CN109665991B - Preparation method of anti-aging agent TMQ - Google Patents
Preparation method of anti-aging agent TMQ Download PDFInfo
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- CN109665991B CN109665991B CN201710957725.3A CN201710957725A CN109665991B CN 109665991 B CN109665991 B CN 109665991B CN 201710957725 A CN201710957725 A CN 201710957725A CN 109665991 B CN109665991 B CN 109665991B
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention belongs to the technical field of fine chemical engineering, and relates to a preparation method of an anti-aging agent TMQ. Aniline and acetone are used as raw materials, a reaction kettle and a static mixer are combined, and the rubber antioxidant TMQ is prepared by a one-step method. The content of TMQ effective bodies in the product is 53.4-77.5%, compared with the prior art, the combination of a reaction kettle and a static mixer is adopted to carry out forced mixing contact reaction on the liquid flow of the whole reaction system, so that the mass transfer effect of the system is greatly increased, the phenomenon of higher acetone consumption in the traditional process is avoided, meanwhile, the reaction time is shortened to at least 0.05 hour from 6-12 hours, and the method has the advantages of simple operation, reliable equipment, low catalyst consumption, lower cost, higher effective body content and the like.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, relates to a continuous preparation method of an anti-aging agent TMQ, and is a green and environment-friendly preparation process.
The invention relates to a method for preparing an anti-aging agent TMQ (2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer) by continuous catalytic condensation, which is an environment-friendly and efficient preparation process. A circulating pump, a static mixer and the like are added on the traditional intermittent kettle type reactor to realize the continuity of TMQ production, thereby shortening the reaction time, reducing the raw material consumption, reducing the power cost, reducing the labor intensity and keeping the stability of production and product quality.
Background
The anti-aging agent TMQ is a di-, tri-or tetra-polymer of 2,2, 4-trimethyl-1, 2-dihydroquinoline, also called anti-aging agent RD, is a ketoamine anti-aging agent, is a faint yellow to ruin poise color particle or sheet, is mainly used as a rubber anti-aging agent, has annual demand of 10 ten thousand tons in China, is one of rubber anti-aging agent products with the largest demand in domestic and foreign markets,
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 'one-step method' process comprises the following steps: aniline and acetone are condensed and polymerized under the action of a catalyst to directly obtain an anti-aging agent TMQ polycondensation liquid of a di-polymer, a tri-polymer and a tetra-polymer containing 2,2, 4-trimethyl-1, 2-dihydroquinoline, and the TMQ polycondensation liquid is neutralized by liquid alkali, divided into water, distilled and the like to obtain TMQ. The 'two-step method' comprises the following process steps: aniline and acetone are subjected to condensation reaction under the action of a catalyst, the reaction solution or neutralized reaction solution is distilled or rectified to obtain 2,2, 4-trimethyl-1, 2-dihydroquinoline, namely a TMQ monomer, then the TMQ monomer is subjected to polymerization reaction under the action of the catalyst to obtain a di-, tri-or tetra-polymer of the 2,2, 4-trimethyl-1, 2-dihydroquinoline, and the anti-aging agent TMQ is obtained through neutralization, water diversion and distillation. In order to accelerate the reaction process, a solvent such as toluene, xylene, cyclohexane, etc. may be added to the reaction, so that the TMQ synthesis method may be classified into a "solvent method" or a "solvent-free method".
At present, the industrial production method of the anti-aging agent TMQ at home and abroad mainly adopts an intermittent process, uses hydrochloric acid as a catalyst to carry out polycondensation reaction on aniline and acetone (the process can be mainly divided into the processes of salifying, polycondensation, neutralization, distillation, granulation and the like, namely, the process comprises the steps of salifying aniline and hydrochloric acid in a reaction kettle 1 to obtain aniline hydrochloride, then the aniline hydrochloride is transferred into another reaction kettle to carry out polycondensation reaction with a large amount of acetone to obtain TMQ polycondensation liquid, the TMQ polycondensation liquid is transferred into a third reaction kettle to carry out the processes of neutralization and water diversion, and the oil phase is distilled and granulated to obtain the anti-aging agent TMQ). The method has the defects of high labor intensity, frequent operation and unstable product quality, and simultaneously, the traditional batch kettle type process has the phenomena of less acetone and higher acetone consumption which are actually participated in the reaction because the temperature of a reaction system is high and a large amount of acetone is vaporized after contacting materials, and the acetone consumption per ton of the product is about 710 plus 740kg, which is much higher than 676kg of theoretical amount.
CN102153511 discloses a method for preparing 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (antioxidant RD), in which aniline and acetone are continuously fed into a reaction tower filled with solid acid catalyst, and the reactants are condensed, the method is simple and convenient to operate and has small waste water amount, but the solid acid catalyst is difficult to be used in the industrial production of the process.
CN102010369 discloses a method for continuously preparing 2,2, 4-trimethyl-1, 2-dihydroquinoline (antioxidant RD monomer), aniline and acetone are continuously fed into a reaction tower filled with a solid acid catalyst, and a reactant containing TMQ overflows and is extracted.
At present, no report of adopting continuous process industrial production exists at home and abroad.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the TMQ preparation method which improves the stability, improves the labor intensity in the production process of the anti-aging agent TMQ, reduces the acetone consumption, saves the power and the labor cost and solves the problems of low productivity, high acetone consumption and unstable product quality in the prior art.
The invention provides a preparation method of an anti-aging agent TMQ. The preparation method takes aniline and acetone as raw materials, adopts a reaction kettle and a static mixer combination, and prepares the rubber antioxidant TMQ by a one-step method.
The preparation method is realized by the following steps: aniline, acetone and catalyst are passed through respective conveying equipment, one part or all of one or two or three substances are continuously fed into reaction still or static mixer, at the same time the material in the reaction still is fed into the static mixer by means of conveying pump to make forced reaction, one part of the material at the outlet of static mixer is circularly fed into the reaction still, another part of the material is fed into intermediate tank to obtain TMQ polycondensation reaction liquor, then the neutralization water-separation and oil-phase distillation granulation are implemented to obtain TMQ.
In the preparation method, the catalyst is one of hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, copper halide, titanic acid and titanate.
In the preparation method, the reaction temperature (the temperature controlled by the static mixer and the reaction kettle) is 90-160 ℃, and the reaction time is 0.05-3 hours.
Further, the reaction temperature is 100-130 ℃, and the reaction time is 0.2-1 hour.
In the preparation method, the molar ratio of the aniline to the acetone is 1: 1-6, and the molar ratio of the catalyst to the aniline is 0.01-0.3: 1.
Further, the molar ratio of aniline to acetone is 1: 1.5-3; the molar ratio of the catalyst to the aniline is 1: 0.05-0.15.
In the preparation method, the reaction kettle is combined with a static mixer, and the static mixer can be one or a group of static mixers consisting of several static mixers.
In the preparation method, a reaction kettle is combined with a static mixer, and the reaction kettle is provided with stirring equipment and the like.
In the preparation method, a reaction kettle is combined with a static mixer, and the reaction kettle is provided with an acetone fractionating tower.
The acetone fractionating tower has the function of separating unreacted acetone and water generated in the reaction, and the separated acetone can be directly used as a raw material.
In the preparation method, the flow ratio of the material entering the reaction kettle to the TMQ polycondensation reaction liquid entering the intermediate tank is 1-50: 1.
Has the advantages that:
1. compared with the prior art, the rubber antioxidant TMQ is prepared by combining the reaction kettle and the static mixer, the liquid flow of the whole reaction system is subjected to forced mixing contact reaction through the static mixer, the mass transfer effect of the system is greatly increased, the phenomena of less acetone and higher acetone consumption (the acetone consumption per ton product is reduced to about 680 kg) which are caused by the fact that a large amount of acetone is vaporized after contacting materials due to high temperature of the reaction system in the traditional kettle type process and actually participate in the reaction are avoided, the reaction time is shortened to be at least 0.05 hour from 6-12 hours in the traditional process, and the energy consumption is obviously reduced. The method has the advantages of simple operation, low consumption of the catalyst, raw materials and the like, low cost and high content of the effective body.
2. Aniline and acetone are used as raw materials, and the anti-aging agent TMQ is prepared by a solvent-free one-step method in the presence of a catalyst, wherein the conversion per pass of the anti-aging agent TMQ can reach over 90 percent in terms of aniline, and the content of effective bodies (di-tri-polymer and tetramer) of the TMQ product can reach 53.4-77.5 percent.
3. The reaction kettle and the static mixer are combined, no special requirements are required on the reaction kettle and the static mixer, no amplification effect exists, and therefore, the capacity is not limited, continuous production can be realized, and the device has the advantages of reliable equipment, low energy consumption and consumption, low production cost, stable product quality and the like.
Detailed Description
The following examples are provided to further illustrate the advantageous effects of the present invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
According to a typical embodiment of the invention, the preparation method of the rubber antioxidant TMQ comprises the step of preparing the rubber antioxidant TMQ by using aniline and acetone as raw materials and under the action of a catalyst (hydrochloric acid) in a one-step method.
The invention discloses a method for preparing a rubber antioxidant TMQ, wherein part of aniline is added into a reaction kettle at one time, the aniline and hydrochloric acid are continuously conveyed into the reaction kettle after the aniline and hydrochloric acid are stirred and heated to the reaction temperature, materials in the reaction kettle are continuously conveyed into a static mixer through a material conveying pump connected to the bottom, acetone is continuously introduced into the static mixer, the aniline and the acetone are forcedly mixed and reacted in the static mixer, the reaction materials at the outlet of the static mixer are divided into two parts, one part enters the reaction kettle, the other part enters an intermediate tank to obtain TMQ polycondensation reaction liquid, the TMQ polycondensation reaction liquid in the intermediate tank is added into liquid alkali for neutralization, standing and layering are carried out, the material temperature of an oil phase is controlled to be 180-260 ℃ under the vacuum of-0.098 MPa, unreacted raw materials aniline and an unpolymerized TMQ monomer are recovered through distillation and are used in the reaction. And cooling the kettle material, and granulating to obtain the finished product of the anti-aging agent TMQ, wherein the content of effective bodies in the product reaches 53.4-77.5%.
The residence time of the aniline in the static mixer is generally 0.05 to 3 hours, preferably 0.2 to 1 hour. Under normal pressure, the reaction temperature is controlled to be 90-160 ℃, and preferably 100-130 ℃. The flow ratio of the material entering the reaction kettle from the outlet of the static mixer to the TMQ polycondensation reaction liquid entering the intermediate tank is 1-50: 1, and preferably 6-10: 1. Directly separating and recovering the acetone through an acetone fractionating tower on the reaction kettle, discharging reaction water, and then mechanically applying the acetone to a raw material storage tank.
Example 1
400g of aniline was introduced into a 1000m1 reactor with stirrer, thermometer and discharge line (top connected to a fractionating column, acetone and water from the reaction entering the fractionating column, bottom connected to a transfer pump), heated to 120 ℃, under normal pressure, aniline and hydrochloric acid enter a reaction kettle by adopting a metering pump continuous feeding mode, the flow rate of the aniline is 2000g/h, the flow rate of the hydrochloric acid is 150g/h, the materials are conveyed into a static mixer by a metering pump connected with the bottom of the reactor at the flow rate of 8000g/h, simultaneously, acetone is continuously introduced into the static mixer at a flow rate of 8000g/h, the reaction temperature is controlled to be 120 ℃, the retention time of the mixed materials in the static mixer is measured to be 2 minutes, 15000g/h materials enter a reaction kettle at the outlet of the static mixer, and feeding 1000g/h of material into a tundish to prepare the anti-aging agent TMQ polycondensation reaction liquid. The water produced in the reaction and the excessive acetone pass through a fractionating tower on the reaction kettle, the acetone is recovered, the water produced in the reaction is separated, and the single-pass conversion rate of the aniline in the reaction reaches 75.4 percent. Adding liquid alkali into the polycondensation reaction liquid of the anti-aging agent TMQ for neutralization, standing for layering, carrying out a wastewater treatment system on the lower layer of wastewater, carrying out reduced pressure distillation on the upper layer of feed liquid to recover unreacted aniline and an unpolymerized TMQ monomer (the recovered aniline and the monomer are continuously used in the reaction), and granulating to obtain the finished product of the anti-aging agent TMQ, wherein the one-way yield is 67.8%, the content of effective bodies (di-polymers, tri-polymers and tetramers) reaches 64.2%, and the acetone consumption per ton product is about 680.5 kg.
Example 2
The main operating conditions were the same as in example 1, but the static mixer was changed to a static internal mixer group consisting of 5 static internal mixers, in which the residence time of the mixture in the static mixer was 10 minutes. The conversion rate of aniline was found to be 93.7%, and the content of antioxidant TMQ active ingredient was found to be 72.0%. The acetone consumption per ton product is about 678.2kg
Example 3
The main operating conditions were the same as in example 1, but the acetone addition was varied (acetone flow was constant), i.e. acetone was continuously added to the reactor together with aniline and hydrochloric acid. The conversion rate of aniline was found to be 53.7%, and the content of the antioxidant TMQ active ingredient was found to be 63.9%. The acetone consumption of the ton product is reduced to about 684.5 kg.
Example 4
The main operating conditions were the same as in example 1, except that the catalyst was changed to 60% sulfuric acid, wherein the conversion of aniline was 53.7% and the content of antioxidant TMQ active ingredient was 57.2%. The acetone consumption of ton product is converted to 687.5 kg.
Example 5
The main operating conditions were the same as in example 1, but the acetone addition was partially modified: namely, 2000g/h flow acetone, 2000g/h flow aniline and 150g/h flow hydrochloric acid are continuously added into a reaction kettle, and 6000g/h flow acetone is continuously added into a static mixer. The conversion rate of aniline was found to be 70.7%, and the content of antioxidant TMQ active ingredient was found to be 68.4%. The acetone consumption of the ton product is reduced to about 681.3 kg.
Examples 6 to 19
The catalyst and experimental procedure of example 1 was employed. Under the condition that other conditions are not changed, the single-pass conversion rate and the content of the effective body of the product of the reaction are inspected by changing the conditions of the ratio of the aniline to the acetone, the ratio of the aniline to the catalyst, different reaction temperature and reaction time, the flow ratio of materials entering a reaction kettle and a tundish and the like during the reaction, and the results are shown in the following table.
Example 20
Putting 400g of aniline into a 1000m1 reactor with a stirrer, a thermometer and a discharge pipeline (the upper part is connected to a fractionating tower, so that water generated by the reaction of acetone and the water enters the fractionating tower, the bottom is connected with a delivery pump), heating to 130 ℃, under normal pressure, continuously feeding aniline and hydrochloric acid into a reaction kettle by adopting a metering pump, wherein the flow rate of aniline is 1000g/h, the flow rate of hydrochloric acid is 150g/h, the materials are conveyed into a static mixer by the metering pump connected with the bottom of the reactor at the flow rate of 8000g/h, simultaneously continuously feeding acetone into the static mixer at the flow rate of 8000g/h, continuously feeding aniline at the flow rate of 1000g/h, controlling the reaction temperature to be 140 ℃, measuring the retention time of the mixed materials in the static mixer to be 3 minutes, discharging from the outlet of the static mixer, and feeding 15000g/h of the materials into the reaction kettle, and feeding 1000g/h of material into a tundish to prepare the anti-aging agent TMQ polycondensation reaction liquid. The water produced in the reaction and excessive acetone pass through a fractionating tower on the reaction kettle, the acetone is recovered, the water produced in the reaction is separated, and the single-pass conversion rate of the aniline in the reaction reaches 73.2%. Adding alkali into the polycondensation reaction liquid of the anti-aging agent TMQ for neutralization, standing and layering, carrying out a wastewater treatment system on the lower layer of wastewater, carrying out reduced pressure distillation on the upper layer of feed liquid to recover unreacted aniline and an unpolymerized TMQ monomer (the recovered aniline and the monomer are continuously used in the reaction), and granulating to obtain the finished product of the anti-aging agent TMQ, wherein the once-through yield is 66.6%, the content of effective bodies (di-polymer, tri-polymer and tetramer) reaches 67.3%, and the acetone consumption per ton product is about 681.1 kg.
Examples 21 to 28
The catalyst and experimental procedure of example 20 was employed. Under the condition that the total mole ratio of the aniline, the acetone and the catalyst, the reaction temperature, the reaction time and other conditions are not changed, the one-way conversion rate and the content of the effective bodies of the products of the reaction are examined by changing the conditions of the ratio of the aniline, the acetone and the catalyst added into the reaction kettle and the static mixer, 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 the present invention may be modified and varied by changing the flow rate or flow ratio of acetone or the like to the reaction vessel and the static internal mixer, mixing and preheating the raw materials before they are fed to the reaction vessel or the static mixer, and the like. Any modification, equivalent replacement, improvement and the like (such as the use of acetone derivatives, aniline and acetone reaction intermediates and the like) which are within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (5)
1. A preparation method of an anti-aging agent TMQ is characterized by comprising the following steps: aniline and acetone are used as raw materials, a reaction kettle and a static mixer are combined, and the rubber antioxidant TMQ is prepared by a one-step method; the method is realized by the following steps: aniline, acetone and catalyst are conveyed by respective conveying equipment, one part or all of one or two or three substances continuously enter a reaction kettle or a static mixer, materials in the reaction kettle are conveyed into the static mixer to carry out forced reaction, one part of the materials at the outlet of the static mixer circularly enter the reaction kettle, the other part of the materials enter an intermediate tank to obtain TMQ polycondensation reaction liquid, and then neutralization, water separation and oil phase distillation granulation are carried out to obtain TMQ; the reaction temperature for preparing the rubber antioxidant TMQ by the one-step method is 100-130 ℃, the reaction time is 0.2-1 hour, and the reaction temperature is controlled by a static mixer and a reaction kettle; the molar ratio of the aniline to the acetone is 1: 1-6, the molar ratio of the catalyst to the aniline is 0.01-0.3: 1, the catalyst is hydrochloric acid or sulfuric acid, and the flow ratio of a material entering a reaction kettle to a TMQ polycondensation reaction liquid entering a tundish is 1-50: 1.
2. The preparation method according to claim 1, wherein the molar ratio of aniline to acetone is 1: 1.5-3; the molar ratio of the catalyst to the aniline is 1: 0.05-0.15.
3. The process according to claim 1, wherein the reaction vessel is combined with a static mixer, and the static mixer is one or a combination of several static mixers.
4. The method according to claim 1, wherein the reaction vessel is combined with a static mixer, the reaction vessel is provided with a stirring device; the reaction kettle is provided with an acetone fractionating tower.
5. The process according to claim 4, wherein the acetone fractionating tower separates unreacted acetone from water produced by the reaction, and the separated acetone is directly used as a raw material.
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Families Citing this family (5)
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| CN112142657A (en) * | 2019-06-26 | 2020-12-29 | 中石化南京化工研究院有限公司 | Preparation method of anti-aging agent TMQ |
| CN112142658A (en) * | 2019-06-26 | 2020-12-29 | 中石化南京化工研究院有限公司 | Preparation method of low primary amine antioxidant TMQ |
| CN112552234B (en) * | 2019-09-10 | 2022-11-25 | 中石化南京化工研究院有限公司 | Preparation method of TMQ (Tetramethylbenzidine) anti-aging agent |
| CN113735766B (en) * | 2020-05-27 | 2023-08-29 | 中国石油化工股份有限公司 | Preparation method of anti-aging agent |
| CN114315713B (en) * | 2020-10-10 | 2024-01-30 | 中石化南京化工研究院有限公司 | Preparation method of low primary amine TMQ (TMQ) anti-aging agent |
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