CN112142658A - Preparation method of low primary amine antioxidant TMQ - Google Patents
Preparation method of low primary amine antioxidant TMQ Download PDFInfo
- Publication number
- CN112142658A CN112142658A CN201910560864.1A CN201910560864A CN112142658A CN 112142658 A CN112142658 A CN 112142658A CN 201910560864 A CN201910560864 A CN 201910560864A CN 112142658 A CN112142658 A CN 112142658A
- Authority
- CN
- China
- Prior art keywords
- tmq
- acetone
- primary amine
- aniline
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Quinoline Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, and is characterized in that TMQ polycondensation reaction liquid is separated to respectively obtain light components, heavy components and the like, the light components comprise recovered acetone, recovered aniline and the like which are used as recovered raw materials for application, the heavy components are continuously dropwise added with acetone for reaction, and primary amine compounds in the reaction liquid are eliminated to control the content of the primary amine compounds in TMQ finished products, the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline dimer serving as an effective component of the common TMQ finished products is more than 50%, the content of harmful components IBA (isopropyl diphenylamine) is less than 0.01%, primary amine can be controlled within 1%, and the highest primary amine can be controlled within 0.05%. Therefore, in the subsequent use process, the harm brought by the primary amine compound in the TMQ is reduced by more than 90 percent.
Description
Technical Field
The invention relates to a preparation method of an anti-aging agent TMQ, in particular to a preparation method for realizing low primary amine content in the anti-aging agent TMQ, 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 mainly comprises aniline and acetone which are condensed under an acidic condition to generate a monomer TMDQ (2, 2, 4-trimethyl-1, 2-dihydroquinoline), then TMDQ is polymerized to generate reaction liquid of di-, tri-and tetramers of TMDQ, and TMQ is obtained by liquid alkali neutralization, distillation 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.
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%.
Meanwhile, the reaction mechanism of the anti-aging agent TMQ is quite complex, and numerous side reactions exist, so that the components of the anti-aging agent TMQ are also extremely complex, and the content of the di-tri-tetra-polymer of 2,2, 4-trimethyl-1, 2-dihydroquinoline which is a main useful substance is generally 40-50%. The side reaction of aniline and acetone can produce isopropyl diphenylamine and other complex primary amine compounds, and the primary amine compounds are not only unfavorable for rubber vulcanization and cause reversion and blooming of soluble sulfur, but also generate strong carcinogens and are harmful to human health.
CN103539962A proposes a method for preparing a low-amine rubber antioxidant TMQ, aniline and hydrochloric acid are added into a reactor, the mixture is stirred and heated to 130 ℃, the mixture is stirred for 30 minutes, and the amount of the hydrochloric acid is 6-10% of the weight of the aniline; putting 2,2, 4-trimethyl-1, 2-dihydroquinoline monomer into a reactor, wherein the adding amount is 70-80% of the mass of aniline, continuously dropwise adding acetone when controlling the temperature to be 120-: 1-4, controlling the adding time and temperature, and after the dropwise adding is finished, keeping the temperature to 140 ℃ and keeping the temperature for 4 hours; stopping heating, adding sodium hydroxide aqueous solution, stirring for 30 minutes, controlling the pH value to be 11 after neutralization, and then standing for 60 minutes; separating and removing the water phase to obtain an organic phase; and distilling to remove the monomer under the vacuum state to obtain the antioxidant TMQ product. The content of primary amine compound is less than 2%. The method needs to add 2,2, 4-trimethyl-1, 2-dihydroquinoline monomer with higher purity, the addition amount of the monomer reaches 70-80% of the mass of aniline, and the monomer has complex preparation conditions, higher boiling point, difficult separation and the like.
At present, the 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 is mainly characterized by simple synthesis method, short flow and mature process. The defects are that the effective content of the product is not high, and the content of the product quinoline dimer can only reach 20-25%; the primary amine compound content is high, generally 8-10%, which is not effective for producing rubber products, especially high-end rubber products such as rubber for belt speed layer of racing tire.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and realizes the control of the content of primary amine in a finished product through the improvement of a technological process in the production process of TMQ, thereby reducing the damage of primary amine compounds to the health of human bodies in the subsequent use and processing processes.
The invention provides a preparation method of a low primary amine antioxidant TMQ.
The preparation method of the invention is realized by the following modes: carrying out polycondensation reaction on aniline and acetone under the action of a catalyst to generate TMQ polycondensation reaction liquid, and separating the TMQ polycondensation reaction liquid to respectively obtain light components, heavy components and the like; and continuously adding acetone into the heavy component for reaction to obtain a low primary amine TMQ reaction solution. And (3) neutralizing the low primary amine TMQ reaction solution by using liquid alkali, dividing water, distilling an oil phase to obtain the low primary amine TMQ, and mechanically using a light component as a recovery raw material.
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 0.01-10 h and the reaction temperature is 90-200 ℃.
The heavy component is continuously added to react with acetone, the mass ratio of the heavy component to the acetone is 1:0.1-10, the reaction time is 0.1-10 h, and the reaction temperature is 30-280 ℃.
The catalyst is one or more of hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, oxalic acid and other acidic substances.
The TMQ polycondensation reaction liquid is separated in distillation or rectification, fractionation and other modes.
The light components comprise recovered acetone, recovered aniline and the like, and can be used as recovered raw materials for reuse.
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-; under reduced pressure (1-500 kPa), the gas phase temperature is 60-100 ℃.
The heavy component comprises: 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) primary amine compounds such as aniline and isopropyl diphenylamine; 4) Small amounts of pentameric, hexameric multimers of TMQ monomers.
The low primary amine TMQ reaction solution contains: 1) monomers and di-, tri-, tetramers of TMQ; 2) the catalyst and TMQ monomer, di-, tri-, tetramer, isopropyl aniline and other substances form salts, such as TMQ monomer salt, TMQ dimer salt and the like; 3) small amounts of pentamers, hexamers, etc. of TMQ monomers; 4) trace isopropyl diphenylamine and other primary amine compounds.
The invention has the advantages of
The invention controls the content of the primary amine compound in the TMQ finished product by separating light components (acetone, aniline and the like) in the TMQ reaction liquid, reacting the heavy components with the acetone again and eliminating the primary amine compound in the reaction liquid, generally, the content of the effective component 2,2, 4-trimethyl-1, 2-dihydroquinoline dimer of the TMQ finished product is more than 50 percent, the content of a harmful component IBA (isopropyl diphenylamine) is less than 0.01 percent, and the primary amine can be controlled within 1 percent and can be controlled within 0.05 percent at most. Therefore, in the subsequent use process, the harm brought by the primary amine compound in the TMQ is reduced by more than 90 percent, 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
Hydrochloric acid is used as a catalyst for illustration. The embodiment comprises four steps:
dehydrating aniline and hydrochloric acid to form salt, and adding acetone to perform polycondensation reaction to obtain TMQ polycondensation reaction liquid;
separating TMQ polycondensation reaction liquid to obtain a light component and a heavy component;
adding acetone into the heavy component to continue reacting to obtain low primary amine TMQ reaction liquid;
adding liquid alkali into the reaction liquid of the low primary amine TMQ for neutralization and water separation, and distilling the oil phase to obtain the low primary amine TMQ finished product
Thereby realizing the control of the primary amine compound in the TMQ finished product in the process of preparing the TMQ by catalyzing aniline and acetone.
Specifically, the method comprises the following steps:
the method comprises the following steps: 620 g of aniline and 48.8 g of 30% hydrochloric acid are added into a 2000ml reactor with a thermometer and a reflux condenser, the mixture is stirred for 2 hours at 120 ℃ to remove water in the hydrochloric acid, then 848 g of acetone is added dropwise within 3 hours under the stirring condition of 130 ℃ and is maintained for 0.5 hour to obtain TMQ reaction liquid, and the reaction liquid is distilled to sequentially obtain recovered acetone (normal pressure, gas phase temperature of 55-120 ℃), recovered aniline (100 KPa, gas phase temperature of 60-100 ℃) and heavy component kettle liquid.
Step two: 200 g of heavy component kettle liquid in the step I is taken, 500 g of acetone is dripped under the condition of maintaining the temperature of 120 ℃ for 130 ℃,4 hours are dripped, the acetone is added for 1 hour, then 8.5 g of 32 percent liquid alkali is added for neutralization, the water phase is separated, the organic phase is distilled under the vacuum condition of-0.098 MPa, 165.4 g of the kettle liquid, namely the finished product of the anti-aging agent TMQ, is obtained, and the detection shows that the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 57.09 percent, the content of IBA is 0.004 percent and the content of primary amine is 0.71 percent.
Example 2
The other conditions were the same as in example 1, except that in the step (II), the amount of acetone added was 700 g and the addition time was 5 hours. 174.3 g of an anti-aging agent TMQ finished product is obtained, and through detection, the contents of 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers are 53.22%, the IBA content is 0.001% and the primary amine content is 0.41%.
Example 3
The other conditions were the same as in example 1, except that in the step II, the amount of acetone added was 300 g and the addition time was 4 hours. 151.0 g of finished product of the anti-aging agent TMQ is obtained, and the detection shows that the content of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 59.22%, the content of IBA is 0.009%, and the content of primary amine is 0.93%.
Example 4
The other conditions are the same as example 1, except that in the step (i), the addition amount of the acetone is 1048 g, and the dropping time is 4 hours; in the second step, the dropping amount of the acetone is 300 g, and the dropping time is 2 hours. 167.0 g of an anti-aging agent TMQ finished product is obtained, and the detection shows that the content of 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers is 56.94%, the IBA content is 0.006% and the primary amine content is 0.66%.
Example 5
Otherwise, the process was as in example 1, except that sulfuric acid was used as the catalyst
143.4 g of finished product TMQ of the anti-aging agent is obtained, and through detection, the contents of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers are 64.31%, the IBA content is 0.004% and the primary amine content is 0.30%.
Example 6
Other conditions were the same as in example 1 except that p-toluenesulfonic acid was used as a catalyst
Step two, 166.3 g of finished product TMQ of the anti-aging agent is obtained, and through detection, the content of the di-, tri-and tetramers of 2,2, 4-trimethyl-1, 2-dihydroquinoline is 69.30%, the content of IBA is 0.002%, and the content of primary amine is 0.43%.
Example 7
The other conditions were the same as in example 1 except that p-oxalic acid was used as a catalyst
Step two, obtaining 133.5 g of finished product of the anti-aging agent TMQ, and detecting that the contents of the 2,2, 4-trimethyl-1, 2-dihydroquinoline di-, tri-and tetramers are 60.38%, the IBA content is 0.005% and the primary amine content is 0.24%.
Example 8
The other conditions were the same as in example 1, except that in the step (II), the amount of acetone added was 1100 g, and the addition time was 5 hours. 205.3 g of finished product of the anti-aging agent TMQ is obtained, and the detection shows that the content of the di-, tri-and tetramers of the 2,2, 4-trimethyl-1, 2-dihydroquinoline is 50.22%, the content of IBA is 0.001% and the content of primary amine is 0.04%.
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 system and the reaction material ratio of aniline, etc., temperature, addition manner and time, 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 a low primary amine 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 polycondensation reaction liquid, and the TMQ polycondensation reaction liquid is separated to obtain a light component and a heavy component respectively; continuously adding acetone into the heavy component to react to obtain low primary amine TMQ reaction liquid; neutralizing the reaction liquid of the TMQ with liquid alkali, dividing water, and distilling an oil phase to obtain TMQ; the light component is used as a recycling raw material for recycling.
2. The method of claim 1, wherein: the polycondensation reaction comprises the molar ratio of aniline, acetone and catalyst of 1 (1.5-7) to 0.001-0.5, the reaction time of 0.01-10 h and the reaction temperature of 90-200 ℃.
3. The method of claim 1, wherein: the heavy component is continuously added to react with acetone, the mass ratio of the heavy component to the acetone is 1 (0.1-10), the reaction time is 0.1-10 h, and the reaction temperature is 30-280 ℃.
4. The preparation method according to claim 1, wherein the separation of the TMQ reaction liquid comprises distillation or rectification, fractional distillation.
5. The method according to claim 1, wherein the light components include recovered acetone and recovered aniline, and the light components can be used as recovered raw materials for reuse.
6. The preparation method of claim 1, wherein the catalyst is selected from one or more of hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid and oxalic acid.
7. The method according to claim 5, wherein the recovered acetone comprises acetone, aniline, water and mesityl oxide, and the separation conditions are normal pressure and the vapor phase temperature is 55-120 ℃.
8. The process according to claim 4, wherein the aniline recovered comprises aniline, acetone, water, 2, 4-trimethyl-1, 2-dihydroquinoline and dimer and multimer, isopropyldiphenylamine, under normal or reduced pressure; under the condition of normal pressure, the gas phase temperature is 121-200 ℃; the gas phase temperature is 60-100 ℃ under the reduced pressure condition of 1-500 kPa.
9. The method of claim 1, wherein the heavy fraction comprises: 1) monomers and di-, tri-, tetramers of TMQ; 2) salts formed by the catalyst and aniline, TMQ monomer and isopropyl aniline, 3) primary amine compounds such as aniline and isopropyl diphenylamine; 4) Multimers of TMQ monomers.
10. The process according to claim 1, wherein the reaction solution of a lower primary amine TMQ comprises: 1) monomers and di-, tri-, tetramers of TMQ; 2) the catalyst forms salts with TMQ monomer, di-, tri-, tetramer and isopropyl aniline; 3) multimers of TMQ monomers; 4) traces of isopropyl diphenylamine and other primary amine compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910560864.1A CN112142658A (en) | 2019-06-26 | 2019-06-26 | Preparation method of low primary amine antioxidant TMQ |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910560864.1A CN112142658A (en) | 2019-06-26 | 2019-06-26 | Preparation method of low primary amine antioxidant TMQ |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112142658A true CN112142658A (en) | 2020-12-29 |
Family
ID=73869848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910560864.1A Pending CN112142658A (en) | 2019-06-26 | 2019-06-26 | Preparation method of low primary amine antioxidant TMQ |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112142658A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354580A (en) * | 2021-06-15 | 2021-09-07 | 中石化南京化工研究院有限公司 | Method for removing primary amine impurities in anti-aging agent TMQ |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012144710A (en) * | 2010-12-20 | 2012-08-02 | Sumitomo Chemical Co Ltd | Method for producing composition containing polycondensate of aniline with acetone |
| CN103467372A (en) * | 2012-06-08 | 2013-12-25 | 中国石油化工股份有限公司 | Combined production method for antioxidant RD and antioxidant FR |
| CN103539962A (en) * | 2013-10-21 | 2014-01-29 | 科迈化工股份有限公司 | Method for preparing low-amine rubber anti-aging agent 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 |
-
2019
- 2019-06-26 CN CN201910560864.1A patent/CN112142658A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012144710A (en) * | 2010-12-20 | 2012-08-02 | Sumitomo Chemical Co Ltd | Method for producing composition containing polycondensate of aniline with acetone |
| CN103467372A (en) * | 2012-06-08 | 2013-12-25 | 中国石油化工股份有限公司 | Combined production method for antioxidant RD and antioxidant FR |
| CN103539962A (en) * | 2013-10-21 | 2014-01-29 | 科迈化工股份有限公司 | Method for preparing low-amine rubber anti-aging agent 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354580A (en) * | 2021-06-15 | 2021-09-07 | 中石化南京化工研究院有限公司 | Method for removing primary amine impurities in anti-aging agent TMQ |
| CN113354580B (en) * | 2021-06-15 | 2022-08-09 | 中石化南京化工研究院有限公司 | Method for removing primary amine impurities in anti-aging agent TMQ |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111039865A (en) | Preparation method of anti-aging agent TMQ | |
| CN114835661A (en) | Industrial preparation method of a-acetyl-r-butyrolactone | |
| CN111039864B (en) | Preparation method of anti-aging agent | |
| CN112142658A (en) | Preparation method of low primary amine antioxidant TMQ | |
| CN110845704A (en) | Preparation process of high-temperature-resistant glycidylamine epoxy resin | |
| CN112661787B (en) | Preparation method of antioxidant tri (2, 4-di-tert-butylphenyl) phosphite | |
| CN112441973B (en) | Preparation method of low primary amine TMQ | |
| CN103613785B (en) | A kind of take solid sulphuric acid as the polymeric preparation method of 2,2,4-trimethylammonium-1,2-dihyaroquinoline of catalyzer | |
| CN112142657A (en) | Preparation method of anti-aging agent TMQ | |
| CN102584696A (en) | Catalytic synthesis method for rubber antioxidant RD | |
| CN113087662B (en) | Method for removing primary amine impurities in anti-aging agent TMQ | |
| CN103613538B (en) | Catalytic synthesis process of rubber antioxidant 224 | |
| CN112552234B (en) | Preparation method of TMQ (Tetramethylbenzidine) anti-aging agent | |
| US3694171A (en) | Method for purifying cyclic phosphonitrilic chlorides | |
| CN103232325B (en) | A kind of method being prepared hexalin by tetrahydrobenzene | |
| CN112979421A (en) | Synthesis process of condensation by-product | |
| CN105566238A (en) | Method for preparation of 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethyl butyl)phenol] | |
| CN112225683B (en) | Preparation method and application of pentaerythritol tetra-mercapto carboxylic ester | |
| JP5707935B2 (en) | High purity 2,2-bis (4-aminophenyl) propane and process for producing the same | |
| CN114315712B (en) | Method for purifying 2, 4-trimethyl-1, 2-dihydroquinoline polymer | |
| CN110818548A (en) | Method for preparing benzylidene acetone | |
| CN117924167A (en) | Method for purifying TMQ dimer | |
| CN114315713B (en) | Preparation method of low primary amine TMQ (TMQ) anti-aging agent | |
| CN104496842B (en) | preparation method of hindered phenol antioxidant 1019 | |
| CN102992964A (en) | Method for producing bisphenol F |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201229 |
|
| RJ01 | Rejection of invention patent application after publication |