CN104311408B - The preparation method of 4,4 '-oxydibenzoic acids - Google Patents
The preparation method of 4,4 '-oxydibenzoic acids Download PDFInfo
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- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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Abstract
The present invention relates to the preparation of high polymer monomer, specifically a kind of preparation method of 4,4 '-oxydibenzoic acids.Specifically, 4- chlorobenzoic acid, 4-HBA and acid binding agent are added in polar high-boiling solvent, condensation reaction at 140~280 DEG C, the content of the 4- chlorobenzoic acid into reaction system is reacted in 0.1-0.5%, the mass concentration that polar solvent to polar solvent in reaction system is then diluted with water is 20~60%, 4,4 '-oxydibenzoic acids are precipitated.The method of the present invention raw material is easy to get, and simple process, reaction condition is mild, reacts under normal pressure, and preparation cost is low, and yield is high, and quality is high.
Description
Technical field
The present invention relates to the preparation of high polymer monomer, specifically a kind of preparation method of 4,4 '-oxydibenzoic acids.
Background technique
4,4 '-oxydibenzoic acids are a kind of important high polymer monomers, mainly for the preparation of high performance polyphenyl and are disliked
Azoles resin, poly- aromatic aldehyde resin, high-performance fiber, insulating materials and thermoplastic liquid crystal polymer.Currently, related 4,4 '-hexichol
The preparation method of ether dioctyl phthalate is mainly the following method.
1,052 300 A of Chinese patent CN discloses one kind and synthesizes 4,4 '-oxydibenzoic acids by paranitrobenzoic acid
Method.This method generates p-nitrophenyl first cyanogen using paranitrobenzoic acid as raw material, prior to phosphorus oxychloride and ammonia, then with nitrous
Hydrochlorate and carbonate carry out condensation reaction and 4,4 '-dicyan yl diphenyl ethers are made, and finally hydrolyze in alkaline solution and are made 4,4 '-two
Phenylate dioctyl phthalate, yield 73.5%.The deficiency of this method is: entire reaction time consumption is long, at high cost, and intermediate is to nitro
Benzonitrile is deadly poisonous compound.
European patent EP 1211235 discloses a kind of method for synthesizing 4,4 '-oxydibenzoic acids by diphenyl ether, the method with
Diphenyl ether is raw material, under trifluoro-methanyl sulfonate catalysis, prepares 4,4 '-diacetyls two through Fu Ke acylation reaction with acetic anhydride
Then phenylate reacts again with NaClO and sloughs obtained 4, the 4 '-oxydibenzoic acids of trichloromethyl.The deficiency of this method is: Fu Ke
Acylation reaction will use expensive catalyst trifluoro-methanyl sulfonate, and reflection also uses a large amount of LiClO4, it is difficult work
Industry metaplasia produces.
Chinese patent CN 1048808 discloses a kind of synthetic method of 4,4 '-oxydibenzoic acids, and this method is used first
Parabromotoluene and paracresol exist in Fu acid agent KOH is made 4,4 '-diformazan yl diphenyl ethers through being condensed, then with potassium permanganate through two
Secondary oxidation obtains product.The deficiency of this method is: needing to carry out two-step oxidation, time-consuming, and produces using potassium permanganate oxidation
Raw a large amount of waste water, environmental pollution are serious.
Chinese patent CN 101774909 discloses one kind and synthesizes 4,4 '-diphenyl ether diformazans by 4,4 '-diformazan yl diphenyl ethers
The method of acid.The method with 4,4 '-diformazan yl diphenyl ethers be raw material, catalyst (cobalt salt and manganese salt) effect under, through dioxygen oxidation
Obtain product.4,4 '-diformazan yl diphenyl ethers: catalyst is at high cost, and the reaction time is long.
Summary of the invention
It is an object of that present invention to provide a kind of preparation methods of 4,4 '-oxydibenzoic acids.
To achieve the above object, the invention adopts a technical scheme as:
A kind of preparation method of 4,4 '-oxydibenzoic acids, 4- chlorobenzoic acid, 4-HBA and acid binding agent are added
Into polar high-boiling solvent, the content < of the 4- chlorobenzoic acid into reaction system is reacted in condensation reaction at 140~280 DEG C
0.5%, reaction system is then diluted with water, makes the mass concentration 20~60% of polar solvent, i.e. 4,4 '-diphenyl ether two of precipitation
Formic acid.
The polar solvent after diluting is removed by filtration salt after being dehydrated, recyclable to apply.
It will be containing the lower dehydration of polar solvent aqueous solution decompression, when vapo(u)rizing temperature rises to 105 DEG C of (vacuum degree 20-
30mmHg), dehydration terminates.Cooling obtains polar solvent after being filtered to remove inorganic salts, can be applied to next time instead after analyzing its content
It answers.The water that distillation obtains is recyclable to be applied.
The molar ratio of the 4- chlorobenzoic acid, 4-HBA and acid binding agent are as follows: 4- chlorobenzoic acid: 4- hydroxy benzenes first
Acid: acid binding agent=1:1~1.3:0.5~1.5；
The additional amount of the polar high-boiling solvent is 2-3 times of 4- chlorobenzoic acid and 4-HBA total weight.
The acid binding agent is the mixing of one or more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide.
The polar high-boiling solvent is sulfolane, dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF)
And their mixture.
The reaction time is 16~24 hours.
The water is tap water or distilled water.
Advantage for present invention:
The method of the present invention raw material is easy to get, and simple process, reaction condition is mild, reacts under normal pressure, and entire technique focuses on environmental protection,
Waste water is not generated in technical process, substantially reduces environmental protection pressure.After polar solvent dehydration after water dilution, it is removed by filtration salt, it can
Recovery substantially reduces cost of material, and yield is high, and quality is high, improves the competitiveness of product.
Specific embodiment
Embodiment 1
The sulfolane of 120g is added in the four-hole boiling flask of 500ml, is added with stirring the 4- chlorobenzoic acid and 29.0g of 31.3g
4-HBA, add 15.2g potassium carbonate, stirring, which is warming up at 143~145 DEG C, reacts, middle control after reaction 16 hours
Sampling analysis, with the content of 4- chlorobenzoic acid less than 0.5% (GC normalizing content) for reaction end.If not arriving reaction end,
Continue the insulation reaction at 143~145 DEG C, until the content of 4- chlorobenzoic acid is less than 0.5% (GC normalizing content).Reaction terminates
Afterwards, 100 DEG C are cooled to hereinafter, starting that 250ml water is added dropwise, with the addition of dampening, a large amount of solids are precipitated.After being added to water,
40~50 DEG C of stirrings, one hour (revolving speed 100-150r/min), filtering, and filter is washed with 100ml water (water temperature is about at 40 DEG C)
Cake.49.5g product is obtained after drying, content is 99.4% (HPLC normalizing content), yield 95.9%.
The lower dehydration of sulfolane aqueous solution decompression will be contained, vapo(u)rizing temperature reaches 105 DEG C (vacuum degree 20-30mmHg), dehydration
Terminate, what is obtained is salt (mainly potassium chloride) and sulfolane mixture, is cooled to 50 DEG C, and filtering obtains sulfolane 106g, recycles
Sulfolane contain 4-HBA, after its content of gas spectrum analysis, feeding intake for next group 4-HBA is determined after conversion
Amount.Distillation, which obtains water, to apply.
Key reaction is as follows:
Embodiment 2
In the four-hole boiling flask of 500ml be added 130g dimethyl sulfoxide, be added with stirring 31.3g4- chlorobenzoic acid and
30.4g4- hydroxybenzoic acid adds 30.4g potassium hydroxide, and stirring, which is warming up at 163~165 DEG C, reacts, after reaction 16 hours
Middle control sampling analysis, with the content of 4- chlorobenzoic acid less than 0.5% (GC normalizing content) for reaction end.If not arriving reaction eventually
Point continues the insulation reaction at 163~165 DEG C, until the content of 4- chlorobenzoic acid is less than 0.5% (GC normalizing content).Reaction
After, 100 DEG C are cooled to hereinafter, starting that 300ml water is added dropwise, and with the addition of dampening, a large amount of solids are precipitated.It is finished to water addition
Afterwards, 40~50 DEG C of stirrings, one hour (revolving speed 100-150r/min), filtering, and washed with 100ml water (water temperature is about at 40 DEG C)
Filter cake.46.6g product is obtained after drying, content is 99.3% (HPLC normalizing content), yield 90.3%.
The lower dehydration of dimethyl sulphoxide aqueous solution decompression will be contained, vapo(u)rizing temperature reaches 105 DEG C (vacuum degree 20-30mmHg),
Dehydration terminates, and what is obtained is salt (mainly potassium chloride) and dimethyl sulfoxide mixture, is cooled to 40 DEG C, filtering obtains dimethyl
Sulfoxide 113g, the dimethyl sulfoxide of recycling contain 4-HBA, and after its content of gas spectrum analysis, next group 4- is determined after conversion
The inventory of hydroxybenzoic acid.Distillation, which obtains water, to apply.
Embodiment 3
The sulfolane recycled in 140g embodiment 1 is added in the four-hole boiling flask of 500ml, is added with stirring 31.3g4-
Chlorobenzoic acid and 33.1g4- hydroxybenzoic acid add 9.6g sodium hydroxide, and stirring, which is warming up at 180~182 DEG C, reacts, instead
Middle control sampling analysis after answering 16 hours, with the content of 4- chlorobenzoic acid less than 0.5% (GC normalizing content) for reaction end.If not yet
Have to reaction end, continue the insulation reaction at 180~182 DEG C, until the content of 4- chlorobenzoic acid is less than 0.5% (GC normalizing
Content).After reaction, 100 DEG C are cooled to hereinafter, starting that 350ml water is added dropwise, with the addition of dampening, a large amount of solids are precipitated.To
After water is added, 40~50 DEG C of stirrings, one hour (revolving speed 100-150r/min), filtering, and (water temperature about exists with 100ml water
40 DEG C) washing filter cake.44.2g product is obtained after drying, content is 99.0% (HPLC normalizing content), yield 85.6%.
The lower dehydration of sulfolane aqueous solution decompression will be contained, vapo(u)rizing temperature reaches 105 DEG C (vacuum degree 20-30mmHg), dehydration
Terminate, what is obtained is salt (mainly potassium chloride) and sulfolane mixture, is cooled to 50 DEG C, and filtering obtains sulfolane 126g, recycles
Sulfolane contain 4-HBA, after its content of gas spectrum analysis, feeding intake for next group 4-HBA is determined after conversion
Amount.Distillation, which obtains water, to apply.
Embodiment 4
The n,N-Dimethylformamide of 140g is added in the four-hole boiling flask of 500ml, is added with stirring 31.3g4- chlorobenzoic acid
With 35.9g4- hydroxybenzoic acid, 31.8g sodium carbonate is added, stirring, which is warming up at 140~142 DEG C, reacts, after reaction 16 hours
Middle control sampling analysis, with the content of 4- chlorobenzoic acid less than 0.5% (GC normalizing content) for reaction end.If not arriving reaction eventually
Point continues the insulation reaction at 140~142 DEG C, until the content of 4- chlorobenzoic acid is less than 0.5% (GC normalizing content).Reaction
After, 100 DEG C are cooled to hereinafter, starting that 300ml water is added dropwise, and with the addition of dampening, a large amount of solids are precipitated.It is finished to water addition
Afterwards, 40~50 DEG C of stirrings, one hour (revolving speed 100-150r/min), filtering, and washed with 100ml water (water temperature is about at 40 DEG C)
Filter cake.41.4g product is obtained after drying, content is 97.4% (HPLC normalizing content), yield 80.3%.
The lower dehydration of n,N-Dimethylformamide aqueous solution decompression will be contained, vapo(u)rizing temperature reaches 105 DEG C of (vacuum degree 20-
30mmHg), dehydration terminates, and what is obtained is salt (mainly potassium chloride) and n,N-Dimethylformamide mixture, is cooled to 30 DEG C,
Filtering, obtains n,N-Dimethylformamide 113g, and the n,N-Dimethylformamide of recycling contains 4-HBA, gas spectrum analysis its
After content, the inventory of next group 4-HBA is determined after conversion.Distillation, which obtains water, to apply.
Claims (4)
1. the preparation method of 4,4 '-oxydibenzoic acid of one kind, it is characterised in that: by 4- chlorobenzoic acid, 4-HBA and
Acid binding agent is added in polar solvent, condensation reaction at 140~280 DEG C, reacts the content of the 4- chlorobenzoic acid into reaction system
< 0.5%, is then diluted with water reaction system, makes the mass concentration 20~60% of polar solvent, i.e. 4,4 '-diphenyl ether two of precipitation
Formic acid；
The polar solvent is sulfolane, dimethyl sulfoxide or N,N-dimethylformamide and their mixture；
The polar solvent after diluting is removed by filtration salt after being dehydrated, recyclable to apply；
The molar ratio of the 4- chlorobenzoic acid, 4-HBA and acid binding agent are as follows: 4- chlorobenzoic acid: it 4-HBA: ties up
Sour agent=1:1~1.3:0.5~1.5；
The additional amount of the polar solvent is 2-3 times of 4- chlorobenzoic acid and 4-HBA total weight.
2. by the preparation method of 4,4 '-oxydibenzoic acids described in claim 1, it is characterised in that: the acid binding agent is carbonic acid
The mixing of one or more of potassium, sodium carbonate, potassium hydroxide, sodium hydroxide.
3. by the preparation method of 4,4 '-oxydibenzoic acids described in claim 1, it is characterised in that: the reaction time is 16
~24 hours.
4. by the preparation method of 4,4 '-oxydibenzoic acids described in claim 1, it is characterised in that: the water is tap water
Or distilled water.
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| CN1052300A (en) * | 1989-12-08 | 1991-06-19 | 鞍山钢铁学院 | By p-nitrobenzoic acid synthetic 4,4 '-the phenyl ether dioctyl phthalate |
| WO1999059526A2 (en) * | 1998-05-21 | 1999-11-25 | Smithkline Beecham Corporation | Protease inhibitors |
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| RU2409554C1 (en) * | 2009-06-23 | 2011-01-20 | Государственное образовательное учреждение высшего профессионального образования Ярославский государственный университет им. П.Г. Демидова | Method for synthesis of 4-(3,4-diaminophenoxy)benzoic acid |
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