feeding ratio is as high as 7 or 7.5 in a toluene solvent, because the water washing operation can be carried out only below 84 ℃ of the azeotropic point of toluene and water; the feeding ratio of the aromatic hydrocarbon solvent oil with the boiling range of 140-200 ℃ reaches 8 or 8.5 at the temperature of 100 ℃, and the feeding ratio reaches 9.5 or higher when mother liquor is used for recrystallization.
The mixed solvent composed of methanol and aromatic hydrocarbon solvent has the function of latent solvent for 4, 4' -butylidene bis (6-tert-butyl-m-cresol) product, so that the solubility of the product in the mixed solvent is greatly increased at lower temperature, for example, when toluene is used as recrystallization solvent, after a certain amount of toluene solution is added into reaction materials, the materials can be completely dissolved and split into phases at 46 ℃, acid water can be easily separated out, a large amount of methanol solvent is contained in the separated acid water, the methanol solvent can be repeatedly used, and for the problem of reducing the acid concentration, the acid water is intensively collected and then used for absorbing hydrogen chloride, and the acid water is reused after reaching a certain concentration. This avoids the problem of a decrease in product yield due to a decrease in acid concentration. The acid water can be partially or completely used for the next reaction and material preparation, and a certain amount of concentrated hydrochloric acid is supplemented when the acid water is used.
The material after separating the acid water contains the residual methanol and a very small amount of acid water, can be neutralized by a small amount of alkali liquor, the alkali liquor is preferably ammonia water, and then the temperature is raised to evaporate the methanol, no obvious water phase exists, when the water phase exists, the water phase is separated firstly, and when the temperature is raised to evaporate under stirring, the bumping phenomenon of the material cannot be generated. The distilled methanol contains byproducts, raw materials, solvents and the like, and can be directly used for next use without treatment, so that the yield of the product can be greatly reduced.
After the distilled methanol is kept stand for layering, the solvent can be merged into the mother liquor for next use, the methanol phase can also be used for next production materials, when the temperature of the materials is raised to 100-plus-110 ℃, the distillation is stopped, then the temperature is reduced to be below the azeotropic point of the solvent and water, or when the solvent without the azeotropic point is just below the boiling point of water of 100 ℃, water is added for washing, the salt generated by neutralization is mainly washed away, the washed materials are cooled for crystallization after being heated again to be completely dissolved, the temperature is reduced to be below 30 ℃, the filtration is carried out, the filter cake is washed by the aliphatic hydrocarbon solvent, the washing liquid and the mother liquor are separately collected, and the filter cake is dried in vacuum to obtain the product.
The aliphatic hydrocarbon solvent is preferably petroleum ether, 120 # solvent oil or heptane, more preferably heptane.
During the acid water separation, there are some filths in phase interface department, need be followed the aqueous phase and be drawn together, the process of drawing off the acid water, phase interface department has some filths can be followed the acid water and drawn, is equivalent to the washing operation of a time among the recrystallization process, helps the improvement of product melting point and luminousness index.
Compared with the prior art, the invention has the following beneficial effects:
the invention solves the problem that a large amount of acid water needs to be neutralized in the production process, avoids using a large amount of alkali liquor, and simultaneously avoids the pollution problem of neutralized products caused by using the alkali liquor. The process of acid water separation helps the improvement of product melting point and luminousness index, and the acid water of branch can be partly or whole used repeatedly, reduces the cost of treating pollution, has very big economic benefits, and the acid water is used for absorbing industry hydrogen chloride waste gas and can reuse after reaching certain concentration, is favorable to green's industrial application.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the present invention.
Example 1
Adding 111 g of 6-tert-butyl-m-cresol, 100 ml of methanol and 30 g of concentrated hydrochloric acid (mass fraction is 36%) into a 1000 ml four-neck flask with a reflux device and a stirrer, heating the materials to 40 ℃ under stirring, slowly adding a mixture of 10 ml of methanol and 24 g of n-butyl aldehyde by using an atmospheric burette for 60 minutes, keeping the temperature of the materials under the condition of 75 +/-3 ℃ methanol reflux for 4 hours under stirring, adding 500 ml of 200# petroleum aromatic hydrocarbon solvent oil, keeping the temperature under stirring to completely dissolve the materials at 73 +/-2 ℃, stopping stirring, standing for layering, separating 73 ml of acid water by using a bottle changing method, neutralizing the organic phase of the materials to be neutral by using 1.5 ml of ammonia water reagent under stirring, and standing until no aqueous phase is found. Heating the organic phase under stirring to evaporate volatile matters such as methanol, stopping heating when the temperature of the material is raised to 100 ℃, evaporating 41 milliliters of methanol, washing the material once by adding 20 milliliters of distilled water, stirring and cooling under the condition that the organic phase is completely dissolved after water separation, reducing the temperature to 20 ℃, performing suction filtration, washing a filter cake by 100 milliliters of aromatic hydrocarbon solvent oil, washing by three times by using 100 milliliters of heptane, drying for 4 hours at 70 ℃ in vacuum, weighing 99 grams of the product, obtaining the yield of 76.7 percent, and dissolving: 210.2-211.5 ℃, light transmittance (425, 500): 94.8, 97.1.
Example 2
This example was the same as example 1 except that in a 1000 ml four-necked flask equipped with a reflux apparatus and a stirrer, 111 g of 6-t-butyl-m-cresol and 73 ml of the acid water separated in example 1 were charged, and 5 g of concentrated hydrochloric acid (mass fraction: 36%) and 40 ml of methanol were further added. After separating off the acid water, 700 ml of the mother liquor of aromatic hydrocarbon solvent oil produced in example 1 was added. As a result: the weight of the product is 95 g, the yield is 73.6 percent, and the dissolution process is as follows: 209.8-210.8 ℃, light transmittance (425, 500): 95.8, 97.0.
Example 3
Into a 1000 ml four-necked flask equipped with a reflux apparatus and a stirrer, 111 g of 6-t-butyl-m-cresol and 70 ml of the acid water separated in example 2 were charged, and further, 5 g of concentrated hydrochloric acid (mass fraction: 36%) and 30 ml of the methanol liquid distilled out in example 2 were added and phase-separated. The other operations were the same as example 2, and the results were: the weight of the product is 87.5 g, the yield is 67.8 percent, and the dissolution process is as follows: 208.1-209.1 ℃, light transmittance (425, 500): 94.7, 97.1.
Example 4
The same as the device and the operation method of the embodiment 1, except that: changing 200# petroleum aromatic hydrocarbon solvent oil into 500 ml of toluene, adding the toluene, completely dissolving the materials at 46 ℃, and separating 71 ml of acid water phase; after the organic phase was neutralized with 2.5 ml of ammonia water, the temperature was raised to distill off methanol, and 95 ml of distillate was obtained. After the temperature of the material is reduced to 85 ℃, 20 ml of distilled water is added for washing once, and 20 ml of water and 100 ml of toluene are added for washing once again after the temperature is raised and the material is completely dissolved. Otherwise, the procedure of example 1 was followed. The weight of the product is 81.5 g, the yield is 63.2 percent, and the solution process is as follows: 210.7-211.7 ℃, light transmittance (425, 500): 96.9, 98.5.
Example 5
The same as the device and the operation method of the embodiment 1, except that: the procedure of example 1 was repeated except that the 200# petroleum aromatic solvent oil was changed to 500 ml of xylene, 84 ml of acid water was separated and 61 ml of methanol was distilled off. As a result: the weight of the product is 91.5 g, the yield is 71 percent, and the solution process is as follows: 209.1-211.1 ℃, light transmittance (425, 500): 96.3, 98.1.
Comparative example 1
The same apparatus, ingredients and operation as in example 1, except that: after the reaction is finished, 700 ml of water is added, 100 ml of heptane is added after water washing is carried out for multiple times, pumping filtration is carried out after material beating, 100 ml of heptane is used again for washing filter cakes for three times, the filter cakes are dried for 4 hours under vacuum at 90 ℃, the weight of the product is 106 g, the yield is 82%, and the dissolving process is finished; 208.3-209.4 ℃, light transmittance (425, 500): 92.2, 94.7.
Claims (7)
1. A method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) by a one-pot method is characterized by comprising the following steps: in the method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) by using 6-tert-butyl-m-cresol and n-butyl aldehyde as raw materials, methanol as a solvent and hydrochloric acid as a catalyst, an aromatic hydrocarbon solvent and a mixed solvent consisting of the methanol solvent and the aromatic hydrocarbon solvent are added after the condensation reaction is finished, so that a reaction mixture is completely dissolved and layered at the reflux temperature of the methanol, an acid water layer is separated, an organic layer is heated to evaporate the remaining methanol, and a crystallized product is obtained by post-treatment;
the volume weight ratio of the using amount of the methanol solvent to the using amount of the reactant 6-tert-butyl-m-cresol is 0.5-1.5;
the volume weight ratio of the using amount of the aromatic hydrocarbon solvent to the using amount of the reactant 6-tert-butyl-m-cresol is 2.5-10;
the aromatic hydrocarbon solvent is one or more of toluene, xylene, trimethylbenzene or petroleum aromatic hydrocarbon solvent oil.
2. The one-pot method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) according to claim 1, wherein the post-treatment comprises neutralization, water washing, temperature reduction, suction filtration and vacuum drying of a filter cake to obtain a crystalline product.
3. The one-pot process for preparing 4, 4' -butylidenebis (6-tert-butyl-m-cresol) according to claim 1, wherein an aromatic hydrocarbon solvent is used for product purification.
4. The one-pot process for preparing 4, 4' -butylidenebis (6-tert-butyl-m-cresol) according to claim 1, wherein the reflux temperature of methanol is 72-78 ℃.
5. The one-pot process for preparing 4, 4' -butylidenebis (6-tert-butyl-m-cresol) according to claim 1, wherein the amount of the aromatic hydrocarbon solvent is larger than the amount of the reaction material dissolved in the mixed solvent under the condition of refluxing methanol.
6. The one-pot process for preparing 4, 4' -butylidenebis (6-tert-butyl-m-cresol) according to claim 1, wherein the aromatic hydrocarbon solvent is used in an amount of the aromatic hydrocarbon solvent which is lower than a temperature at which the aromatic hydrocarbon solvent and water generate an azeotropic point or which does not generate an azeotropic point but dissolves the whole amount of the reaction mixture at 100 ℃.
7. The one-pot method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) according to claim 1, characterized in that 6-tert-butyl-m-cresol, methanol and concentrated hydrochloric acid are added and stirred, the temperature of the materials is heated to 30-40 ℃, a mixture of methanol and n-butyl aldehyde is added dropwise for 30-60 minutes, then the materials are kept and stirred for 4 hours under the condition of methanol reflux at 72-78 ℃, after the condensation reaction is finished, an aromatic hydrocarbon solvent is added, the materials are kept and stirred to be completely dissolved, the stirring is stopped, the acid water is separated after the materials are kept standing and layered, the materials are neutralized to be neutral by an ammonia water reagent under the stirring of an organic phase, the methanol volatile matter is evaporated under the stirring of the organic phase, the materials are washed by water, the temperature is reduced, the filtration is carried out, and.
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| US2831897A (en) * | 1954-04-09 | 1958-04-22 | Monsanto Chemicals | Process of making 4, 4'-alkylidene bisphenols |
| JP2007269711A (en) * | 2006-03-31 | 2007-10-18 | Api Corporation | Method for producing 4,4'-butylidenebis(6-tert-butyl-3-methylphenol) improved in hue |
| CN104591972A (en) * | 2014-12-05 | 2015-05-06 | 沈阳师范大学 | Preparation method for 4,4'-butylidenebis(6-tert-butyl-3-methylphenol) |
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Denomination of invention: Preparation of 4,4 '- butylene bis (6-tert butyl m-cresol) by one pot method Effective date of registration: 20211130 Granted publication date: 20201218 Pledgee: Industrial Commercial Bank of China Ltd. Zibo Zhangdian branch Pledgor: Zibo Wanke Chemical Co.,Ltd. Registration number: Y2021980013667 |