CN111039865A - Preparation method of anti-aging agent TMQ - Google Patents
Preparation method of anti-aging agent TMQ Download PDFInfo
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- CN111039865A CN111039865A CN201811196739.9A CN201811196739A CN111039865A CN 111039865 A CN111039865 A CN 111039865A CN 201811196739 A CN201811196739 A CN 201811196739A CN 111039865 A CN111039865 A CN 111039865A
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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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- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, and relates to a preparation method of an anti-aging agent TMQ, which comprises the steps of separating TMQ polycondensation reaction liquid to respectively obtain light components, TMQ monomers, kettle liquid and the like, wherein the light components comprise recovered acetone, recovered aniline and the like which are used as recovered raw materials for mechanical application, and the kettle liquid is used as a catalyst for condensation and polymerization for mechanical application, so that the use amount of the catalyst is reduced, the three-waste emission is reduced, and the environment-friendly production of the TMQ is realized.
Description
Technical Field
The invention relates to a preparation method of an anti-aging agent TMQ, in particular to a preparation method of the anti-aging agent TMQ for realizing the recycling of a catalyst, which is a preparation method of the anti-aging agent TMQ with relatively low cost and environmental protection, and belongs to the technical field of organic synthesis.
Background
The anti-aging agent TMQ is a di-, tri-or tetra-polymer of 2,2, 4-trimethyl-1, 2-dihydroquinoline, is also called anti-aging agent RD, is mainly used as an antioxidant for rubber and rubber products, is suitable for natural rubber, synthetic rubber and latex, has stronger inhibiting effect on the catalytic oxidation of harmful metal ions such as copper, manganese and the like, and has good compatibility with rubber, low volatility, small blooming property and high extraction resistance. The rubber is widely used by rubber processing industry at home and abroad, and is added to common tires, radial tires or other rubber products to achieve better protection efficiency.
The anti-aging agent TMQ is prepared by firstly condensing aniline and acetone under acidic conditions to generate a monomer TMDQ (2, 2, 4-trimethyl-1, 2-dihydroquinoline), polymerizing the TMDQ to generate reaction liquid of di-tri-tetramer, tetramer of TMDQ, neutralizing with liquid alkali, distilling and the like. The general process of production: dehydrating aniline and hydrochloric acid to obtain aniline hydrochloride; carrying out polycondensation reaction on aniline hydrochloride and acetone to obtain TMQ polycondensation liquid; adding liquid alkali into the polycondensation liquid for neutralization and water separation; and distilling and granulating the oil phase to obtain a TMQ finished product.
CN86100665A and RU2009148 use hydrochloric acid as catalyst, and toluene organic solvent to take away water generated by condensation reaction of aniline and acetone to form 2,2, 4-trimethyl-1, 2-dihydroquinoline. JP56014516 synthesizes 2,2, 4-trimethyl-1, 2-dihydroquinoline monomer by using p-toluenesulfonic acid and zinc chloride as catalysts, toluene as solvent and aniline and acetone as raw materials. The method has the disadvantages that the used catalysts, namely p-toluenesulfonic acid and zinc chloride, cannot be regenerated and recycled after being consumed, more waste liquid is generated, equipment is corroded, and the toxicity of toluene is high. JP58136625 uses copper chloride as catalyst, aniline and acetone as raw materials, and the amount of catalyst is 5% (mole ratio) of aniline. In this method, it is difficult to separate the catalyst layer during neutralization and washing and difficult to filter the catalyst.
JP57011967 and EP01893834 use BF3 as a catalyst to condense aniline and acetone, and the aniline conversion rate is low. Boron trifluoride used as a catalyst is difficult to prepare and expensive, and boron trifluoride and products thereof are highly toxic and cause water pollution after decomposition.
CN102584696A adopts a one-step solvent-free method, utilizes solid acid resin as a catalyst, cancels a hydrochloric acid catalyst in the traditional process, effectively utilizes front cut fraction, and prepares the rubber antioxidant TMQ through the steps of salifying, condensing, neutralizing, decompressing, distilling and the like.
CN108003095A describes a more common production method of TMQ: 1) batch kettle method: the method comprises the steps of putting raw material aniline and a catalyst into a kettle at one time, feeding acetone in a continuous dropwise manner, and generally keeping the feeding reaction time for 2-7 hours. Under normal pressure, the reaction temperature is controlled to be 90-150 ℃, acetone is directly separated and recovered through a fractionating tower on a reaction kettle, and then the acetone is mechanically applied to a raw material storage tank. 2) Continuous tower process: aniline and catalyst titanate are continuously fed from the top of the tower, acetone is vaporized and then fed from the bottom of the tower in a gas phase manner, and continuous reaction is carried out in the tower. Under normal pressure, the reaction temperature is controlled to be 90-150 ℃. The retention time of the materials in the tower is 3-7 hours. The acetone and the water generated in the reaction process are simultaneously evaporated, then the acetone is directly separated and recovered by a fractionating tower, and meanwhile, the anti-aging agent TMQ polycondensation reaction liquid generated by the reaction and the like continuously flow into a receiving groove at the bottom of the tower. Adding TMQ polycondensation liquid in a reaction kettle or a receiving tank into liquid alkali for neutralization, standing and layering, controlling the material temperature at 180-260 ℃ under the vacuum condition of-0.098 MPa, and distilling. And cooling the kettle material, and granulating to obtain an anti-aging agent TMQ finished product, wherein the content of effective TMQ di-, tri-and tetramers in the product reaches 60-75%.
At present, the industrial production method of the anti-aging agent TMQ at home and abroad mainly uses hydrochloric acid as a catalyst to carry out polycondensation reaction on aniline and acetone, and has the main characteristics of simple synthesis method, short flow and mature process. However, catalysts such as hydrochloric acid are used, the molar ratio of the catalysts to aniline is generally 1: 1-10, the usage amount is large, a large amount of high-salinity wastewater is generated in the neutralization process, the treatment is needed, and the burden of post-treatment is greatly increased.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and realizes the recycling of the catalyst through process improvement in the TMQ production process, thereby reducing the usage amount of the catalyst, reducing the discharge of three wastes and realizing the environment-friendly production of the TMQ.
The invention provides a preparation method of an anti-aging agent TMQ, which is realized by the following steps: and (2) carrying out polycondensation reaction on aniline and acetone under the action of a catalyst to generate TMQ reaction liquid, and separating the TMQ reaction liquid to respectively obtain a light component, a TMQ monomer, kettle liquid and the like. Adding a TMQ monomer into a catalyst to carry out polymerization reaction, neutralizing a polymerization reaction liquid by using liquid alkali, dividing water, and distilling an oil phase to obtain the TMQ. The residue is used as catalyst for reuse.
Generally, the polycondensation reaction comprises aniline, acetone and catalyst in a molar ratio of 1:1.5-7:0.001-0.5, a reaction time of 0.001-10 h and a reaction temperature of 90-200 ℃.
In the polymerization reaction, the molar ratio of the TMQ monomer to the catalyst is 1:0.001-0.5, the reaction time is 0.001-10 h, and the reaction temperature is 50-200 ℃.
The TMQ reaction liquid is separated in a distillation or rectification mode.
The light components comprise recovered acetone, recovered aniline and the like, and can be used as recovered raw materials for reuse.
The catalyst is one or more of hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, oxalic acid and the like.
The recovered acetone mainly comprises acetone, a small amount of amine, water, mesityl oxide and the like, and the separation conditions are normal pressure and the gas phase temperature is 55-120 ℃.
The recovered aniline mainly comprises aniline, a small amount of acetone, water, 2, 4-trimethyl-1, 2-dihydroquinoline, dimer and polymer, isopropyl diphenylamine and the like, and the separation condition is normal pressure or reduced pressure. Under the normal pressure condition, the gas phase temperature is 121-; the gas phase temperature is 60-100 ℃ under the reduced pressure condition (1-500 KPa).
The TMQ monomer mainly comprises 2,2, 4-trimethyl-1, 2-dihydroquinoline, a small amount of aniline, dimer and polymer of 2,2, 4-trimethyl-1, 2-dihydroquinoline, isopropyl diphenylamine and the like, and the separation conditions are reduced pressure (1-500 KPa) and the gas phase temperature is 101-200 ℃.
The kettle solution contains: 1) monomers and di-, tri-, tetramers of TMQ; 2) the catalyst and alkaline substances such as aniline, TMQ monomer, isopropyl aniline and the like form salts and the like, such as aniline salt, TMQ monomer salt, TMQ dimer salt and the like; 3) Small amounts of aniline, isopropyl diphenylamine, etc.; 5) pentamer, hexamer, etc. of TMQ monomer.
The step of mechanically applying the kettle liquid as a catalyst means that the kettle liquid is mechanically applied to polycondensation and/or polymerization as the catalyst.
It should be noted that the above steps of the present invention, which are not invariable nor in definite sequence, are used as an integral part of TMQ production, including the above processes, and may be crossed and applied therein.
Advantageous effects
The method utilizes the characteristic that the dosage of the catalyst is large (about 90 percent) in the preparation process of the TMQ monomer (namely, aniline and acetone condensation), and the catalyst is small in the preparation process of the monomer to the di-, tri-and tetra-polymers (namely, polymerization), and utilizes the acidity of the catalyst and the alkalinity of aniline substances to form firmer salts, so that the catalyst is not easily decomposed in the separation process of TMQ reaction liquid, the catalyst can be recycled in the early stage aniline and acetone condensation reaction process, the dosage of the catalyst is reduced by 80-95 percent, 90 percent of neutralization liquid alkali and high-salt wastewater are reduced, and the method is a green and environment-friendly synthesis process.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1
The embodiment comprises four steps:
①, dehydrating aniline hydrochloric acid to form salt, adding acetone for polycondensation to obtain TMQ polycondensation liquid, and separating the TMQ polycondensation liquid;
②, polymerizing, neutralizing and distilling the monomer to obtain a TMQ finished product;
step ③, mechanically applying the kettle liquid in step ①, namely adding aniline and the kettle liquid, salifying, adding acetone for condensation polymerization to obtain TMQ condensation polymerization liquid, and separating the TMQ condensation polymerization liquid;
and ④, repeating the step ② to polymerize the monomer, neutralize and distill to obtain the TMQ finished product.
Thereby realizing the recycling of the acid catalyst in the stage of preparing the TMQ monomer by condensing aniline and acetone.
Specifically, the method comprises the following steps:
①, adding 620 g aniline and 48.8 g 30% hydrochloric acid into a 2000ml reactor, stirring for 2 hours at 120 ℃, removing water in the hydrochloric acid, then adding 1348 g acetone under the stirring condition at 130 ℃, maintaining for 0.5 hour, obtaining TMQ reaction liquid, distilling the reaction liquid, and obtaining recovered acetone (normal pressure, gas phase temperature 55-120 ℃), recovered aniline (100 KPa, gas phase temperature 60-100 ℃), TMQ monomer (reduced pressure (30 KPa), gas phase temperature 110-160 ℃) and kettle liquid in sequence, wherein the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramer in the TMQ monomer is 95.91% by detection.
②, adding 2.6 g of 30% hydrochloric acid into 200 g of TMQ monomer in the step ①, stirring for 4 hours at 130 ℃, adding 3.0 g of liquid alkali for neutralization, separating out a water phase, distilling an organic phase under vacuum of-0.098 MPa to obtain 183 g of a kettle liquid, namely an anti-aging agent TMQ finished product, wherein the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 87.32% through detection.
③, adding 620 g of aniline and 50 g of kettle liquid in the step ① into a 2000ml reactor, stirring for 2 hours at 120 ℃, then adding 1348 g of acetone under the stirring condition at 130 ℃, maintaining for 0.5 hour to obtain TMQ reaction liquid, distilling the reaction liquid, and sequentially obtaining recovered acetone, recovered aniline, TMQ monomer and kettle liquid, wherein the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di, tri and tetramer in the TMQ monomer is 94.63 percent through detection.
And ④, repeating the step ②, namely, taking 200 g of TMQ monomer in the step ③, adding 2.6 g of 30% hydrochloric acid, stirring for 4.5 hours at 130 ℃, adding 3.0 g of liquid alkali for neutralization, separating a water phase, distilling an organic phase under vacuum of-0.098 MPa to obtain a kettle liquid, namely 176 g of an anti-aging agent TMQ finished product, wherein the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 88.22% by detection.
Example 2
The other conditions were the same as example 1, except that in step ③, 620 g of aniline and 50 g of the bottom solution obtained in step ① were added to a 2000ml reactor, 1348 g of acetone was added under stirring at 130 ℃ and the mixture was maintained for 0.5 hour to obtain a TMQ reaction solution, and the reaction solution was distilled to obtain successively recovered acetone, recovered aniline, TMQ monomer and bottom solution, and it was confirmed that the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers in TMQ monomer was 93.52%.
186 g of finished product of the antioxidant TMQ is obtained in the step ②, the content of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 89.30% through detection, and 179 g of finished product of the antioxidant TMQ is obtained in the step ④, and the content of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 87.21% through detection.
Example 3
Other conditions were the same as in example 1, except that,
and ②, adding 200 g of TMQ monomer in the step ① into 10 g of kettle liquid in the step ①, stirring for 4 hours at 130 ℃, adding 6.5 g of liquid alkali for neutralization, separating out a water phase, distilling an organic phase under vacuum of-0.098 MPa to obtain 195 g of kettle liquid, namely an anti-aging agent TMQ finished product, wherein the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 80.33% by detection.
Example 4
Other conditions were the same as in example 1, except that,
and ④, adding 200 g of TMQ monomer in the step ③ into 13 g of kettle liquid in the step ①, stirring for 4.5 hours at 130 ℃, adding 8.2 g of liquid alkali for neutralization, separating out a water phase, and distilling an organic phase under vacuum of-0.098 MPa to obtain the kettle liquid, namely 196 g of the finished product of the antioxidant TMQ, wherein the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 81.25 percent through detection.
Example 5
Otherwise, the process was as in example 1, except that sulfuric acid was used as the catalyst
226 g of finished product of the antioxidant TMQ is obtained in the step ②, the content of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 83.30% through detection, and 199 g of finished product of the antioxidant TMQ is obtained in the step ④, and the content of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 77.21% through detection.
Example 6
Other conditions were the same as in example 1 except that p-toluenesulfonic acid was used as a catalyst
206 g of finished product of the anti-aging agent TMQ is obtained in the step ②, the content of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 89.30% through detection, and 152 g of finished product of the anti-aging agent TMQ is obtained in the step ④, and the content of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 87.51% through detection.
Example 7
The other conditions were the same as in example 1 except that p-oxalic acid was used as a catalyst
153 g of finished product of the antioxidant TMQ is obtained in the step ②, the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di, tri and tetramers is 88.22% through detection, and 132 g of finished product of the antioxidant TMQ is obtained in the step ④, and the content of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di, tri and tetramers is 85.03% through detection.
Example 8
Other conditions were the same as in example 1, except that,
and ②, adding excessive distillation kettle liquid into the monomer, polymerizing, neutralizing and distilling to obtain 353 g of an antioxidant TMQ finished product, wherein the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di, tri and tetramers is 58.22% by detection, ④ is to obtain 132 g of the antioxidant TMQ finished product, and the content of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di, tri and tetramers is 90.03% by detection.
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 conversion conditions of the biological system and the reaction material ratio of aniline, etc. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of an anti-aging agent TMQ is characterized in that aniline and acetone are subjected to polycondensation reaction under the action of a catalyst to generate TMQ reaction liquid, the TMQ reaction liquid is separated to respectively obtain a light component, a TMQ monomer and kettle liquid, the TMQ monomer is added into the catalyst to carry out polymerization reaction, the polymerization reaction liquid is neutralized by liquid alkali, water is separated, an oil phase is distilled to obtain the TMQ, and the kettle liquid is used as the catalyst for application.
2. The method of claim 1, wherein: the polycondensation reaction comprises the steps of carrying out the condensation polymerization reaction on aniline, acetone and a catalyst in a molar ratio of 1:1.5-7:0.001-0.5, wherein the reaction time is 0.001-10 h and the reaction temperature is 90-200 ℃; in the polymerization reaction, the molar ratio of the TMQ monomer to the catalyst is 1:0.001-0.5, the reaction time is 0.001-10 h, and the reaction temperature is 50-200 ℃.
3. The method according to claim 1, wherein the separation of the TMQ reaction solution is distillation or rectification.
4. The method according to claim 1, wherein the light components comprise recovered acetone and recovered aniline, and the light components are used as recovered raw materials for recycling.
5. The preparation method of claim 1, wherein the catalyst is one or more of hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, oxalic acid, and the like.
6. The process of claim 4, wherein the recovered acetone comprises acetone, a small amount of amine, water, and mesityl oxide, and the separation conditions are normal pressure and the vapor phase temperature is 55-120 ℃.
7. The process according to claim 4, wherein the aniline recovered comprises aniline, small amounts of acetone, water, 2, 4-trimethyl-1, 2-dihydroquinoline and dimer and multimer, isopropyldiphenylamine, and the separation is carried out under normal or reduced pressure; under the normal pressure condition, the gas phase temperature is 121-; under reduced pressure conditions: 1-500KPa, and the gas phase temperature is 60-100 ℃.
8. The method as claimed in claim 1, wherein the TMQ monomer comprises 2,2, 4-trimethyl-1, 2-dihydroquinoline, small amount of aniline, dimer and polymer of 2,2, 4-trimethyl-1, 2-dihydroquinoline, and isopropyldiphenylamine, and is separated under reduced pressure of 1-500KPa and gas phase temperature of 101-.
9. The method of claim 1, wherein the bottoms comprises: 1) monomers and di-, tri-, tetramers of TMQ; 2) salts formed by the catalyst and alkaline substances, wherein the salts are aniline salts, TMQ monomer salts and TMQ dimer salts; 3) Small amounts of aniline, isopropyl diphenylamine; 4) a homopolymer of TMQ monomer.
10. The process according to claim 1, wherein the step of using the residue as a catalyst is carried out by using the residue as a catalyst in the polycondensation and/or polymerization.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113402457A (en) * | 2021-07-13 | 2021-09-17 | 宁波海利化工有限公司 | Preparation method of efficient antioxidant RD |
| CN113735766A (en) * | 2020-05-27 | 2021-12-03 | 中石化南京化工研究院有限公司 | Preparation method of anti-aging agent |
| CN114057638A (en) * | 2020-08-06 | 2022-02-18 | 中石化南京化工研究院有限公司 | Method for removing impurity primary amine in anti-aging agent TMQ |
| CN114315713A (en) * | 2020-10-10 | 2022-04-12 | 中石化南京化工研究院有限公司 | Preparation method of low primary amine TMQ (tetramethylammonium terephthalate) antioxidant |
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| CN113402457B (en) * | 2021-07-13 | 2022-05-27 | 宁波海利化工有限公司 | Preparation method of efficient antioxidant RD |
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Application publication date: 20200421 |