CN108658761A - A kind of preparation of p-tert-butyl benzoic acid methyl esters - Google Patents
A kind of preparation of p-tert-butyl benzoic acid methyl esters Download PDFInfo
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- CN108658761A CN108658761A CN201810391302.4A CN201810391302A CN108658761A CN 108658761 A CN108658761 A CN 108658761A CN 201810391302 A CN201810391302 A CN 201810391302A CN 108658761 A CN108658761 A CN 108658761A
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- benzoic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention discloses a kind of preparations of p-tert-butyl benzoic acid methyl esters, wherein, composite catalyst is first used to carry out the oxidation of p-tert-butyltoluene in air, obtain p-tert-butyl benzoic acid, then replace traditional concentrated sulfuric acid as catalyst using p-methyl benzenesulfonic acid, esterification is carried out, p-tert-butyl benzoic acid methyl esters is obtained；Simultaneously, the present invention uses special processing procedure to the preparation of p-tert-butyl benzoic acid methyl esters, by methanol, repeatedly band water improves yield and product purity, simultaneously, recycling is realized after handling the water phase of methanol, extraction and catalyst that steam, cost of material is not only greatly reduced, but also equally there is important environment protection significance.
Description
Technical field
The present invention relates to p-tert-butyl benzoic acid methyl esters field more particularly to its preparations.
Background technology
P-tert-butyl benzoic acid methyl esters (MBB) is a kind of important industrial chemicals, is used to prepare sun-screening agent Avobenzone.Mesh
Preceding industrialized preparation method is p-tert-butyl benzoic acid and methanol esterification in the presence of a large amount of concentrated sulfuric acids, prepares MBB.But
It is that there are the uses of a large amount of concentrated sulfuric acids, mainly utilizes the concentrated sulfuric acid to absorb the water that esterification generates.Esterification terminates, first
Divide and go acid layer, in alkali cleaning, washing is rectifying to obtain product MBB.The method will produce a large amount of spent acid although efficiency is very high, and
Aftertreatment technology process is complicated, generates a large amount of waste water.
Also, in conventional production methods, the raw material p-tert-butyl benzoic acid for synthesizing p-tert-butyl benzoic acid methyl esters
Oxygen multi-purpose in the preparation is aoxidized, and is constantly within the scope of explosion limit in stills for air blowing, attached safety protection technique and
Installations and facilities require stringent；Exothermic heat of reaction is violent, and operating mode is severe, to equipment requirement height；The tail gas of discharge is almost pure oxygen (entrainment
Micro organic gas), incineration disposal dare not be carried out, is polluted the environment；By-product terephthalic acid (TPA) amount is more, and raw material is caused to disappear
Consumption is high, influences the purity of product.
Invention content
To solve the above-mentioned problems, present inventor has performed sharp studies, are carried out in air using composite catalyst pair
The oxidation of t-butyltoluene so that oxidation reaction can carry out at relatively low temperature, obtain p-tert-butyl benzoic acid, so
It replaces traditional concentrated sulfuric acid as catalyst using p-methyl benzenesulfonic acid afterwards, carries out esterification, obtain p-tert-butyl benzoic acid methyl esters；Together
When, the method for the invention uses special processing procedure to the preparation of p-tert-butyl benzoic acid methyl esters, multiple by methanol
Band water improves yield and product purity, meanwhile, it is realized after handling the water phase of methanol, extraction and catalyst that steam
Recycling not only greatly reduces cost of material, but also equally has important environment protection significance, thereby completing the present invention.
The present invention provides a kind of preparations of p-tert-butyl benzoic acid methyl esters, embody in the following areas：
(1) a kind of preparation of p-tert-butyl benzoic acid methyl esters, wherein the preparation includes the following steps：
P-tert-butyltoluene, oxidation catalyst are added in stills for air blowing step 1, are passed through air and carry out oxidation reaction, preferably
The control of recovered water is carried out in oxidation reaction process；
Crystallization processing is carried out after step 2, oxidation reaction, is then centrifuged for, is washed, it is wet to obtain p-tert-butyl benzoic acid
Product are dried to obtain p-tert-butyl benzoic acid dry product；
Step 3, the p-tert-butyl benzoic acid dry product that step 2 is obtained, p-methyl benzenesulfonic acid and methanol mixing, are warming up to reflux
Esterification is carried out, methanol is then distilled to recover；
Methanol is added in step 4 into system again, is warming up to reflux and carries out esterification, is then distilled to recover methanol, preferably
Repeat this step 2~4 time, such as 3 times；
After step 5, esterification, water is added to stir 0.1~1h, stands liquid separation and carry out first time extraction, take oil phase, to
In oil phase plus water stirs 0.1~1h, stands liquid separation and extract for the second time, oil phase, rectification process is taken to obtain described to tertiary butyl
Methyl benzoate.
(2) preparation according to above-mentioned (1), wherein in step 1,
The catalyst is cobalt acetate-acetic acid manganese composite catalyst, it is preferable that the cobalt acetate-manganese acetate composite catalyzing
The weight ratio of agent and the p-tert-butyltoluene is 1：(400~600), it is highly preferred that the weight ratio of cobalt acetate and manganese acetate is
(20~30)：1；And/or
It is passed through air with the speed of 1500~2500mL/min, it is preferable that air is passed through with the speed of 2000mL/min.
(3) preparation according to above-mentioned (1) or (2), wherein in step 1,
In 120~130 DEG C carry out oxidation reactions, be preferable over 122~128 DEG C progress oxidation reactions, such as at 125 DEG C into
Row oxidation reaction；And/or
The extraction for carrying out water during the reaction, the extraction of water is carried out preferably by condensing mode.
(4) preparation according to one of above-mentioned (1) to (3), wherein in step 2,
The crystallization processing is cooling crystallization, preferably carries out crystallization, such as 6~8 DEG C/h with the rate of temperature fall of 5~10 DEG C/h
Rate of temperature fall carry out crystallization；And/or
The drying process of p-tert-butyl benzoic acid wet product carries out as follows：100 are risen to the heating rate of 15~25 DEG C/h~
120 DEG C are dried, and preferably rising to 105~110 DEG C with the heating rate of 20 DEG C/h is dried.
(5) preparation according to one of above-mentioned (1) to (4), wherein in step 3,
The molar ratio of p-methyl benzenesulfonic acid and p-tert-butyl benzoic acid dry product is (0.03~0.08)：1, preferably (0.04~
0.07)：1, such as 0.06:1；And/or the molar ratio of methanol and p-tert-butyl benzoic acid dry product is (1~3)：1, preferably (1.5
~2.5)：1, such as 2:1.
(6) preparation according to one of above-mentioned (1) to (5), wherein
The molar ratio of methanol and step 3 p-tert-butyl benzoic acid dry product that step 4 uses is (0.5~2)：1, such as 1:1；
And/or
In step 3 and step 4, rectification process is carried out to the methanol that distillation recovery obtains, is recycled with realizing, preferably
Ground will be distilled to recover obtained methanol and be transferred in rectifying still, and 70~90 DEG C of progress atmospheric distillations obtain recycling methanol.
(7) method according to one of above-mentioned (1) to (6), wherein
In step 3, esterification carries out (1~3) h, such as 2h；And/or
In step 4, esterification carries out (0.1~2) h, such as 1h；And/or
In step 3 and step 4, it is warming up to 70~80 DEG C and flows back, be then distilled to recover in 110~130 DEG C
Methanol.
(8) preparation according to one of above-mentioned (1) to (7), wherein in steps of 5, water is also obtained after extracting for the first time
Phase；Preferably, the water phase obtained after being extracted to first time is distilled, and is collected the water after distillation and is evaporated bottom；It is highly preferred that described
Distillation is following to be carried out：It is carried out at the vacuum degree of 10~15mmHg, less than 70 DEG C, until anhydrous extraction；
Wherein, the washing that the water after distillation is extracted for second, and the bottom that evaporates is p-methyl benzenesulfonic acid, under putting into again
A collection of esterification.
(9) preparation according to one of above-mentioned (1) to (8), wherein in steps of 5, water is also obtained after second of extraction
Phase, it is preferable that the water phase obtained after being extracted to second is distilled, and the water after distillation is collected；It is highly preferred that the distillation is such as
Lower progress：It is carried out at the vacuum degree of 10~15mmHg, less than 70 DEG C, until anhydrous extraction；
Wherein, first time extraction of the water after distillation for next batch reaction.
(10) preparation according to one of above-mentioned (1) to (9), wherein in steps of 5, obtained after being extracted to second
Oil phase carry out following rectifying：Under 2~6mmHg, kettle temperature rise to 130~140 DEG C, temperature rise to 80~100 DEG C of progress；It is preferred that
Under 3~5mmHg, kettle temperature rise to 132~136 DEG C, temperature rise to 85~95 DEG C of progress.
Description of the drawings
Fig. 1 shows the chromatogram for the p-tert-butyl benzoic acid dry product that step (2) obtains in the embodiment of the present invention 1；
Fig. 2 shows the chromatograms for the p-tert-butyl benzoic acid methyl esters that the embodiment of the present invention 2 obtains.
Specific implementation mode
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.
The present invention provides a kind of preparation of p-tert-butyl benzoic acid methyl esters, the preparation includes the following steps：
P-tert-butyltoluene, oxidation catalyst are added in stills for air blowing step 1, are passed through air and carry out oxidation reaction, preferably
The control of recovered water is carried out in oxidation reaction process；
Crystallization processing is carried out after step 2, oxidation reaction, is then centrifuged for, is washed, it is wet to obtain p-tert-butyl benzoic acid
Product are dried to obtain p-tert-butyl benzoic acid dry product；
Step 3, the p-tert-butyl benzoic acid dry product that step 2 is obtained, p-methyl benzenesulfonic acid and methanol mixing, are warming up to reflux
Esterification is carried out, methanol is then distilled to recover；
Methanol is added in step 4 into system again, is warming up to reflux and carries out esterification, is then distilled to recover methanol, preferably
Repeat this step 2~4 time, such as 3 times；
Wherein, methanol is distilled and is added in step 3 and step 4, be repeated a number of times, realize methanol band water,
Reaction efficiency can be greatly increased, so that reaction is carried out to positive direction, obtains the high p-tert-butyl benzoic acid methyl esters of purity.
After step 5, esterification, water is added to stir 0.1~1h, stands liquid separation and carry out first time extraction, take oil phase, to
In oil phase plus water stirs 0.1~1h, stands liquid separation and extract for the second time, oil phase, rectification process is taken to obtain described to tertiary butyl
Methyl benzoate.
According to a kind of preferred embodiment of the present invention, in step 1, the catalyst is that cobalt acetate-manganese acetate is compound
Catalyst.
In further preferred embodiment, in step 1, the cobalt acetate-acetic acid manganese composite catalyst with it is described
The weight ratio of p-tert-butyltoluene is 1：(400~600), such as 1:500.
In embodiment still more preferably, in step 1, in the cobalt acetate-acetic acid manganese composite catalyst,
The weight ratio of cobalt acetate and manganese acetate is (20~30)：1.
Wherein, inventor has found by many experiments, when using cobalt acetate-acetic acid manganese composite catalyst, after crystallization
The yield of the p-tert-butyl benzoic acid arrived is higher than yield when single cobalt acetate or manganese acetate are catalyst.Also, inventor
It was found that using cobalt acetate-acetic acid manganese composite catalyst of consumption proportion of the present invention can make in reaction process heat release it is steady (though
Right reacting balance, but also to cool down, but it is easily controllable to cool down), and use single catalyst or cobalt acetate-acetic acid of other proportionings
When manganese composite catalyst, heat release is violent in reaction process, and must not be controlled without cooling, and at this time since heat release acutely makes
Cooling is not easy to control.
Sky is passed through with the speed of 1500~2500mL/min in step 1 according to a kind of preferred embodiment of the present invention
Gas.
In further preferred embodiment, in step 1, air is passed through with the speed of 2000mL/min.
Wherein, in the present invention, during oxidation reaction prepares p-tert-butyl benzoic acid, using air atmosphere rather than
Pure oxygen atmosphere, in this way, (1) using air as oxidant, raw material economics；(2) after the oxygen reaction in air, residual nitrogen in system
Gas is inert gas, can play the role of the entire oxidation system of protection, improve security of system；(3) due to this step reaction
It is the oxidation process of oxygen, therefore in order to which the total content of oxygen in guarantee system needs to be passed through a large amount of air (relative to pure oxygen
Atmosphere, gas content are high), inventor has found that the large quantity of air being passed through accelerates the mass-and heat-transfer effect of stirring, i.e., is imitated to stirring
Fruit has facilitation, and then promotes the progress of oxidation reaction.
According to a kind of preferred embodiment of the present invention, in step 1, oxidation reaction is carried out in 120~130 DEG C.
In further preferred embodiment, oxidation reaction is carried out in 122~128 DEG C, such as oxygen is carried out at 125 DEG C
Change reaction.
Once studies have reported that mistake reacts 50min, p-tert-butyl benzoic acid is almost in bulk oxidation system at 120 DEG C
Unconverted, decomposition induction time is longer, and when temperature is higher than 150 DEG C, the conversion ratio of p-tert-butyl benzoic acid is only a small amount of to be improved.
But in the present invention, it is successfully realized at 120~130 DEG C and realizes oxidation reaction, main reason is that air mass flow and multiple
The selection for closing catalyst promotes the progress of oxidation.
According to a kind of preferred embodiment of the present invention, in step 1, the extraction of water is carried out during the reaction.
In further preferred embodiment, in step 1, the extraction of water is carried out using condensing mode.
Wherein, there is the generation of water in the oxidation reaction process, and water vapour is water is vaporized under 120~130 DEG C of reactions, so
Condensation extraction is carried out to water vapour afterwards, carries out, and effectively control degree of oxidation, subtracts in this way, the positive of reaction can effectively be controlled
Few transition oxidation, that is, reduce the generation of by-product terephthalic acid (TPA).Inventor is it is discovered by experiment that the control for carrying out recovered water can
So that the yield of p-tert-butyl benzoic acid improves at least 2-3% or more.
According to a kind of preferred embodiment of the present invention, in step 2, the crystallization processing is cooling crystallization.
In further preferred embodiment, in step 2, crystallization is carried out with the rate of temperature fall of 5~10 DEG C/h, such as
The rate of temperature fall of 6~8 DEG C/h carries out crystallization.
Specifically, it is passed through condensed water in kettle external jacket to cool down, preferably temperature in the kettle and the leaving water temperature in chuck
1~3 DEG C of difference is cooled down (i.e. temperature in the kettle is higher than 1~3 DEG C of leaving water temperature), and the regulating valve that leaving water temperature passes through condensed water
It is adjusted.Wherein, inventor by many experiments find, 5~10 DEG C/h (especially 6~8 DEG C/h) rate of temperature fall into
When row crystallization, crystallization best results, specifically, crystallization does not tie wall, and obtained crystal grain is big, crystal seed is good.And in existing skill
In art, multistage crystallization is related to, it is not only complicated for operation in this way, and also crystallization is easy knot wall, and crystal seed is bad.
According to a kind of preferred embodiment of the present invention, in step 2, the drying process of p-tert-butyl benzoic acid wet product is such as
Lower progress：100~120 DEG C are risen under vacuum with the heating rate of 15~25 DEG C/h to be dried.
In further preferred embodiment, in step 2, the drying process of p-tert-butyl benzoic acid wet product as follows into
Row：105~110 DEG C are risen under the vacuum of 500~800Pa with the heating rate of 20 DEG C/h to be dried.
Wherein, inventor has found by many experiments, in 15~25 DEG C/h (especially 20 under the vacuum of 500~800Pa
DEG C/h) heating rate under drying can obtain preferable dry product, the product that otherwise obtains can hair oil, tacky, the reason is that, its
In p-tert-butyltoluene (solvent of washing) do not bring out and cause.
According to a kind of preferred embodiment of the present invention, in step 3, p-methyl benzenesulfonic acid and p-tert-butyl benzoic acid dry product
Molar ratio be (0.03~0.08)：1.
In further preferred embodiment, in step 3, p-methyl benzenesulfonic acid rubs with p-tert-butyl benzoic acid dry product
You are than being (0.04~0.07)：1, such as 0.06:1.
Wherein, in the present invention, p-methyl benzenesulfonic acid is used to substitute traditional concentrated sulfuric acid for catalyst in esterification process, this
Sample reduces the generation of spent acid after reaction.
According to a kind of preferred embodiment of the present invention, in step 3, mole of methanol and p-tert-butyl benzoic acid dry product
Than for (1~3)：1.
In further preferred embodiment, in step 3, the molar ratio of methanol and p-tert-butyl benzoic acid dry product is
(1.5~2.5)：1, such as 2:1.
In embodiment still more preferably, methanol and step 3 p-tert-butyl benzoic acid dry product that step 4 uses
Molar ratio is (0.5~2)：1, such as 1:1.
According to a kind of preferred embodiment of the present invention, in step 3 and step 4, methanol that distillation recovery is obtained into
Row rectification process is recycled with realizing.
In further preferred embodiment, obtained methanol will be distilled to recover and be transferred in rectifying still, 70~90 DEG C into
Row atmospheric distillation obtains recycling methanol.
Wherein, post-treated obtained recycling methanol can carry out the esterification of next batch again, realize and repeat profit
With, reduce production cost and reduce waste discharge, have important environment protection significance.
According to a kind of preferred embodiment of the present invention, in step 3, esterification carries out (1~3) h, such as 2h.
In further preferred embodiment, in step 4, esterification carries out (0.1~2) h, such as 1h.
In embodiment still more preferably, in step 3 and step 4, it is warming up to 70~80 DEG C and flows back, so
Afterwards distillation recovery methanol is carried out in 110~130 DEG C.
According to a kind of preferred embodiment of the present invention, in steps of 5, water phase is also obtained after extracting for the first time.
Wherein, contain p-methyl benzenesulfonic acid in the water phase obtained after extracting for the first time.
In further preferred embodiment, the water phase obtained after being extracted to first time is distilled, after collecting distillation
Water and evaporate bottom.
In embodiment still more preferably, the distillation is following to be carried out：In 10~15mmHg vacuum degree, be less than
It is carried out at 70 DEG C, until anhydrous extraction.
Wherein, the water after distillation can be used for the washing of second of extraction, and the bottom that evaporates is that p-methyl benzenesulfonic acid (is esterified
Catalyst) next group esterification can be put into again.
In this way, greatly reducing production cost, and the discharge of waste material is reduced, there is important environment protection significance.
According to a kind of preferred embodiment of the present invention, in steps of 5, water phase is also obtained after second of extraction.
In further preferred embodiment, the water phase obtained after being extracted to second is distilled, after collecting distillation
Water.
Wherein, this evaporates bottom environmental protection administration is transferred to handle.
In embodiment still more preferably, the distillation is following to be carried out：In 10~15mmHg vacuum degree, be less than
It is carried out at 70 DEG C, until anhydrous extraction.
Wherein, the water after distillation can be used for the first time extraction of next batch reaction, greatly reduce production cost, and
The discharge of waste material is reduced, there is important environment protection significance.
According to a kind of preferred embodiment of the present invention, in steps of 5, the oil phase obtained after being extracted to second carries out such as
Lower rectifying：Under 2~6mmHg, kettle temperature rise to 130~140 DEG C, temperature rise to 80~100 DEG C of progress.
In further preferred embodiment, in steps of 5, the oil phase obtained after being extracted to second carries out following essence
It evaporates：Under 3~5mmHg, kettle temperature rise to 132~136 DEG C, temperature rise to 85~95 DEG C of progress.
According to a kind of preferred embodiment of the present invention, the p-tert-butyltoluene that step 1 uses obtains as follows：
Toluene and the concentrated sulfuric acid are mixed, isobutene is passed through and is alkylated reaction, deacidify after reaction, buck is added to extract
It takes, obtains water phase and organic phase, rectification process is carried out to the organic phase, obtains p-tert-butyltoluene
In further preferred embodiment, the alkylated reaction carries out as follows：8~15h is reacted in 6~14 DEG C,
Preferably, 10.5~11.5h is reacted in 8~10 DEG C.
In embodiment still more preferably, the buck be selected from sodium hydrate aqueous solution, aqueous sodium carbonate and/
Or one or more of sodium bicarbonate aqueous solution, a concentration of the 20~50% of the preferably described buck, such as 30%.
According to a kind of preferred embodiment of the present invention, crystallization mother liquor is generated after the processing of step 2 crystallization, to the crystallization
Mother liquor is post-processed, it is preferable that the post-processing is following to be carried out：Sodium hydrate aqueous solution is added into crystallization mother liquor, extracts
Water phase, then the enriching sulfuric acid into water phase are obtained, remaining p-tert-butyl benzoic acid is precipitated in step 2, filters to tert-butyl benzene first
Acid and the water phase containing waste product sodium sulphate.
Wherein, also contain a large amount of p-tert-butyl benzoic acid after crystallization in crystallization mother liquor, if directly by crystallization mother
Liquid, which is outwelled, not only to be caused waste, influences yield, but also can be polluted, therefore, in the present invention, to the mother liquor after crystallization into
Row post-processing.Specifically, after sodium hydrate aqueous solution being added, remaining p-tert-butyl benzoic acid becomes to tert-butyl benzene in mother liquor
Sodium formate, into water phase.Then water phase is extracted, the concentrated sulfuric acid is added, p-tert-butyl benzoic acid sodium therein becomes pair again
P t butylbenzoic acid is precipitated in water phase, and p-tert-butyl benzoic acid is drying to obtain after filtering.
Therefore, in the present invention, the yield that post-processing not only increases p-tert-butyl benzoic acid is carried out to crystallization mother liquor, and
And the technical grade sulfuric acid sodium that can directly utilize again is obtained.
In further preferred embodiment, the water phase containing waste product sodium sulphate is post-processed, obtains technical grade sulphur
Sour sodium.
It wherein, can remaining catalyst (i.e. cobalt acetate-manganese acetate catalysis in the water phase containing a large amount of waste product sodium sulphate
Agent), therefore, the sodium sulphate that water phase is dried to obtain is waste product sodium sulphate, does not meet industrial scale applications.Also, due to the water phase
It is the abandonment phase after big quantitative response, the sodium sulphate that convection drying obtains can be caused coloured, and then influence its recycling.Together
When, in the preparation process of p-tert-butyltoluene, the concentrated sulfuric acid is used, resulting in this way may be oligomeric containing sulfur-bearing in product
Object, and the waste product sodium sulphate that the sulfur-containing oligomers can cause convection drying to obtain has smell, more affects its recycling.
In actual production, in the preparation of p-tert-butyl benzoic acid, the waste product sodium sulphate probably generates 1-2 daily
Ton, environmental protection pressure are very big.Therefore, in order to increase economic interests, more for environmental protection, it is highly desirable the waste product sodium sulphate to obtaining
It is handled, the very poor sodium sulphate of quality can be converted to technical grade sulfuric acid sodium, reached two class Grade A of technical grade and want
It asks, is recycled.
According to a kind of preferred embodiment of the present invention, the post-processing of the water phase containing waste product sodium sulphate includes following step
Suddenly：
Step a, inorganic base is added into the water phase containing waste product sodium sulphate；
In this way, heavy metal (such as Co and Mn) therein can be precipitated under alkaline condition, it is removed.
Step b, activated carbon is added and carries out decolorization, be then filtered successively, steam water, obtain solid sodium sulfate；
In this way, not only can effectively remove the foreign pigment in sodium sulphate, but also can improve to a certain extent
The smell (but activated carbon cannot remove the smell that sulfur-containing oligomers are brought) of sodium sulphate, greatly improves coloration, the gas of sodium sulphate
Taste.
Step c, the solid sodium sulfate obtained step b is added in organic solvent, carries out reflux and beat to wash, then mistake successively
Filter, drying, obtain technical grade sulfuric acid sodium.
Wherein, sulfur-containing oligomers therein are removed using organic solvent, to remove the smell in sodium sulphate, in this way, obtaining
Sodium sulphate in be practically free of odorous, meet industrial scale applications.
According to a kind of preferred embodiment of the present invention, in step a, the inorganic base is selected from sodium hydroxide, bicarbonate
One or more of sodium and sodium carbonate.
In further preferred embodiment, in step a, inorganic base regulation system pH value to 8~10 is utilized.
According to a kind of preferred embodiment of the present invention, in stepb, the addition of the activated carbon is 2~6g activity
Charcoal/200~400g water.
In further preferred embodiment, in stepb, the addition of the activated carbon be 3~5g activated carbons/
200~400g water.
According to a kind of preferred embodiment of the present invention, in stepb, the decolorization carries out as follows：In 15~50
0.5~5h is carried out at DEG C.
In further preferred embodiment, in stepb, the decolorization carries out as follows：At 20~40 DEG C
Carry out 1~3h.
It is in stepb, described to be filtered into heat preservation filtering according to a kind of preferred embodiment of the present invention.
Wherein, preferably heat preservation filtering, otherwise sodium sulphate can be precipitated, and be filtered, and cause to waste.
In further preferred embodiment, the heat preservation filtering carries out at 30~50 DEG C.
In embodiment still more preferably, the heat preservation filtering carries out at 40 DEG C.
Wherein, solubility property of the sodium sulphate at 30~50 DEG C especially 40 DEG C is best, if do not filtered in the range,
It is how many all to have sodium sulphate precipitation, it causes to waste.
According to a kind of preferred embodiment of the present invention, in step c, the dosage of organic solvent is that 80~400g is organic molten
Agent/40~70g solid sodium sulfates.
In further preferred embodiment, in step c, the dosage of organic solvent be 100~300g organic solvents/
40~70g solid sodium sulfates.
Wherein, solid sodium sulfate is carried out flowing back to beat washing using organic solvent, to remove its smell, especially sulfur-bearing is oligomeric
The smell that object is brought.
According to a kind of preferred embodiment of the present invention, in step c, the organic solvent is selected from methanol, ethyl alcohol, toluene
One or more of with ethyl acetate.
In further preferred embodiment, in step c, the organic solvent is selected from methanol and/or ethyl alcohol.
Wherein, inventor has found after many experiments, and in organic solvent, the best results of methanol and ethyl alcohol can be with
The smell in waste product sodium sulphate is completely removed, and toluene and ethyl acetate can only remove to a certain extent, cannot go completely
It removes, it is therefore preferable that methanol and/or ethyl alcohol.
According to a kind of preferred embodiment of the present invention, the organic solvent used in step c can carry out cycle distillation again
It utilizes.
In this way, the organic solvent can be beaten into the reflux of next time in washing, utilization rate is considerably increased, and reduce useless
Losing for gurry is put.
Advantageous effect possessed by the present invention：
(1) the method for the invention can obtain the p-tert-butyl benzoic acid methyl esters of high yield；
(2) the method for the invention uses special post-processing approach to the preparation of p-tert-butyl benzoic acid, reduces system
The discharge of waste material, makes waste product sodium sulphate be converted into recycling technical grade sulfuric acid sodium, in this way, not only bringing one during standby
Fixed economic benefit, and environment protection significance is more prominent；
(3) the method for the invention uses special processing procedure to the preparation of p-tert-butyl benzoic acid methyl esters, passes through
Repeatedly band water improves yield and product purity to methanol, meanwhile, at the water phase of methanol, extraction and catalyst that steam
Recycling is realized after reason, not only greatly reduces cost of material, but also equally there is important environment protection significance.
Embodiment
The present invention is further described below by way of specific example.But these examples are only exemplary, not to this
The protection domain of invention constitutes any restrictions.
Embodiment 1
(1) 500g p-tert-butyltoluenes, 0.968g cobalt acetates, 0.032g manganese acetates are transferred in stills for air blowing, are warming up to 125
DEG C, and air is passed through with the rate of 2200mL/min, carry out oxidation reaction.In oxidation reaction process control extraction water 24~
26g。
Wherein, after oxidation starts, oxidation process heat release is steady, although reacting balance, also to cool down, but cooling is easy to
Control need not carry out stringent cooling control.
(2) after oxidation reaction, material filtering goes to crystallization kettle, and cooling crystallization is carried out with the rate of 6 DEG C/h, centrifuge,
P-tert-butyltoluene washs, and obtains p-tert-butyl benzoic acid wet product and crystallization mother liquor, with the rate of 20 DEG C/h under 600Pa vacuum
It is warming up to 105 DEG C p-tert-butyl benzoic acid wet product is dried, obtains p-tert-butyl benzoic acid dry product.
Meanwhile it being handled as follows：A concentration of 30% sodium hydrate aqueous solution is added into crystallization mother liquor, extracts to obtain water
Phase, then to neutrality, p-tert-butyl benzoic acid is precipitated enriching sulfuric acid tune pH into water phase filters p-tert-butyl benzoic acid and to contain
The water phase of waste product sodium sulphate；Processing is dried to obtained p-tert-butyl benzoic acid.
Obtained p-tert-butyl benzoic acid is collected, chromatography detection is carried out, sees that Fig. 1, purity reach 99.7531%.Meanwhile it is right
Product carries out nuclear-magnetism characterization, structure warp1H-NMR analyses determine, the peak at 12.74ppm corresponds to the hydrogen on carboxyl, 7.70~
Peak at 8.05ppm corresponds to benzene ring hydrogen, and the peak at 1.34ppm corresponds to the hydrogen on tertiary butyl；It is found that successfully described in synthesis
P-tert-butyl benzoic acid.
Sodium hydroxide is added in the water phase containing waste product sodium sulphate generated to above-mentioned (3), adjusts pH value to 9, is then added
5g activated carbons stir 2h at 30 DEG C, are filtered at 40 DEG C, take filtrate to carry out steaming water process, obtain solid sodium sulfate；The sulphur that will be obtained
Sour sodium solid is added in 300g methanol, and 70 DEG C of reflux beat and wash 4h, are subsequently cooled to 25 DEG C, are filtered under diminished pressure, obtain filter cake, to filter cake into
Row vacuum drying, obtains sodium sulphate, is detected to obtained sodium sulphate, meet two class Grade A standards, is technical grade sulfuric acid sodium.
(3) 534g p-tert-butyl benzoic acids dry product, 30.0g p-methyl benzenesulfonic acid and 192g absolute methanols are mixed, is warming up to
It flows back (76 DEG C), reacts 2h.Then methanol is recycled in air-distillation, obtains 164.36g methanol.
(4) 96g absolute methanols are added into kettle, flow back (76 DEG C) reaction 1h.Then methanol is recycled in air-distillation, obtains
85.69g methanol.
96g absolute methanols are added into kettle again, flow back (76 DEG C) reaction 1h.Then methanol is recycled in air-distillation, obtains
92.77g methanol；At this point, reaction solution sampling carries out GC detections, wherein p-tert-butyl benzoic acid methyl esters is 97.1927%, to tertiary fourth
Yl benzoic acid is 1.6862%.
96g absolute methanols are added into kettle again, flow back (72 DEG C) reaction 1h.Then methanol is recycled in air-distillation, obtains
90.94g methanol；At this point, reaction solution sampling carries out GC detections, wherein p-tert-butyl benzoic acid methyl esters is 98.4084%, to tertiary fourth
Yl benzoic acid is 0.13798%.
(5) after esterification, add water stirring 30min to be washed, stand liquid separation and carry out first time extraction, obtain water
Phase and oil phase：
(5.1) water phase is handled as follows：It is carried out at the vacuum degree of 12mmHg, less than 70 DEG C, until anhydrous extraction,
It is p-methyl benzenesulfonic acid to evaporate bottom, can put into next batch reaction as catalyst；
(5.2) oil phase is handled as follows：To oil phase plus water, 30min is stirred, liquid separation is stood and carries out second of extraction, obtain
Water phase and oil phase：
(5.2.1) handles the water phase being obtained by extraction for the second time as follows：In 12mmHg vacuum degree, less than at 70 DEG C into
Row, until anhydrous extraction, the water after distillation can be used for the first time extraction of next batch reaction；
(5.2.2) carries out following rectification process to the oil phase being obtained by extraction for the second time：Under vacuum degree 4mmHg, kettle temperature rises to
134 DEG C, temperature rise to 90 DEG C, wherein p-tert-butyl benzoic acid methyl esters be 99.7314%.
Nuclear-magnetism characterization, structure warp are carried out to product (p-tert-butyl benzoic acid methyl esters)1H-NMR analysis determinations, 7.41ppm~
Peak at 7.89ppm corresponds to benzene ring hydrogen, and the peak at 3.92ppm corresponds to the hydrogen on methoxyl group, and the peak at 1.31ppm corresponds to
Hydrogen on tertiary butyl；It is found that successfully synthesizing the p-tert-butyl benzoic acid methyl esters.
(6) methanol steamed to above-mentioned (3) and above-mentioned (4) is transferred in rectifying still, is carried out at 78 DEG C of kettle temperature, 64 DEG C of temperature normal
Rectifying, recycling is pressed to obtain rectifying methanol, carry out GC detections, wherein methanol content 99.8819% to it, moisture 0.14%,
It may be repeated utilization.
Embodiment 2
(1) 120 DEG C are warming up to by 500g p-tert-butyltoluenes, 0.952g cobalt acetates, 0.048g manganese acetates, and with
The rate of 2000mL/min is passed through air, carries out oxidation reaction.In oxidation reaction process, 24~26g of control extraction water.
Wherein, after oxidation starts, oxidation process heat release is steady, although reacting balance, also to cool down, but cooling is easy to
Control need not carry out stringent cooling control.
(2) after oxidation reaction, material filtering goes to crystallization kettle, and cooling crystallization is carried out with the rate of 7 DEG C/h, centrifuge,
P-tert-butyltoluene washs, and obtains p-tert-butyl benzoic acid wet product and crystallization mother liquor, 110 DEG C are warming up to the rate of 15 DEG C/h
P-tert-butyl benzoic acid wet product is dried, p-tert-butyl benzoic acid dry product is obtained.
Meanwhile it being handled as follows：A concentration of 40% sodium hydrate aqueous solution is added into crystallization mother liquor, extracts to obtain water
Phase, then to neutrality, p-tert-butyl benzoic acid is precipitated enriching sulfuric acid tune pH into water phase filters p-tert-butyl benzoic acid and to contain
The water phase of waste product sodium sulphate；Processing is dried to obtained p-tert-butyl benzoic acid.
Obtained p-tert-butyl benzoic acid is collected, chromatography detection and nuclear-magnetism detection are carried out, it is as a result similar to Example 1.
Sodium hydroxide is added in the water phase containing waste product sodium sulphate generated to step (3), adjusts pH value to 8, is then added
4g activated carbons stir 3h at 25 DEG C, are filtered at 40 DEG C, take filtrate to carry out steaming water process, obtain solid sodium sulfate；The sulphur that will be obtained
Sour sodium solid is added in 400g methanol, and 65 DEG C of reflux beat and wash 5h, are subsequently cooled to 25 DEG C, are filtered under diminished pressure, obtain filter cake, to filter cake into
Row vacuum drying, obtains sodium sulphate, is detected to obtained sodium sulphate, meet two class Grade A standards, is technical grade sulfuric acid sodium.
(3) 534g p-tert-butyl benzoic acids dry product, 20.7g p-methyl benzenesulfonic acid and 144g absolute methanols are mixed, is warming up to
It flows back (76 DEG C), reacts 2h, methanol is recycled in then air-distillation.
(4) 72g absolute methanols are added into kettle, flow back (76 DEG C) reaction 1h, and methanol is recycled in then air-distillation；
72g absolute methanols are added into kettle again, flow back (76 DEG C) reaction 1h, and methanol is recycled in then air-distillation；
72g absolute methanols are added into kettle again, flow back (72 DEG C) reaction 1h, and methanol is recycled in then air-distillation.
(5) after esterification, add water stirring 20min to be washed, stand liquid separation and carry out first time extraction, obtain water
Phase and oil phase：
(5.1) water phase is handled as follows：It is carried out at the vacuum degree of 15mmHg, less than 70 DEG C, until anhydrous extraction,
It is p-methyl benzenesulfonic acid to evaporate bottom, can put into next batch reaction as catalyst；
(5.2) oil phase is handled as follows：To oil phase plus water, 20min is stirred, liquid separation is stood and carries out second of extraction, obtain
Water phase and oil phase：
(5.2.1) handles the water phase being obtained by extraction for the second time as follows：In 15mmHg vacuum degree, less than at 70 DEG C into
Row, until anhydrous extraction, the water after distillation can be used for the first time extraction of next batch reaction；
(5.2.2) carries out following rectification process to the oil phase being obtained by extraction for the second time：Under vacuum degree 3mmHg, kettle temperature rises to
136 DEG C, temperature rise to 95 DEG C, wherein p-tert-butyl benzoic acid methyl esters be 99.6082%, to the p-tert-butyl benzoic acid first
Ester carries out nuclear-magnetism characterization, as a result similar to Example 1.
(6) methanol steamed to above-mentioned (3) and above-mentioned (4) is transferred in rectifying still, 78 DEG C, normal pressure essence is carried out at 64 DEG C of temperature
It evaporates, recycling obtains rectifying methanol, carries out GC detections, wherein methanol content 99.8714% to it, moisture 0.16%, can be with
It is reused.
Embodiment 3
(1) 500g p-tert-butyltoluenes, 0.952g cobalt acetates, 0.048g manganese acetates are transferred in stills for air blowing, are warming up to 130
DEG C, and air is passed through with the rate of 1800mL/min, carry out oxidation reaction.In oxidation reaction process, control extraction water 24
~26g.
Wherein, after oxidation starts, oxidation process heat release is steady, although reacting balance, also to cool down, but cooling is easy to
Control need not carry out stringent cooling control.
(2) after oxidation reaction, material filtering goes to crystallization kettle, and cooling crystallization is carried out with the rate of 8 DEG C/h, centrifuge,
P-tert-butyltoluene washs, and obtains p-tert-butyl benzoic acid wet product and crystallization mother liquor, with the rate of 25 DEG C/h under 800Pa vacuum
It is warming up to 105 DEG C p-tert-butyl benzoic acid wet product is dried, obtains p-tert-butyl benzoic acid dry product.
Meanwhile it being handled as follows：A concentration of 35% sodium hydrate aqueous solution is added into crystallization mother liquor, extracts to obtain water
Phase, then to neutrality, p-tert-butyl benzoic acid is precipitated enriching sulfuric acid tune pH into water phase filters p-tert-butyl benzoic acid and to contain
The water phase of waste product sodium sulphate；Processing is dried to obtained p-tert-butyl benzoic acid.
Obtained p-tert-butyl benzoic acid is collected, chromatography detection and nuclear-magnetism detection are carried out, it is as a result similar to Example 1.
Sodium hydroxide is added in the water phase containing waste product sodium sulphate generated to above-mentioned (3), adjusts pH value to 10, is then added
3g activated carbons stir 2h at 30 DEG C, are filtered at 40 DEG C, take filtrate to carry out steaming water process, obtain solid sodium sulfate；The sulphur that will be obtained
Sour sodium solid is added in 500g methanol, and 75 DEG C of reflux beat and wash 3h, are subsequently cooled to 25 DEG C, are filtered under diminished pressure, obtain filter cake, to filter cake into
Row vacuum drying, obtains sodium sulphate, is detected to obtained sodium sulphate, meet two class Grade A standards, is technical grade sulfuric acid sodium.
(3) 534g p-tert-butyl benzoic acids dry product, 36.2g p-methyl benzenesulfonic acid and 240g absolute methanols are mixed, is warming up to
It flowing back (76 DEG C), reacts 2h, methanol is recycled in then air-distillation,.
(4) 120g absolute methanols are added into kettle, flow back (76 DEG C) reaction 1h, and methanol is recycled in then air-distillation；
120g absolute methanols are added into kettle again, flow back (76 DEG C) reaction 1h, and methanol is recycled in then air-distillation；
120g absolute methanols are added into kettle again, flow back (72 DEG C) reaction 1h, and methanol is recycled in then air-distillation.
(5) after esterification, add water stirring 40min to be washed, stand liquid separation and carry out first time extraction, obtain water
Phase and oil phase：
(5.1) water phase is handled as follows：It is carried out at the vacuum degree of 10mmHg, less than 70 DEG C, until anhydrous extraction,
It is p-methyl benzenesulfonic acid to evaporate bottom, can put into next batch reaction as catalyst；
(5.2) oil phase is handled as follows：To oil phase plus water, 40min is stirred, liquid separation is stood and carries out second of extraction, obtain
Water phase and oil phase：
(5.2.1) handles the water phase being obtained by extraction for the second time as follows：In 10mmHg vacuum degree, less than at 70 DEG C into
Row, until anhydrous extraction, the water after distillation can be used for the first time extraction of next batch reaction；
(5.2.2) carries out following rectification process to the oil phase being obtained by extraction for the second time：Under vacuum degree 5mmHg, kettle temperature rises to
132 DEG C, temperature rise to 85 DEG C, wherein p-tert-butyl benzoic acid methyl esters be 99.6424%, to the p-tert-butyl benzoic acid first
Ester carries out nuclear-magnetism characterization, as a result similar to Example 1.
(6) methanol steamed to above-mentioned (3) and above-mentioned (4) is transferred in rectifying still, 78 DEG C, normal pressure essence is carried out at 64 DEG C of temperature
It evaporates, recycling obtains rectifying methanol, carries out GC detections, wherein methanol content 99.8912% to it, moisture 0.12%, can be with
It is reused.
Comparative example
Comparative example 1
The process for repeating embodiment 1, difference lies in：(1) 1g cobalt acetate single catalysts are used to replace cobalt acetate-manganese acetate
Composite catalyst；(2) air is passed through with the rate of 1000mL/min, carries out oxidation reaction (reaction temperature is constant).
It was found that in comparative example 1, in oxidation reaction process, decomposition induction time is longer, also, comparative example 1 obtains after crystallization
To p-tert-butyl benzoic acid yield compared with the p-tert-butyl benzoic acid that embodiment 1 obtains after crystallization low yield 5% (with reality
The yield for applying the p-tert-butyl benzoic acid that example 1 obtains after crystallization is 100% meter).
Comparative example 2
The process for repeating embodiment 1, difference lies in：When carrying out oxidation reaction, the control without recovered water.
It was found that the purity of product is low compared with the purity of product after 1 crystallization of embodiment after crystallization, illustrate, if without adopting
The control of water outlet can cause the generation of by-product to increase.
Comparative example 3
The process for repeating embodiment 1, difference lies in：When carrying out esterification, without methanol distillation and add (i.e.
The process with water without methanol).
It was found that in esterification reaction process, reaction efficiency is far below embodiment 1.
Comparative example 4
The process for repeating embodiment 1, difference lies in：When handling waste product sodium sulphate, toluene, acetic acid is respectively adopted
Ethyl ester replaces methanol and carries out flowing back to beat washing.
It was found that even if after process multi-reflow is beaten and washed, obtained sodium sulphate still has apparent smell, does not meet work
Industry grade application.
Experimental example
1 chromatography of experimental example detects
(1) the p-tert-butyl benzoic acid dry product obtained to embodiment 1 carries out chromatography detection, and the results are shown in Figure 1.
(2) the p-tert-butyl benzoic acid methyl esters obtained to embodiment 2 carries out chromatography detection, as a result as shown in Figure 2 and Table 1.
Table 1：
It is described the invention in detail above in association 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 preparation of p-tert-butyl benzoic acid methyl esters, which is characterized in that the preparation includes the following steps：
P-tert-butyltoluene, oxidation catalyst are added in stills for air blowing step 1, are passed through air and carry out oxidation reaction, preferably in oxygen
Change the control that recovered water is carried out in reaction process；
Crystallization processing is carried out after step 2, oxidation reaction, is then centrifuged for, washs, obtain p-tert-butyl benzoic acid wet product, is done
It is dry to obtain p-tert-butyl benzoic acid dry product；
Step 3, the p-tert-butyl benzoic acid dry product that step 2 is obtained, p-methyl benzenesulfonic acid and methanol mixing, are warming up to reflux and carry out
Then esterification is distilled to recover methanol；
Methanol is added in step 4 into system again, is warming up to reflux and carries out esterification, is then distilled to recover methanol, preferably repeats
This step 2~4 time, such as 3 times；
After step 5, esterification, water is added to stir 0.1~1h, stands liquid separation and carry out first time extraction, oil phase is taken, to oil phase
In plus water stir 0.1~1h, stand liquid separation and carry out second and extract, oil phase, rectification process is taken to obtain described to tert-butyl benzene first
Sour methyl esters.
2. preparation according to claim 1, which is characterized in that in step 1,
The catalyst be cobalt acetate-acetic acid manganese composite catalyst, it is preferable that the cobalt acetate-acetic acid manganese composite catalyst with
The weight ratio of the p-tert-butyltoluene is 1：(400~600), it is highly preferred that the weight ratio of cobalt acetate and manganese acetate be (20~
30)：1；And/or
It is passed through air with the speed of 1500~2500mL/min, it is preferable that air is passed through with the speed of 2000mL/min.
3. preparation according to claim 1 or 2, which is characterized in that in step 1,
Oxidation reaction is carried out in 120~130 DEG C, is preferable over 122~128 DEG C of progress oxidation reactions, such as carry out oxygen at 125 DEG C
Change reaction；And/or
The extraction for carrying out water during the reaction, the extraction of water is carried out preferably by condensing mode.
4. the preparation according to one of claims 1 to 3, which is characterized in that in step 2,
The crystallization processing is cooling crystallization, preferably carries out crystallization, such as the drop of 6~8 DEG C/h with the rate of temperature fall of 5~10 DEG C/h
Warm rate carries out crystallization；And/or
The drying process of p-tert-butyl benzoic acid wet product carries out as follows：100~120 DEG C are risen to the heating rate of 15~25 DEG C/h
It is dried, preferably rising to 105~110 DEG C with the heating rate of 20 DEG C/h is dried.
5. the preparation according to one of Claims 1-4, which is characterized in that in step 3,
The molar ratio of p-methyl benzenesulfonic acid and p-tert-butyl benzoic acid dry product is (0.03~0.08)：1, preferably (0.04~
0.07)：1, such as 0.06:1；And/or
The molar ratio of methanol and p-tert-butyl benzoic acid dry product is (1~3)：1, preferably (1.5~2.5)：1, such as 2:1.
6. the preparation according to one of claim 1 to 5, which is characterized in that
The molar ratio of methanol and step 3 p-tert-butyl benzoic acid dry product that step 4 uses is (0.5~2)：1, such as 1:1；With/
Or
In step 3 and step 4, rectification process is carried out to the methanol that distillation recovery obtains, is recycled with realizing, it is preferable that will
It is distilled to recover obtained methanol to be transferred in rectifying still, 70~90 DEG C of progress atmospheric distillations obtain recycling methanol.
7. the preparation according to one of claim 1 to 6, which is characterized in that
In step 3, esterification carries out (1~3) h, such as 2h；And/or
In step 4, esterification carries out (0.1~2) h, such as 1h；And/or
In step 3 and step 4, it is warming up to 70~80 DEG C and flows back, then carry out distillation recovery methanol in 110~130 DEG C.
8. the preparation according to one of claim 1 to 7, which is characterized in that in steps of 5, also obtained after extracting for the first time
Water phase；Preferably, the water phase obtained after being extracted to first time is distilled, and is collected the water after distillation and is evaporated bottom；It is highly preferred that institute
State the following progress of distillation：It is carried out at the vacuum degree of 10~15mmHg, less than 70 DEG C, until anhydrous extraction；
Wherein, the washing that the water after distillation is extracted for second, and the bottom that evaporates is p-methyl benzenesulfonic acid, puts into next group again
Esterification.
9. the preparation according to one of claim 1 to 8, which is characterized in that in steps of 5, also obtained after second of extraction
Water phase, it is preferable that the water phase obtained after being extracted to second is distilled, and the water after distillation is collected；It is highly preferred that the distillation
It is following to carry out：It is carried out at the vacuum degree of 10~15mmHg, less than 70 DEG C, until anhydrous extraction；
Wherein, first time extraction of the water after distillation for next batch reaction.
10. the preparation according to one of claim 1 to 9, which is characterized in that in steps of 5, obtained after being extracted to second
Oil phase carry out following rectifying：Under 2~6mmHg, kettle temperature rise to 130~140 DEG C, temperature rise to 80~100 DEG C of progress；It is preferred that
Under 3~5mmHg, kettle temperature rise to 132~136 DEG C, temperature rise to 85~95 DEG C of progress.
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| CN101648866A (en) * | 2009-09-18 | 2010-02-17 | 刘忠春 | Preparation technology of p-tert-butyl benzoic acid |
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| CN107311868A (en) * | 2017-06-23 | 2017-11-03 | 北京理工大学 | A kind of method for preparing p-tert-butyl benzoic acid methyl esters |
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| CN101648866A (en) * | 2009-09-18 | 2010-02-17 | 刘忠春 | Preparation technology of p-tert-butyl benzoic acid |
| CN104876814A (en) * | 2015-05-28 | 2015-09-02 | 江西亨通科技发展有限公司 | Synthetic method of avobenzone |
| CN107311868A (en) * | 2017-06-23 | 2017-11-03 | 北京理工大学 | A kind of method for preparing p-tert-butyl benzoic acid methyl esters |
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