CN106083543B - A method of preparing sun-screening agent intermediate 2,4-DihydroxyBenzophenone - Google Patents
A method of preparing sun-screening agent intermediate 2,4-DihydroxyBenzophenone Download PDFInfo
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- CN106083543B CN106083543B CN201610416678.7A CN201610416678A CN106083543B CN 106083543 B CN106083543 B CN 106083543B CN 201610416678 A CN201610416678 A CN 201610416678A CN 106083543 B CN106083543 B CN 106083543B
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Abstract
The invention discloses a kind of method for preparing sun-screening agent intermediate 2,4-DihydroxyBenzophenone, this method is using resorcinol and benzenyl trichloride as raw material, condensation reaction is carried out, 2,4-DihydroxyBenzophenone is made, and the solvent after reaction is purified, recovery, this method is easy to operate, preparation condition is mild, environmentally protective, product quality obtained is high, and wherein yield is 95%~98%, purity is 95%~99%, and isomer impurities are 1%~4%.
Description
Technical field
The invention belongs to daily-use chemical industry technical fields, are related to a kind of preparation method of organic intermediate, in particular to
The preparation method of the intermediate 2,4-DihydroxyBenzophenone of sun-screening agent ESCALOL 567.
Background technique
2,4-DihydroxyBenzophenone (2,4-dihydroxybenzophenone, BP-1), abbreviation benzophenone-1, again
Claim ultraviolet absorbing agent UV-0 (trade name UV-214), structural formula is as shown in following formula I:
BP-1 is in faint yellow acicular crystal or white powder, molecular formula C at room temperature13H10O3.BP-1 is long wave in belonging to
(290nm~400nm) ultraviolet absorbing agent converts light energy into thermal energy using own molecular structure, as ultraviolet absorbing agent
It is widely used in cosmetic industry；And the various of light stabilization are played as needing to avoid photooxidation reaction in industrial trade
The additive of material, such as polyvinyl chloride, polystyrene, epoxy resin, celluosic resin, unsaturated-resin, coating and not
The light stabilizer of saturated rubber etc.；It is alternatively arranged as synthesizing the raw material of other benzophenone ultraviolet absorbents.
Due to the specific use of ultraviolet absorbing agent BP-1, the research in the field is more active always, in the prior art, BP-1
Synthetic route have it is following several:
(1) using resorcinol, chlorobenzoyl chloride as raw material, alchlor is that catalyst condensation generates 2,4- dihydroxy hexichol first
Ketone, such as: CN103073406A, the price of chlorobenzoyl chloride is higher in the method, and while post-processing can generate a large amount of aluminium wastewater,
Easily cause environmental pollution, the higher cost of large-scale production.
It (2) is that raw material carries out condensation reaction synthesis 2,4-DihydroxyBenzophenone using resorcinol, benzenyl trichloride, this
Method synthesis yield is high, and post-processing is simple, such as: CN101628865A, CN101323564A.But the method can generate largely
2-3 tons/ton of phenol wastewater, not only processing cost is high, but also environmental pollution is serious.Since 2,4-DihydroxyBenzophenone is
ESCALOL 567 (sun-screening agent) important intermediate is done, thus 2,4-DihydroxyBenzophenone contaminated wastewater is asked
Topic becomes the very big stumbling-block of this sun-screening agent development.
Therefore, need to develop that a kind of input cost is low, and environmental pollution is small, and the preparation 2 that reaction yield is high, 4- dihydroxy two
The method of Benzophenone.
Summary of the invention
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that: use resorcinol, trichloromethyl
Benzene is raw material, and water/alcohol is solvent, and condensation generates 2,4-DihydroxyBenzophenone, and by condition optimizing, obtained product purity is
95-99%, yield 95-98%, and certain processing is carried out to the waste water generated after reaction, successfully realize water phase
Recycled emits no waste water, environmentally protective, reduces the pollution to environment, so as to complete the present invention.
The purpose of the present invention is to provide following aspect:
(1) present invention provides a kind of method for preparing sun-screening agent intermediate 2,4-DihydroxyBenzophenone, and this method includes
Following steps:
Resorcinol and solvent are added in a kettle, benzenyl trichloride is added into system for step 1), be condensed anti-
It answers；
Step 2) is optionally cooled down, and filtering is made crude product, is optionally purified, and 2,4- dihydroxy two is made
Benzophenone；
Step 3) post-processes obtained filtrate, and solvent recovery is applied.
(2) the present invention also provides the 2,4-DihydroxyBenzophenones according to made from the above method, wherein reaction yield is
95%~98%；Purity is 95%~99%；Isomer impurities are 1%~4%.
The method for preparing 2,4-DihydroxyBenzophenone provided according to the present invention, has the advantages that
(1) 2,4-DihydroxyBenzophenone of method preparation provided by the invention, purity are 95%~99%, isomers
Impurity is 1%~4%, can be directly used for preparing sun-screening agent ESCALOL 567 etc., is not necessarily to additional rectifying, steaming
It the purification process such as evaporates, has saved cost；
(2) mild reaction condition of the present invention reacts homogeneous before this, after product is gradually precipitated, improve anti-
Product yield, by low temperature crystallization, the i.e. separable product of filtering；
(3) technique of the present invention carries out certain processing to the waste water generated after reaction, successfully realizes water phase
Recycled, emit no waste water, it is environmentally protective, reduce the pollution to environment；
(4) method provided by the invention also has the characteristics that easy, easily controllable and industrialized production.
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.Here as " exemplary "
Illustrated any embodiment should not necessarily be construed as preferred or advantageous over other embodiments.
The present invention described below.
According to the first aspect of the invention, a kind of side preparing sun-screening agent intermediate 2,4-DihydroxyBenzophenone is provided
Method, which is characterized in that method includes the following steps:
Resorcinol and the first solvent are added in a kettle, benzenyl trichloride is added into system, contracts for step 1)
Close reaction.
In the present invention, it is related to benzenyl trichloride and is hydrolyzed to chlorobenzoyl chloride, thus the first solvent is aqueous solvent, and raw material
Benzenyl trichloride is not soluble in water, therefore selecting the first solvent is to select organic solvent-water mixed solvent.
In first solvent, organic solvent is selected from small molecular alcohol solvent, preferably methanol, ethyl alcohol, a kind of in isopropanol
Or a variety of, more preferable ethyl alcohol, wherein in the first solvent the volume fraction of alcoholic solvent be 2%-20%, preferably 5%-15%, it is more excellent
Select 8%-12%.
In the preferred embodiment of the present invention, the organic solvent in the first solvent selects ethyl alcohol.Alcohol-water mixing
Solvent is being suitable for entire reaction process, can not only disperse reactant well, and the use of ethyl alcohol can inhibit isomers
The generation of impurity, after the reaction was completed, solvent processing or reclaimer operation are simple, and solvent toxicity is small, safe operation.
The inventors discovered that the first solvent of ratio described in selection step 1) can be completely dissolved reaction during the reaction
Raw material, and be conducive to the precipitation of reaction product 2,4-DihydroxyBenzophenone；If the volume content of organic solvent in the first solvent
Less than 2%, then the benzenyl trichloride dissolution being added is insufficient, cannot effectively contact with resorcinol, be unfavorable for reacting；If first
The volume content of organic solvent is greater than 20% in solvent, then product is not easy to be precipitated after the reaction was completed, and organic solvent content improves,
Production cost is increased, the risk for causing environmental pollution is increased.
In the preferred embodiment of the present invention, configured first solvent is added in reaction kettle first, so
After resorcinol is added, start to stir, dissolve resorcinol, and increase system reaction temperature, be added benzenyl trichloride, start
It is reacted.During the reaction since solubility of the product 2,4-DihydroxyBenzophenone in the first solvent is smaller, with
The progress of reaction, product can be conducive to reaction and carried out, be improved yield by being precipitated in solvent.
In the present invention, the mass ratio of the resorcinol and the first solvent is the quality of resorcinol: the first solvent
Quality=1: 2~1: 16, preferably 1: 4~1: 8.The inventors discovered that when the quality of resorcinol: the quality of the first solvent is less than
When 1: 2, resorcinol content is high, and by-product may be generated in condensation reaction, reduces product yield；When the matter of resorcinol
Amount: when the quality of the first solvent is greater than 1: 16, excessive solvent is introduced in reaction system, causes reaction raw materials concentration too low, instead
It answers rate to reduce, and will cause the waste of solvent, the increase of cost.
In the present invention in step 1, the ratio between mole of the resorcinol and benzenyl trichloride is mole of resorcinol
Amount: mole=1 of benzenyl trichloride: 1~1: 2, preferably 1: 1~1: 1.5, more preferable 1: 1~1: 1.3；Wherein, resorcinol
Mole with the molar amount of its molecule, the mole of benzenyl trichloride is with the molar amount of its molecule.Step 1) of the present invention
In, resorcinol II reacts according to the following formula with to benzenyl trichloride, (wherein TCMB is benzotrichloride)
By formula II it is found that resorcinol is reacted with benzenyl trichloride by the chemical equivalent of 1:1, for react fully into
Row, when carrying out condensation reaction, the present invention selects resorcinol another raw material opposite with benzenyl trichloride slightly excessive, preferably makes
A possibility that benzenyl trichloride is excessive, reduces phenol wastewater pollution, and when the mole of resorcinol and benzenyl trichloride it
When than being greater than 1:2, benzenyl trichloride is largely excessive, and the yield of product no longer obviously increases, and deposits in system after reaction
In a large amount of benzenyl trichlorides, wastage of material is caused.Preferably, when after reaction, excessive benzenyl trichloride being recycled, is used for
New reaction.
In the present invention, the adding manner of benzenyl trichloride is the mode being added dropwise, with the progress of stirring, benzenyl trichloride
Dispersion is in the reaction system, excessive so as to avoid local concentration rapidly, carries out condensation reaction sufficiently, and by-product is few, improves
The yield of condensation reaction.
In the present invention, the when a length of 0.5~5h, preferably 1~3h of benzenyl trichloride is added.To the addition speed of benzenyl trichloride
It spends fast, is added dropwise and bring effect is unobvious, and when the duration that benzenyl trichloride is added is greater than 5h, the quality of product is no longer
It obviously increases, but increases time cost.
The temperature of system is 20~90 DEG C, preferably 40~70 DEG C when benzenyl trichloride is added.The inventors discovered that reaction
When the temperature of system is 20~90 DEG C, condensation reaction can be carried out rapidly, and by-product is few in product obtained.
In step 1) of the present invention, after adding benzenyl trichloride, insulation reaction, the temperature of insulation reaction are carried out to reaction system
Degree is 20~100 DEG C, and preferably 50~90 DEG C, insulation reaction is more preferably higher than carried out under dropping temperature.
The inventors discovered that condensation reaction be not enough, in system still when the time of insulation reaction being less than 1h
There are the residues of a large amount of reaction raw materials, not only reduce the yield of product, and cause a large amount of wastes of raw material；Work as insulation reaction
Time be greater than 10h when, the yield of product no longer significantly improves, not only waste time, moreover, when insulation reaction time continue
More by-products are produced when extension, in system, therefore, the present invention selects the time of insulation reaction for 1~10h, and preferably 3
~8h.
Step 2), cooling system, filtering are made crude product, are optionally purified, and 2,4- dihydroxy hexichol first is made
Ketone.
By cooling system, product is precipitated, temperature of reaction system is cooled to 0~30 DEG C, preferably 5~10 DEG C.This hair
In bright, it is not required to addition other materials and changes system composition, only pass through and change system temperature, the separation of product can be completed, thus
Avoid the introducing of other impurity in product.
In the present invention, system temperature cooling rate is 10 DEG C/h~60 DEG C/h, preferably 15 DEG C/h~30 DEG C/h.Cooling speed
Rate is fast, and nucleus is quickly formed, and can generate many tiny nucleus, because not having enough time so that product molecule on nucleus
It adheres to and grows to crystal very greatly, thus form many tiny crystal, cause crystal to separate difficulty with solution, and carry more
Impurity.The speed of cooling rate is very big to the qualitative effects of crystal, and in order to make crystal have certain granularity, present invention selection is cold
But rate is 10 DEG C/h~60 DEG C/h.
In step 2) of the present invention, it is separated by filtration removing liquid phase, the present invention is not specially limited the mode of filtering, can make
It with any one filter type in the prior art, such as natural filtration, is filtered under diminished pressure, the present invention is preferably filtered under diminished pressure, a side
The rate that face is filtered under diminished pressure is fast, is on the other hand filtered under diminished pressure to the more thorough of liquid phase substance removing.
In a preferred embodiment, obtained crude product is purified.Simple filtering may cause in filter cake
Remain the complete raw material of unreacted, the impurity such as by-product of product in condensation reaction, filter cake is carried out after purification, products therefrom
Purity significantly improve.The preferred recrystallization method of way of purification.
It recrystallizes the second solvent used and is selected from small molecular alcohol solvent or alcohol-water mixed solvent, preferably methanol, ethyl alcohol, isopropyl
Alcohol, alcohol-water (2:1~3:1, volume ratio).In a preferred embodiment, due to reaction raw materials and product 2,4- dihydroxy
The dissolution in alcohol-water (3:1, volume ratio) of base benzophenone, and residual solvent is easy to recycle after recrystallization, small toxicity, therefore
Second solvent preferred alcohol-water (3:1).
The mass ratio for recrystallizing crude product made from the second solvent used and step 2) is to recrystallize the second solvent used
Quality: quality=5:1~20:1 of crude product made from step 2), preferably 5:1~15:1.When the second solvent usage is excessive, 2,
4- dihydroxy benaophenonel crystallization content is less, and product is caused to lose；When the second solvent usage is too small, purification effect is unobvious.
The temperature of recrystallization is 0~30 DEG C, preferably 2~10 DEG C, more preferable 2~5 DEG C.
Optionally, recrystallization, filtered filter cake being dried, it is preferred to use vacuum drying method is dried,
Drying temperature is preferably 45 DEG C~80 DEG C, more preferably 55 DEG C~70 DEG C, such as 60 DEG C.
In the present invention, purified rear 2,4-DihydroxyBenzophenone reaction yield obtained is 95%~98%, and purity is
95%~99%, isomer impurities are 1%~4%.
Step 3) post-processes the filtrate of crude product, and solvent recovery is applied.
The present invention has hydrogen chloride generation in the condensation reaction, and system generates a large amount of chloride ions in acidity.Preferably, exist
Before removing removing chloride, the filtrate pH value of crude product is adjusted to 7~11, preferably 7~9 with alkaline matter.
In the present invention, the alkaline matter be selected from inorganic base and organic base, inorganic base be selected from sodium hydroxide, potassium hydroxide,
Sodium carbonate, potassium carbonate etc., organic base are selected from methylamine, ethamine, triethylamine etc., preferably sodium hydroxide.Above-mentioned organic base is inorganic
Alkali is optionally directly added into filtrate or is added in filtrate after wiring solution-forming, can for the purpose of it good can be dissolved in filtrate
Neutralization reaction is effectively carried out with filtrate.
In the present invention, the filtrate of crude product is post-processed, to realize the recycled of solvent.Post-processing includes using
Absorption method purifies filtrate, and the adsorbent has ion adsorption capacity.Common adsorbent includes:
1) inorganic adsorbent, including atlapulgite, active carbon, diatomite or natural clay, can effectively binding molecule or
Ion.If active carbon has pore since microcrystalline carbon is irregular alignment in structure between interconnection, in activation
Carbon tissue defects can be generated, therefore it is a kind of porous carbon, bulk density is low, large specific surface area.The specific surface of normal activated carbon
Product is in 500~1700m2Between/g, there is very strong absorption property, including physical absorption and chemisorption.
2) synthetic adsorbent, including ion exchange resin, ion exchange resin are that (have the work of exchange ion with functional group
Property group), have reticular structure, insoluble high-molecular compound.The type of chemical active radical determines resin in resin
Main character and classification.Ion exchange resin is divided into resin cation and resin anion (R.A.) two major classes, they can respectively with it is molten
Cation and anion in liquid carry out ion exchange.Ion exchange resin aperture is smaller, is suitable for absorption inorganic ions.
Ion exchange resin of the present invention is selected from anion exchange resin, preferably strong-base anion-exchange resin, more
It is preferred that the strong-base anion-exchange resin containing quaternary ammonium group, most preferably chlorine-based strong alkali anion exchange resin.
When being purified, the mass ratio of the ion exchange resin dosage and amount of filtrate is the matter of ion exchange resin
Amount: quality=1 of filtrate: 100~10: 100, preferably 1: 100~5: 100, achievable chloride ion is effective within this range
Absorption.The quality of ion exchange resin: the quality of filtrate is less than 1: 100, then ion exchange resin adsorption capacity is wanted lower than purifying
It asks, chloride ion content is still higher in filtrate；The quality of ion exchange resin: the quality of filtrate is greater than 10: 100, adsorption capacity
Reach requirement level, but ion exchange resin is excessive, increases production cost.
Optionally, the ion exchange resin is regenerated, is recycled, number can be used to be not less than 10 times.
The inventors discovered that balance is not achieved in the adsorption process short time when temperature is lower than 20 DEG C, and increasing temperature can make
The rate of adsorption is accelerated, and the case where adsorbance increase occurs, and when temperature is higher than 60 DEG C, desorption phenomenon aggravation, thus the present invention
In, the temperature of adsorption reaction is 20 DEG C~60 DEG C, preferably 30 DEG C~50 DEG C.
The inventors discovered that being stirred, making during adsorption reaction under the conditions of selected adsorbent and adsorption temp
Adsorbent and filtrate come into full contact with, and are greatly improved adsorption efficiency, it is preferable that mixing time is 1h~6h, more preferable 2h~4h.
Recycling design is applied for lower batch of condensation reaction, it is preferable that when recycling design is applied, is added suitable fresh molten
Agent, it is highly preferred that solvent additional amount is the 10wt%~50wt%, preferably 20wt%~30wt% of solvent inventory for the first time.
The inventors discovered that condensation reaction is directly applied if do not handled filtrate, isomer impurities ratio in product
It is higher, up to 10~15%, after adsorption treatment, isomer impurities can be controlled in the effect with reacting in the first batch as 1~
4%.The Isomers In Products impurity of preparation is mainly identified by LC-MS and is detected.
The present invention provides the 2,4-DihydroxyBenzophenones according to made from the above method, wherein 2, the 4- dihydroxy
Benzophenone, reaction yield are 95%~98%, and purity is 95%~99%, and isomer impurities are 1%~4%.
Embodiment
Embodiment 1
It (1) will be through primary first-order equation 10% ethanol-water solution of 660.6g after the recovery and 110.1g (1.0mol) resorcinol
It is added in tetra- mouthfuls of glass reaction bottles of 2000mL of belt stirrer, thermometer, addition funnel and condenser pipe, starts to stir, by body
System is heated to 60 DEG C, in 234.6g (1.2mol) benzenyl trichloride is slowly added dropwise in 2h, after being added dropwise, under the conditions of 80 DEG C after
Continuous insulation reaction 6h.
(2) after completion of the reaction, with 30 DEG C/h rate of temperature fall cooling system temperature to 25 DEG C, vacuum filtration, filter cake is 2,
4- dihydroxy benaophenonel crude product, with alcohol-water (3:1, volume ratio) quality: the quality of the crude product=thick production of 10:1 dissolution
Product are recrystallized at 5 DEG C, and vacuum filtration, filter cake obtains faint yellow acicular crystal 2,4- in -0.1MPa, 60 DEG C of dry 12h
Dihydroxy benaophenonel 210.1g, yield 98%, purity 98%, isomer impurities 2%.
(3) filtrate is neutralized to PH to 7 with NaOH solution, and 2% chloride ion exchanger resin of filtrate weight is then added,
40 DEG C of stirring 3h, filtering, filtrate, which directly covers, uses condensation reaction.Filter cake, that is, chloride ion exchanger resin can continue next batch
Absorption.
Embodiment 2
It (1) will be through primary first-order equation 20% ethanol-water solution of 880.8g after the recovery and 110.1g (1.0mol) resorcinol
It is added in tetra- mouthfuls of glass reaction bottles of 2000mL of belt stirrer, thermometer, addition funnel and condenser pipe, starts to stir, by body
System is heated to 70 DEG C, in 234.6g (1.2mol) benzenyl trichloride is slowly added dropwise in 3h, after being added dropwise, under the conditions of 60 DEG C after
Continuous insulation reaction 2h.
(2) after completion of the reaction, with 20 DEG C/h rate of temperature fall cooling system temperature to 25 DEG C, vacuum filtration, filter cake is 2,
4- dihydroxy benaophenonel crude product, with ethyl alcohol quality: the quality of crude product=15:1 dissolves crude product, carries out weight at 5 DEG C
Crystallization, vacuum filtration, filter cake obtain faint yellow acicular crystal 2,4-DihydroxyBenzophenone in -0.1MPa, 60 DEG C of dry 12h
205.7g, yield 96%, purity 99%, isomer impurities 1%.
(3) filtrate is neutralized to PH to 8 with NaOH solution, and 5% chloride ion exchanger resin of filtrate weight is then added,
30 DEG C of stirring 4h, filtering, filtrate, which directly covers, uses condensation reaction.Filter cake, that is, chloride ion exchanger resin can continue next batch
Absorption.
Embodiment 3
It (1) will be through primary first-order equation 2% ethanol-water solution of 660.6g after the recovery and 110.1g (1.0mol) resorcinol
It is added in tetra- mouthfuls of glass reaction bottles of 2000mL of belt stirrer, thermometer, addition funnel and condenser pipe, starts to stir, by body
System is heated to 60 DEG C, in 254.1g (1.3mol) benzenyl trichloride is slowly added dropwise in 1h, after being added dropwise, under the conditions of 80 DEG C after
Continuous insulation reaction 8h.
(2) after completion of the reaction, with 30 DEG C/h rate of temperature fall cooling system temperature to 25 DEG C, vacuum filtration, filter cake is 2,
4- dihydroxy benaophenonel crude product, with ethyl alcohol quality: the quality of crude product=5:1 dissolves crude product, is tied again at 2 DEG C
Crystalline substance, vacuum filtration, filter cake obtain faint yellow acicular crystal 2,4-DihydroxyBenzophenone in -0.1MPa, 60 DEG C of dry 12h
212.1g, yield 99%, purity 95%, isomer impurities 4%.
(3) filtrate is neutralized to PH to 7 with NaOH solution, and 3% chloride ion exchanger resin of filtrate weight is then added,
50 DEG C of stirring 1h, filtering, filtrate, which directly covers, uses condensation reaction.Filter cake, that is, chloride ion exchanger resin can continue next batch
Absorption.
Comparative example 1
It (1) will be through primary first-order equation 10% ethanol-water solution of 660.6g after the recovery and 110.1g (1.0mol) resorcinol
It is added in tetra- mouthfuls of glass reaction bottles of 2000mL of belt stirrer, thermometer, addition funnel and condenser pipe, starts to stir, by body
System is heated to 60 DEG C, in 234.6g (1.2mol) benzenyl trichloride is slowly added dropwise in 2h, after being added dropwise, under the conditions of 80 DEG C after
Continuous insulation reaction 6h.
(2) after completion of the reaction, with 30 DEG C/h rate of temperature fall cooling system temperature to 25 DEG C, vacuum filtration, filter cake is 2,
4- dihydroxy benaophenonel crude product, with alcohol-water (3:1, volume ratio) quality: the quality of the crude product=thick production of 10:1 dissolution
Product are recrystallized at 5 DEG C, and vacuum filtration, filter cake obtains product after purification in -0.1MPa, 60 DEG C of dry 12h.
(3) filtrate is neutralized to PH to 7 with NaOH solution, and 2% atlapulgite of filtrate weight is then added, stirs at 40 DEG C
3h is mixed, is filtered, filtrate, which directly covers, uses condensation reaction.
Gained product after purification is faint yellow acicular crystal 2,4-DihydroxyBenzophenone 209.3g, yield 85%, purity
87%, isomer impurities 11%.It follows that isomer impurities content is higher using atlapulgite as adsorbent, influence to produce
The yield of product and post-processing.
Comparative example 2
It (1) will be through primary first-order equation 10% ethanol-water solution of 660.6g after the recovery and 110.1g (1.0mol) resorcinol
It is added in tetra- mouthfuls of glass reaction bottles of 2000mL of belt stirrer, thermometer, addition funnel and condenser pipe, starts to stir, by body
System is heated to 60 DEG C, in 234.6g (1.2mol) benzenyl trichloride is slowly added dropwise in 2h, after being added dropwise, under the conditions of 80 DEG C after
Continuous insulation reaction 6h.
(2) after completion of the reaction, with 30 DEG C/h rate of temperature fall cooling system temperature to 25 DEG C, vacuum filtration, filter cake is 2,
4- dihydroxy benaophenonel crude product, with alcohol-water (3:1, volume ratio) quality: the quality of the crude product=thick production of 10:1 dissolution
Product are recrystallized at 5 DEG C, and vacuum filtration, filter cake obtains product after purification in -0.1MPa, 60 DEG C of dry 12h.
(3) filtrate is neutralized to PH to 7 with NaOH solution, and 2% active carbon of filtrate weight is then added, and stirs at 40 DEG C
3h, filtering, filtrate, which directly covers, uses condensation reaction.
Gained product after purification is faint yellow acicular crystal 2,4-DihydroxyBenzophenone 211.8g, yield 89%, purity
90%, isomer impurities 7%.It follows that isomer impurities content is higher using active carbon as adsorbent, product is influenced
Yield and post-processing.
It is described the invention in detail above in conjunction with detailed description and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention
In the range of.Scope of protection of the present invention is subject to the appended claims.
Claims (10)
1. a kind of method for preparing 2,4-DihydroxyBenzophenone, which is characterized in that method includes the following steps:
Resorcinol and the first solvent are added in a kettle, benzenyl trichloride is added into system for step 1), be condensed anti-
It answers；First solvent is ethanol-water mixed solvent, and the volume fraction of the ethyl alcohol in ethanol-water mixed solvent is 8%-12%；
The ratio between mole of the resorcinol and benzenyl trichloride is the mole of resorcinol: the mole of benzenyl trichloride
=1:1~1:1.3；Wherein, the mole of resorcinol is with the molar amount of its molecule, and the mole of benzenyl trichloride is with its point
The molar amount of son；
Step 2), cooling system, filtering are made crude product, are purified, and product 2,4-DihydroxyBenzophenone, reaction is made
Yield is 95%~98%；Purity is 95%~99%；Isomer impurities are 1%~4%；
Temperature of reaction system is cooled to 0~30 DEG C, and cooling rate is 15 DEG C/h~30 DEG C/h；
It is purified using the method for recrystallization；Recrystallize the second that the second solvent used is selected from ethyl alcohol or 2:1~3:1 volume ratio
Alcohol-water mixed solvent；
The mass ratio for recrystallizing crude product made from the second solvent used and step 2) is the second solvent quality: step 2) is made
Crude product quality=5:1~20:1；
The temperature of recrystallization is 2~5 DEG C；
Step 3) post-processes the filtrate of crude product, and solvent recovery is applied；
The post-processing includes that the filtrate pH value of crude product is adjusted with alkaline matter to 7~11, is carried out using absorption method to filtrate
Purifying；
Synthetic adsorbent used is chlorine-based strong alkali anion exchange resin；
The mass ratio of the ion exchange resin dosage and amount of filtrate is the quality of ion exchange resin: quality=1 of filtrate:
100~5:100；
The temperature of adsorption reaction is 20 DEG C~60 DEG C；Adsorption reaction process is stirred, and mixing time is 1h~6h.
2. preparation method according to claim 1, which is characterized in that in step 1), the resorcinol and solvent
Mass ratio is the quality of resorcinol: quality=1:2~1:16 of solvent.
3. preparation method according to claim 2, which is characterized in that in step 1), the resorcinol and solvent
Mass ratio is the quality of resorcinol: quality 1:4~1:8 of solvent.
4. preparation method according to claim 1, which is characterized in that in step 1), system when benzenyl trichloride is added
Temperature be 40~70 DEG C；And/or
The mode that benzenyl trichloride is added is the mode being added dropwise；And/or
When a length of 1~3h of benzenyl trichloride is added；And/or
The temperature of insulation reaction is 50~90 DEG C；And/or
The time of insulation reaction is 3~8h.
5. preparation method according to claim 1, which is characterized in that in step 2), temperature of reaction system is cooled to 5~10
℃；And/or
Recrystallize the alcohol-water that the second solvent used is 3:1 volume ratio；And/or
The mass ratio for recrystallizing crude product made from the second solvent used and step 2) is the second solvent quality: step 2) is made
Crude product quality=5:1~15:1.
6. preparation method according to claim 1, which is characterized in that in step 3), the alkaline matter is selected from inorganic base
And organic base, inorganic base are selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, organic base is selected from methylamine, ethamine, three second
Amine；
Regulating step 2) pH value of system is made to 7~9.
7. preparation method according to claim 1, which is characterized in that in step 3), the ion exchange resin can be followed
Ring uses, and access times are not less than 10 times.
8. preparation method according to claim 1, which is characterized in that in step 3), the temperature of adsorption reaction is 30 DEG C~
50℃；
Mixing time is 2h~4h；
Recycling design is applied for lower batch of condensation reaction.
9. preparation method according to claim 8, which is characterized in that when recycling design is applied, add suitable fresh molten
Agent, solvent additional amount are 10wt%~50wt% of solvent inventory for the first time.
10. preparation method according to claim 9, which is characterized in that solvent additional amount is solvent inventory for the first time
20wt%~30wt%.
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| CN112142576B (en) * | 2019-06-27 | 2022-04-08 | 江苏紫奇化工科技有限公司 | Clean production method of 2,4-dihydroxy benzophenone |
| CN111302920B (en) * | 2020-01-15 | 2022-03-25 | 湖北美凯化工有限公司 | Production method of ultraviolet absorbent BP-3 |
| CN112321407A (en) * | 2020-10-29 | 2021-02-05 | 马鞍山科思化学有限公司 | Novel process for preparing sunscreen agent 2-hydroxy-4-n-octoxy benzophenone |
| CN116042068A (en) * | 2022-12-30 | 2023-05-02 | 安徽朗凯奇建材有限公司 | Photo-curing acrylate film-spraying waterproof material and preparation method thereof |
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| CN103241885A (en) * | 2013-05-15 | 2013-08-14 | 绍兴奇彩化工有限公司 | Method for treating acid waste water of disperse dye |
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