CN116143691A - Method for preparing anti-aging agent TMQ and co-producing mesitylene - Google Patents
Method for preparing anti-aging agent TMQ and co-producing mesitylene Download PDFInfo
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- CN116143691A CN116143691A CN202111375808.4A CN202111375808A CN116143691A CN 116143691 A CN116143691 A CN 116143691A CN 202111375808 A CN202111375808 A CN 202111375808A CN 116143691 A CN116143691 A CN 116143691A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
Abstract
The invention belongs to the technical field of fine chemical engineering, and provides a method for preparing TMQ and co-producing mesitylene. Adding part of aniline into a reaction kettle at one time, heating hydrochloric acid with stirring to remove water in the hydrochloric acid, heating to a reaction temperature, continuously introducing acetone into the reaction kettle to react, and removing reaction water while reacting; and then sealing the reaction system, heating and boosting the pressure for reaction, adding liquid alkali for neutralization, adjusting to be alkaline, separating water, distilling an oil phase, and removing unreacted acetone, water and a front cut fraction to obtain TMQ. Rectifying the front fraction to obtain mesitylene. The content of effective bodies in the anti-aging agent TMQ finished product reaches 45-65%, and the content of trimethylbenzene reaches more than 99.0%. Thereby reducing the production cost of the trimethylbenzene, reducing the energy consumption and the material consumption, and being a green and environment-friendly synthesis process.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, relates to a preparation method for co-production of an anti-aging agent TMQ and mesitylene, and is an environment-friendly preparation process.
Background
The anti-aging agent TMQ is a di, tri and tetra polymer of 2, 4-trimethyl-1, 2-dihydroquinoline, also called an anti-aging agent RD, is a ketoamine anti-aging agent, is light yellow to ruin poise particles or flakes, is mainly used as a rubber anti-aging agent, has annual demand of 10 ten thousand tons at home and abroad, and is one of the most demanded rubber anti-aging agent products in the market at home and abroad.
The main raw materials for synthesizing the anti-aging agent TMQ are aniline and acetone (or derivatives thereof), and the process can be roughly divided into a one-step method or a two-step method. The process of the one-step method comprises the following steps: and (3) performing condensation and polymerization reaction on aniline and acetone under the action of a catalyst to directly obtain an anti-aging agent TMQ polycondensation liquid containing two, three and four polymers of 2, 4-trimethyl-1, 2-dihydroquinoline, and neutralizing the TMQ polycondensation liquid by liquid alkali, separating water, distilling and the like to obtain TMQ. The process of the two-step method is as follows: and (3) performing condensation reaction on aniline and acetone under the action of a catalyst, distilling or rectifying the reaction liquid or the neutralized reaction liquid to obtain 2, 4-trimethyl-1, 2-dihydroquinoline, namely TMQ monomer, performing polymerization reaction on the TMQ monomer under the action of the catalyst to obtain di-, tri-and tetra-polymers of the 2, 4-trimethyl-1, 2-dihydroquinoline, and neutralizing, water splitting and distilling to obtain the anti-aging agent TMQ. In order to accelerate the reaction process, solvents such as toluene, xylene, and cyclohexane are added to the reaction, so the TMQ synthesis method can be classified into "solvent method" or "solvent-free method" and the like.
CN108003095a describes a more common production method for TMQ: 1) Batch kettle process: raw materials of aniline and a catalyst are put into a kettle at one time, acetone is fed in a continuous dropwise manner, and the feeding reaction time is generally 2-7 hours. And under normal pressure, controlling the reaction temperature to be 90-150 ℃, directly separating and recovering the acetone through a fractionating tower on the reaction kettle, and then applying the acetone into a raw material storage tank. 2) Continuous tower process: aniline and catalyst titanate are continuously fed from the top of the tower, acetone is gasified and then is fed from the bottom gas phase, and continuous reaction is carried out in the tower. The reaction temperature is controlled to be 90-150 ℃ under normal pressure. The retention time of the materials in the tower is 3-7 hours. And simultaneously evaporating acetone and water generated in the reaction process, directly separating and recovering the acetone through a fractionating tower, and continuously flowing an anti-aging agent TMQ polycondensation reaction liquid and the like generated by the reaction into a tower bottom receiving groove. Adding TMQ polycondensation liquid in a reaction kettle or a receiving tank into liquid alkali for neutralization, standing for layering, distilling an oil phase, and granulating to obtain an anti-aging agent TMQ finished product.
Mesitylene, also known as 1,3, 5-trimethylbenzene, is an important organic synthetic raw material for preparing trimesic acid, antioxidants, epoxy resin curing agents, polyester resin stabilizers and alkyd resin plasticizers, and 2,4, 6-trimethylamine is prepared for producing reactive brilliant blue, K-3R and other dyes.
The main sources are as follows: 1) From C9 aromatics. 2) Obtained in reforming heavy aromatics, wherein mesitylene is about 11.8%. However, it is difficult to separate by the rectification method because its boiling point (164.7 ℃) is very similar to that of o-methylethylbenzene (165.15 ℃). 3) The isomerization process with pseudocumene as material has single pass yield of 1,3, 5-trimethylbenzene of 21.6%, purity over 95% and by-product of 4-7% durene and 9% xylene. The reaction catalyst is aluminum-deficient hydrogen mordenite: copper: nickel: binder = 85.2:0.5:15. under this condition, the conversion of the pseudocumene was 46%, the selectivity was 47% and the single pass yield of the mesitylene was 21.6%. HF-BF for Mitsubishi gas Co., ltd 3 Separating xylene, isomerizing, and high-boiling by-product containing high-concentration 1,3, 5-trimethylbenzeneThe product can be obtained by distillation and refining. 4) The acetone is dehydrated and synthesized under the catalysis of sulfuric acid, and the yield is 13-15%. Adding concentrated sulfuric acid at 0-5deg.C, and standing at room temperature for 18-24 hr. And (3) carrying out steam distillation on the product to separate 1,3, 5-trimethylbenzene, then carrying out alkali washing and water washing, distilling and collecting a fraction at 210 ℃, adding 15g of metallic sodium into the fraction, heating to a near boiling point, distilling 2/3 of liquid, distilling the residue to 210 ℃, and efficiently fractionating and collecting a fraction at 163-167 ℃ to obtain 430-470g of 1,3, 5-trimethylbenzene.
Disclosure of Invention
The invention aims to simultaneously coproduce a mesitylene product with high added value in the process of preparing an anti-aging agent TMQ, thereby providing improved economic benefit.
The invention provides a method for preparing an anti-aging agent TMQ and co-producing mesitylene. The preparation method is realized by the following steps:
step (1): aniline, acid catalyst, acetone and the like are added into a reactor to remove water; or aniline and acid catalyst are used for removing water, and then acetone is added;
step (2): heating the material obtained in the step (1) to a certain temperature, reacting for a period of time under stirring, and removing water;
step (3): reacting the reaction solution obtained in the step (2) for a period of time at a certain temperature and pressure;
step (4): adding liquid alkali into the reaction liquid obtained in the step (3) for neutralization, separating water, distilling an oil phase, and sequentially removing acetone, water and a front cut fraction to obtain TMQ;
step (5): rectifying and separating the front fraction obtained in the step (4) to sequentially obtain mesitylene, aniline and kettle liquid containing TMQ monomers; aniline and TMQ monomers are used mechanically.
Preferably, the acid catalyst is one or more of hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, oxalic acid, copper halide, titanic acid, titanate and other acidic substances.
Preferably, the aniline, acid catalyst and acetone molecular ratio in step (1) is 1:0.1-0.001: 6-20.
Preferably, the aniline, acid catalyst and acetone molecular ratio in step (1) is 1:0.05-0.005: 10-15.
Preferably, the removal of water in steps (1) and (2) means that the water content in the mixed solution is controlled to be 0.3% or less.
Preferably, the reaction temperature in step (2) is 100-150℃and the reaction time is 1-10 hours.
Preferably, the reaction temperature in step (3) is 120-180 ℃, the reaction time is 1-8 hours, and the reaction pressure is 0.8-4.0MPa.
Preferably, in step (4), the oil phase is distilled, the vapour phase temperature of the removed front cut is 60-150 ℃, the liquid phase temperature is 110-180 ℃ and the pressure is 0.1-2.0 kpa.
Preferably, the main composition of the front-end fraction obtained in step (4) is 0.3-1.0% aniline, 35.0-76.0% mesitylene, 5.0-18.0% TMQ monomer.
Preferably, the main composition of TMQ obtained in step (4) is 45-58% of di-, tri-, tetra-polymer of 2, 4-trimethyl-1, 2-dihydroquinoline, 0.0-0.05% of aniline, 0-0.3% of isopropyl diphenylamine, 0% of mesitylene, 0-3.0% of TMQ monomer and 85-98 ℃.
Preferably, the mesitylene content obtained in step (5) reaches 99.5%. The content of the impurity aniline is 0.0-0.05%.
Preferably, the kettle liquid containing TMQ monomer mainly comprises the following components: 0-20% of mesitylene, 65.0-90.0% of 2, 4-trimethyl-1, 2-dihydroquinoline, 0-5.0% of primary amine, 0-3.0% of isopropyl diphenylamine and 0.0-3.0% of 2, 4-trimethyl-1, 2-dihydroquinoline dimer.
Advantageous effects
In the process of preparing the anti-aging agent TMQ, different reaction conditions are controlled through sectional reaction, and meanwhile, the high-added-value mesitylene product is co-produced, so that the economic benefit is improved. Compared with the traditional processes of separating and reforming heavy aromatics by C9 aromatics, an isomerization method and the like, the invention has the advantages that: (1) raw materials of aniline and acetone are bulk commodity, and the cost is low and the raw materials are easy to obtain; (2) the conventional acid catalyst is used, the source is wide, and the generated wastewater is easy to treat; (3) the process is simple, and TMQ and trimethylbenzene are combined; (4) the rectification method is easy to separate, and the purity of the obtained mesitylene product is higher.
Detailed Description
The synthetic method of the present invention will be described in detail with reference to examples. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
According to the method for preparing the rubber antioxidant TMQ and co-producing mesitylene, part of aniline, hydrochloric acid and stirring are added into a reaction kettle at one time, the temperature is raised, the moisture in the hydrochloric acid is removed, then the temperature is raised to the reaction temperature, and acetone is continuously introduced into the reaction kettle for reaction, and the reaction water is removed while the reaction is carried out; and then sealing the reaction system, heating, boosting, reacting for a period of time under stirring, decompressing, adding liquid alkali for neutralization, adjusting to alkalinity, separating water, distilling an oil phase, and removing unreacted acetone, water and a front fraction to obtain TMQ. Rectifying the front fraction to obtain mesitylene, aniline and kettle liquid containing TMQ monomer. Aniline and kettle liquid containing TMQ monomer are used mechanically.
And (3) obtaining TMQ polycondensation reaction liquid, adding TMQ polycondensation liquid in the intermediate tank into liquid alkali for neutralization, standing for layering, controlling the material temperature to be 200-240 ℃ under the vacuum of-0.098 MPa, and distilling to recover unreacted raw material aniline, unpolymerized TMQ monomer and the like to be used in the reaction. Cooling the kettle material, and granulating to obtain an anti-aging agent TMQ finished product, wherein the content of an effective body in the product reaches 52-63%.
The reaction time of aniline and acetone in a reaction kettle is 4-6 hours, and the temperature of the reaction kettle is controlled to be 105-140 ℃; the molar ratio of the aniline to the acetone is 1:2-6, and the molar ratio of the catalyst to the aniline is 0.01-0.3:1. Acetone is directly separated and recovered through an acetone fractionating tower on the reaction kettle, reaction water is discharged, and then the acetone is used in a raw material storage tank.
Example 1
Polycondensation reaction: 460ml of aniline, 10ml of 31% hydrochloric acid are added into a 1000ml reactor, the temperature is raised to 110 ℃ with stirring, the reaction is maintained for 2 hours, the water in the hydrochloric acid is removed, and the water content is detected to be 0.5%. And (3) continuously introducing 1600mL of acetone (the molar ratio of the acetone to the aniline is 1:3.5) at the speed of 200mL/h at the temperature of 110 ℃ to carry out polycondensation, and allowing water generated during the polycondensation and excessive acetone to pass through a fractionating tower connected with the reactor to simultaneously recover the acetone and separate water generated during the reaction. The water content of the reaction solution was measured to be 0.5%.
High pressure reaction: transferring the reaction solution into an autoclave, adding 1600mL acetone (the molar ratio of the acetone to the aniline is 1:3.5), controlling the reaction temperature to 150 ℃, stirring and reacting for 3 hours, wherein the system pressure is 1.9MPa, reducing the pressure, cooling to 100 ℃, adding 24 ml of 16% sodium hydroxide solution of liquid alkali for neutralization, separating water, distilling the oil phase under normal pressure, removing the acetone and the water, then entering into negative pressure distillation, controlling the material temperature to 180 ℃ under the vacuum of-0.098 MPa, and extracting 470g of front fraction to obtain 332g of TMQ finished product. The detection front-end packets are: aniline content 0.3%, mesitylene 72.5%, TMQ monomer content 19.3%; the main composition of the TMQ finished product is as follows: 48.58% of di-, tri-and tetra-polymers of 2, 4-trimethyl-1, 2-dihydroquinoline, 0.01% of aniline, 0.11% of isopropyl diphenylamine, 0.00% of mesitylene, 0.25% of TMQ monomer and a softening point of 88.6 ℃;
and (3) rectifying: under normal pressure, the front cut fraction is rectified by a packed rectifying column, the reflux ratio is controlled to be 5, the kettle temperature is 180-210 ℃, and the cut fraction at 165-169 ℃ is collected to obtain 325g of 1,3, 5-trimethylbenzene (mesitylene) with the content of 99.0 percent, and the content of the impurity aniline is 0.02 percent. 142g of residual kettle liquid, the main composition of which is detected to be 13.5 percent of mesitylene, 73.3 percent of TMQ monomer, 1.0 percent of primary amine, 0.8 percent of isopropyl diphenylamine and 2.5 percent of 2, 4-trimethyl-1, 2-dihydroquinoline dimer. The kettle liquid is used as a recovery raw material and is used in the polycondensation reaction.
Example 2
Polycondensation reaction: 460ml of aniline, 10ml of 31% hydrochloric acid are added into a 1000ml reactor, the temperature is raised to 110 ℃ with stirring, the reaction is maintained for 3 hours, the water in the hydrochloric acid is removed, and the water content is detected to be 0.2%. And (3) continuously introducing 1600mL of acetone (the molar ratio of the acetone to the aniline is 1:3.5) at the speed of 200mL/h at the temperature of 130 ℃ to carry out polycondensation, and allowing water generated during the polycondensation and excessive acetone to pass through a fractionating tower connected with the reactor to simultaneously recover the acetone and separate water generated during the reaction. Detecting the water content of the polycondensation reaction liquid to be 0.5%.
High pressure reaction: transferring the reaction liquid into an autoclave, adding 2000 mL acetone, controlling the reaction temperature to be 180 ℃, stirring and reacting for 5 hours, wherein the system pressure is 3.5MPa, reducing the pressure to 100 ℃, adding 24 ml of 16% sodium hydroxide solution of liquid alkali for neutralization, separating water, distilling the oil phase at normal pressure, removing acetone and water, then entering negative pressure distillation, controlling the material temperature to be 180 ℃ under the vacuum of-0.099 MPa, namely 1000Pa, and extracting 512g of front fraction to obtain 349g of TMQ finished product. The detection front-end packets are: aniline content 0.03%, mesitylene 78.8%, TMQ monomer content 16.5%; the main composition of the TMQ finished product is as follows: 45.12 percent of di, tri and tetra polymers of 2, 4-trimethyl-1, 2-dihydroquinoline, 0.00 percent of aniline, 0.08 percent of isopropyl diphenylamine, 0.00 percent of mesitylene, 0.34 percent of TMQ monomer and 92.4 ℃ of softening point.
And (3) rectifying: under normal pressure, the front cut fraction is rectified by a packed rectifying column, the reflux ratio is controlled to be 7, the kettle temperature is 180-210 ℃, and the cut fraction at 165-169 ℃ is collected, thus obtaining 365g of 1,3, 5-trimethylbenzene (mesitylene) with the content of 99.5 percent, and the content of the impurity aniline is 0.04 percent. 140g of residual kettle liquid, the main composition of which is detected to be 8.3 percent of mesitylene, 85.3 percent of TMQ monomer, 1.0 percent of primary amine, 0.4 percent of isopropyl diphenylamine and 4.5 percent of 2, 4-trimethyl-1, 2-dihydroquinoline dimer. The kettle liquid is used as a recovery raw material and is used in the polycondensation reaction.
Example 3
The main operating conditions were the same as in example 1, except that sulfuric acid was used as a catalyst, to obtain 386g of TMQ finished product. The detection front-end packets are: aniline content 0.03%, mesitylene 85.8%, TMQ monomer content 12.5%; the main composition of the TMQ finished product is as follows: 56.1 percent of di, tri and tetra polymers of 2, 4-trimethyl-1, 2-dihydroquinoline, 0.00 percent of aniline, 0.18 percent of isopropyl diphenylamine, 0.00 percent of mesitylene, 0.04 percent of TMQ monomer and the softening point of 95.5 ℃; under normal pressure, rectifying the front fraction by using a packed rectifying column, controlling the reflux ratio to be 5, controlling the kettle temperature to be 180-210 ℃, and collecting the fraction at 165-169 ℃ to obtain 465g of 1,3, 5-trimethylbenzene (mesitylene) with the content of 99.1%, wherein the content of the impurity aniline is 0.004%.
Examples 4 to 9
The experimental procedure of example 2 was used. Under the condition that other conditions are unchanged, the product quality of TMQ and trimethylbenzene is examined by changing the types of acid catalysts and the proportions of acetone and aniline and different reaction temperatures and reaction times, and the results are shown in the following table.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention, such as changing the kind of acid catalyst and the reaction temperature/time, different reaction modes, such as batch and continuous, etc. Any modification, equivalent replacement, improvement, etc. (e.g., using acetone derivatives, aniline derivatives, reaction intermediates of aniline and acetone, etc.) within the spirit and principles of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The method for preparing the anti-aging agent TMQ and co-producing mesitylene is characterized by comprising the following steps of: step (1): aniline and an acid catalyst, and acetone are added into a reactor to remove water; or aniline and acid catalyst are used for removing water, and then acetone is added; step (2): heating the material obtained in the step (1), reacting under stirring, and removing water; step (3): reacting the reaction solution obtained in the step (2) for a period of time at a certain temperature and pressure; step (4): adding liquid alkali into the reaction liquid obtained in the step (3) for neutralization, separating water, distilling an oil phase, and sequentially removing acetone, water and a front cut fraction to obtain TMQ; step (5): rectifying and separating the front fraction obtained in the step (4) to sequentially obtain mesitylene, aniline and kettle liquid containing TMQ monomers; aniline and TMQ monomers are used mechanically.
2. The method according to claim 1, characterized in that: the acid catalyst is one or more of hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, oxalic acid, copper halide, titanic acid, titanate and other acidic substances.
3. The method according to claim 1, characterized in that: the molecular ratio of the aniline, the acid catalyst and the acetone in the step (1) is 1:0.1-0.001: 6-20, preferably aniline, acid catalyst and acetone in a molecular ratio of 1:0.05-0.005: 10-15.
4. The method according to claim 1, characterized in that: the moisture removal in the steps (1) and (2) is to control the water content in the mixed solution to be below 0.3%.
5. The method according to claim 1, characterized in that: the reaction temperature in the step (2) is 100-150 ℃ and the reaction time is 1-10 hours.
6. The method according to claim 1, characterized in that: the reaction temperature in the step (3) is 120-180 ℃, the reaction time is 1-8 hours, and the reaction pressure is 0.8-4.0MPa.
7. The method according to claim 1, characterized in that: in the step (4), the oil phase is distilled, the gas phase temperature of the removed front fraction is 60-150 ℃, the liquid phase temperature is 110-180 ℃, and the pressure is 0.1-2.0 kpa.
8. The method according to claim 1, characterized in that: the aniline content in the front fraction obtained in the step (4) is 0.3-1.0%, the mesitylene is 35.0-76.0%, and the TMQ monomer content is 5.0-18.0%.
9. The method according to claim 1, characterized in that: 45-58% of di-, tri-and tetra-polymers of 2, 4-trimethyl-1, 2-dihydroquinoline in TMQ obtained in the step (4), 0.0-0.05% of aniline, 0-0.3% of isopropyl diphenylamine, 0-3.0% of mesitylene, 0-3.0% of TMQ monomer and 85-98 ℃ of softening point.
10. The method according to claim 1, characterized in that: 99.5% of mesitylene obtained in the step (5) and 0.0-0.05% of impurity aniline; the kettle liquid containing TMQ monomer mainly comprises the following components: 0-20% of mesitylene, 65.0-90.0% of 2, 4-trimethyl-1, 2-dihydroquinoline, 0-5.0% of primary amine, 0-3.0% of isopropyl diphenylamine and 0.0-3.0% of 2, 4-trimethyl-1, 2-dihydroquinoline dimer.
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