阅读说明：本技术 一种防老剂的制备方法 (Preparation method of anti-aging agent ) 是由 韦志强 付春 黄伟 高留冕 郁铭 于 2020-05-27 设计创作，主要内容包括：本发明属于精细化工技术领域,提供一种防老剂的制备方法。制备方法以苯胺和丙酮为原料,采用反应釜与密闭反应器组合,先反应釜后密闭反应器一步法制备橡胶防老剂TMQ。通过以下方式来实现：苯胺、丙酮、催化剂先在釜式反应器中反应,反应液经输送泵输送至密闭反应器中,再在密闭反应器进行强制反应,密闭反应器出口得到TMQ缩聚反应液,再与液碱进行中和、分水,油相蒸馏造粒得到TMQ。与现有的技术相比,通过调节苯胺、丙酮等原料在反应釜和密闭反应器中不同的反应时间,可以控制苯胺和丙酮的消耗,是指控制苯胺消耗在520-560kg/t,控制丙酮消耗在650-730kg/t,不仅降低消耗,同时调整消耗,降低生产成本。(The invention 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 closed reactor combination, and prepares the rubber antioxidant TMQ by a one-step method of the reaction kettle and the closed reactor. The method is realized by the following steps: aniline, acetone and a catalyst are firstly reacted in a kettle type reactor, reaction liquid is conveyed into a closed reactor through a conveying pump and then is subjected to forced reaction in the closed reactor, TMQ polycondensation reaction liquid is obtained at the outlet of the closed reactor, and then is neutralized and divided with liquid alkali, and oil phase distillation granulation is carried out to obtain TMQ. Compared with the prior art, the consumption of the aniline and the acetone can be controlled by adjusting different reaction time of the raw materials such as the aniline, the acetone and the like in the reaction kettle and the closed reactor, namely controlling the consumption of the aniline at 560kg/t and controlling the consumption of the acetone at 650-730kg/t, so that the consumption is reduced, and meanwhile, the consumption is adjusted, and the production cost is reduced.)

1. A preparation method of an 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 a rubber anti-aging agent TMQ is prepared in one step by the reaction kettle and the closed reactor; the preparation method comprises the following steps: aniline, acetone and a catalyst are firstly reacted in a kettle type reactor, reaction liquid is conveyed into a closed reactor through a conveying pump and then is subjected to forced reaction in the closed reactor, TMQ polycondensation reaction liquid is obtained at the outlet of the closed reactor, and then is neutralized and divided with liquid alkali, and oil phase distillation granulation is carried out to obtain TMQ; the consumption of the aniline and the acetone is controlled by adjusting different reaction time of the aniline and the acetone raw materials in the reaction kettle and the closed reactor.

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 of claim 1, wherein the closed reactor is one or more of a static mixer or a static mixer group, a microchannel reactor, a micro-flow field reactor and a tubular reactor.

4. The preparation method of claim 1, wherein the temperature of the reaction kettle is controlled to be 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 hour.

6. The method according to claim 1, wherein the molar ratio of aniline to acetone is 1:2 to 6, and the molar ratio of catalyst to aniline is 0.01 to 0.3: 1.

7. The preparation method of claim 1, wherein the consumption of the aniline and the acetone is controlled by adjusting different reaction time of the raw materials of the aniline and the acetone in the reaction kettle and the closed reactor: the consumption of aniline is controlled at 520-560kg/t, and the consumption of acetone is controlled at 650-730 kg/t.

8. The preparation method according to claim 1 or 7, characterized in that the different reaction time of the raw materials of aniline and acetone in the reaction kettle and the closed reactor is adjusted to be 8-1200: 1.

9. The preparation method according to claim 1 or 7, wherein the different reaction time of the raw materials of aniline and acetone in the reaction kettle and the closed reactor is adjusted to increase aniline consumption and reduce acetone consumption when the reaction time of the raw materials in the reaction kettle and the closed reactor is 8-600: 1.

10. The preparation method according to claim 1 or 7, characterized in that the reaction time of the raw materials of aniline and acetone in the reaction kettle and the closed reactor is adjusted to be different; when the reaction time of materials in a reaction kettle and a closed reactor is 601-1200: 1, the consumption of acetone is increased, and the consumption of aniline is reduced.

Technical Field

The invention belongs to the technical field of fine chemical engineering, relates to a preparation method for adjusting the raw material consumption of an anti-aging agent TMQ, and is an 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. Two-stage reactions such as an additional closed reactor and the like are carried out on the kettle type reactor, so that the continuous production of TMQ is realized, and the consumption of different raw materials is adjusted by adjusting the reaction time of the materials in the two reactors, thereby reducing the cost of the raw materials.

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 technical process of the two-step method comprises the following 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 the traditional batch kettle type process has the phenomena of less acetone and higher acetone consumption which actually participate in the reaction because a large amount of acetone is vaporized after contacting materials due to high reaction system temperature.

CN102153511 discloses a method for preparing 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (anti-aging agent TMQ), 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 the amount of waste water is small, but the solid acid catalyst is difficult to be used in the industrial production of the process.

The theoretical consumption of aniline for TMQ ton product is 542kg/t, the theoretical consumption of acetone is 676kg/t, and in practice, the consumption of aniline for domestic TMQ production is 560kg/t at 530 ℃ and the consumption of acetone for domestic TMQ production is 780kg/t at 700 ℃. In TMQ, the anti-aging di-, tri-and tetra-polymers of 2,2, 4-trimethyl-1, 2-dihydroquinoline are mainly used, so that in industrial production, the content is generally 40-50%, and the high-content TMQ products with the effective body content of more than 70% sold in the market only account for 5% or even lower of the whole TMQ market dosage, and the products with the effective body content of more than 90% are fewer and less. According to known literature and tests, an additional 50% of impurities do not contribute to the aging properties of the product.

Disclosure of Invention

The invention aims to provide a method for adjusting the consumption of raw materials of aniline and acetone in TMQ production on the premise of ensuring the quality of TMQ products by adjusting process conditions and equipment aiming at about 50 percent of other impurities without anti-aging effect, thereby reducing the production cost of TMQ.

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 closed reactor combination, and prepares the rubber antioxidant TMQ by a one-step method of the reaction kettle and the closed reactor. The preparation method is realized by the following steps: aniline, acetone and a catalyst are firstly reacted in a kettle type reactor, reaction liquid is conveyed into a closed reactor through a conveying pump and then is subjected to forced reaction in the closed reactor, TMQ polycondensation reaction liquid is obtained at the outlet of the closed reactor, and then is neutralized and divided with liquid alkali, and oil phase distillation granulation is carried out to obtain TMQ. The consumption of the aniline and the acetone is controlled by adjusting different reaction time of the raw materials such as the aniline, the acetone and the like in the reaction kettle and the 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 temperature of the reaction kettle is controlled to be 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, different reaction times of raw materials such as aniline, acetone and the like in the reaction kettle and the closed reactor are adjusted, namely 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 is increased, and the consumption of acetone is reduced, which is the consumption level of TMQ aniline and acetone raw materials.

In the preparation method, the kettle type reactor is provided with a stirrer, an acetone fractionating tower and the like.

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 consumption of the aniline and the acetone is controlled by adjusting different reaction time of the raw materials such as the aniline, the acetone and the like in the reaction kettle and the closed reactor, namely controlling the consumption of the aniline at 560kg/t and controlling the consumption of the acetone at 650-730 kg/t.

Has the advantages that:

1. compared with the prior art, the rubber antioxidant TMQ is prepared by adopting closed reactors such as a first kettle type reactor and a second static mixer, on one hand, 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 which actually participate in the reaction due to the fact that a large amount of acetone is vaporized after contacting materials because the temperature of the reaction system is high and only adopting a kettle type process are avoided, and on the other hand, the phenomena of higher IBA content and even unqualified IBA content of the product, which are caused by only adopting the closed devices such as the static mixer or a microflow field and a microchannel, are avoided.

2. The consumption of the aniline and the acetone is adjusted by adjusting different reaction time of the aniline, the acetone and other raw materials 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 in the market.

3. 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-tetramer, tri-tetramer and tetramer) of the TMQ product is 50-63 percent.

4. The reaction kettle and the closed reactor are combined, no special requirements are required for the reaction kettle and the closed reactor, no amplification effect exists, and therefore, the capacity 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 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 method for preparing the rubber antioxidant TMQ comprises the steps of adding part of aniline into a reaction kettle at one time, stirring and heating to a reaction temperature, then continuously conveying the aniline, hydrochloric acid and acetone into the reaction kettle, continuously conveying the materials in the reaction kettle into a static mixer through a material conveying pump connected to the bottom of the reaction kettle, forcibly mixing and reacting, allowing an outlet of the static mixer to enter an intermediate tank to obtain TMQ polycondensation reaction liquid, adding the TMQ polycondensation liquid in the intermediate tank into liquid alkali for neutralization, standing and layering, controlling the material temperature of an oil phase under the vacuum of-0.098 MPa, distilling and recovering unreacted aniline, an unpolymerized TMQ monomer and the like, and applying the unreacted aniline, the unpolymerized TMQ monomer and the like in the reaction. And cooling the kettle material, and granulating to obtain an anti-aging agent TMQ finished product, wherein the content of effective bodies in the product reaches 52-63%.

The reaction time of the aniline and the acetone in the reaction kettle is 4-6 hours, and the temperature of the reaction kettle is controlled to be 105-140 ℃; controlling the temperature in a static mixer to be 110-130 ℃, and controlling the reaction time to be 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 and acetone in the reaction kettle and the 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. 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, hydrochloric acid and acetone enter a reaction kettle by adopting a metering pump continuous feeding mode, the flow rate of aniline is 200g/h, the flow rate of hydrochloric acid is 15 g/h, the flow rate of acetone is 800g/h, the residence time of the mixed material in the reaction kettle is measured to be 180 minutes, the material is conveyed into a static mixer through a metering pump connected with the bottom of the reactor at the flow rate of 340g/h, controlling the reaction temperature of the static mixer to be 120 ℃, measuring the retention time of the mixed material in the static mixer to be 4 minutes, and feeding the material into an intermediate tank at the outlet of the static mixer to prepare the anti-aging agent TMQ polycondensation reaction liquid. And (3) passing the water generated in the reaction and excessive acetone through a fractionating tower on the reaction kettle, recovering the acetone and separating the water generated in the reaction, wherein after 24 hours, the single-pass conversion rate of the aniline in the reaction is 85.0%. 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 one-way yield is 77.4%, the content of effective bodies (di-polymer, tri-polymer and tetramer) reaches 50.5%, 555kg of aniline consumption and 680kg of acetone consumption are reduced by one ton of TMQ products, and compared with 540kg of aniline consumption and 710kg of acetone consumption which are reduced by a kettle reactor independently, the aniline consumption is increased, and the acetone consumption is reduced.

Example 2

The main operating conditions were the same as in example 1, but with a microfluidic field reactor of 1cm diameter and 50m length, the residence time of the mixture in the microfluidic field reactor being 10 minutes. The conversion rate of aniline was found to be 89.2%, and the content of antioxidant TMQ active ingredient was found to be 52.0%. The TMQ ton product is equivalent to the consumption of 565kg aniline and the consumption of 685kg acetone.

Example 3

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 3 static internal mixers, in which the residence time of the mixture in the static mixer was 2 minutes. The conversion rate of aniline was found to be 90.5%, and the content of antioxidant TMQ active ingredient was found to be 54.8%. The TMQ ton product is converted into 538kg/t aniline consumption and 713kg/t acetone consumption.

Example 4

The main operation conditions were the same as in example 1, except that the volume of the reaction vessel was changed, the reaction time of the materials in the reaction vessel was 6 hours, and the conversion rate of aniline was 91.5% and the content of the antioxidant TMQ active ingredient was 52.7%. The TMQ ton product is converted into aniline consumption of 562kg/t and acetone consumption of 692 kg/t.

Examples 5 to 11

The catalyst and experimental procedure of example 1 was employed. Under the condition that other conditions are not changed, the consumption of the aniline and the acetone is considered 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 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 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 changed in various ways, such as changing the flow rate or flow ratio of materials such as acetone into a closed reactor such as a reaction kettle and a static internal mixer, mixing and preheating raw materials before entering the reaction kettle or the closed reactor, 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.