CN109438341B - Anti-aging agent TMQ and preparation method thereof - Google Patents
Anti-aging agent TMQ and preparation method thereof Download PDFInfo
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- CN109438341B CN109438341B CN201811245995.2A CN201811245995A CN109438341B CN 109438341 B CN109438341 B CN 109438341B CN 201811245995 A CN201811245995 A CN 201811245995A CN 109438341 B CN109438341 B CN 109438341B
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
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Abstract
The invention belongs to the field of rubber auxiliaries, and particularly relates to an anti-aging agent TMQ and a preparation method thereof. The preparation method comprises the following steps: aniline and acetone are used as raw materials, and an anti-aging agent TMQ is prepared under the action of a catalyst in the presence of a solvent, wherein the catalyst is a strongly acidic molecular sieve H-MCM-22, and the silica-alumina ratio of the catalyst is controlled to be 10-100. Compared with the prior art, the method for preparing the rubber antioxidant TMQ by adopting the strong acid molecular sieve H-MCM-22 catalyst has the advantages of simple production process, short reaction time, less generation of three wastes, high per pass conversion rate of raw materials, high content of effective bodies of products and the like, and is a new technology with higher industrial value.
Description
Technical Field
The invention belongs to the field of rubber auxiliaries, and particularly relates to an anti-aging agent TMQ and a preparation method thereof.
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 color, 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. Persistence in the rubber imparts long-term resistance to thermal ageing to the rubber compound. The rubber material can be prevented from being catalyzed and oxidized by heavy metal, has high molecular weight, is slow to migrate in a rubber material matrix, and is not easy to bloom.
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. The process can be divided into a one-step method and a two-step method. The two-step method is that firstly, monomer is prepared by condensation, and after the residual reactant is recovered, monomer polymerization is carried out under acidic condition; whereas the one-step process is to complete both monomer preparation and polymerization simultaneously and then recover the remaining reactants. The two-step process has long process and large consumption, but the content of effective substances in the obtained product is high; the one-step process is simple, the consumption is low, but the content of effective substances is low.
Acid catalysts of the anti-aging agent TMQ can be divided into two categories of protonic acid catalysts and Lewis acid catalysts, and different catalysts are required to be selected in different stages of monomer condensation and polymerization so as to achieve ideal reaction effect. For example, hydrochloric acid is commonly used as a liquid catalyst in the traditional production method of RD, but the hydrochloric acid is consumed by using sodium hydroxide in the post-treatment process, and the hydrochloric acid cannot be recycled. In addition, hydrochloric acid, which is a frequently used catalyst for preparing RD, has the defects of low aniline conversion rate, poor product quality, serious three-waste pollution, high requirement on equipment and long production period.
There are also literature and patent reports that high conversion of aniline can be maintained using strongly acidic ion exchange resins. The use of the catalyst is beneficial to the separation of the catalyst and the improvement of the yield, and meets the requirement of environmental protection. However, the strong-acid cation exchange resin has low content of effective acid, poor heat resistance and long reaction time which can reach more than 25 hours at most, and the resin is easy to break and inconvenient to recover and has large loss, thus being not beneficial to industrial production.
JP55-40661 discloses a method for producing an anti-aging agent TMQ by condensation of aniline and acetone using p-toluenesulfonic acid as a catalyst, which has the advantages of high reaction activity, large catalyst amount, difficult recovery, low reaction yield, high production cost, difficult control of monomer production, complex product components, serious environmental pollution and difficult industrial production, and the catalyst is decomposed to generate sulfur dioxide gas in a high-temperature link in the production process.
The anti-aging agent TMQ synthesized by the technology has low dimer content, poor anti-aging effect of products, serious production three wastes, high cost and non-green process.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an anti-aging agent TMQ and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the anti-aging agent TMQ is characterized in that aniline and acetone are used as raw materials, and the anti-aging agent TMQ is prepared under the action of a catalyst in the presence of a solvent, wherein the catalyst is a strongly acidic molecular sieve; the strongly acidic molecular sieve is H-MCM-22, and the silica-alumina ratio of the strongly acidic molecular sieve H-MCM-22 is between 10 and 100. Preferably, the silica-alumina ratio of the strongly acidic molecular sieve H-MCM-22 is between 30 and 60.
Wherein, the solvent is one of benzene, toluene, xylene, cyclohexane and trimethylbenzene.
The feeding mass ratio of the aniline to the acetone is 1:1-10, the feeding mass ratio of the aniline to the solvent is 1:1-10, the reaction temperature is 100--1-26h-1。
Preferably, the feeding mass ratio of the aniline to the acetone is 1:2-5, the feeding mass ratio of the aniline to the solvent is 1:2-5, the reaction temperature is 130--1-14h-1。
The reaction feeding adopts forward flow feeding or reverse flow feeding; when the reaction adopts downstream feeding, aniline, acetone and a solvent are mixed uniformly in advance according to the feeding proportion and then fed at one time; when the reaction adopts countercurrent feeding, aniline and a solvent are uniformly mixed in advance according to the feeding proportion and then are fed into the reactor with acetone steam in a countercurrent mode.
A continuous production process is adopted.
The treatment process is that the product flowing out of the reactor is subjected to liquid separation to generate water, and the solvent, the residual raw materials and the unpolymerized monomers are recovered from the upper solvent phase through reduced pressure distillation to obtain the finished TMQ product.
Vacuum distilling to recover solvent and residual material, controlling vacuum degree at-0.09 Mpa and gas phase temperature at 80-180 deg.C.
Recovering unpolymerized monomer by reduced pressure distillation, controlling the vacuum degree to be less than-0.098 Mpa and the distillation gas phase temperature to be 240-280 ℃.
The invention also discloses an anti-aging agent TMQ which is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that: according to the technical scheme, aniline and acetone are used as raw materials, the rubber antioxidant TMQ is prepared under the catalysis of solid acid in the presence of a solvent, the single-pass conversion rate of the aniline can reach 90-95%, the content of effective bodies (di-, tri-and tetramers) in a product RD can reach 85-90%, and the content of dimers is 60-70%.
According to the technology related to the patent, the strong acid molecular sieve is used as the catalyst, compared with liquid hydrochloric acid catalysis, the catalyst can be recovered and reused, and meanwhile, due to the fact that an alkali neutralization step is omitted, almost no waste water is generated, and the technology is more green and environment-friendly; meanwhile, the molecular sieve catalyst is not easy to break, the strong acid cation exchange resin has longer service life and is easier to produce and convert, and the problems of easy breakage and low service life in the production process of the ion exchange resin solid acid catalyst are solved.
The technology of the patent adopts a strong acid molecular sieve as a catalyst, and screens the TMQ monomer polymerization process through the diameter of a pore channel of the molecular sieve by means of the structural characteristics of the molecular sieve while making full use of the strong acid and the reusability of the molecular sieve. The catalyst carrier H-MCM-22 molecular sieve pore channel structure is mainly distributed at 0.4-1.82nm, raw materials, TMQ monomers and dimers are allowed to pass through in the catalysis process, trimers and the products above are not allowed to pass through, and from the perspective of molecular diameter, the catalyst related by the patent can effectively control the polymerization degree of the TMQ monomers, and because the products above the dimers cannot be generated and separated in the catalyst pore channel, the polymerization degree of the products can be effectively controlled by catalyzing TMQ polymerization by using the catalyst, the dimers are prevented from further polymerizing with the monomers, so that the generation of the trimers and tetramers in the products is controlled, and the product quality is improved.
In conclusion, compared with the prior art, the method for preparing the rubber antioxidant TMQ by adopting the strong acid molecular sieve H-MCM-22 catalyst has the advantages of simple production process, short reaction time, less three wastes, high per pass conversion rate of raw materials, high content of effective bodies of products and the like, and is a new technology with higher industrial value.
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 following preferred embodiments.
Example 1
A method for synthesizing a novel anti-aging agent TMQ. The method comprises the steps of taking aniline and acetone as raw materials, and preparing an anti-aging agent TMQ under the action of a catalyst in the presence of a solvent toluene, wherein the catalyst is an H-MCM-22 type molecular sieve, and the silica-alumina ratio of the molecular sieve is 60. Reaction is carried out byFeeding downstream, namely uniformly mixing aniline, acetone and solvent toluene in a feeding ratio of 1:3:3 in advance, and controlling the feeding mass airspeed to be 5h-1Carrying out continuous feeding; the temperature in the reaction process is controlled to be 135-140 ℃, and the reaction pressure is 1.0 Mpa.
Separating the product flowing out of the reactor to obtain water, distilling the upper solvent phase under reduced pressure, and recovering the solvent, the residual raw materials and the unpolymerized monomer to obtain a finished TMQ product; vacuum distilling to recover solvent and residual material, controlling vacuum degree at-0.09 Mpa and gas phase temperature at 80-180 deg.C. Recovering unpolymerized monomer by reduced pressure distillation, controlling the vacuum degree to be less than-0.098 Mpa and the distillation gas phase temperature to be 240-280 ℃. (the same below)
Through detection, in the embodiment, the single-pass conversion rate of the aniline is 90.5%, the content of effective bodies (di-tetramer, tri-tetramer) in the product TMQ can reach 88.6%, and the content of dimer is 62.3%.
Example 2:
a method for synthesizing a novel anti-aging agent TMQ. The method comprises the steps of taking aniline and acetone as raw materials, and preparing an anti-aging agent TMQ under the action of a catalyst in the presence of a solvent xylene, wherein the catalyst is an H-MCM-22 type molecular sieve, and the silica-alumina ratio of the molecular sieve is 100. Adopting forward flow feeding for reaction, uniformly mixing aniline, acetone and dimethylbenzene according to a feeding ratio of 1:3:3, and controlling the feeding mass airspeed to be 5h-1Carrying out continuous feeding; controlling the temperature at 130-135 deg.C and the reaction pressure at 0.5 Mpa;
according to the detection, in the embodiment, the single-pass conversion rate of the aniline is 75.8%, the content of effective bodies (di-tetramer, tri-tetramer and tetramer) in the product TMQ can reach 57.1%, and the content of the dimer is 45.8%.
Example 3: a method for synthesizing a novel anti-aging agent TMQ. The method comprises the steps of taking aniline and acetone as raw materials, and preparing an anti-aging agent TMQ under the action of a catalyst in the presence of a solvent trimethylbenzene, wherein the catalyst is an H-MCM-22 type molecular sieve, and the silica-alumina ratio of the molecular sieve is 10. Adopting forward flow feeding for reaction, uniformly mixing aniline, acetone and solvent toluene according to the feeding ratio of 1:3:3, and controlling the feeding mass airspeed to be 0.7h-1To carry outContinuously feeding; controlling the temperature to 145-150 ℃ and the reaction pressure to 1.0Mpa in the reaction process;
according to the detection, in the embodiment, the single-pass conversion rate of the aniline is 89.9%, the content of effective bodies (di-tetramer, tri-tetramer and tetramer) in the product TMQ can reach 41.1%, and the content of dimer is 27.6%.
Example 4: a method for synthesizing a novel anti-aging agent TMQ. The method comprises the steps of taking aniline and acetone as raw materials, and preparing an anti-aging agent TMQ under the action of a catalyst in the presence of a solvent toluene, wherein the catalyst is an H-MCM-22 type molecular sieve, and the silica-alumina ratio of the molecular sieve is 60. The reaction adopts countercurrent feeding, aniline and solvent toluene are mixed uniformly in a feeding ratio of 1:2:2 in advance, and then are reversely fed into a reactor together with acetone steam (the mass ratio of the acetone steam to the aniline is 1: 3). Controlling the feed mass space velocity to be 14h-1Carrying out continuous feeding; controlling the temperature at 135 deg.C and the reaction pressure at 0.5 Mpa;
through detection, in the embodiment, the single-pass conversion rate of the aniline is 93.1%, the content of effective bodies (di-tetramer, tri-tetramer and tetramer) in the product TMQ can reach 86.4%, and the content of dimer is 66.8%.
Example 5: a method for synthesizing a novel anti-aging agent TMQ. The method comprises the steps of taking aniline and acetone as raw materials, and preparing an anti-aging agent TMQ under the action of a catalyst in the presence of a solvent toluene, wherein the catalyst is an H-MCM-22 type molecular sieve, and the silica-alumina ratio of the molecular sieve is 40. Adopting forward flow feeding for reaction, uniformly mixing aniline, acetone and solvent toluene according to the feeding ratio of 1:5:5, and controlling the feeding mass airspeed to be 0.1h-1Carrying out continuous feeding; controlling the temperature at 100 deg.C and the reaction pressure at 0.1 Mpa; according to the detection, in the embodiment, the single-pass conversion rate of the aniline is 84.8%, the content of effective bodies (di-tetramer, tri-tetramer and tetramer) in the product TMQ can reach 45.2%, and the content of dimer is 29.7%.
Example 6: a method for synthesizing a novel anti-aging agent TMQ. The method comprises the steps of taking aniline and acetone as raw materials, and preparing an anti-aging agent TMQ under the action of a catalyst in the presence of a solvent toluene, wherein the catalyst is an H-MCM-22 type molecular sieve, and the silica-alumina ratio of the molecular sieve is 30. The reaction adopts concurrent feeding and is carried out in advanceUniformly mixing aniline, acetone and solvent toluene according to a feeding ratio of 1:10:10, and controlling the feeding mass airspeed to be 26h-1Carrying out continuous feeding; controlling the temperature at 200 ℃ and the reaction pressure at 3.0Mpa in the reaction process; according to the detection, in the embodiment, the single-pass conversion rate of the aniline is 68.5%, the content of effective bodies (di-tetramer, tri-tetramer and tetramer) in the product TMQ can reach 40.8%, and the content of dimer is 22.5%.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (1)
1. A preparation method of an anti-aging agent TMQ is characterized in that aniline and acetone are used as raw materials, the anti-aging agent TMQ is prepared under the action of a catalyst under the condition that a solvent toluene exists, the catalyst is an H-MCM-22 type molecular sieve, the silica-alumina ratio of the molecular sieve is 60, countercurrent feeding is adopted in reaction, aniline and the solvent toluene are uniformly mixed in advance according to the feeding ratio of 1:2:2, the mixture is reversely fed into a reactor with acetone steam, the mass ratio of acetone to aniline is 1:3, and the feeding mass space velocity is controlled to be 14H-1Carrying out continuous feeding; the temperature in the reaction process is controlled to be 135 ℃, and the reaction pressure is 0.5 Mpa.
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| CN112657488A (en) * | 2019-10-15 | 2021-04-16 | 中石化南京化工研究院有限公司 | Polyacid type solid catalyst |
| CN113402457B (en) * | 2021-07-13 | 2022-05-27 | 宁波海利化工有限公司 | Preparation method of efficient antioxidant RD |
| CN114149366B (en) * | 2021-10-26 | 2024-04-12 | 中国石油化工股份有限公司 | Preparation method of rubber antioxidant TMQ |
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