CN109665991A - A kind of preparation method of anti-aging agent TMQ - Google Patents
A kind of preparation method of anti-aging agent TMQ Download PDFInfo
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- CN109665991A CN109665991A CN201710957725.3A CN201710957725A CN109665991A CN 109665991 A CN109665991 A CN 109665991A CN 201710957725 A CN201710957725 A CN 201710957725A CN 109665991 A CN109665991 A CN 109665991A
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- acetone
- tmq
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- aniline
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Quinoline Compounds (AREA)
Abstract
The invention belongs to technical field of fine, are related to the preparation method of anti-aging agent TMQ a kind of.Using aniline and acetone as raw material, combined using reaction kettle with static mixer, one-step method prepares rubber antioxidant TMQ.The effective body content 53.4 ~ 77.5% of product TMQ, compared with prior art, using the combination of reaction kettle and static mixer, entire reaction system liquid flow is forcibly reacted in a mixed contact manner, the mass transfer effect for considerably increasing system, the phenomenon that avoiding traditional handicraft acetone comparatively high consumption, the simultaneous reactions time foreshortened to minimum 0.05 hour from 6 ~ 12 hours, have many advantages, such as that easy to operate, equipment is reliable, catalyst consumption is low, cost is relatively low, effective body content is higher.
Description
Technical field
The invention belongs to technical field of fine, are related to the continuous preparation method of anti-aging agent TMQ a kind of, are a kind of green
The preparation process that colour circle is protected.
The present invention relates to a kind of continuous catalysis condensations to prepare anti-aging agent TMQ(2,2,4- trimethyl -1,2- dihyaroquinolines
Condensate) method, be a kind of preparation process of environment-friendly high-efficiency.On traditional intermittent tank reactor, additional cycles pump and
Static mixer etc., realize TMQ production on it is continuous, so as to shorten the reaction time, reduce consumption of raw materials, reduction power cost,
The stability for reducing labor intensity, keeping production and product quality.
Background technique
Anti-aging agent TMQ is two, three, four condensates also known as anti-aging agent RD of 2,2,4- trimethyl -1,2- dihyaroquinolines,
It is a kind of ketone amines antioxidants, moors coloured particles or thin slice to ruins to be faint yellow, be mainly used as rubber antioxidant, domestic annual requirement
It is one of the rubber antioxidant product having the call on domestic and international market up to 100,000 tons,
The primary raw material of synthesis anti-aging agent TMQ be aniline and acetone (or derivatives thereof), technique can substantially be divided into " one-step method " or
Two kinds of " two-step method "." one-step method " technical process are as follows: condensation, polymerization reaction occur under the action of catalyst for aniline, acetone, directly
Obtain two, three, the four polymeric anti-aging agent TMQ polycondensation liquid containing 2,2,4- trimethyl -1,2- dihyaroquinolines, TMQ polycondensation liquid
It neutralized through liquid alkaline, divide water, distillation etc. and obtain TMQ." two-step method " technical process are as follows: aniline, acetone occur under the action of catalyst
Reaction solution after condensation reaction, reaction solution or neutralization obtains 2,2,4- trimethyl -1,2- dihyaroquinolines by distillation or rectifying
That is TMQ monomer, TMQ monomer carries out polymerization reaction under the action of catalyst again later, obtains 2,2,4- trimethyl -1,2- dihydros
Two, three, four condensates of quinoline, then it is neutralized, divide water, distillation obtain anti-aging agent TMQ.Sometimes for reaction process is accelerated, again
Can in the reaction be added toluene, dimethylbenzene, hexamethylene equal solvent, therefore TMQ synthetic method can be divided into again it is " solvent method " or " solvent-free
Method " etc..
The industrial process of anti-aging agent TMQ mainly uses batch process both at home and abroad at present, uses hydrochloric acid as catalysis
Agent, which carries out polycondensation reaction to aniline and acetone, (can substantially be divided into the processes such as salt, polycondensation, neutralization, distillation, granulation: i.e. in technique
Aniline and hydrochloric acid are dehydrated into salt in reaction kettle 1, obtain " at the salt process " of anilinechloride, anilinechloride is transferred to separately later
" polycondensation step " for carrying out polycondensation reaction in one reaction kettle with a large amount of acetone, obtains TMQ polycondensation liquid, is transferred in third reaction kettle
Carry out " neutralize, divide water conservancy project sequence ", oil, which is mutually distilled, is granulated etc., obtains anti-aging agent TMQ), it is simple to be mainly characterized by synthetic method
Single, process is short, technical maturity.The disadvantage is that large labor intensity, frequent operation, unstable product quality, while traditional batch autoclave
There is the acetone for vaporizing after a large amount of acetone contacting material because temperature of reaction system is high and actual participation being caused to react in technique
Less, the phenomenon that acetone comparatively high consumption, ton product acetone consumes about 710-740kg, more much higher than the 676kg of theoretical amount.
CN102153511, which is disclosed, a kind of prepares 2,2,4- trimethyl -1,2- dihyaroquinoline condensates (anti-aging agent RD)
Method, aniline and acetone continuously squeezed into the reaction tower equipped with solid acid catalyst by this method, and reactant is condensed again, should
Method is easy to operate, and wastewater flow rate is small, but solid acid catalyst is difficult to use in the industrialized production of this technique.
CN102010369 discloses a kind of 2,2,4- trimethyl -1,2- dihyaroquinoline (anti-aging agent RD lists of continuous preparation
Body) method, aniline and acetone is continuously passed through the reaction tower equipped with solid acid catalyst by this method, the reactant containing TMQ
Overflow extraction, this method is easy to operate, and wastewater flow rate is small, but it is not high to equally exist the solid acid catalyst service life, it is difficult to industrial metaplasia
The problem of production.
At home and abroad there is no the reports using continuous process industrialized production at present.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of raising stability, change
Labor intensity in kind anti-aging agent TMQ production process reduces acetone consumption, saves power and cost of labor, it is raw to solve the prior art
Low yield, acetone comparatively high consumption, unstable product quality TMQ preparation method.
The present invention provides the preparation method of anti-aging agent TMQ a kind of.The preparation method is using aniline and acetone as raw material, using anti-
Kettle is answered to combine with static mixer, one-step method prepares rubber antioxidant TMQ.
The preparation method is accomplished by the following way: three kinds of aniline, acetone, catalyst substances are set by respectively conveying
It is standby, it is any one or two kinds of or three kinds of substances part or all continuously into reaction kettle or static mixer, while it is anti-
It answers the material in kettle to be delivered in static mixer through delivery pump, carries out pressure reaction, the material of static mixer outlet, one
Divide and be recycled into reaction kettle, another part enters pans, obtains TMQ polycondensation reaction liquid, then carry out the mutually steaming of neutralization Fen Shui, oil
It evaporates granulation and obtains TMQ.
In the preparation method, catalyst is hydrochloric acid, sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, copper halide, metatitanic acid and titanium
One kind of acid esters.
In the preparation method, reaction temperature (static mixer and reaction kettle control temperature) is 90 ~ 160 DEG C, reaction
Time is 0.05 ~ 3 hour.
Further, reaction temperature is 100 ~ 130 DEG C, and the reaction time is 0.2 ~ 1 hour.
In the preparation method, the molar ratio of aniline and acetone is 1:1 ~ 6, and the molar ratio of catalyst and aniline is 0.01
~0.3:1。
Further, the molar ratio of aniline and acetone is 1:1.5 ~ 3；The molar ratio of catalyst and aniline be 1:0.05 ~
0.15。
In the preparation method, reaction kettle is combined with static mixer, and static mixer can be one or by several
The static mixer group of composition.
In the preparation method, reaction kettle is combined with static mixer, and reaction kettle is with equipment such as stirrings.
In the preparation method, reaction kettle is combined with static mixer, and acetone fractionating column is had on reaction kettle.
The acetone fractionating column, effect are to separate unreacted acetone with the water that reaction generates, third after separation
Ketone can be applied directly as raw material.
It is 1 into material in reaction kettle and the TMQ polycondensation reaction flow quantity ratio for entering pans in the preparation method
~50:1。
The utility model has the advantages that
1, it compared with prior art, is combined using reaction kettle with static mixer, prepares rubber antioxidant TMQ, pass through static state
Mixer is forcibly reacted in a mixed contact manner entire reaction system liquid flow, considerably increases the mass transfer effect of system,
It is existing because temperature of reaction system is high to avoid traditional caldron process, vaporizes after a large amount of acetone contacting material and causes reality
It participates in the phenomenon that acetone is few, acetone comparatively high consumption of reaction (consumption of ton product acetone is reduced to about 680kg), the reaction time is from biography
System technique foreshortens to minimum 0.05 hour for 6 ~ 12 hours, and energy consumption significantly reduces.Operation of the present invention is simple, catalyst, raw material etc.
Consumption is low, and cost is relatively low, and effective body content is higher.
2, using aniline and acetone as raw material, in the presence of a catalyst, solventess ore-step process prepares anti-aging agent TMQ, with aniline
Counting its conversion per pass can reach 90% or more, and the effective body content of product TMQ (two, three, the tetramer) is up to 53.4 ~ 77.5%.
3, the reaction kettle in the present invention and static mixer combination, to reaction kettle and static mixer without particular/special requirement, nothing
Enlarge-effect, so as to realize continuous production, has equipment reliable so there is no limit for production capacity, and energy consumption, consumption are lower,
The advantages such as lower production costs, stable product quality.
Specific embodiment
Beneficial effects of the present invention are further illustrated below in conjunction with embodiment.
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
The preparation method of a kind of typical embodiment according to the present invention, rubber antioxidant TMQ includes with aniline and third
Ketone is raw material, and one-step method prepares rubber antioxidant TMQ under the action of catalyst (hydrochloric acid).
The method that the present invention prepares rubber antioxidant TMQ, part aniline is disposably put into reaction kettle, and stirring is warming up to anti-
After answering temperature, aniline, hydrochloric acid are continuously delivered in reaction kettle, the material-handling pump that the material in reaction kettle is linked through bottom
It is continuously delivered in static mixer, while being continuously passed through acetone in static mixer, aniline and acetone are in static mixing
Forced Mixing is reacted in device, and the reaction mass of static mixer outlet is divided into two parts, and a part enters in reaction kettle, another part
Into in pans, TMQ polycondensation reaction liquid is obtained, liquid alkaline is added in the TMQ polycondensation liquid in pans and is neutralized, stratification, oil
Mutually under -0.098MPa vacuum, 180 ~ 260 DEG C of material temperature are controlled, unreacted raw material aniline, unpolymerized TMQ monomer are distilled to recover
Equal sets are in reaction.Be granulated after kettle material is cooling and anti-aging agent TMQ finished product be made, in product effectively body content reach 53.4 ~
77.5%。
Residence time of the aniline in static mixer is generally 0.05 ~ 3 hour, preferably 0.2 ~ 1 hour.In normal pressure
Under, control reaction temperature is 90 ~ 160 DEG C, preferably 100 ~ 130 DEG C.Static mixer outlet enter in reaction kettle material with into
The TMQ polycondensation reaction flow quantity ratio for entering pans is 1 ~ 50:1, preferably 6 ~ 10:1.It is straight by the acetone fractionating column on reaction kettle
It connects separation and recovery acetone and reaction water is discharged, then acetone set is used in raw material storage tank.
Embodiment 1
By the aniline of 400g put into 1000m1 with blender, thermometer and discharging pipeline (top is connected to a fractionating column,
So that acetone is entered fractionating column with the water generated is reacted, bottom links delivery pump) reactor in, 120 DEG C are warming up to, in normal pressure
Under, aniline, hydrochloric acid are entered in reaction kettle by the way of metering pump continuous charging, and aniline flow is 2000g/h, and hydrochloric acid flow is
150g/h, material are delivered in static mixer with the metering pump that the reacted device bottom of the flow of 8000g/h links, while quiet
Flow in state mixer with 8000g/h is continuously passed through acetone, and control reaction temperature is 120 DEG C, measures mixed material in static state
In mixer the residence time be 2 minutes, static mixer outlet, 15000g/h material enters in reaction kettle, 1000g/h material into
Enter in pans, anti-aging agent TMQ polycondensation reaction liquid is made.The water and excessive acetone generated when reaction passes through on reaction response kettle
Fractionating column, recycling acetone simultaneously separates the water that reaction generates, and aniline conversion per pass is to 75.4% in reaction.Afterwards by anti-aging agent TMQ
Lower layer's waste water is carried out waste water treatment system by polycondensation reaction liquid, liquid feeding alkali neutralization, static layering, and upper layer feed liquid is evaporated under reduced pressure back
After receiving unreacted aniline, unpolymerized TMQ monomer (aniline of recycling continues set in reacting with monomer), it is granulated and is made anti-
Old agent TMQ finished product, one-way yield 67.8%, effective body (two, three, the tetramer) content reach 64.2%, ton product acetone consumption folding
Calculate about 680.5kg.
Embodiment 2
Prevailing operating conditions change mixer in the static state that static mixer forms for mixer in 5 static state with embodiment 1
Group, wherein mixed material residence time in static mixer is 10 minutes.The conversion ratio for measuring aniline is 93.7%, anti-aging agent
The effective body content 72.0% of TMQ.Ton product acetone consumption conversion about 678.2kg
Embodiment 3
Prevailing operating conditions change the adding manner (acetone flow is constant) of acetone, i.e. acetone and aniline, salt with embodiment 1
Acid is continuously added in reaction kettle together.The conversion ratio for measuring aniline is 53.7%, the effective body content 63.9% of anti-aging agent TMQ.Ton
Product acetone consumption conversion about 684.5kg.
Embodiment 4
Prevailing operating conditions change the sulfuric acid that catalyst is 60% with embodiment 1, wherein the conversion ratio of aniline is 53.7%, is prevented
The old effective body content 57.2% of agent TMQ.Ton product acetone consumption conversion about 687.5kg.
Embodiment 5
Prevailing operating conditions with embodiment 1, but partly change acetone adding manner: i.e. with 2000g/h flow acetone with
The aniline of 2000g/h flow, 150 g/h flows hydrochloric acid be continuously added in reaction kettle together, with 6000g/h flow acetone company
It is added in static mixer continuously.The conversion ratio for measuring aniline is 70.7%, the effective body content 68.4% of anti-aging agent TMQ.Ton product
Acetone consumption conversion about 681.3kg.
Embodiment 6-19
Using the catalyst and experimental method of embodiment 1.In the case where other conditions are constant, by changing aniline when reacting
With the ratio of acetone, the ratio of aniline and catalyst, different reaction temperatures and reaction time, into reaction kettle with into pans object
Expect that conditions, conversion per pass and the effective body content of product, the results for investigating reaction such as flow-rate ratio are as shown in the table.
Embodiment 20
By the aniline of 400g put into 1000m1 with blender, thermometer and discharging pipeline (top is connected to a fractionating column,
So that acetone is entered fractionating column with the water generated is reacted, bottom links delivery pump) reactor in, 130 DEG C are warming up to, in normal pressure
Under, aniline, hydrochloric acid are entered in reaction kettle by the way of metering pump continuous charging, and aniline flow is 1000g/h, and hydrochloric acid flow is
150g/h, material are delivered in static mixer with the metering pump that the reacted device bottom of the flow of 8000g/h links, while quiet
Flow in state mixer respectively with 8000g/h is continuously passed through acetone, is continuously passed through aniline with the flow of 1000g/h, control is anti-
Answering temperature is 140 DEG C, and measuring mixed material residence time in static mixer is 3 minutes, static mixer outlet,
15000g/h material enters in reaction kettle, and 1000g/h material enters in pans, and anti-aging agent TMQ polycondensation reaction liquid is made.Reaction
When the water that generates and excessive acetone by the fractionating column on reaction response kettle, recycling acetone simultaneously separates the water that reaction generates, instead
Answer middle aniline conversion per pass to 73.2%.Afterwards by anti-aging agent TMQ polycondensation reaction liquid, liquid feeding alkali neutralization, static layering, by lower layer
Waste water carries out waste water treatment system, and unreacted aniline, the unpolymerized TMQ monomer (benzene of recycling are recycled in feed liquid vacuum distillation in upper layer
Amine and monomer continue set in react) after, it is granulated obtained anti-aging agent TMQ finished product, one-way yield 66.6%, effective body (two,
Three, the tetramer) content reaches 67.3%, ton product acetone consumption conversion about 681.1kg.
Embodiment 21-28
Using the catalyst and experimental method of embodiment 20.Aniline, acetone, catalyst total moles when reaction temperature, time etc.
In the case that condition is constant, the items such as ratio of aniline and acetone, catalyst in reaction kettle and static mixer are added by changing
Part, conversion per pass and the effective body content of product, the result for investigating reaction are as shown in the table.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied, such as changes acetone material into reaction kettle and into mixing in static state
The flow of device or its flow proportional are being mixed, are being preheated into raw material before reaction kettle or static mixer etc..It is all in this hair
Within bright spirit and principle, etc. any modification, equivalent replacement, improvement and so on (as used acetone derivatives, aniline derivatives
Object, aniline and acetone reaction intermediates etc.), it should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of anti-aging agent TMQ, it is characterised in that: using aniline and acetone as raw material, using reaction kettle and static state
Mixer combination, one-step method prepare rubber antioxidant TMQ,；It is accomplished by the following way: three kinds of aniline, acetone, catalyst objects
Matter by respective conveying equipment, it is any one or two kinds of or three kinds of substances part or all continuously into reaction kettle or static state
In mixer, the material in simultaneous reactions kettle is delivered in static mixer, carries out pressure reaction, the object of static mixer outlet
Material, a part are recycled into reaction kettle, and another part enters pans, obtain TMQ polycondensation reaction liquid, then neutralize and divided
Mutually distillation granulation obtains TMQ for water, oil.
2. preparation method according to claim 1, it is characterised in that the catalyst be hydrochloric acid, sulfuric acid, benzene sulfonic acid, to first
Benzene sulfonic acid, copper halide, metatitanic acid and titanate esters one kind.
3. preparation method according to claim 1, it is characterised in that the one-step method prepares the anti-of rubber antioxidant TMQ
Answering temperature is 90 ~ 160 DEG C, and the reaction time is 0.05 ~ 3 hour；The reaction temperature is controlled by static mixer and reaction kettle.
4. preparation method according to claim 3, it is characterised in that the one-step method prepares the anti-of rubber antioxidant TMQ
Answering temperature is 100 ~ 130 DEG C, and the reaction time is 0.2 ~ 1 hour.
5. preparation method according to claim 1, it is characterised in that the molar ratio of aniline and acetone is 1:1 ~ 6, catalyst
Molar ratio with aniline is 0.01 ~ 0.3:1.
6. preparation method according to claim 5, it is characterised in that the molar ratio of aniline and acetone is 1:1.5 ~ 3；Catalysis
The molar ratio of agent and aniline is 1:0.05 ~ 0.15.
7. preparation method according to claim 1, it is characterised in that the reaction kettle is combined with static mixer, static
Mixer is one or by several static mixer group formed.
8. preparation method according to claim 1, it is characterised in that the reaction kettle is combined with static mixer, reaction
Kettle has mixing plant；Acetone fractionating column is had on reaction kettle.
9. preparation method according to claim 8, it is characterised in that acetone fractionating column gives birth to unreacted acetone and reaction
At water separation, the acetone after separation directly applies as raw material.
10. preparation method according to claim 1, it is characterised in that into material in reaction kettle and enter pans
TMQ polycondensation reaction flow quantity ratio is 1 ~ 50:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142657A (en) * | 2019-06-26 | 2020-12-29 | 中石化南京化工研究院有限公司 | Preparation method of anti-aging agent TMQ |
| CN112142658A (en) * | 2019-06-26 | 2020-12-29 | 中石化南京化工研究院有限公司 | Preparation method of low primary amine antioxidant TMQ |
| CN112552234A (en) * | 2019-09-10 | 2021-03-26 | 中石化南京化工研究院有限公司 | Preparation method of TMQ (tetramethylbenzidine) antioxidant |
| 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 |
| 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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142657A (en) * | 2019-06-26 | 2020-12-29 | 中石化南京化工研究院有限公司 | Preparation method of anti-aging agent TMQ |
| CN112142658A (en) * | 2019-06-26 | 2020-12-29 | 中石化南京化工研究院有限公司 | Preparation method of low primary amine antioxidant TMQ |
| CN112552234A (en) * | 2019-09-10 | 2021-03-26 | 中石化南京化工研究院有限公司 | Preparation method of TMQ (tetramethylbenzidine) antioxidant |
| CN112552234B (en) * | 2019-09-10 | 2022-11-25 | 中石化南京化工研究院有限公司 | Preparation method of TMQ (Tetramethylbenzidine) anti-aging agent |
| 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 |
| CN113735766B (en) * | 2020-05-27 | 2023-08-29 | 中国石油化工股份有限公司 | Preparation method of anti-aging agent |
| 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 |
| CN114315713B (en) * | 2020-10-10 | 2024-01-30 | 中石化南京化工研究院有限公司 | Preparation method of low primary amine TMQ (TMQ) anti-aging agent |
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