CN108276275A - A kind of method that metal oxide oxidation catalyst oxidation prepares 4,4`- oxydibenzoic acids - Google Patents
A kind of method that metal oxide oxidation catalyst oxidation prepares 4,4`- oxydibenzoic acids Download PDFInfo
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- CN108276275A CN108276275A CN201810191980.6A CN201810191980A CN108276275A CN 108276275 A CN108276275 A CN 108276275A CN 201810191980 A CN201810191980 A CN 201810191980A CN 108276275 A CN108276275 A CN 108276275A
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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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Abstract
The invention discloses a kind of metal oxide oxidation catalysts to aoxidize the method for preparing 4,4' oxydibenzoic acids.It includes the following steps：By paraxylene base ether under oxidant, organo-metallic catalyst, ligand and Additive, occur oxidation reaction in a solvent, oxidizing reaction temperature is 85 145 DEG C, and the gauge pressure of reaction is 1.0 5.0MPa, and the reaction time is 5 for 24 hours；After reaction, post-treated to obtain 4,4' oxydibenzoic acids；Wherein：The organo-metallic catalyst is selected from one or both of cobalt acetate, manganese acetate, cerous acetate, cobalt nitrate, manganese nitrate, acetylacetone cobalt, ferric acetyl acetonade or ammonium ceric nitrate, and the additive is alkaline matter.The present invention uses metal oxide for catalyst, and hydrogen peroxide, air or oxygen reduce the generation of manufacturing cost and the three wastes as oxidant, alleviate environmental protection pressure, but also have the characteristics that easily controllable and industrialized production.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, are related to a kind of method of synthesis 4,4'- oxydibenzoic acids, specifically
It says, is related to a kind of method that metal oxide oxidation catalyst oxidation prepares 4,4'- oxydibenzoic acids.
Background technology
4,4'- oxydibenzoic acids, (4,4'-Oxybisbenzoic acid), light brown in appearance powdered crystalline, fusing point
329 DEG C, content >=98% is the monomer purposes of liquid crystal polymer.For electronics and medical industry.It and dihydric phenol and other
Aromatic dibasic acid is copolymerized the full polyarylate based thermoplastic liquid crystal polymer (TLCP) to be formed, and can be used to prepare high intensity, high-modulus
Liquid crystal fiber, special engineering plastics and high molecular weight flame retardant, industrially have been widely used.It is alternatively arranged as non-liquid crystal polymerization
The additive of object, roasting temperature and the viscosity for reducing polymer are easy to process and insulating materials is made etc..Secondly it or one
The important polymer monomer of kind, is used to prepare synthetic resin, insulating materials and liquid crystal fiber etc., in national defense industry and civilian industry
On have wide future.
It discloses in the prior art and obtains the system of 4,4'- oxydibenzoic acids through Ullmann condensation reactions by phenol and halobenzene
Preparation Method.(Tian Z,Li G,Deng Y.Synthesis and characterization of poly(ethylene
terephthalate)modifted with 4,4'-oxybis(benzoic acid)[J].Polymeric
Materialsence&Cngineering,1996,47(1):99-112.).The preparation method needs 200 DEG C or more of high temperature,
Prolonged heating, therefore product is of poor quality, yield is not high.But also can be there are many isomers generation, separation is difficult.
Invention content
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of " one kettle way " metal oxide oxidation catalysts
Aoxidize the method for preparing 4,4'- oxydibenzoic acids.The method of the present invention is environmentally protective, the three wastes are few, at low cost, easy to operate, instead
Answer mild condition, product yield high.
In the present invention, using paraxylene base ether as raw material, in the presence of organo-metallic catalyst and ligand, by sky
Gas, oxygen or hydrogen peroxide oxidation, obtain 4, the 4'- oxydibenzoic acids of high-quality, and reactive chemistry formula is as follows：
Technical scheme of the present invention is specifically described as follows.
The present invention provides a kind of method that metal oxide oxidation catalyst oxidation prepares 4,4'- oxydibenzoic acids, including following
Step：By paraxylene base ether under oxidant, organo-metallic catalyst, ligand and Additive, oxygen occurs in a solvent
Change reaction, oxidizing reaction temperature is 85-145 DEG C, and the gauge pressure of reaction is 1.0-5.0MPa, reaction time 5-24h；Reaction terminates
Afterwards, post-treated to obtain 4,4'- oxydibenzoic acids；Wherein：
The organo-metallic catalyst be selected from cobalt acetate, manganese acetate, cerous acetate, cobalt nitrate, manganese nitrate, acetylacetone cobalt,
The molar ratio of one or both of ferric acetyl acetonade or ammonium ceric nitrate, organo-metallic catalyst and paraxylene base ether is 1:
1000~1：50；The additive is alkaline matter；The solvent be selected from acetic acid, dimethyl succinate, diethyl succinate or
It is any in diethyl malonate.
In the present invention, oxidant is any in air, oxygen or hydrogen peroxide.
In the present invention, when oxidant is hydrogen peroxide, using 30wt% hydrogen peroxide, hydrogen peroxide and paraxylene base ether
Molar ratio is 2:1~5:1.
In the present invention, the molar ratio of organo-metallic catalyst and paraxylene base ether is 1:200~1：50.
In the present invention, ligand is selected from pyridine, 2,2- bipyridyls, Phen, triethylamine, acetylacetone,2,4-pentanedione, EDTA or second two
Any one of amine；The molar ratio of ligand and paraxylene base ether is 1:100~1:20.
In the present invention, the molar ratio of ligand and xylyl ether is 1:100~1:50.
In the present invention, additive is any in sodium carbonate, sodium acetate or sodium hydroxide, additive and xylyl ether
Molar ratio be 1:100~1:20；The volume mass of solvent and xylyl ether ratio is 1:1~30:1mL/g.
In the present invention, oxidizing reaction temperature is 90-120 DEG C, and the gauge pressure of reaction is 1.0-4.0MPa, reaction time 8-
20h.Under normal pressure when gauge pressure is 0.
In the present invention, oxidizing reaction temperature is 90-110 DEG C, and the gauge pressure of reaction is 1.0-2.0MPa, reaction time 9-
12h。
In the present invention, post-processing includes being filtered to remove organo-metallic catalyst, addition water and extraction agent extraction successively, having
Machine is mutually dry, filter, concentration and the step of column chromatography.If occurring emulsion in extraction process, can be added suitable sodium chloride into
Row demulsification, then vibrates, liquid separation again.Extraction times can be 1-5 times, and preferably washing times are 2-4 times, more preferable 3 times；It is organic
It is mutually dry to use anhydrous magnesium sulfate.
Compared to the prior art, the beneficial effects are mainly as follows the following aspects：
1, the oxidation reaction stage selects organo-metallic catalyst, avoids the use of initiator, particular avoid halogen
The use of class initiator so that 4,4'- oxydibenzoic acids do not contain initiator in final products, have high-quality, can be used for
The fields such as food, medicine, detergents and cosmetic.
2, when oxidation reaction uses hydrogen peroxide as oxidant, product only has water, without other pollutants, has warp
The characteristics of Ji, environmental protection, green high-efficient.
3, the present invention is easy to operate, and reaction condition is mild, and post-processing is simple, and product yield high is suitable for mass producing.
Specific implementation mode
The content of present invention is further explained and described below by way of specific implementation mode, but case study on implementation is understood not to
Limiting the scope of the invention.
Embodiment 1
By the paraxylene base ether of 1.9827g (0.01mol), cobalt acetate, the 0.0036g of 0.0025g (1mol%)
Acetylacetone cobalt, the sodium hydroxide additive of 0.0040g (0.1equiv) and the solvent succinic acid two of 3mL of (1equiv)
The pyridine ligand of methyl esters and 0.007971g (0.1equiv), puts into dry reaction test tube, after being warming up to 90 DEG C, in air
In reacted, under normal pressure after insulation reaction 12h, stop reaction.Reaction system is extracted 3 times with ethyl acetate, it is acquired
Product solvent is removed under reduced pressure, column chromatography for separation obtains 4,4'- oxydibenzoic acids, obtains product 2.2952g, and yield is
89%.
Embodiment 2
By 1.9827g (0.01mol) paraxylene base ether, cobalt acetate, the 0.0036g of 0.0025g (1mol%)
The solvent diethyl succinate of the acetylacetone cobalt of (1equiv), the sodium hydroxide of 0.012g (0.3equiv) and 5ml and
The pyridine ligand of 0.02391g (0.3equiv), puts into the hydrothermal reaction kettle of inner liner polytetrafluoroethylene, it is noted that uses preceding elder generation
Whether inspection equipment has damage, addition solvent and raw material into hydrothermal reaction kettle container, and after stirring and dissolving, nitrogen is blown into container
Gas for a period of time, makes system be in inert atmosphere, and hydrothermal reaction kettle lid, which is tightened, in use adds catalyst and place it in
In baking oven, after being warming up to 100 DEG C, oxygen tank is connected, it is 1.0MPa or so to make pressure (gauge pressure), after insulation reaction 8h, is stopped anti-
It answers.It waits for that autoclave body cooled to room temperature opens kettle cover, is extracted reaction system 3 times with ethyl acetate, obtained product decompression
Solvent is removed, column chromatography for separation obtains 4,4'- oxydibenzoic acids, obtains product 2.2178g, yield 86%.
Embodiment 3
By 1.9827g (0.01mol) paraxylene base ether, cobalt acetate, the 0.0036g of 0.0025g (1mol%)
The acetylacetone cobalt of (1equiv), the sodium carbonate of 0.0212g (0.2equiv), 30% hydrogen peroxide and 4mL of 0.03mol
Solvent acetic acid and 0.007971g (0.1equiv) pyridine ligand, put into dry and clean pressure pipe, be warming up to
After 100 DEG C, in the case where pressure (gauge pressure) is 2.0MPa after insulation reaction 6h, stop reaction, reaction system is extracted 3 with ethyl acetate
Secondary, solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains 4,4'- oxydibenzoic acids, obtains product 2.3725g,
Yield is 92%.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, according to the technical essence of the invention to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention, used herein is each
A bibliography, which is hereby incorporated by reference.
Claims (10)
1. a kind of method that metal oxide oxidation catalyst oxidation prepares 4,4'- oxydibenzoic acids, which is characterized in that including following step
Suddenly：By paraxylene base ether under oxidant, organo-metallic catalyst, ligand and Additive, aoxidize in a solvent
Reaction, oxidizing reaction temperature are 85-145 DEG C, and the gauge pressure of reaction is 1.0-5.0MPa, reaction time 5-24h；Reaction terminates
Afterwards, post-treated to obtain 4,4'- oxydibenzoic acids；Wherein：
The organo-metallic catalyst is selected from cobalt acetate, manganese acetate, cerous acetate, cobalt nitrate, manganese nitrate, acetylacetone cobalt, acetyl
The molar ratio of one or both of acetone iron or ammonium ceric nitrate, organo-metallic catalyst and paraxylene base ether is 1:1000~
1：50；The additive is alkaline matter；The solvent is selected from acetic acid, dimethyl succinate, diethyl succinate or malonic acid
It is any in diethylester.
2. according to the method described in claim 1, it is characterized in that, oxidant is any in air, oxygen or hydrogen peroxide
Kind.
3. according to the method described in claim 2, it is characterized in that, when oxidant is hydrogen peroxide, using 30wt% hydrogen peroxide,
The molar ratio of hydrogen peroxide and paraxylene base ether is 2:1~5:1.
4. according to the method described in claim 1, it is characterized in that, the molar ratio of organo-metallic catalyst and paraxylene base ether
It is 1:200~1：50.
5. according to the method described in claim 1, it is characterized in that, ligand is selected from pyridine, 2,2- bipyridyls, Phen, three
Any one of ethamine, acetylacetone,2,4-pentanedione, EDTA or ethylenediamine；The molar ratio of ligand and paraxylene base ether is 1:100~1:20.
6. according to the method described in claim 1, it is characterized in that, the molar ratio of ligand and xylyl ether is 1:100~1:
50。
7. according to the method described in claim 1, it is characterized in that, additive is in sodium carbonate, sodium acetate or sodium hydroxide
Any, the molar ratio of additive and xylyl ether is 1:100~1:20；The volume mass of solvent and xylyl ether ratio is
1:1~30:1mL/g.
8. according to the method described in claim 1, it is characterized in that, oxidizing reaction temperature is 90-120 DEG C, the gauge pressure of reaction is
1.0-4.0MPa, reaction time 8-20h.
9. the method according to claim 1 or 8, which is characterized in that oxidizing reaction temperature is 90-110 DEG C, the gauge pressure of reaction
For 1.0-2.0MPa, reaction time 9-12h.
10. according to the method described in claim 1, it is characterized in that, post-processing includes being filtered to remove metal organic catalysis successively
The step of water and extraction agent extraction, organic phase drying, filtering, concentration and column chromatography is added in agent.
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| CN201810191980.6A CN108276275A (en) | 2018-03-08 | 2018-03-08 | A kind of method that metal oxide oxidation catalyst oxidation prepares 4,4`- oxydibenzoic acids |
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| CN201810191980.6A CN108276275A (en) | 2018-03-08 | 2018-03-08 | A kind of method that metal oxide oxidation catalyst oxidation prepares 4,4`- oxydibenzoic acids |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591231A (en) * | 2022-03-02 | 2022-06-07 | 河南阿尔法医药科技有限公司 | Method for large-scale production of 4-formic acid-2, 2' -bipyridine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774909A (en) * | 2010-02-24 | 2010-07-14 | 常州市阳光医药原料有限公司 | Method for preparing 4, 4'-diphenyl ether dicarboxylic acid |
| CN107698436A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
-
2018
- 2018-03-08 CN CN201810191980.6A patent/CN108276275A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774909A (en) * | 2010-02-24 | 2010-07-14 | 常州市阳光医药原料有限公司 | Method for preparing 4, 4'-diphenyl ether dicarboxylic acid |
| CN107698436A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591231A (en) * | 2022-03-02 | 2022-06-07 | 河南阿尔法医药科技有限公司 | Method for large-scale production of 4-formic acid-2, 2' -bipyridine |
| CN114591231B (en) * | 2022-03-02 | 2024-02-20 | 河南阿尔法医药科技有限公司 | Method for large-scale production of 4-formic acid-2, 2' -bipyridine |
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