CN114773264B - Preparation device and preparation method of rubber antioxidant TMQ - Google Patents
Preparation device and preparation method of rubber antioxidant TMQ Download PDFInfo
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- 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 invention belongs to the field of anti-aging agents, and particularly relates to a preparation device and a preparation method of a rubber anti-aging agent TMQ. The preparation device comprises an acetone preheater, an acetone polymerization tower, a semi-finished product synthesis tower, a semi-finished product receiving kettle and a reaction kettle which are connected in sequence; the semi-finished product synthesis tower is provided with an aniline feeding hole; the acetone polymerization tower is internally provided with alkaline resin, and the semi-finished product synthesis tower is internally provided with acidic resin; the acetone preheater, the acetone polymerization tower, the semi-finished product synthesis tower, the semi-finished product receiving kettle and the reaction kettle are all provided with heaters. The patent firstly develops a catalyst for controlling acetone polymerization and a corresponding control step, controls the acetone polymerization in a range mainly comprising dimer, and then generates a TMQ monomer by a polymerization reaction with aniline under the action of a second catalyst.
Description
Technical Field
The invention belongs to the field of anti-aging agents, and particularly relates to a preparation device and a preparation method of a rubber anti-aging agent TMQ.
Background
The rubber antioxidant TMQ is a ketoamine antioxidant, has very effective protection on thermal oxidation aging, has very strong inhibition effect on metal catalytic oxidation, has low toxicity, and is widely applied to various products of synthetic rubber and natural rubber such as chloroprene rubber, butadiene styrene rubber, butadiene rubber, isoprene rubber and the like. Because of its light yellow colour, it can also be used in sanitary rubber products.
The anti-aging agent TMQ is almost suitable for all types of elastomers under various application conditions, and the temperature application range is wide. The persistence in the rubber provides the rubber compound with a long-term resistance to thermal aging. Can prevent the sizing material from being catalyzed and oxidized by heavy metal. High molecular weight, slow migration in the rubber matrix and difficult blooming.
The anti-aging agent TMQ is synthesized by condensation and polymerization reaction at the temperature of 130-140 ℃ by taking aniline and acetone as raw materials and acid as a catalyst. At present, the application field of TMQ is mainly antioxidants of various rubber and plastic products and is also a very representative quinoline antioxidant variety. During the application of the product, some problems have also been found with such products:
firstly, the effective content of an anti-aging agent TMQ product is generally not high, most of anti-aging agent TMQ manufacturers adopt one-step production at present, the effective content (the sum of dimer, trimer and tetramer) of the product is generally between 40 and 50 percent, and the rest 50 to 60 percent is a mixture of dozens of complex components. In the process of applying TMQ to the processing of rubber and plastic products, the aging resistance effect of the non-effective components is weak, and the problems of high VOCs, large residual VOCs of finished products, frosting of the finished products and the like in the processing process are easily caused. And the application in rubber and plastic products with parts in close contact with human bodies also has the problems of toxicity and the like, and influences the expanded application of the anti-aging agent TMQ.
The existence of the problems leads the second generation TMQ product to be produced at the same time, the product adopts a two-step synthesis technology, and the effective content of the product is improved to 75-85%. Such products are generally referred to as high TMQ or anti-aging agents FR. Compared with the first generation product, the high-content TMQ has more remarkable improvement in the aspects of formula dosage, product performance and the like compared with the first generation product, and a plurality of articles and patents are reported and reported around the synthesis process of the second generation product.
For example: 1) patent CN 103613537a indicates that using solid acid to catalyze antioxidant RD, an antioxidant RD product with 80% -90% of effective content can be obtained.
2) Patent CN 102114432B discloses that an antioxidant RD is prepared by catalyzing a solid acid catalyst prepared by compounding D002 type strong-acid cation exchange resin and aromatic sulfonic acid substances. If a one-step method is adopted, the content of the dimer in the RD product is 25-35%, and the total amount of the di-polymer, the tri-polymer and the tetramer is 50-60%. If the two-step synthesis is adopted, the content of the dimer in the RD product is 50-60%, and the total amount of the di-polymer, the tri-polymer and the tetramer is 70-80%.
3) Patent CN105017144A shows that sulfonic acid type imidazolyl ionic liquid is used as a catalyst to synthesize the anti-aging agent RD in a one-step solvent-free mode, the single-pass conversion rate of aniline is 70%, and the content of effective bodies of the product is 50-60%.
4) Patent CN101353447A teaches the use of nanocomposite solid superacid SO 4 2- _CoFe 2 O 4 As a catalyst, the antioxidant RD is synthesized in a one-step kettle way, and the finished product of the antioxidant RD with the effective content of 70-90 percent can be obtained.
5) Patent CN102584696B shows that the antioxidant RD is synthesized in a one-step kettle manner by using strong acid ion exchange resin NRW150 as a catalyst, and the effective content is 65%.
6) Patent CN106187878A teaches that the anti-aging agent RD is synthesized in a microchannel reactor by a solvent-free one-step method using hydrochloric acid as a catalyst, with a product conversion rate of 85-99% and a dimer content of 40-75%.
However, although the product index and application performance of the high-content anti-aging agent product are obviously improved, the content of the non-effective components is still above 15 percent, which is undeniable, and further expansion of the application of the product is limited to a certain extent. In addition, the synthesis route of the high-content antioxidant TMQ is long, and the rectification and separation steps are multiple, so that the production cost of the product is higher than that of the first-generation antioxidant product, and the market application of the product is further hindered.
Therefore, the development of a quinoline polymer anti-aging agent with higher purity, which further reduces the content of non-effective components, is a necessary way for further expanding the application of the anti-aging agent TMQ. Meanwhile, a synthetic route with lower production cost is developed in a targeted manner, and the method is also very necessary for accelerating the market popularization of the high-purity anti-aging agent.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation device and a preparation method of a rubber antioxidant TMQ.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation device of a rubber antioxidant TMQ comprises an acetone preheater, an acetone polymerization tower, a semi-finished product synthesis tower, a semi-finished product receiving kettle and a reaction kettle which are connected in sequence;
the semi-finished product synthesis tower is provided with an aniline feeding hole; the acetone polymerization tower is internally provided with alkaline resin, and the semi-finished product synthesis tower is internally provided with acidic resin; the acetone preheater, the acetone polymerization tower, the semi-finished product synthesis tower, the semi-finished product receiving kettle and the reaction kettle are all provided with heaters.
The alkaline resin is 8 percent of KF/NaY.
The acidic resin is high-temperature resistant strong-acid ion exchange resin; preferably, the acidic resin is LXC-105.
The mass ratio of the basic resin to the acidic resin is 0.29: 1.
A method for preparing the rubber antioxidant TMQ by using the preparation device of the rubber antioxidant TMQ comprises the following steps:
s1: starting heaters of the acetone preheater, the acetone polymerization tower and the semi-finished product synthesis tower, and heating the acetone preheater, the acetone polymerization tower and the semi-finished product synthesis tower to set temperatures;
s2: injecting a certain amount of aniline into the semi-finished product receiving kettle, starting a circulating pump and a heater of the semi-finished product receiving kettle, preheating the aniline to a process temperature, and starting an acetone feeding pump to start a synthesis reaction; after the acetone starts to be introduced, the temperature in the acetone vaporizer, the acetone polymerization tower and the semi-finished product synthesis tower is controlled to be unchanged;
s3: when the acetone introduction amount reaches a certain requirement, starting an aniline feeding pump, continuing the synthesis reaction, and simultaneously starting a valve of an extraction pipeline to extract a semi-finished product;
s4: after collected, the extracted semi-finished product is distilled under reduced pressure to remove acetone and aniline in the semi-finished product, and after the residual semi-finished product is mixed with a catalyst, polymerization reaction is carried out in a reaction kettle at a certain temperature;
s5: after the polymerization reaction is finished, adding liquid alkali to neutralize the catalyst in the reaction system, standing for layering, separating a lower water phase, performing reduced pressure rectification on an upper oil phase, and recycling a distillate which is an unreacted monomer to the polymerization reaction; and (4) obtaining an organic matter at the bottom of the rectifying tower, namely the finished TMQ product.
Step S1, heating the acetone vaporizer to 60-80 ℃; heating the acetone polymerization tower to 70-90 ℃; the temperature of the semi-finished product synthesis tower is raised to 100-120 ℃.
In the step S2, controlling the first aniline injection amount to be 40-60% of the volume of the semi-finished product receiving kettle; controlling the preheating temperature of the aniline in the semi-finished product receiving kettle to be 100-120 ℃; the feeding airspeed of the acetone is controlled to be 2 to 3 hours by the calculation of the catalyst in the acetone polymerization tower -1 ；
Before the aniline feeding pump is started in the step S3, the molar ratio of the acetone introduction amount to the aniline amount which is fed into the receiving kettle in advance is controlled to be 4-13: 1; after an aniline feeding pump is started, controlling the feeding molar ratio of acetone to aniline to be 4-13: 1; after the aniline feeding pump is started, the feeding airspeed of the aniline is controlled to be 0.1-0.2h -1 。
In step S4, the catalyst is one or more of hydrochloric acid, sulfuric acid and nitric acid, the polymerization temperature is controlled at 80-120 ℃, and the polymerization time is controlled at 5-10 h.
In step S5, the molar ratio of the added liquid alkali to the catalyst is 1-2: 1; the vacuum distillation is controlled to be less than-0.096 Mpa, and the rectification is completed when the temperature of the tower kettle is more than or equal to 270 ℃; the monomer recovered from the previous distillation is fed to the next step S4 for reaction.
Compared with the prior art, the invention has the beneficial effects that:
the technology related by the patent is the biggest difference from other reported patents in that the high-purity TMQ with the effective content of more than 95% can be stably synthesized, and simultaneously compared with other reported patents and documents, the technology has the advantages that the synthesis of acetone dimers is controlled, the acetone dimers and aniline are controlled to react to obtain semi-finished product monomers, the monomers are controlled to carry out polymerization reaction to obtain the high-purity TMQ three-step method, the generation rate of non-effective components can be effectively controlled, and the effective content of products is further controlled to be more than 95%;
the original process control points are as follows:
1) the mechanism of formation of TMQ (shown in fig. 2) is presumed to be that acetone and acetone are first condensed and dehydrated to produce dimeric acetone, and then dimeric acetone is reacted with aniline and dehydrated to produce TMQ monomer, which is then polymerized under the action of an acidic catalyst to produce the anti-aging agent TMQ. The processes of the prior easily-reported documents and patents are optimized on the basis of a catalyst or process conditions, so that acetone and aniline are used for synthesizing an anti-aging agent TMQ or a monomer in the same system at one time, and a step-by-step synthesis scheme of controlling the polymerization of acetone and then reacting with aniline is not considered.
2) Different from the prior reported technology, the method develops a catalyst for controlling acetone polymerization and a corresponding control step for the first time, controls the acetone polymerization in a range mainly comprising dimer, and then generates the TMQ monomer by polymerization reaction with aniline under the action of a second catalyst, and the thought is not reported at present.
3) The catalyst and the control conditions for the reaction of aniline and dimeric acetone are optimized simultaneously, so that TMQ monomers are mainly generated in the reaction process, and then the monomers purified by rectification are subjected to polymerization reaction under the action of catalyst sulfuric acid to generate a high-purity antioxidant TMQ finished product with the effective content of more than 95%.
Drawings
FIG. 1 shows a schematic diagram of a rubber antioxidant TMQ production apparatus;
FIG. 2 is a schematic diagram of the mechanism of TMQ generation;
FIG. 3 is a graph of the amounts of addition, reaction parameters, and results for various examples.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments.
FIG. 1 shows a preparation device of a rubber antioxidant TMQ, which comprises an acetone preheater 1, an acetone polymerization tower 2, a semi-finished product synthesis tower 3, a semi-finished product receiving kettle 4 and a reaction kettle 5 which are connected in sequence;
the semi-finished product synthetic tower is provided with an aniline feeding hole; the acetone polymerization tower is internally provided with alkaline resin, and the semi-finished product synthesis tower is internally provided with acidic resin; the acetone preheater, the acetone polymerization tower, the semi-finished product synthesis tower, the semi-finished product receiving kettle and the reaction kettle are all provided with heaters.
Example 1: a method for preparing the rubber antioxidant TMQ by using the preparation device of the rubber antioxidant TMQ comprises the following steps: (1) adding 8% of KF/NaY resin catalyst into an acetone polymerization tower, adding high-temperature-resistant strong-acid cation exchange resin of Xian blue-X LXC-105 into a semi-finished product synthesis tower, and controlling the mass ratio of the two catalysts to be 0.29: 1; and starting an acetone vaporizer to heat the medium and raise the temperature to 70 ℃, starting an acetone polymerization tower heater and raising the temperature to 80 ℃, starting a semi-finished product synthesis tower heater and raising the temperature to 120 ℃.
(2) Firstly, 50% aniline volume is injected into the semi-finished product receiving kettle, the circulating pump and the semi-finished product receiving kettle heater are started, the acetone feeding pump is started after aniline is preheated to 100 ℃, and the feeding airspeed of acetone is controlled to be 3h -1 Starting a synthesis reaction (calculated by 8 percent of KF/NaY resin catalyst), and controlling the temperature of each part in the reactor to be consistent with the preheating temperature in the reaction process;
(3) when the molar weight of the acetone is 7 times of the molar weight of the aniline pre-added into the receiving kettle, starting an aniline feeding pump to control the feeding airspeed of the aniline to be 0.2h -1 (based on LXC-105 high-temperature-resistant strong-acid cation exchange resin), the feed molar ratio of acetone to aniline is 7: 1. Continuing the synthesis reaction, and simultaneously opening a valve of the extraction pipeline to extract the semi-finished product.
(4) Collecting the collected semi-finished products, distilling under reduced pressure to remove acetone and aniline, mixing the residual semi-finished products with 25% dilute sulfuric acid and monomers (see step 5) recovered by rectification in the previous batch, performing polymerization reaction in a reaction kettle at 100 ℃, and stopping the reaction after 7 hours of reaction.
(5) After the polymerization reaction is finished, adding liquid alkali to neutralize dilute sulfuric acid in the reaction system, standing for layering, separating a lower-layer water phase, performing reduced pressure rectification on an upper-layer oil phase, and recycling a distillate which is an unreacted monomer to the polymerization reaction; and obtaining an organic matter at the bottom of the rectifying tower, namely the finished TMQ product.
By chromatographic analysis, the content of TMQ dimer in the finished product is 70.6%, the content of tripolymer is 20.8%, the content of tetramer is 4.5%, and the total content of di-tri-tetramer and tetramer is 95.9%.
Figure 3 shows the quantities of charge and the reaction parameters for the different examples and gives the total effective content of the final product.
Example 2: compared with example 1, only the acetone polymerization tower is not filled with the catalyst, and the rest conditions are not changed. In the reaction process, as the catalyst is not used for catalyzing the selective polymerization of the acetone, the acetone basically does not react in the heating process and reacts with the aniline under the action of the acid catalyst, so that a plurality of byproducts are generated, and the effective content of the final product is low.
Example 3: compared with example 1, only the semi-finished product synthesis tower is not filled with catalyst, and the rest conditions are unchanged. In the reaction process, as no catalyst is used for catalyzing the reaction of dimeric acetone and aniline, the generation amount of monomers is less, the main product is acetone polymer, and the acetone polymer is further polymerized under the catalysis of sulfuric acid in the second step, so that the effective content of the product is seriously lower.
Example 4: compared with example 1, the space velocity of acetone feeding is increased greatly, and the rest conditions are unchanged. In the reaction process, the acetone has insufficient selectivity and low conversion rate due to too short residence time on the surface of the catalyst, and reacts with aniline under the action of an acid catalyst, so that a plurality of byproducts are generated, and the effective content of the final product is low. However, the effective content of the product is already improved compared with that without the catalyst (example 2), and the catalyst effect can be embodied.
Example 5: compared with example 1, the aniline feeding space velocity is increased greatly, and the rest conditions are unchanged. In the reaction process, the conversion rate is insufficient due to the short residence time of the aniline on the surface of the catalyst, so that the proportion of the acetone polymer in the semi-finished product is higher, and the effective content of the final product is lower. However, the effective content of the product is already increased compared with that without the catalyst (example 3), and the catalyst effect can be shown.
Example 6: compared with example 1, only the temperature of the acetone polymerization tower is increased, and the rest conditions are not changed. In the reaction process, as the polymerization temperature of the acetone is increased, the selectivity of dimeric acetone is greatly reduced, so that the monomer content in the semi-finished product is low, and the effective content of the final product is low.
Example 7: compared with example 1, only the temperature of the semi-finished synthesis column is increased, and the rest conditions are unchanged. In the reaction process, as the temperature is increased in the monomer synthesis process, the monomer selectivity is greatly reduced, so that the monomer content in the semi-finished product is low, and the effective content of the final product is low.
Example 8: compared with example 1, the feeding ratio of acetone and aniline is reduced, and the rest conditions are unchanged. In the reaction process, the reaction efficiency between the acetone and the aniline is reduced due to the slightly low proportion of the acetone in the reaction system, so that the monomer content in the semi-finished product is slightly reduced, and the influence on the effective content of the final product is small.
Example 9: the polymerization catalyst alone had an increased sulfuric acid concentration compared to example 1, with the remaining conditions unchanged. In the reaction process, as the concentration of the polymerization catalyst is increased, the polymerization reaction is more violent under the same condition, and a product with high polymerization degree is easily generated, so that the final effective content of the product is lower.
In examples 10 and 11, the temperature and time for the polymerization reaction of the monomers are reduced, so that the polymerization reaction cannot reach the optimal conditions, the effective content of the product is low, and the yield of the final product is low.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A method for preparing a rubber antioxidant TMQ by using a preparation device of the rubber antioxidant TMQ is characterized in that,
the preparation device of the rubber antioxidant TMQ comprises an acetone preheater, an acetone polymerization tower, a semi-finished product synthesis tower, a semi-finished product receiving kettle and a reaction kettle which are connected in sequence; the semi-finished product synthesis tower is provided with an aniline feeding hole; the acetone polymerization tower is internally provided with alkaline resin, and the semi-finished product synthesis tower is internally provided with acidic resin; the acetone preheater, the acetone polymerization tower, the semi-finished product synthesis tower, the semi-finished product receiving kettle and the reaction kettle are all provided with heaters; the alkaline resin is 8 percent of KF/NaY; the acidic resin is LXC-105;
the preparation method comprises the following steps:
s1: starting heaters of the acetone preheater, the acetone polymerization tower and the semi-finished product synthesis tower, and heating the acetone preheater, the acetone polymerization tower and the semi-finished product synthesis tower to set temperatures; wherein, the temperature of the acetone vaporizer is raised to 60-80 ℃; heating the acetone polymerization tower to 70-90 ℃; heating the semi-finished product synthesis tower to 120 ℃;
s2: injecting a certain amount of aniline into the semi-finished product receiving kettle, starting a circulating pump and a heater of the semi-finished product receiving kettle, preheating the aniline to a process temperature, and starting an acetone feeding pump to start a synthesis reaction; after the acetone starts to be introduced, the temperature in the acetone vaporizer, the acetone polymerization tower and the semi-finished product synthesis tower is controlled to be unchanged; the injection amount of the aniline for the first time is controlled to be 40-60% of the volume of the semi-finished product receiving kettle; controlling the preheating temperature of the aniline in the semi-finished product receiving kettle to be 100-120 ℃; the feeding airspeed of the acetone is controlled to be 2 to 3 hours by the calculation of the catalyst in the acetone polymerization tower -1 ；
S3: when the acetone introduction amount reaches a certain requirement, starting an aniline feeding pump, continuing the synthesis reaction, and simultaneously starting a valve of an extraction pipeline to extract a semi-finished product; before starting the aniline feeding pump, controlling the molar ratio of the acetone introduction amount to the aniline amount which is fed into the semi-finished product receiving kettle in advance to be 4-13: 1; after an aniline feeding pump is started, controlling the feeding molar ratio of acetone to aniline to be 4-13: 1; after the aniline feed pump is started, the feeding airspeed of the aniline is controlled to be 0.1-0.2h -1 ；
S4: after collected, the extracted semi-finished product is distilled under reduced pressure to remove acetone and aniline in the semi-finished product, and after the residual semi-finished product is mixed with a catalyst, polymerization reaction is carried out in a reaction kettle at a certain temperature; the catalyst is one or more of hydrochloric acid, sulfuric acid and nitric acid, and the polymerization reaction temperature is controlled to be 80-120 ℃; the polymerization reaction time is controlled to be 5-10 h;
s5: after the polymerization reaction is finished, adding liquid alkali to neutralize the catalyst in the reaction system, standing for layering, separating a lower water phase, performing reduced pressure rectification on an upper oil phase, and recycling a distillate which is an unreacted monomer to the polymerization reaction; organic matters obtained from the rectifying tower are finished TMQ; wherein the molar ratio of the added liquid alkali to the catalyst is 1-2: 1; the vacuum distillation is controlled to be less than-0.096 Mpa, and the rectification is finished when the temperature of the tower kettle is more than or equal to 270 ℃; the monomer recovered by the previous distillation is added to the next step S4 for reaction.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210694381.2A CN114773264B (en) | 2022-06-20 | 2022-06-20 | Preparation device and preparation method of rubber antioxidant TMQ |
| PCT/CN2022/105676 WO2023245776A1 (en) | 2022-06-20 | 2022-07-14 | Apparatus and method for preparing rubber antioxidant tmq |
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| CN202210694381.2A CN114773264B (en) | 2022-06-20 | 2022-06-20 | Preparation device and preparation method of rubber antioxidant TMQ |
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| CN114773264B true CN114773264B (en) | 2022-09-30 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101724174A (en) * | 2008-10-17 | 2010-06-09 | 南化集团研究院 | Method for preparing anti-aging agent RD |
| CN102114432A (en) * | 2009-12-30 | 2011-07-06 | 江苏圣奥化学科技有限公司 | Composite solid acid catalyst |
| CN102153511A (en) * | 2010-02-12 | 2011-08-17 | 江苏圣奥化学科技有限公司 | Industrial synthetic method for rubber antioxidant (RD) |
| CN103772175A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Combined technique for synthesizing iso-propylidene acetone and sec-butyl alcohol |
| CN106673979A (en) * | 2016-11-22 | 2017-05-17 | 江苏苏源辉普化工有限公司 | Mesityl oxide and preparation method thereof |
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2022
- 2022-06-20 CN CN202210694381.2A patent/CN114773264B/en active Active
- 2022-07-14 WO PCT/CN2022/105676 patent/WO2023245776A1/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724174A (en) * | 2008-10-17 | 2010-06-09 | 南化集团研究院 | Method for preparing anti-aging agent RD |
| CN102114432A (en) * | 2009-12-30 | 2011-07-06 | 江苏圣奥化学科技有限公司 | Composite solid acid catalyst |
| CN102153511A (en) * | 2010-02-12 | 2011-08-17 | 江苏圣奥化学科技有限公司 | Industrial synthetic method for rubber antioxidant (RD) |
| CN103772175A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Combined technique for synthesizing iso-propylidene acetone and sec-butyl alcohol |
| CN106673979A (en) * | 2016-11-22 | 2017-05-17 | 江苏苏源辉普化工有限公司 | Mesityl oxide and preparation method thereof |
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| WO2023245776A1 (en) | 2023-12-28 |
| CN114773264A (en) | 2022-07-22 |
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