CN110105296A - The synthetic method of benzotriazole sodium salt and benzotriazole - Google Patents
The synthetic method of benzotriazole sodium salt and benzotriazole Download PDFInfo
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- CN110105296A CN110105296A CN201910390846.3A CN201910390846A CN110105296A CN 110105296 A CN110105296 A CN 110105296A CN 201910390846 A CN201910390846 A CN 201910390846A CN 110105296 A CN110105296 A CN 110105296A
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- benzotriazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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Abstract
The invention discloses a kind of benzotriazole sodium salt and the synthetic methods of benzotriazole.The synthetic method includes: using o-phenylenediamine and sodium nitrite as raw material, through micro passage reaction or micro passage reaction and tank reactor tandem reaction, one-step synthesis benzotriazole sodium salt.It applies the technical scheme of the present invention, benzotriazole sodium salt is synthesized using micro passage reaction, avoid the problem being difficult to control because diazo-reaction heat release is violent reaction early period, the intrinsic safety for improving technique has the advantages that high production efficiency, economy are strong, is easy to industrialize, continuous production can be achieved.
Description
Technical field
The present invention relates to technical field of petrochemical industry, in particular to three nitrogen of a kind of benzotriazole sodium salt and benzo
The synthetic method of azoles.
Background technique
Benzotriazole (BTA) is the light brown acicular crystal of white, is a kind of important fine chemical product, is mainly used as
Corrosion inhibiter, metal antirusting agent, photograph antifoggant and the organic synthesis intermediate of copper and copper alloy；It is also widely used for coating addition
Agent, the preservative of synthetic detergent, anti-coagulants, lube oil additive, synthetic dyestuffs intermediate, Polymer material stabilizer, plant
Object growth regulator, anti-blushing agent, vapour phase inhibitor and UV absorbers.Benzotriazole makes with the cooperation of a variety of corrosion inhibiter
With corrosion mitigating effect can be improved；It can also be used cooperatively with a variety of antisludging agents, Biocidal algae-killing agent, to closing recirculated cooling water
System can generate preferable corrosion mitigating effect.Benzotriazole such as is added in automobile antifreezing agent, coating, protection can be played
The effect of material；In mechanical processing process, benzotriazole is added in cutting oil, the copper of processing can be made non-discolouring.
The autoclave interval that patent (CN105237488A) reports a kind of benzotriazole is combined to method, passes through adjacent benzene two
Amine pressurization one-step synthesis benzotriazole.But since diazo-reaction process heat release is violent, reaction heat is (adjacent up to -1400kJ/kg
Phenylenediamine), it reacts adiabatic temperature rise itself and reaches 140 DEG C, reaction process is difficult to control, and largely limits production capacity.
Document (ultrasound -- research [D] the Zhejiang Polytechnical University of ultraviolet cooperative reinforcing hydrogen peroxide degradation benzotriazole,
2014) a large amount of nitrogen can be generated by reporting the heated thermal decomposition of benzotriazole.And autoclave intervalization is reacted, and there is part in the process
The phenomenon that overheat, benzotriazole are unavoidably decomposed, and there are security risks.
It can be seen that pure autoclave interval is combined to BTA reaction process and is difficult to control, risk in commercial process
Greatly, therefore, urgent need will develop a kind of more safe and efficient BTA synthesis technology.
Summary of the invention
The present invention is intended to provide the synthetic method of a kind of benzotriazole sodium salt and benzotriazole, to provide a kind of letter
The method of single, mild synthesis benzotriazole sodium salt and benzotriazole.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of synthesis of benzotriazole sodium salt
Method.The synthetic method include: using o-phenylenediamine and sodium nitrite as raw material, through micro passage reaction or micro passage reaction with
Tank reactor tandem reaction, one-step synthesis benzotriazole sodium salt.
Further, specifically includes the following steps: S1, o-phenylenediamine and water are thermally formed by investment to preparing in A kettle
Liquid phase is as first material；Sodium nitrite, water are thrown to preparation B kettle and stirred to dissolved clarification as second material；S2, by first material
It is pumped into micro passage reaction with second material, micro passage reaction obtains the aqueous solution of benzotriazole sodium salt after reaction,
Or micro passage reaction discharges to tank reactor, tank reactor obtains the water-soluble of benzotriazole sodium salt after reaction
Liquid.
Further, the mass percentage of o-phenylenediamine is 50%~100% in first material；Nitrous in second material
The mass percentage of sour sodium is 10%~60%.
Further, in S1, preparing and preparing temperature in A kettle is 70~200 DEG C；Preparing and preparing temperature in B kettle is 10~200
℃。
Further, in S2, the reaction temperature of micro passage reaction is 250~320 DEG C, and the reaction time is 0.1~5min.
Further, in S2, the temperature in tank reactor is 250~320 DEG C, and the reaction time is 0~5 hour.
Further, in S1, the amount for controlling the charging of first material and second material makes the adjacent benzene two in first material
The molar ratio of sodium nitrite in amine and second material is 1:1.0~1:1.1.
Further, filtering is further included the steps that before first material and second material are pumped into micro passage reaction.
According to another aspect of the present invention, a kind of synthetic method of benzotriazole is provided.The synthetic method includes upper
The synthetic method of any benzotriazole sodium salt is stated, and is acidified benzotriazole sodium salt to obtain benzotriazole.
Further, acidification post-synthesis is carried out in benzotriazole sodium salt further include the steps that washing, distillation；It is preferred that
, the terminal pH of acidification is 5~7；Preferably, the vacuum degree of distillation is 0.1~1.0kPa.
It applies the technical scheme of the present invention, benzotriazole sodium salt is synthesized using micro passage reaction, before avoiding reaction
Phase because diazo-reaction heat release acutely due to the problem that is difficult to control, improve the intrinsic safety of technique, with high production efficiency,
Economy is strong, is easy to industrialize, the advantages of continuous production can be achieved.
Specific 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.
Benzotriazole (BTA) reaction process is combined to for the pure autoclave interval mentioned in background technique to be difficult to control,
The big technical problem of risk in commercial process, the present invention is intended to provide a kind of simple, mild reactive mode is closed
At BTA.
Micro passage reaction is miniature between 10 to 1000 microns using the characteristic size of precision processing technology manufacture
Reactor, heat exchange efficiency and mixed effect are higher by more times than traditional tank reactor, and wide variety of conventional reactor may be implemented
In the reaction that cannot achieve.The technology is mainly used for preparation and the household chemicals of organic synthesis, micron and nano material at present
The fields such as production.In this application, the creative synthesis that micro passage reaction is applied to benzotriazole of inventor.
A kind of typical embodiment according to the present invention provides a kind of synthetic method of benzotriazole sodium salt.The synthesis
Method includes: using o-phenylenediamine and sodium nitrite as raw material, and through micro passage reaction and tank reactor tandem reaction, a step is closed
At benzotriazole sodium salt.
It applies the technical scheme of the present invention, benzotriazole sodium salt is synthesized using micro passage reaction, before avoiding reaction
Phase because diazo-reaction heat release acutely due to the problem that is difficult to control, improve the intrinsic safety of technique, with high production efficiency,
Economy is strong, is easy to industrialize, the advantages of continuous production can be achieved.
In an of the invention specific embodiment, the synthetic method of benzotriazole sodium salt specifically includes the following steps:
O-phenylenediamine and water are thermally formed liquid phase as first material to preparing in A kettle by investment by S1；By sodium nitrite, water throw to
B kettle is prepared to stir to dissolved clarification as second material；First material and second material are pumped into micro passage reaction, microchannel by S2
Reactor discharges to tank reactor, and tank reactor obtains the aqueous solution of benzotriazole sodium salt after reaction.In difference
Preparation kettle in o-phenylenediamine and sodium nitrite are configured to solution respectively in advance, convenient for being pumped into the stream of micro passage reaction
Speed and dosage control, enable to reaction to carry out under good control.
Preferably, in first material o-phenylenediamine mass percentage be 50%~100% (such as optional 55%,
60%, 65%, 70%, 80%, 90% etc.)；Because water consumption is related to the pressure under reaction condition, water is few, reaction end
Pressure is low, and the requirement to equipment reduces.The mass percentage of sodium nitrite is 10%~60% (for example, can in second material
Select 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% etc.), it is saturated concentration at this temperature, concentration is got over
The temperature of height, feed pipe heat preservation is higher, 60% be close to the sodium nitrite concentration at 100 DEG C, improve its concentration equally and be for
Raising production capacity reduces water consumption, reduces reaction pressure.
Because o-phenylenediamine is that homogeneously, temperature is higher than 100 DEG C, and system is then with pressure under the conditions of preparing temperature and being higher than 70 DEG C
Power, and this pressure is unsuitable excessively high, it is preferred, therefore, that, it prepares and prepares temperature be 70~200 DEG C (such as optional 80 DEG C, 90 in A kettle
DEG C, 100 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C etc.).Sodium nitrite concentration is greater than 40% when B kettle is higher than 10 DEG C,
Positive pressure in B kettle is prepared in 100~200 DEG C of ranges.A kettle and B kettle are prepared by normal pressure to pressurization, for reaction, is prepared
The material of kettle is all finally to be heated to reaction temperature by heat exchanger or mixer, as long as preparing the temperature limited in kettle makes material
At homogeneous, in order to feed metering, it is preferred, therefore, that, preparing and preparing temperature in B kettle is 10~200 DEG C (such as optional 20
DEG C, 50 DEG C, 60 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C etc.).
Preferably, in S2, the reaction temperature of micro passage reaction is 250~320 DEG C, and the reaction time is 0.1~5min.
240 DEG C are reaction lower limit temperatures, but ineffective for micro passage reaction, when reaction temperature is controlled to 250 DEG C~320 DEG C
When, reaction effect significantly improves, and the reaction time intermittently changes reaction on year-on-year basis and greatly shortens, and feed stock conversion is greater than 99.5%, product
Yield is greater than intervalization reaction level, and technique intrinsic safety improves.
Preferably, in S2, the temperature in tank reactor is 250~320 DEG C, and the reaction time is 0~5 hour.
Raw materials components mole ratio theoretical amount is o-phenylenediamine: sodium nitrite=1:1.If charge proportion o-phenylenediamine: sodium nitrite
Molar ratio is greater than 1, then o-phenylenediamine is excessive after reaction, and not exclusively, post-processing influences product quality for conversion；Sodium nitrite is used
It measures excessively high, causes wastage of material, the starting point that also should reduce material loss with microchannel plate is disagreed, and post-processing can also generate more
More nitrous oxides exhaust gas.Preferably, in S1, the amount for controlling the charging of first material and second material makes in first material
The molar ratio of sodium nitrite in o-phenylenediamine and second material is 1:1.0~1:1.1
Preferably, filtering is further included the steps that before first material and second material are pumped into micro passage reaction；This
It is because the purpose of micro passage reaction internal gutter characteristic size is generally micron order, is filtered step is to remove solution
In insoluble impurity that may be present, prevent blocking reactor duct, thus guarantee the reaction in micro passage reaction it is smooth into
Row.Preferably, in S2 tank reactor after reaction blanking when temperature be lower than 100 DEG C, preferably 50~80 DEG C, with acidification
50~80 DEG C of temperature it is corresponding.
Under invention thought guidance of the invention, a kind of typical embodiment, provides a kind of benzo three according to the present invention
The synthetic method of nitrogen azoles.This method includes the synthetic method of above-mentioned benzotriazole sodium salt, and by benzotriazole sodium salt into
Row acidification obtains benzotriazole.
Benzotriazole sodium salt is synthesized using micro passage reaction, benzene then can be obtained to the acidification of benzotriazole sodium salt
And triazole, the problem being difficult to control because diazo-reaction heat release is violent reaction early period is avoided, the essence of technique is improved
Safety has the advantages that high production efficiency, economy are strong, is easy to industrialize, continuous production can be achieved.
Preferably, acidification post-synthesis is carried out in benzotriazole sodium salt further include the steps that washing, distillation；So as to
To obtain more pure benzotriazole.Preferably, the terminal pH of acidification is 5~7；To guarantee that benzotriazole sodium salt is maximum
Limit is converted into benzotriazole, and not will cause the waste of acid and lower the difficulty of subsequent processing.
Preferably, the vacuum degree of distillation is 0.1~1.0kPa.It controls under the vacuum condition, corresponding BTA product boiling point is
150~190 DEG C.BTA sodium salt is stablized in Synthesis liquid, but BTA product can be decomposed at 200 DEG C or more, generates gas, and it is hidden to there is safety
Suffer from, it is therefore necessary to which control distillation condition of high vacuum degree guarantees process safety to control BTA vapo(u)rizing temperature lower than decomposition temperature.
Beneficial effects of the present invention are further illustrated below in conjunction with embodiment.
Embodiment 1
(1) stainless steel material micro passage reaction, 2 deblocking reaction plates, total volume 16.4mL device: are used.Tank reactor
Using 316L stainless steel cauldron, total volume 1000mL.Correlative connecting line is all made of conduction oil jacket hot tracing.
(2) it synthesizes: 300g o-phenylenediamine being thrown into A kettle, being heated to 120 DEG C makes it liquefy completely, protects under nitrogen protection
It is warm stand-by.220g sodium nitrite, 300g water are thrown and sufficiently dissolved into B kettle, heat preservation for standby use at 50 DEG C.
The ratio uniform feeding of two strands of materials of A kettle and B kettle 1:1.5~2.5 in mass ratio, micro passage reaction temperature control 280
DEG C, add up to residence time 60s, reaction pressure reaches 4.5MPa.Micro passage reaction discharging sampling middle control analysis, o-phenylenediamine turn
Rate is up to 95.1%.Production expects that tank reactor relays continuous insulation reaction, controls 280 DEG C of heat preservation 1h.
After insulation reaction, cool down pressure release, releases kettle material, obtains the aqueous solution of BTA sodium salt, o-phenylenediamine conversion ratio reaches
99.9%, BTA yield 99.2%.
Reaction kettle material is acidified with hydrochloric acid or sulfuric acid, separates oil reservoir.Oil reservoir washed, be dehydrated after in 185 DEG C,
High vacuum distillation is carried out under the conditions of 0.5kPa, until 200 DEG C of kettle temperature stoppings, obtaining rice white fraction 280.13g, yield 85.6%.
Distillation still residue 13.32g, BTA content 86.9%.Acidified aqueous layer and washing water are laminated simultaneously, through crystallization, filtering, collect filter cake, apply
It is washed to lower batch of oil reservoir.
To the water layer crystallization filter cake of embodiment 1 carry out post-processing apply (it is so-called to apply, be to analyse this part water layer is cooling
Crystalline substance can recycle major part BTA in water, for example the crystallization filter cake set of upper batch is used this batch of oil reservoir washing, this batch of acidifying water
Layer with washing water is laminated and crystallization, filter cake covers again to be used next group oil reservoir and goes to wash, and such mode is applied, and both ensure that production
Quality also ensures product yield), acquired results are as shown in table 1 below:
Table 1
| Embodiment number | Apply lot number | O-phenylenediamine conversion ratio/% | BTA yield/% | BTA fraction yield/% |
| Embodiment 1 | In the first batch | 99.9 | 99.2 | 85.6 |
| Embodiment 2 | Set 1 | 99.9 | 99.1 | 98.5 |
| Embodiment 3 | Set 2 | 99.9 | 99.3 | 98.7 |
| Embodiment 4 | Set 3 | 99.9 | 99.3 | 98.6 |
Embodiment 5
On the basis of embodiment 1, it prepares and 100g water is added in A kettle o-phenylenediamine, A kettle holding temperature is reduced to 90 after dissolved clarification
DEG C, other conditions are constant.After reaction, the aqueous solution of BTA sodium salt, o-phenylenediamine conversion ratio 99.9%, BTA yield are obtained
99.2%.
Embodiment 6-8
On the basis of embodiment 1, change the residence time of micro passage reaction and tank reactor, acquired results are as follows
Table 2:
Table 2
Embodiment 9-11
Change the reaction temperature of micro passage reaction and tank reactor on the basis of embodiment 1, acquired results are as follows
Shown in table 3:
Table 3
| Number | Micro passage reaction temperature/DEG C | Tank reactor temperature/DEG C | O-phenylenediamine conversion ratio/% | BTA yield/% |
| Embodiment 9 | 270 | 270 | 99.9 | 99.0 |
| Embodiment 10 | 290 | 290 | 99.9 | 99.3 |
| Embodiment 11 | 310 | - | 99.9 | 99.5 |
Note: "-" indicates that micro passage reaction directly discharges, and keeps the temperature without tank reactor.
Embodiment 12-19
Response data statistics under the conditions of other:
Note: "-" indicates that micro passage reaction directly discharges, and keeps the temperature without tank reactor.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements: using micro- logical
Road reactor carries out the synthesis of benzotriazole, and up to 99.9% or more, benzotriazole yield reaches the conversion ratio of raw material
98% or more, it is highly-safe, the reaction time is short, side reaction is few.
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.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of benzotriazole sodium salt characterized by comprising with o-phenylenediamine and sodium nitrite be original
Material, through micro passage reaction or micro passage reaction and tank reactor tandem reaction, one-step synthesis benzotriazole sodium salt.
2. synthetic method according to claim 1, which is characterized in that specifically includes the following steps:
O-phenylenediamine and water are thermally formed liquid phase as first material to preparing in A kettle by investment by S1；By sodium nitrite, water
It throws to preparation B kettle and stirs to dissolved clarification as second material；
The first material and the second material are pumped into the micro passage reaction, the micro passage reaction reaction by S2
After obtain the aqueous solution of benzotriazole sodium salt or the micro passage reaction discharges to the tank reactor, it is described
Tank reactor obtains the aqueous solution of benzotriazole sodium salt after reaction.
3. synthetic method according to claim 2, which is characterized in that the quality percentage of o-phenylenediamine in the first material
Content is 50%~100%；The mass percentage of sodium nitrite is 10%~60% in the second material.
4. synthetic method according to claim 2, which is characterized in that preparing temperature in the S1, in the preparation A kettle is
70~200 DEG C；It is 10~200 DEG C that temperature is prepared in the preparation B kettle.
5. synthetic method according to claim 2, which is characterized in that in the S2, the reaction of the micro passage reaction
Temperature is 250~320 DEG C, and the reaction time is 0.1~5min.
6. synthetic method according to claim 2, which is characterized in that the temperature in the S2, in the tank reactor
It is 250~320 DEG C, the reaction time is 0~5 hour.
7. synthetic method according to claim 2, which is characterized in that in the S1, control the first material and described
The amount of the charging of second material makes rubbing for o-phenylenediamine in the first material and the sodium nitrite in the second material
You are than being 1:1.0~1:1.1.
8. synthetic method according to claim 2, which is characterized in that pumped by the first material and the second material
Further include the steps that filtering before entering the micro passage reaction.
9. a kind of synthetic method of benzotriazole, which is characterized in that including benzene such as described in any item of the claim 1 to 8
And the synthetic method of Sodium Triazolyl Salt, and be acidified the benzotriazole sodium salt to obtain benzotriazole.
10. synthetic method according to claim 9, which is characterized in that after the benzotriazole sodium salt is acidified
The synthetic method further includes the steps that washing, distillation；
Preferably, the terminal pH of the acidification is 5~7；
Preferably, the vacuum degree of the distillation is 0.1~1.0kPa.
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| CN110590687A (en) * | 2019-11-07 | 2019-12-20 | 山东豪迈化工技术有限公司 | Preparation method of benzotriazole |
| CN111732550A (en) * | 2020-06-18 | 2020-10-02 | 江苏扬农化工集团有限公司 | Continuous production method of benzotriazole with adjustable form |
| CN115594644A (en) * | 2022-09-06 | 2023-01-13 | 上海朗亿功能材料有限公司（Cn） | Preparation method of benzotriazole ultraviolet absorbent |
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Application publication date: 20190809 |