CN106008378A - Preparation method of benzotriazole ultraviolet light absorber - Google Patents
Preparation method of benzotriazole ultraviolet light absorber Download PDFInfo
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- CN106008378A CN106008378A CN201610373059.4A CN201610373059A CN106008378A CN 106008378 A CN106008378 A CN 106008378A CN 201610373059 A CN201610373059 A CN 201610373059A CN 106008378 A CN106008378 A CN 106008378A
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- benzotriazole ultraviolet
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- ultraviolet stabilizer
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- 0 *c1ccccc1N Chemical compound *c1ccccc1N 0.000 description 4
- OZLBAJSDAUQQRZ-UHFFFAOYSA-N Nc(cccc1)c1[NH2+2] Chemical compound Nc(cccc1)c1[NH2+2] OZLBAJSDAUQQRZ-UHFFFAOYSA-N 0.000 description 1
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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
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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Abstract
The invention discloses a preparation method of a benzotriazole ultraviolet light absorber. The method comprises the following steps: adding an azo dye intermediate represented by formula I to hydrazine hydrate, carrying out reduction to form an intermediate nitrogen oxide represented by formula II, and reducing the intermediate nitrogen oxide represented by formula II with hydrogen to prepare the benzotriazole ultraviolet light absorber represented by formula III, wherein the formula I, the formula II and the formula III are respectively shown in the description. The preparation method allows wastewater generated in the invention to be environmentally-friendly.
Description
Technical field
The present invention relates to ultra-violet absorption field, particularly to the preparation side of a kind of Benzotriazole Ultraviolet Stabilizer
Method.
Background technology
Plastics and other macromolecular materials, be exposed under daylight or high-energy ray, owing to absorbing UV energy, can send out
Third contact of a total solar or lunar eclipse oxidative degradation, causes depolymerization to deteriorate, hydraulic performance decline.UV absorbent is a kind of light stabilizer, and it can be inhaled
Receive the ultraviolet part in sunlight and fluorescence light source, and itself does not changes.Plastics and other macromolecular materials add
Optionally absorb high-octane ultraviolet after entering UV absorbent, be allowed to become harmless energy and discharge or consume.
Benzotriazole is one of common UV absorbent, shown in following reaction equation A of its stable mechanism:
Benzotriazole ultraviolet absorbent, also referred to as Benzotriazole Ultraviolet Stabilizer, its absorbance is also than other
UV absorbent want height, and it has that oil resistant, resistance to variable color, volatility be low, toxicity is little good with polymer compatibility excellent
Point, is widely used in synthetic material and goods.At present, conventional reducing process prepares benzotriazole ultraviolet absorbent, i.e.
Ortho-nitraniline (or its substituent) makes diazonium salt solution through diazo-reaction, is then allowed to make centre with alkyl phenol coupling
Body dyestuff, finally becomes final products by its reduction closed loop；It reacts shown in following reaction equation B:
At present, the synthetic technology of azo dye intermediate is mature on the whole, and reduction technique is always the heat of chemical circles research
Point, easily occurs azo bond fracture to generate by-product aminated compounds when its difficult point is azo dye intermediate reduction.Azo contaminates
Material intermediate reduction closed loop is that the mechanism of BTA compounds is not yet fully apparent from, but the sight gained universal acceptance at present
Point is: azo dye intermediate may firstly generate hydrazine class compound, and primary response (ring-closure reaction) is then that hydrazine class compound divides
In son, dehydration generates BTA nitrogen oxides and is further reduced into final products, and side reaction is then that hydrazine class compound divides
Splitting is two molecular amine, and two molecular amine can react with other materials in reaction system；Its primary response and side reaction are the most anti-
Answer shown in equation C:
The Chinese patent that application notification number is CN104327002A, Shen Qing Publication day is on February 4th, 2015 discloses one
The production technology of Benzotriazole Ultraviolet Stabilizer, in this production technology, azo dye intermediate reduction closed loop uses such as lower section
Method: in former intermediate dye synthetic system, is directly added into hydrazine hydrate and carries out a reduction, adds in the purification system of a reduction
Zinc powder carries out two step reduction, purifies and get final product.It is disadvantageous in that, uses zinc reduction can produce substantial amounts of zinc-containing water, right
Environmental pollution is serious.
The Chinese patent that application notification number is CN104610179A, Shen Qing Publication day is on May 13rd, 2015 discloses one
Plant the method for continuously synthesizing of Benzotriazole Ultraviolet Stabilizer, reduced form solid catalyst is loaded in fixed bed reactors；
By compound shown in Formulas I and alkali dissolution in a solvent, it is 0.015～300h at volume space velocity-1Under conditions of be continually fed into fixing
Bed reactor, and it is passed through hydrogen, heating, making Hydrogen Vapor Pressure in fixed bed reactors is 0.1～10MPa, and temperature is 40～220
℃；Reactant liquor continue from fixed bed reactors lower end flow out, the reactant liquor of outflow is cooled, gas-liquid separation, liquid filter, filtrate
Solvent, purification are evaporated off, to obtain final product.It is disadvantageous in that, this method needs to test on a fixed bed, and its reaction condition is relatively
For harsh, on large-scale production, application has certain limitation.
United States Patent (USP) US4230867 discloses the preparation method of a kind of 2-aryl-2H-benzotriazole, in reduced pressure
Under in adjacent nitroazobenzene, be passed through H continuously2Carry out catalytic reaction.It is disadvantageous in that, research finds, this hydrogenating reduction
The reduction of method is wayward, and it is readily obtained byproduct of reaction.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of Benzotriazole Ultraviolet Stabilizer, which solve waste water and give up
The problem of environmental pollution that gurry causes, has the effect of the waste water more environmental protection of generation.
The above-mentioned technical purpose of the present invention has the technical scheme that
The preparation method of a kind of Benzotriazole Ultraviolet Stabilizer, comprises the following steps:
Step 1: azo dye intermediate shown in formula I, alkali and the first solvent are mixed, adds hydrazine hydrate reduction reaction；
Step 2: mixed solution step 1 obtained carries out purifying for the first time, obtains the intermediate nitrogen oxides as shown in Formula II
Solution；
Step 3: the solution of the intermediate nitrogen oxides as shown in Formula II step 2 obtained and catalyst mixing, is passed through hydrogen
Reduction reaction；
Step 4: mixed solution step 3 obtained carries out crystallize process, obtains the benzotriazole ultraviolet as shown in formula III
The crude product of absorbent；
Step 5: crude product step 4 obtained and the mixing of the second solvent, carries out second time and purifies, obtain highly purified such as formula III
Shown Benzotriazole Ultraviolet Stabilizer；
Wherein, Formulas I is:
Formula II is:
Formula III is:
More preferably: in described step 1, based on molal weight, described hydrazine hydrate and azo dye shown in formula I
The amount ratio of intermediate is 0.5～1.0: 1；Described hydrazine hydrate uses the mode being slowly added dropwise under controlled temperature conditions to add to system
In.
More preferably: in described step 1, alkali selects sodium hydroxide or potassium hydroxide；Based on molal weight, described alkali
The amount ratio of azo dye intermediate shown in formula I is 0.5～1.5: 1；Described first solvent by 80～100wt% virtue
Fragrant race's solvent and the 3rd solvent composition of 0～20wt%, described 3rd solvent is selected from petroleum ether or C3～C4Ketone or C1～C4Alcohol；；
By weight, the amount ratio of described first solvent and azo dye intermediate shown in formula I is 1～20: 1；Described step 1
In, the reaction of described hydrazine hydrate reduction is carried out at 60～80 DEG C, and its reaction directing terminal is in the middle of azo dye shown in formula I
The residual quantity of body is less than the 0.5wt% of its initial inventory.
More preferably: in described step 2, the step purified for the first time is: the mixing obtained with acid neutralization procedure 1 is molten
Liquid；Isolating oil phase, oil phase, through washing, obtains the solution of intermediate nitrogen oxides as shown in Formula II.
More preferably: described acid is sulphuric acid or hydrochloric acid；System pH after neutralizing with acid is 6～7.
More preferably: in described step 3, by weight, in the middle of described catalyst and azo dye shown in formula I
The amount ratio of body is 1%～5%: 1, and Pt/C selected by described catalyst.
More preferably: in described step 3, the consumption of described hydrogen is controlled by the Hydrogen Vapor Pressure of system, described hydrogen
During gas reduction, Hydrogen Vapor Pressure perseverance is 0.5～0.8MPa；Hydrogen reducing reaction is carried out at 50～75 DEG C, and its reaction directing terminal is
Hydrogen-sucking amount is less than the 0.1wt% of its initial amount less than 0.05MPa/min and/or the intermediate nitrogen oxides as shown in Formula II.
More preferably: in described step 4, the step that crystallize processes is: crosses and filters catalyst；Take reducing solution to be cooled to
0～10 DEG C, separating out solid, the pH to 8.5～9.5 of regulation aqueous phase separates out solid, merges two solids, obtain as shown in formula III
The crude product of Benzotriazole Ultraviolet Stabilizer.
More preferably: in described step 5, second time purifies and uses crystallisation by cooling method, and described second time purifies and uses
The second solvent be made up of the aromatic solvent of 20～50wt% and the 4th solvent of 50～80wt%, described 4th solvent select
C3～C4Ketone or C1～C4Alcohol.
More preferably: described aromatic solvent selects toluene or dimethylbenzene.
In sum, the method have the advantages that
1. the present invention uses two stage reduction methods, and its first step uses hydrazine hydrate to be reducing agent, and second step uses hydrogenation method reduction, its
The material that primary response generates is only major product, water and nitrogen, its waste water more environmental protection produced, and has fewer environmental impacts；It produces
Raw waste water only needs i.e. to can reach discharging standards, energy-saving and emission-reduction by simple process；
2. the present invention first carries out a reduction by hydrazine hydrate method to raw material, can reduce chain carrier with hydrazine hydrate for reducing agent,
Slowed down reaction speed, reduces the side reaction that relatively unstable azo dye intermediate shown in formula I produces；It addition, such as formula
Intermediate nitrogen oxides shown in II is less to the sensitivity of reducing condition, is difficult to open loop again and generates amine by-product, and it can be
It is reduced into product under the strongest hydroconversion condition；By two kinds of reducing agents with the use of, the increase of side reaction can be reduced, carry
High yield, reduces and pollutes；Two steps use hydrogenation method reduction simultaneously, and the air in system and the air in solvent can be arranged by hydrogen
Go out, reduce reaction substrate or the probability of product oxidation, its purity improving product further and content；
3. the present invention uses raw material, solvent, catalyst, pH condition and consumption thereof are all tested through large-scale production, in this condition
The situation of lower catalyst poisoning almost can be avoided completely, and has preferable large-scale production prospect；
4., in the sample that prepared by the present invention, the purity of crude product is minimum respectively reaches 90.9%；And the yield of sterling and purity are
Low respectively reach 87.7% and 97.9%.
Detailed description of the invention
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
The present embodiment can be made after reading this specification by member as required does not has the amendment of creative contribution, but as long as at this
All protected by Patent Law in the right of invention.
Embodiment 1-4: the preparation method of Benzotriazole Ultraviolet Stabilizer, comprises the steps:
Step 1: add azo dye intermediate shown in formula I, alkali, the first solvent in reactor；Control temperature be 60～
80 DEG C, it is added dropwise over hydrazine hydrate, time for adding at least 30 minutes slowly, stirs 1～4 hour；Sampling HPLC detection, such as Formulas I
The residual quantity of shown azo dye intermediate is less than the 0.5wt% of its initial inventory, and hydrazine hydrate reduction has reacted；
Step 2: addition sulphuric acid (or hydrochloric acid) is neutralized to the pH of system in the mixed solution that step 1 obtains is 6～7, stands and divides
Layer takes oil phase, and oil phase obtains the solution of the intermediate nitrogen oxides as shown in Formula II after washing；
Step 3: the solution of the intermediate nitrogen oxides as shown in Formula II step 2 obtained moves on in autoclave, adds catalysis
Agent Pt/C, is passed through hydrogen；Controlling reaction temperature is 50～65 DEG C and to adjust Hydrogen Vapor Pressure be 0.5～0.8MPa (constant), works as suction
Hydrogen amount is less than 0.05MPa/min, is warming up to 75 DEG C and is incubated 0.5～3 hour, and hydrogen reducing has reacted；
Step 4: mixed solution Filtration of catalyst step 3 obtained, is cooled to reducing solution 5～10 DEG C and separates out solid,
Separate aqueous phase and regulate its pH to 8.5～9.5, separating out solid；Merge two solids, obtain as shown in formula III and triazole
The crude product of class UV absorbent；
Step 5: add part the second solvent in the crude product that step 4 obtains, be warming up to 50～75 DEG C and be incubated 0.5～2 hour,
It is incubated and is slowly added to remaining second solvent, to system close to molten clear or lucky molten clear (range estimation), after heat filtering, take filtrate fall
Temperature, to 0～10 DEG C, is collected the solid separated out, is obtained highly purified Benzotriazole Ultraviolet Stabilizer as shown in formula III；
Wherein, the raw material information of embodiment 1 to 4 is as shown in table 1, and the consumption of raw material is with its active ingredient.
Gathering step 4 obtains in embodiment 1 to 4 crude product and the high purity product information that step 5 obtains respectively, product is believed
Breath result is as shown in table 3；Wherein content and purity use the test of HPLC method.
The raw material information statistics of table 1 embodiment 1-4
The preparation method of Benzotriazole Ultraviolet Stabilizer, comprises the steps:
Step 1: add azo dye intermediate shown in formula I, alkali, the first solvent in reactor；Control temperature be 60～
80 DEG C, it is added dropwise over hydrazine hydrate, time for adding at least 30 minutes slowly, stirs 1～4 hour；Sampling HPLC detection, such as Formulas I
The residual quantity of shown azo dye intermediate is less than the 0.5wt% of its initial inventory, and hydrazine hydrate reduction has reacted；
Step 2: addition sulphuric acid (or hydrochloric acid) is neutralized to the pH of system in the mixed solution that step 1 obtains is 6～7, stands and divides
Layer takes oil phase, and oil phase obtains the solution of the intermediate nitrogen oxides as shown in Formula II after washing；
Step 3: the solution of the intermediate nitrogen oxides as shown in Formula II step 2 obtained moves on in reduction kettle, then will urge
Agent Pt/C use water is pulled an oar, and sucks in reduction kettle by vacuum, opens nitrogen valve to pressure 0.5～0.8MPa (constant), intensification
It is that hydrogen-sucking amount is less than 0.05MPa/min, HPLC detection centre as shown in Formula II to 50～75 DEG C of reaction to reaction directing terminal
Body nitrogen oxides is less than the 0.1wt% of its initial amount, and hydrogen reducing has reacted；
Step 4: be slowly vented by reduction kettle, is filled with 0.1～0.5MPa nitrogen, Filtration of catalyst；Before filtering, point water still is used
Nitrogen is replaced, and pipeline preheats, and filters end steam and catalyst blowback is entered in reduction kettle；
Material stands 0.5～1 hour, separates lower floor's aqueous phase and extremely neutralizes in still, be cooled to 0～5 DEG C with chilled brine, is centrifuged and obtains
Solid；The pH to 8.5～9.5 of regulation mother solution, separates out solid；Merge two solids, obtain the benzotriazole as shown in formula III
The crude product of UV absorbent；
Step 5: add crude product and part the second solvent that step 4 obtains in reactor, is warming up to 50～75 DEG C and is incubated extremely
Few 1 hour, be incubated and be slowly added to remaining second solvent, to close to molten clearly or close to molten clearly, heat filtering take filtrate be down to 0～
10 DEG C, collect the solid separated out, obtain highly purified Benzotriazole Ultraviolet Stabilizer as shown in formula III；
Wherein, the raw material information of embodiment 5 to 8 is as shown in table 2, and the consumption of raw material is with its active ingredient.
Gathering step 4 obtains in embodiment 5 to 8 crude product and the high purity product information that step 5 obtains respectively, product is believed
Breath result is as shown in table 3；Wherein content and purity use the test of HPLC method.
The raw material information statistics of table 2 embodiment 5-8
The product information statistics of table 3 embodiment 1-8
Claims (10)
1. the preparation method of a Benzotriazole Ultraviolet Stabilizer, it is characterised in that comprise the following steps:
Step 1: azo dye intermediate shown in formula I, alkali and the first solvent are mixed, adds hydrazine hydrate reduction reaction；
Step 2: mixed solution step 1 obtained carries out purifying for the first time, obtains the intermediate nitrogen oxides as shown in Formula II
Solution；
Step 3: the solution of the intermediate nitrogen oxides as shown in Formula II step 2 obtained and catalyst mixing, is passed through hydrogen
Reduction reaction；
Step 4: mixed solution step 3 obtained carries out crystallize process, obtains the benzotriazole ultraviolet as shown in formula III
The crude product of absorbent；
Step 5: crude product step 4 obtained and the mixing of the second solvent, carries out second time and purifies, obtain highly purified such as formula III
Shown Benzotriazole Ultraviolet Stabilizer；
Wherein, Formulas I is:
Formula II is:
Formula III is:
The preparation method of Benzotriazole Ultraviolet Stabilizer the most according to claim 1, it is characterised in that described step
In 1, based on molal weight, the amount ratio of described hydrazine hydrate and azo dye intermediate shown in formula I is 0.5～1.0: 1；Institute
Stating hydrazine hydrate uses the mode being slowly added dropwise under controlled temperature conditions to add to system.
The preparation method of Benzotriazole Ultraviolet Stabilizer the most according to claim 1, it is characterised in that described step
In 1, alkali selects sodium hydroxide or potassium hydroxide；Based on molal weight, described alkali and azo dye intermediate shown in formula I
Amount ratio is 0.5～1.5: 1；
Described first solvent selects the aromatic solvent of 80～100wt% and the 3rd solvent of 0～20wt% to form, and the described 3rd
Solvent is selected from petroleum ether or C3～C4Ketone or C1～C4Alcohol；By weight, described first solvent and azo dye shown in formula I
The amount ratio of intermediate is 1～20: 1；
In described step 1, the reaction of described hydrazine hydrate reduction is carried out at 60～80 DEG C, and its reaction directing terminal is shown in formula I
The residual quantity of azo dye intermediate less than the 0.5wt% of its initial inventory.
The preparation method of Benzotriazole Ultraviolet Stabilizer the most according to claim 1, it is characterised in that described step
In 2, the step purified for the first time is: the mixed solution obtained with acid neutralization procedure 1；Isolating oil phase, oil phase, through washing, obtains
The solution of the intermediate nitrogen oxides as shown in Formula II.
The preparation method of Benzotriazole Ultraviolet Stabilizer the most according to claim 4, it is characterised in that described acid is
Sulphuric acid or hydrochloric acid；System pH after neutralizing with acid is 6～7.
The preparation method of Benzotriazole Ultraviolet Stabilizer the most according to claim 1, it is characterised in that described step
In 3, by weight, the amount ratio of described catalyst and azo dye intermediate shown in formula I is 1%～5%: 1, described in urge
Agent selects Pt/C.
The preparation method of Benzotriazole Ultraviolet Stabilizer the most according to claim 1, it is characterised in that described step
In 3, the consumption of described hydrogen is controlled by the Hydrogen Vapor Pressure of system, during described hydrogen reducing Hydrogen Vapor Pressure perseverance be 0.5～
0.8MPa；Hydrogen reducing reaction carry out at 50～75 DEG C, its reaction directing terminal be hydrogen-sucking amount be less than 0.05MPa/min and/
Or the intermediate nitrogen oxides as shown in Formula II is less than the 0.1wt% of its initial amount.
The preparation method of Benzotriazole Ultraviolet Stabilizer the most according to claim 1, it is characterised in that described step
In 4, the step that crystallize processes is: crosses and filters catalyst；Take reducing solution and be cooled to 0～10 DEG C, separate out solid, the pH of regulation aqueous phase
Separate out solids to 8.5～9.5, merge two solids, obtain the thick of Benzotriazole Ultraviolet Stabilizer as shown in formula III
Product.
The preparation method of Benzotriazole Ultraviolet Stabilizer the most according to claim 1, it is characterised in that described step
In 5, second time purify use crystallisation by cooling method, described second time purify use the second solvent by 20～50wt% aromatic series
Solvent and the 4th solvent composition of 50～80wt%, C selected by described 4th solvent3～C4Ketone or C1～C4Alcohol.
10. according to the preparation method of the Benzotriazole Ultraviolet Stabilizer described in claim 3 or 9, it is characterised in that described
Aromatic solvent selects toluene or dimethylbenzene.
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| CN108148009A (en) * | 2017-12-29 | 2018-06-12 | 天津利安隆新材料股份有限公司 | A kind of method that Benzotriazole Ultraviolet Stabilizer is prepared using catalytic hydrogen transfer method |
| CN108658880A (en) * | 2018-06-26 | 2018-10-16 | 广东工业大学 | A kind of preparation method of ultra-violet absorber |
| CN109843957A (en) * | 2017-09-29 | 2019-06-04 | 豪雅镜片泰国有限公司 | Manufacturing method, optical component resin, eyeglass and the glasses of optical component resin |
| CN111282592A (en) * | 2019-11-29 | 2020-06-16 | 浙江工业大学 | Carbon-supported alkaline ionic liquid-metal catalyst, preparation thereof and application thereof in catalytic transfer hydrogenation reaction |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109843957A (en) * | 2017-09-29 | 2019-06-04 | 豪雅镜片泰国有限公司 | Manufacturing method, optical component resin, eyeglass and the glasses of optical component resin |
| CN109843957B (en) * | 2017-09-29 | 2022-06-21 | 豪雅镜片泰国有限公司 | Method for producing resin for optical member, spectacle lens, and spectacles |
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| CN108148009A (en) * | 2017-12-29 | 2018-06-12 | 天津利安隆新材料股份有限公司 | A kind of method that Benzotriazole Ultraviolet Stabilizer is prepared using catalytic hydrogen transfer method |
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| CN108658880B (en) * | 2018-06-26 | 2021-09-03 | 广东工业大学 | Preparation method of ultraviolet absorbent |
| CN111282592A (en) * | 2019-11-29 | 2020-06-16 | 浙江工业大学 | Carbon-supported alkaline ionic liquid-metal catalyst, preparation thereof and application thereof in catalytic transfer hydrogenation reaction |
| CN111282592B (en) * | 2019-11-29 | 2023-07-21 | 浙江工业大学 | Carbon-supported alkaline ionic liquid-metal catalyst, preparation thereof and application thereof in catalytic transfer hydrogenation reaction |
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Application publication date: 20161012 |