CN113735766B - Preparation method of anti-aging agent - Google Patents
Preparation method of anti-aging agent Download PDFInfo
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- CN113735766B CN113735766B CN202010460382.1A CN202010460382A CN113735766B CN 113735766 B CN113735766 B CN 113735766B CN 202010460382 A CN202010460382 A CN 202010460382A CN 113735766 B CN113735766 B CN 113735766B
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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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Abstract
The application belongs to the technical field of fine chemical engineering, and provides a preparation method of an anti-aging agent. The preparation method takes aniline and acetone as raw materials, adopts a reaction kettle and a closed reactor to be combined, and prepares the rubber anti-aging agent TMQ by a one-step method of firstly reacting the kettle and then closing the reactor. This is achieved by: aniline, acetone and a catalyst react in a kettle reactor, reaction liquid is conveyed into a closed reactor through a conveying pump, forced reaction is carried out in the closed reactor, TMQ polycondensation reaction liquid is obtained at an outlet of the closed reactor, neutralization and water separation are carried out with liquid alkali, and oil phase distillation granulation is carried out to obtain TMQ. Compared with the prior art, the consumption of aniline and acetone can be controlled by adjusting different reaction time of raw materials such as aniline, acetone and the like in a reaction kettle and a closed reactor, namely the consumption of aniline is controlled to be 520-560kg/t, the consumption of acetone is controlled to be 650-730kg/t, the consumption is reduced, and meanwhile, the consumption is adjusted, so that the production cost is reduced.
Description
Technical Field
The application belongs to the technical field of fine chemical engineering, relates to a preparation method for adjusting raw material consumption of an anti-aging agent TMQ, and is an environment-friendly preparation process.
The application relates to a method for preparing an anti-aging agent TMQ (2, 4-trimethyl-1, 2-dihydroquinoline polymer) by continuous catalytic condensation. The kettle type reactor is additionally provided with a closed reactor and other two-stage reactions, so that the continuous production of TMQ is realized, and meanwhile, the reaction time of materials in the two reactors is adjusted to adjust the consumption of different raw materials, thereby reducing the cost of the raw materials.
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 color particles or flakes, is mainly used as a rubber anti-aging agent, has annual demand of 10 ten thousand tons at home and abroad, 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.
The existing industrial production method of the anti-aging agent TMQ at home and abroad mainly adopts an intermittent method process, uses hydrochloric acid as a catalyst to carry out polycondensation reaction on aniline and acetone (the process can be mainly divided into the procedures of salifying, polycondensing, neutralizing, distilling, granulating and the like, namely, the aniline and the hydrochloric acid are dehydrated to form salt in a reaction kettle 1 to obtain the salt forming procedure of aniline hydrochloride, then the aniline hydrochloride is transferred into a polycondensation procedure of polycondensation reaction between the aniline hydrochloride and a large amount of acetone in another reaction kettle to obtain TMQ polycondensation liquid, and the TMQ polycondensation liquid is transferred into a third reaction kettle to carry out the procedures of neutralizing and separating, and oil phase is distilled, granulating and the like to obtain the anti-aging agent TMQ). The method has the defects of high labor intensity, frequent operation and unstable product quality, and meanwhile, the traditional batch kettle process has the phenomena of less acetone and higher consumption of acetone which actually participate in the reaction because a large amount of acetone is vaporized after contacting materials due to high temperature of a reaction system.
CN102153511 discloses a method for preparing 2, 4-trimethyl-1, 2-dihydroquinoline polymer (anti-aging agent TMQ), which continuously pumps aniline and acetone into a reaction tower filled with a solid acid catalyst, and condenses the reactants, the method is simple and convenient to operate, the amount of waste water is small, but the solid acid catalyst is difficult to be used in the industrial production of the process.
TMQ ton products consume 542kg/t of aniline theoretical quantity, 676kg/t of acetone theoretical quantity, and in practice TMQ production in China, aniline consumption is 530-560kg/t, and acetone consumption is 700-780kg/t. As the TMQ is mainly the di-, tri-and tetra-polymers of 2, 4-trimethyl-1, 2-dihydroquinoline which can play an anti-aging role, the content of the TMQ is generally 40-50% in industrial production, and the high-content TMQ product with the effective body content of more than 70% sold in the market only accounts for 5% or even lower of the using amount of the whole TMQ market, so that the product with the effective body content of more than 90% is less. According to known literature and tests, it has been shown that a further 50% of impurities do not contribute to the ageing properties of the product.
Disclosure of Invention
The application aims at providing a method for adjusting consumption of aniline and acetone raw materials in TMQ production on the premise of guaranteeing TMQ product quality by adjusting process conditions and equipment aiming at about 50% of other impurities without anti-aging effect, thereby reducing TMQ production cost.
The application 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 closed reactor to be combined, and prepares the rubber anti-aging agent TMQ by a one-step method of firstly reacting the kettle and then closing the reactor. The preparation method is realized by the following steps: aniline, acetone and a catalyst react in a kettle reactor, reaction liquid is conveyed into a closed reactor through a conveying pump, forced reaction is carried out in the closed reactor, TMQ polycondensation reaction liquid is obtained at an outlet of the closed reactor, neutralization and water separation are carried out with liquid alkali, and oil phase distillation granulation is carried out to obtain TMQ. The consumption of aniline and acetone is controlled by adjusting different reaction time of raw materials such as aniline, acetone and the like in a reaction kettle and a closed reactor.
In the preparation method, the catalyst is one of hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, copper halide, titanic acid and titanate.
In the preparation method, the closed reactor refers to one or more of a static mixer or a static mixer group, a microchannel reactor, a micro-flow field reactor and a tubular reactor.
In the preparation method, the reaction kettle is controlled to be at 105-140 ℃ and the reaction time is 4-6 hours;
in the preparation method, the temperature of the closed reactor is controlled to be 110-130 ℃, and the reaction time is 0.005-0.5 hour;
in the preparation method, the molar ratio of aniline to acetone is 1:2-6, and the molar ratio of the catalyst to aniline is 0.01-0.3:1.
In the preparation method, by adjusting different reaction time of raw materials such as aniline, acetone and the like in the reaction kettle and the closed reactor, the reaction time of the materials in the reaction kettle and the closed reactor is adjusted to be 40-1200:1; when the reaction time of the materials in the reaction kettle and the closed reactor is 8-600:1, the consumption of aniline is increased, and the consumption of acetone is reduced; when the reaction time of the materials in the reaction kettle and the closed reactor is 601-1200:1, the consumption of acetone is increased, and the consumption of aniline is reduced.
In the preparation method, the consumption of aniline rises and the consumption of acetone decreases, which means the consumption level of TMQ aniline and acetone raw materials.
In the preparation method, a kettle-type reactor is provided with stirring, an acetone fractionating tower and the like.
The acetone fractionating tower is used for separating unreacted acetone from water generated by the reaction, and the separated acetone can be directly used as a raw material.
In the preparation method, the consumption of aniline and acetone is controlled by adjusting different reaction time of raw materials such as aniline, acetone and the like in a reaction kettle and a closed reactor, namely the consumption of aniline is controlled to be 520-560kg/t, and the consumption of acetone is controlled to be 650-730kg/t.
The beneficial effects are that:
1. compared with the prior art, the rubber aging inhibitor TMQ is prepared by adopting the closed reactors such as the first kettle type reactor and the second static mixer, on one hand, the forced mixing contact reaction is carried out on the liquid flow of the whole reaction system through the static mixer, so that the mass transfer effect of the system is greatly improved, the phenomena of less acetone and higher acetone consumption, which are caused by the fact that a large amount of acetone contacts materials and is actually involved in the reaction, are avoided due to the fact that the kettle type process is adopted only, and on the other hand, the phenomena of higher or even unqualified IBA content of harmful substances of products are avoided due to the fact that the static mixer or the closed equipment such as micro-flow field and micro-channels are adopted only.
2. The consumption of the aniline and the acetone is regulated by regulating the different reaction time of the raw materials such as the aniline, the acetone and the like in the reaction kettle and the closed reactor, and the production cost is reduced along with the price fluctuation of the aniline and the acetone on the market.
3. The method takes aniline and acetone as raw materials, prepares the anti-aging agent TMQ by a solvent-free one-step method in the presence of a catalyst, and the single pass conversion rate of the anti-aging agent TMQ can reach more than 90 percent by counting aniline, and the effective body content (two, three and four polymers) of the product TMQ is 50 to 63 percent.
4. The reaction kettle and the closed reactor are combined, special requirements and amplification effects are not generated on the reaction kettle and the closed reactor, so that the productivity is not limited, continuous production can be realized, and the method has the advantages of reliable equipment, low energy consumption and consumption, low production cost, stable product quality and the like.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
According to an exemplary embodiment of the application, 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 through a one-step method under the action of a catalyst (hydrochloric acid).
According to the method for preparing the rubber antioxidant TMQ, part of aniline is added into a reaction kettle at one time, hydrochloric acid is stirred and heated to the reaction temperature, then aniline, hydrochloric acid and acetone are continuously conveyed into the reaction kettle, materials in the reaction kettle are continuously conveyed into a static mixer through a material conveying pump connected with the bottom, forced mixing reaction is carried out, an outlet of the static mixer enters an intermediate tank to obtain TMQ polycondensation reaction liquid, TMQ polycondensation reaction liquid in the intermediate tank is added into liquid alkali for neutralization, standing and layering are carried out, the temperature of the materials is controlled to be 200-240 ℃ under the vacuum of-0.098 MPa, and unreacted raw material aniline, unpolymerized TMQ monomers and the like are distilled and recovered 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 ℃; controlling the temperature to be 110-130 ℃ in a static mixer, and reacting for 0.005-0.1 hour; 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. When the reaction time of materials such as aniline, acetone and the like in a reaction kettle and a static mixer is 8-600:1, the consumption of aniline is increased, and the consumption of acetone is reduced; when the reaction time of the materials in the reaction kettle and the static mixer is 601-1200:1, the consumption of acetone is increased, and the consumption of aniline is reduced. 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
400g of aniline is put into a reactor with a stirrer, a thermometer and a discharge pipeline (the upper part of the reactor is connected to a fractionating tower, acetone and water generated by reaction enter the fractionating tower, the bottom of the reactor is connected with a conveying pump), the temperature is raised to 120 ℃, under normal pressure, aniline, hydrochloric acid and acetone enter the reaction kettle in a metering pump continuous feeding mode, the flow rate of the aniline is 200g/h, the flow rate of the hydrochloric acid is 15 g/h, the flow rate of the acetone is 800g/h, the residence time of the mixture in the reaction kettle is 180 minutes, the mixture is conveyed into a static mixer through a metering pump connected with the bottom of the reactor at the flow rate of 340g/h, the reaction temperature of the static mixer is controlled to 120 ℃, the residence time of the mixture in the static mixer is controlled to 4 minutes, the mixture enters an intermediate tank at an outlet of the static mixer, and the anti-aging agent TMQ polycondensation reaction liquid is prepared. And (3) passing the water generated during the reaction and excessive acetone through a fractionating tower on a reaction kettle, recovering the acetone, separating the water generated during the reaction, and after 24 hours, enabling the single-pass conversion rate of aniline in the reaction to reach 85.0%. And neutralizing the anti-aging agent TMQ polycondensation reaction liquid with liquid caustic soda, standing for layering, carrying out a wastewater treatment system on the lower-layer wastewater, carrying out reduced pressure distillation on the upper-layer wastewater to recover unreacted aniline and unpolymerized TMQ monomers (the recovered aniline and the monomers are continuously used in the reaction), and granulating to obtain an anti-aging agent TMQ finished product, wherein the single-pass yield is 77.4%, the content of effective bodies (second, third and fourth polymers) reaches 50.5%, the conversion aniline consumption of TMQ ton products is 555kg, the acetone consumption is 680kg, and compared with the aniline consumption of 540kg and the acetone consumption of 710kg of ton products converted by a single kettle reactor, the aniline consumption is improved, and the acetone consumption is reduced.
Example 2
The main operating conditions were the same as in example 1, but with a 1cm diameter and a 50m length of the microflow field reactor, wherein the residence time of the mixture in the microflow field reactor was 10 minutes. The conversion of aniline was measured to be 89.2% and the content of the antioxidant TMQ active body was measured to be 52.0%. TMQ ton product conversion aniline consumed 565kg and acetone consumed 685kg.
Example 3
The main operating conditions were the same as in example 1, except that the static mixer was changed to a static internal mixer group consisting of 3 static internal mixers, in which the residence time of the mixture in the static mixer was 2 minutes. The conversion of aniline was measured to be 90.5% and the content of the antioxidant TMQ active body was measured to be 54.8%. TMQ ton product conversion aniline consumed 538kg/t and acetone consumed 713kg/t.
Example 4
The main operation conditions are the same as in example 1, but the volume of the reaction kettle is changed, the reaction time of the materials in the reaction kettle is 6 hours, and the conversion rate of the aniline is 91.5%, and the content of the anti-aging agent TMQ effective body is 52.7%. TMQ ton product conversion aniline consumed 562kg/t and acetone consumed 692kg/t.
Examples 5 to 11
The catalyst and experimental procedure of example 1 were used. Under the condition that other conditions are unchanged, the consumption of aniline and acetone is inspected by changing the conditions of the reaction conditions such as the proportion of aniline to acetone, the proportion of aniline to catalyst, different reaction temperatures and reaction time, the reaction time of materials in a reaction kettle and a closed reactor and the like, and the results are shown in the following table:
the above description is only a preferred embodiment of the present application, and is not intended to limit the present application, and it will be apparent to those skilled in the art that various modifications and variations can be made in the present application, such as changing the flow rate or the ratio of the material such as acetone to the reaction vessel and the closed reactor such as the static internal mixer, mixing the raw materials before the material is fed to the reaction vessel or the closed reactor, preheating, 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 application are intended to be included in the scope of the present application.
Claims (7)
1. The preparation method of the anti-aging agent is characterized in that aniline and acetone are used as raw materials, a reaction kettle and a closed reactor are combined, and the rubber anti-aging agent TMQ is prepared by a one-step method of firstly reacting the kettle and then closing the reactor; the preparation method comprises the following steps: aniline, acetone and a catalyst react in a kettle reactor, reaction liquid is conveyed into a closed reactor through a conveying pump, forced reaction is carried out in the closed reactor, TMQ polycondensation reaction liquid is obtained at an outlet of the closed reactor, neutralization and water separation are carried out with liquid alkali, and oil phase distillation granulation is carried out to obtain TMQ; the consumption of aniline and acetone is controlled by adjusting different reaction time of aniline and acetone raw materials in a reaction kettle and a closed reactor; the different reaction time means that the reaction time of materials in a reaction kettle and a closed reactor is adjusted to be 8-1200:1, and when the reaction time ratio of the materials to the closed reactor is 8-600:1, the consumption of aniline is increased, and the consumption of acetone is reduced; at 601-1200:1, the acetone consumption increases and the aniline consumption decreases.
2. The method of claim 1, wherein the catalyst is one of hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, copper halide, titanic acid and titanate.
3. The preparation method according to claim 1, wherein the closed reactor is one or more of a static mixer or a static mixer group, a microchannel reactor, a microfluidic field reactor and a tubular reactor.
4. The preparation method of claim 1, wherein the reaction kettle is controlled to be at a temperature of 105-140 ℃ and the reaction time is 4-6 hours.
5. The preparation method according to claim 1, wherein the temperature of the closed reactor is controlled to be 110-130 ℃ and the reaction time is 0.005-0.5 hours.
6. The preparation method according to claim 1, wherein the molar ratio of aniline to acetone is 1:2-6, and the molar ratio of catalyst to aniline is 0.01-0.3:1.
7. The preparation method according to claim 1, wherein the consumption of aniline and acetone is controlled by adjusting different reaction time of aniline and acetone raw materials in a reaction kettle and a closed reactor: controlling aniline consumption at 520-560kg/t and acetone consumption at 650-730kg/t.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316941A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Method for continuous neutralization and water separation of polycondensation liquid in production process of antioxidant TMQ |
| CN108003095A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of antioxidant TMQ and preparation method thereof |
| CN109665991A (en) * | 2017-10-16 | 2019-04-23 | 中国石油化工股份有限公司 | A kind of preparation method of anti-aging agent TMQ |
| CN111039865A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Preparation method of anti-aging agent TMQ |
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- 2020-05-27 CN CN202010460382.1A patent/CN113735766B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316941A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Method for continuous neutralization and water separation of polycondensation liquid in production process of antioxidant TMQ |
| CN108003095A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of antioxidant TMQ and preparation method thereof |
| CN109665991A (en) * | 2017-10-16 | 2019-04-23 | 中国石油化工股份有限公司 | A kind of preparation method of anti-aging agent TMQ |
| CN111039865A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Preparation method of anti-aging agent TMQ |
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