CN110818573B - Preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane - Google Patents
Preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane Download PDFInfo
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- CN110818573B CN110818573B CN201911116979.8A CN201911116979A CN110818573B CN 110818573 B CN110818573 B CN 110818573B CN 201911116979 A CN201911116979 A CN 201911116979A CN 110818573 B CN110818573 B CN 110818573B
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- C07—ORGANIC CHEMISTRY
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
Abstract
The invention provides a preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, which takes the form of mixed acid formed by solid acid and liquid acid as a catalyst and adopts azeotropic distillation to recycle the liquid acid in reaction liquid, thereby not only fully playing respective advantages of the solid acid and the liquid acid and achieving the purposes of reducing the dosage of the liquid acid and improving the yield of MOCA, but also effectively reducing the dosage of neutralizing alkali, reducing the discharge amount of salt-containing wastewater, greatly reducing resource consumption, reducing the cost of industrial production and relieving the burden on the environment.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and relates to a preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, in particular to a method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, which takes a mixed acid form of solid acid and liquid acid as a catalyst and adopts an azeotropic distillation process to recycle liquid acid in reaction mother liquor, so that the MOCA yield is ensured, the discharge amount of alkali liquor consumed by neutralization and salt-containing wastewater is reduced, and the purposes of reducing resource consumption and reducing wastewater discharge amount are achieved.
Background
3,3 '-dichloro-4, 4' -diaminodiphenylmethane (commonly known as MOCA, molecular formula: C)13H12Cl2N2Molecular weight: 267.15), CAS number 101-14-4, white or light yellow crystal at room temperature, good storage stability, and can be used as cross-linking agent and curing agent of polyurethane and epoxy resin, and vulcanizing agent of rubber, and can be used for preparing products with high electric resistance. The method is widely applied to the fields of automobile industry, machine manufacturing industry, mining industry, sports facilities and the like, so that the research on the synthesis process of the method has important significance.
In 1953, DuPont company in the United states firstly developed a synthesis process route of MOCA, which adopts o-chloroaniline, formaldehyde and hydrochloric acid as raw materials, salifies the o-chloroaniline and the hydrochloric acid, then dropwise adds the formaldehyde for condensation, and then obtains the MOCA through the steps of neutralization, steam distillation, washing, recrystallization and the like. The domestic Suzhou Xiangyuan chemical industry Co., Ltd also uses o-chloroaniline, formaldehyde and hydrochloric acid as raw materials, and the MOCA is synthesized through the steps of acidification, condensation, neutralization, washing, drying and the like. In both methods, liquid hydrochloric acid is used as a catalyst, a large amount of alkali liquor is used for neutralizing unreacted acid liquor after the reaction is finished, more than 5 tons of salt-containing wastewater can be generated when one ton of MOCA is produced, the treatment cost of the salt-containing wastewater is high, and the method of dilution discharge is adopted in industry, so that serious environmental pollution can be caused. The method has the disadvantages of low yield, long reaction period, complex operation, higher production cost and more byproducts.
In order to solve the problem, patent CN105294448A discloses a method for preparing 4,4 '-diaminodiphenylmethane derivatives by using solid acid as a catalyst, the method uses solid acid such as HY-type molecular sieve to catalyze formaldehyde and o-chloroaniline for condensation to prepare 4, 4' -diaminodiphenylmethane derivatives, but the method has the problems of low yield of 50% -70%, difficulty in realizing industrialization and the like.
Patent CN103936594A discloses a method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using cation exchange resin, which uses cation exchange resin to replace liquid acid to catalyze the condensation reaction of o-chloroaniline and formaldehyde, and can reduce the discharge of salt-containing wastewater, but under the optimized conditions that n (o-chloroaniline):n (formaldehyde) ═ 2.0: 1 and the amount of catalyst is 4kg, the reaction is carried out at 95 ℃ for 7h, the yield of the method is only 32.5%, the regeneration process of cation exchange resin is complex, and the regeneration process also generates a large amount of inorganic and organic wastewater.
Patent CN107417544A discloses a method for synthesizing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using heteropoly acid, which uses heteropoly acid as catalyst instead of common liquid acid, although the yield of MOCA can be ensured to be more than 80%, but heteropoly acid catalyst needs to be recovered by organic solvent recrystallization, the catalyst is difficult to recover, and industrialization is difficult to realize.
In the traditional process, liquid acid is used as a catalyst, so that equipment corrosion and pollution are serious, the equipment is difficult to recycle, resinous impurities are easy to generate in the reaction, and the yield of MOCA is reduced. The method needs neutralization, water washing and other processes, has the defects of multiple operation procedures, large three-waste discharge and the like, and does not accord with the green chemical development concept. Solid acid catalysis has many advantages over liquid acid catalysis, such as: the catalyst and the product are easy to separate, can be regenerated and used, omits the operation processes of neutralization, water washing and the like, and reduces the discharge amount of three wastes. However, according to the current research results, the problems of low yield of MOCA caused by insufficient conversion of intermediates or more byproducts and complicated operation of recycling and reusing the catalyst are generally existed.
Disclosure of Invention
The invention aims to provide a method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, which has high yield, less wastewater discharge and environmental protection. The method is improved on the basis of the traditional process for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, namely, a mixed acid form formed by adding solid acid and liquid acid is used as a catalyst for synthesizing MOCA, o-chloroaniline raw material and liquid acid form o-chloroaniline hydrochloride, the o-chloroaniline hydrochloride and formaldehyde solution react under the catalytic action of the solid acid to produce MOCA acid salt, and an azeotropic distillation process is adopted to carry out azeotropic distillation on a reaction system so that azeotrope of hydrochloric acid and water is evaporated out for recycling, and then the azeotrope is neutralized by alkali solution. On one hand, the production process can greatly reduce the dosage of liquid acid by adding the solid acid, reduce the corrosion degree to equipment, reduce the generation of polymeric byproducts and further improve the yield of MOCA. On the other hand, the hydrochloric acid distilled off by azeotropy can be recycled, the consumption of the hydrochloric acid and sodium hydroxide consumed by subsequent neutralization is reduced, the discharge amount of salt-containing wastewater is further reduced, and the method has remarkable economic and environmental benefits.
The purpose of the invention is realized by the following method:
a preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane specifically comprises the following steps:
(1) salifying: adding mixed acid consisting of solid acid and hydrochloric acid into a reaction kettle according to a certain proportion, dropwise adding o-chloroaniline at a certain temperature under the protection of nitrogen, and stirring to react to form o-chloroaniline hydrochloride;
(2) condensation: mixing the o-chloroaniline hydrochloride obtained in the step (1) and formaldehyde according to a certain proportion, and mixing and stirring for a period of time under the protection of nitrogen and at a certain temperature to react to obtain a condensation reaction solution;
(3) and (3) filtering: and (3) filtering the solid acid to remove the reaction system, and returning to the step (1) for recycling.
(4) Azeotropic distillation: carrying out azeotropic distillation on the condensation reaction liquid obtained in the step (2) to obtain hydrochloric acid distillate, and returning to the step (1) for recycling;
(5) neutralizing: adding the distilled reaction liquid obtained in the step (4) into a sodium hydroxide solution with a certain concentration for neutralization, heating to 100-110 ℃, and preserving heat for half an hour;
(6) separation: separating the neutralized liquid obtained in the step (5) to obtain an upper water layer, and washing and drying a lower oil layer to obtain the MOCA product.
The mass mol ratio range of the hydrochloric acid to the o-chloroaniline in the step (1) is 0.5-1.5: 1;
the solid acid in the step (1) is selected from one or more of H beta, HY, HZSM-5 molecular sieve and cation acid resin; the using amount of the solid acid is 4-20 wt% of the mass of the o-chloroaniline; preferably 7-12 wt%;
the salt forming temperature in the step (1) is 20-80 ℃, and preferably 50-60 ℃;
the concentration of the hydrochloric acid in the step (1) is 10 to 30 percent, preferably 20 to 25 percent;
the molar ratio of the o-chloroaniline to the formaldehyde in the step (2) is 1.5-3: 1;
the concentration range of the formaldehyde aqueous solution in the step (2) is 15-35%, preferably 20-30%;
the condensation temperature in the step (2) is 60-110 ℃, the time is 1-6 h, preferably 70-90 ℃, and the time is 3-6 h;
and (3) the pH value of the neutralization control system in the step (5) is 7-11.
Compared with the prior art, the invention has the following advantages:
(1) the product has stable quality and high yield: according to the invention, MOCA is catalytically synthesized in the form of mixed acid consisting of solid acid and liquid acid, the prepared MOCA product has stable quality, the yield is more than 85%, and meanwhile, the addition of the solid acid can reduce the using amount of the used liquid acid, reduce the corrosion degree on equipment, reduce the generation of polymeric byproducts and further improve the yield of MOCA;
(2) the mixed acid is recycled, so that the product cost is reduced: the solid acid is directly recycled and reused, and the liquid acid is recycled and reused for next salification through azeotropic distillation, so that the consumption of newly supplemented hydrochloric acid can be reduced, and the MOCA production cost can be reduced; hydrochloric acid is distilled out by azeotropy, so that the consumption of alkali in the neutralization process is reduced, and the discharge amount of salt-containing wastewater is reduced.
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FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
The following examples further illustrate the process of the present invention. All percentages and ratios of ingredients are by mass unless otherwise indicated.
Example 1
Under the protection of nitrogen, 182.5kg of hydrochloric acid with the concentration of 20 percent and 4 weight percent of HY molecular sieve are added to the bottom of a reaction kettle, 127.63kg of o-chloroaniline is dropwise added into the reaction kettle under the mechanical stirring at the temperature of 30 ℃, the temperature is raised to 60 ℃ after the dropwise addition, 75kg of formaldehyde aqueous solution with the concentration of 20 percent is dropwise added into the o-chloroaniline hydrochloride slurry, the temperature is kept for 3 hours at the temperature of 90 ℃ after the dropwise addition of the formaldehyde is finished, then the temperature is raised to 108 ℃, 181.67kg of hydrochloric acid is evaporated, and the concentration of the hydrochloric acid is 13.39 percent. And then, dropwise adding 46.7kg of 30% sodium hydroxide aqueous solution into the reaction solution for neutralization until the pH value is 7-8, maintaining the temperature at 90 ℃ in the neutralization process, heating the reaction material to 100 ℃, stirring for 30min, standing and settling to form an aqueous phase and an organic phase, separating the aqueous phase through a liquid separation step, and washing and drying the residual oil phase to obtain the MOCA product. The MOCA product has the mass of 236.91kg, the yield of 88.7 percent and the purity of 94.6 percent. Compared with the traditional process comparative example 1, the experiment reduces the consumption of the neutralized NaOH by 93.3kg and the wastewater amount by 275kg (1.03t/tMOCA), and the distilled hydrochloric acid solution is reused for the next reaction in a form of acid supplementation.
Example 2
121.7kg of hydrochloric acid with the concentration of 30 percent and 7 weight percent of H beta molecular sieve are added into the bottom of a reaction kettle under the condition of nitrogen protection, 127.63kg of o-chloroaniline is dripped into the reaction kettle under the mechanical stirring at the temperature of 60 ℃, the temperature is raised to 80 ℃ after the dripping is finished, 100kg of formaldehyde aqueous solution with the concentration of 15 percent is dripped into the o-chloroaniline hydrochloride slurry, the temperature is kept for 3 hours at the temperature of 90 ℃ after the dripping of the formaldehyde is finished, then the temperature is raised to 108 ℃, 182.5kg of hydrochloric acid is evaporated, and the concentration of the hydrochloric acid is 16.69 percent. And then, dropwise adding 46.7kg of 30% sodium hydroxide aqueous solution into the reaction solution for neutralization until the pH value is 7-8, maintaining the temperature at 90 ℃ in the neutralization process, heating the reaction material to 100 ℃ after neutralization, stirring for 30min, standing and settling to form an aqueous phase and an organic phase, separating the aqueous phase through a liquid separation step, and washing and drying the residual oil phase to obtain the MOCA product. The MOCA product has the mass of 235.84kg, the yield of 88.3 percent and the purity of 94.7 percent. Compared with the traditional process comparative example 1, the experiment reduces the consumption of 93.3kg of the neutralized NaOH and the wastewater amount by 239.16kg (0.90t/t MOCA), and the distilled hydrochloric acid solution is reused for the next reaction in a form of acid supplementation.
Example 3
Under the protection of nitrogen, 20 wt% HY molecular sieve and 182.5kg of 30% hydrochloric acid solution are placed at the bottom of a reaction kettle, 127.63kg of o-chloroaniline is dropwise added into the reaction kettle at 60 ℃, the reaction temperature is kept at 60 ℃, 75kg of 20% formaldehyde solution (500mol) is dropwise added into the o-chloroaniline hydrochloride slurry, after the dropwise addition of formaldehyde is completed, the temperature is kept at 60 ℃ for 5 hours, then the temperature is raised to 108 ℃, 184kg of hydrochloric acid is evaporated, and the concentration of the evaporated hydrochloric acid is 13.25%. And then, 68.88kg of 30% sodium hydroxide aqueous solution is dropwise added into the reaction solution for neutralization until the pH value is 10-11, the temperature is maintained at 60 ℃ in the neutralization process, the reaction material is heated to 100 ℃ after the neutralization is finished, the reaction material is stirred for 30min, then the reaction material is kept stand and settled to form a water phase and an organic phase, the water phase is separated out through a liquid separation step, and the residual oil phase is washed and dried to obtain the MOCA product. The MOCA product has the mass of 233.71 kg, the yield of 87.5 percent and the purity of 94.9 percent. Compared with the traditional process comparative example 1, the experiment reduces the consumption of the neutralized NaOH by 137.8kg and reduces the wastewater amount by 321.7kg (1.21t/t MOCA). The distilled hydrochloric acid is reused in the next batch.
Example 4
Under the protection of nitrogen, 12 wt% of HZSM-5 molecular sieve and 146kg of 25% hydrochloric acid aqueous solution are placed at the bottom of a reaction kettle, 127.62kg of o-chloroaniline is dropwise added into the reaction kettle at 80 ℃, the reaction temperature is kept at 80 ℃, 75kg of 20% formaldehyde aqueous solution is dropwise added into the o-chloroaniline hydrochloride slurry, after the dropwise addition of formaldehyde is completed, the temperature is kept for 2 hours at 100 ℃, then the temperature is raised to 108 ℃, 145.17kg of hydrochloric acid is evaporated, and the concentration of the hydrochloric acid is 14.31% by evaporation. And then, dropwise adding 46.7kg of 30% sodium hydroxide aqueous solution into the reaction solution for neutralization until the pH value is 9-10, maintaining the temperature at 100 ℃ in the neutralization process, keeping the reaction material at 100 ℃ after neutralization, stirring for 30min, standing and settling to form an aqueous phase and an organic phase, separating the aqueous phase through a liquid separation step, and washing and drying the residual oil phase to obtain the MOCA product. The MOCA product has the mass of 231.04kg, the yield of 86.5 percent and the purity of 93.1 percent. Compared with the traditional process comparative example 1, the amount of the neutralized NaOH is reduced by 93.3kg, and the amount of the waste water is reduced by 238.5kg (0.89t/t MOCA). The mixture is applied to the next batch of reaction.
EXAMPLES 5-7 use of distilled HCl
The hydrochloric acid distilled off in example 4 was used in succession in examples 5 to 7, the application stability was investigated and the experimental results were as follows:
TABLE 1 Table of data for hydrochloric acid
Comparative example 1 (traditional Process for liquid acid)
Under the condition of nitrogen protection, 208.57kg of 35% hydrochloric acid aqueous solution (2000mol) is placed at the bottom of a reaction kettle, 127.51kg of o-chloroaniline (1000mol) is dripped into the reaction kettle at 60 ℃, the reaction temperature is kept at 60 ℃, then 42.86kg of 35% formaldehyde aqueous solution (500mol) is dripped into the o-chloroaniline hydrochloride slurry, after the formaldehyde is dripped, the temperature is kept at 60 ℃ for 5 hours, then 193.17kg of 30% sodium hydroxide aqueous solution is dripped into the reaction liquid for neutralization until the pH value is 10-11, the temperature is kept at 60 ℃ in the neutralization process, the reaction material is heated to 100 ℃ and stirred for 30 minutes after the neutralization is finished, then the reaction material is stood and settled to form an aqueous phase and an organic phase, the aqueous phase is separated through a liquid separation step, and the residual oil phase is washed and dried to obtain the MOCA product. The MOCA product has the mass of 223.56kg, the yield of 83.7 percent and the purity of 91.2 percent.
Comparative example 2 (solid acid Process)
Under the protection of nitrogen, 8g of HY molecular sieve is placed at the bottom of a reaction kettle, 127.51kg of o-chloroaniline is dropwise added into the reaction kettle at 160 ℃, 42.86kg of 35% formaldehyde aqueous solution is dropwise added into the o-chloroaniline hydrochloride slurry, after the dropwise addition of formaldehyde is finished, the temperature is kept for 5 hours at 60 ℃, then the mixture is kept still and settled to form a water phase and an organic phase, the water phase is separated through a liquid separation step, and the residual oil phase is filtered, washed and dried to obtain the MOCA product. The MOCA product has the mass of 187.77kg, the yield of 70.3 percent and the purity of 87.4 percent.
The invention is not limited to the embodiments of the invention described.
The structure and the implementation of the present invention are described herein by using specific examples, and the above description of the examples is only used to help understand the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (14)
1. A preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane specifically comprises the following steps:
(1) salifying: adding mixed acid consisting of solid acid and hydrochloric acid into a reaction kettle according to a certain proportion, dropwise adding o-chloroaniline at a certain temperature under the protection of nitrogen, and stirring to react to form o-chloroaniline hydrochloride; the solid acid is selected from one or a combination of more of H beta, HY and HZSM-5 molecular sieves;
(2) condensation: mixing the o-chloroaniline hydrochloride obtained in the step (1) and a formaldehyde water solution according to a certain proportion, and mixing and stirring for a period of time under the protection of nitrogen at a certain temperature to react to obtain a condensation reaction solution;
(3) and (3) filtering: filtering the solid acid and removing the solid acid out of the reaction system, and returning the solid acid to the step (1) for recycling;
(4) azeotropic distillation: carrying out azeotropic distillation on the condensation reaction liquid obtained in the step (2) to obtain hydrochloric acid distillate, and returning to the step (1) for recycling;
(5) neutralizing: adding the distilled reaction liquid obtained in the step (4) into a sodium hydroxide solution with a certain concentration for neutralization, heating to 100-110 ℃, and preserving heat for half an hour;
(6) separation: separating the neutralized liquid obtained in the step (5) to obtain an upper water layer, and washing and drying a lower oil layer to obtain the MOCA product.
2. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 1, wherein the molar mass ratio of hydrochloric acid to o-chloroaniline in step (1) is 0.5 to 1.5: 1.
3. the method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 1, characterized in that the amount of solid acid used in step (1) is 4-20 wt% of o-chloroaniline.
4. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 3, characterized in that the amount of solid acid used in step (1) is 7-12 wt% of o-chloroaniline.
5. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 1, wherein the salt formation temperature in step (1) is 20-80 ℃.
6. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 5, wherein the salt formation temperature in step (1) is 50-60 ℃.
7. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 1, wherein the hydrochloric acid concentration in step (1) is 10% to 30%.
8. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 7, wherein the hydrochloric acid concentration in step (1) is 20% to 25%.
9. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 1, wherein the molar ratio of o-chloroaniline to formaldehyde in step (2) is 1.5-3: 1.
10. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 1, wherein the hydrochloric acid concentration in step (1) is 10% to 30%.
11. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 10, wherein the hydrochloric acid concentration in step (1) is 20% to 25%.
12. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 1, wherein the condensation temperature in step (2) is 60-110 ℃ and the reaction time is 1-6 h.
13. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 12, wherein the condensation temperature in step (2) is 70-90 ℃ and the reaction time is 3-6 h.
14. The method for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane according to claim 1, wherein the pH of the neutralization control system in the step (5) is 7-11.
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