CN108484381A - A kind of method that Anderson types polyacid catalysis oxidation prepares 4,4`- oxydibenzoic acids - Google Patents
A kind of method that Anderson types polyacid catalysis oxidation prepares 4,4`- oxydibenzoic acids Download PDFInfo
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- CN108484381A CN108484381A CN201810191963.2A CN201810191963A CN108484381A CN 108484381 A CN108484381 A CN 108484381A CN 201810191963 A CN201810191963 A CN 201810191963A CN 108484381 A CN108484381 A CN 108484381A
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- polyacid
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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
- 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
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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Abstract
The invention discloses a kind of methods that Anderson types polyacid catalysis oxidation prepares 4,4' oxydibenzoic acids.It is as follows：1) oxidation reaction is occurred into a solvent for paraxylene base ether, heteropolyacid catalyst, oxidant and additive；2) after oxidation reaction, it is filtered to remove heteropolyacid catalyst, is extracted, organic and water phase is obtained；3) organic phase is dry successively, filters, concentrates and purifies, and obtains 4,4' oxydibenzoic acids；Wherein：Heteropolyacid catalyst is Anderson type polyacid parents or the parent that Anderson type polyacid is modified.The present invention uses Anderson types polyacid for catalyst, and reactivity is high, and reaction condition is mild, environmental-friendly；Single-minded high selectivity, recoverable are suitable for industrialized production.Hydrogen peroxide, air or oxygen can reduce cost, and reduce three waste discharge as oxidant, mitigate environmental protection pressure.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, are related to polyoxometallate catalysis more particularly to a kind of Anderson
The method that type polyacid catalysis 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%.It is poly- that it and dihydric phenol and other aromatic dibasic acids are copolymerized the full polyarylate based thermoplastic liquid crystal to be formed
Object (TLCP) is closed, can be used to prepare high intensity, the liquid crystal fiber of high-modulus, special engineering plastics and high molecular weight flame retardant, in work
Have been widely used in industry.It is alternatively arranged as the additive of non-liquid crystalline polymers, the roasting temperature and viscosity for reducing polymer are convenient for
Process and be made insulating materials etc..Secondly it or a kind of important polymer monomer, are used to prepare synthetic resin, insulation material
Material and liquid crystal fiber etc., there is wide future in national defense industry and civilian industry.
Traditional 4,4'- oxydibenzoic acid production methods are that one kind is using 4,4 '-diformazan yl diphenyl ethers as raw material, by first
Base is oxidized to carboxyl, and reaction needs 200 DEG C or more of high temperature, prolonged to heat, thus product is of poor quality, and yield is not
It is high.Another kind of is to connect corresponding group using diphenyl ether as raw material, be then converted into carboxyl.Such as with phenol and halobenzene through Ullmann
Condensation reaction prepares 4,4'- oxydibenzoic acids, (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.),
It can there are many isomers to generate, and separation is difficult；Most of and using toluene bromide and paracresol as raw material simultaneously, cost is more expensive, limit
Its use is made.
Invention content
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of Anderson types polyacid catalysis oxidations
The method for preparing high-quality 4,4'- oxydibenzoic acids.This method is one kettle way, easy to operate, and reaction condition is mild, product
High income；Catalyst is environmental-friendly simultaneously, is easily recycled recycling.
In the present invention, using paraxylene base ether as raw material, in the presence of Halogen heteropolyacid catalyst, by oxidant oxygen
Change, obtains 4, the 4'- oxydibenzoic acids of high-quality, reactive chemistry formula is as follows：
Technical scheme of the present invention is specifically described as follows.
A kind of method that Anderson types polyacid catalysis oxidation prepares 4,4'- oxydibenzoic acids, is as follows：
1) oxidation reaction is occurred into a solvent for paraxylene base ether, heteropolyacid catalyst, oxidant and additive；Oxidation
Agent is any in air, oxygen or hydrogen peroxide；
2) after oxidation reaction, it is filtered to remove heteropolyacid catalyst, ethyl acetate is added and water is extracted, obtain
Organic and water phase；
3) organic phase is dry successively, filters, concentrates and purifies, and obtains 4,4'- oxydibenzoic acids；Wherein：
In step 1), heteropolyacid catalyst is polyacid parent or the parent that polyacid is modified；The molecular formula of the polyacid parent
With [NH4]3[M1Mo6O18(OH)6] or [NH4]4[M2Mo6O18(OH)6] indicate, the molecular formula [N of the parent of the polyacid modification
(C4H9)4]3[M1Mo6O18(OH)3{(OCH2)3CR }] or [N (C4H9)4]4[M2Mo6O18(OH)3{(OCH2)3CR }] it indicates, wherein：
M1For Mn, Fe or Al, M2For Cu, Co or Ni, R NH2、CH2OH、CH3Or NO2。
In the present invention, in step 1), the molar ratio of heteropolyacid catalyst and paraxylene base ether is 1:1000~1:50.
In the present invention, in step 1), the molar ratio of heteropolyacid catalyst and paraxylene methyl ether is 1:150~1:80.
In the present invention, in step 1), additive is any in sodium acetate, sodium hydroxide or sodium carbonate；Additive and
The molar ratio of paraxylene base ether is 1:100~1:10.
In the present invention, in step 1), the molar ratio of additive and paraxylene base ether is 1:40~1:80.
In the present invention, in step 1), solvent is selected from acetic acid, dimethyl succinate, diethyl succinate or malonic acid diethyl
It is any one or several in ester；The volume mass ratio of solvent and paraxylene base ether is 1:1~50:1mL/g.
In the present invention, in step 1), the temperature of oxidation reaction is 80-150 DEG C, and the gauge pressure of oxidation reaction is 1.0-
5.0MPa, oxidation time 5-22h.It is indicated under normal pressure when gauge pressure is 0.
In the present invention, in step 1), the temperature of oxidation reaction is 80-100 DEG C, and the gauge pressure of oxidation reaction is 1.0-
2.0MPa, 8-12h.
In the present invention, in step 1), when oxidant is hydrogen peroxide, using 30% aqueous hydrogen peroxide solution, hydrogen peroxide
Molar ratio with paraxylene base ether is 2:1~5:1.
In the present invention, in step 2), the heteropolyacid catalyst being obtained by filtration repeatedly is rinsed through water and ethyl acetate, can be followed
Ring is used for the catalytic oxidation of step 1).
In the present invention, in step 3), purifying is using vacuum distillation or column chromatography mode.
Compared to the prior art, the beneficial effects are mainly as follows the following aspects：
(1), the oxidation reaction stage selects Fe-Anderson type heteropolyacid catalysts, avoids the use of initiator, especially
It is that of avoiding the use of halogen initiator, therefore can get 4, the 4'- oxydibenzoic acids of high-quality, and then for eating
The fields such as product, 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 catalyst recycled is applied mechanically repeatedly, does not find decay of activity；
(4), the present invention can greatly reduce the generation of target product manufacturing cost and the three wastes, mitigate environmental protection pressure；
(5), the present invention is easy to operate, reaction condition is mild, is suitable for industrialized production and prepares target product.
Description of the drawings
Fig. 1 is the Anderson type polyoxometallates [NH for being metal center with iron of embodiment 1-34]3[FeMo6O18
(OH)6] infrared spectrogram.
Fig. 2 is the Tris-NH of embodiment 4-52Modification iron is the Anderson types polyacid ([N (C of metal center4H9)4]3
[FeMo6O18{(OCH2)3CNH2}2]) infrared spectrogram.
Fig. 3 is the Anderson type polyoxometallates [NH that iron is metal center in embodiment 24]3[FeMo6O18(OH)6]
Catalyst recycle IR Characterization figure.
Specific implementation mode
It is further explained and described the content of present invention below by way of specific implementation mode, but embodiment is understood not to pair
The limitation of the scope of the present invention.
Embodiment 1
By 1.9827g (0.01mol) paraxylene base ether, the more metals of Fe-Anderson types of 0.01202g (1mol%)
Oxygen hydrochlorate ([NH4]3[FeMo6O18(OH)6]), the solvent acetic acids of the acetic acid sodium additives of 0.0082g (0.1equiv) and 8mL
It puts into dry reaction test tube, after being warming up to 100 DEG C, is reacted in air, at one atm insulation reaction 20h
Afterwards, stop reaction.Reaction system is extracted 3 times with ethyl acetate, solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains
To 4,4'- oxydibenzoic acids, product 2.1405g, yield 83% are obtained.
Embodiment 2
By 1.9827g (0.01mol) paraxylene base ether, the more metals of Fe-Anderson types of 0.01202g (1mol%)
Oxygen hydrochlorate ([NH4]3[FeMo6O18(OH)6]), the carbonic acid sodium additives of 0.0106g (0.1equiv) and 10mL solvent acetic acids
It puts into the hydrothermal reaction kettle of inner liner polytetrafluoroethylene, it is noted that first check whether equipment has damage using preceding, to hydro-thermal reaction
It is added solvent and raw material in kettle container, after stirring and dissolving, nitrogen is blown into container for a period of time, system is made to be in inert atmosphere
In, hydrothermal reaction kettle lid, which is tightened, in use adds catalyst and places it in baking oven, after being warming up to 100 DEG C, connects oxygen
Tank, it is 1.0MPa or so to make pressure (gauge pressure), after insulation reaction 12h, stops reaction.Wait for that autoclave body cooled to room temperature opens kettle
Lid is extracted reaction system 3 times with ethyl acetate, and solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains 4,4'- bis-
Phenylate dioctyl phthalate obtains product 1.8052g, yield 70%.Fig. 3 is Anderson types polyoxometallate in embodiment 2
[NH4]3[FeMo6O18(OH)6] recycled by 6 times, the IR Characterization figure after being reacted in iterative cycles embodiment 2.
Embodiment 3
The paraxylene base ether of 1.9827g (0.01mol), the Fe-Anderson types of 0.01202g (1mol%) is how golden
Belong to oxygen hydrochlorate ([NH4]3[FeMo6O18(OH)6]), the carbonic acid sodium additives of 0.0106g (0.0001mol), peroxide containing 0.03mol
Change 30% hydrogen peroxide of hydrogen and 4mL solvent acetic acids are put into dry and clean pressure pipe, after being warming up to 100 DEG C,
In the case where pressure (gauge pressure) is 1.0MPa after insulation reaction 12h, stop reaction, is extracted reaction system 3 times with ethyl acetate, gained
To product solvent is removed under reduced pressure, column chromatography for separation obtains 4,4'- oxydibenzoic acids, obtains product 2.0115g, and yield is
78%.
Embodiment 4
By the paraxylene base ether of 1.9827g (0.01mol), the Tris Derivatives Modifieds of 0.01883g (1mol%)
Fe-Anderson types polyacid ([N (C4H9)4]3[FeMo6O18{(OCH2)3CNH2}2]), the sodium acetate of 0.0082g (0.1equiv)
Additive, the hydrogen peroxide of 30wt% and the solvent acetic acid of 30mL of the hydrogen peroxide containing 0.03mol are put into dry and clean
Pressure pipe in, after being warming up to 100 DEG C, after insulation reaction 12h, stop reaction in the case where pressure (gauge pressure) is 1.0MPa, use acetic acid
Ethyl ester extracts reaction system 3 times, and solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains 4,4'- diphenyl ether diformazans
Acid obtains product 2.1920g, yield 85%.
Embodiment 5
By the paraxylene base ether of 1.9827g (0.01mol), the Tris Derivatives Modifieds of 0.01883g (1mol%)
Fe-Anderson types polyacid ([N (C4H9)4]3[FeMo6O18{(OCH2)3CNH2}2]), the sodium carbonate of 0.0106g (0.1equiv)
Additive, the hydrogen peroxide of the 30wt% of the hydrogen peroxide containing 0.03mol and the solvent diethyl malonate of 30mL put into drying
And in clean pressure pipe, after being warming up to 100 DEG C, in the case where pressure (gauge pressure) is 1.0MPa after insulation reaction 18h, stop anti-
It answers, is extracted reaction system 3 times with ethyl acetate, solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains 4,4'- bis-
Phenylate dioctyl phthalate obtains product 2.3983g, yield 93%.
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 Anderson types polyacid catalysis oxidation prepares 4,4'- oxydibenzoic acids, which is characterized in that specific step
It is rapid as follows：
1) oxidation reaction is occurred into a solvent for paraxylene base ether, heteropolyacid catalyst, oxidant and additive；Oxidant selects
It is any from air, oxygen or hydrogen peroxide；
2) after oxidation reaction, it is filtered to remove heteropolyacid catalyst, ethyl acetate is added and water is extracted, obtain organic
And water phase；
3) organic phase is dry successively, filters, concentrates and purifies, and obtains 4,4'- oxydibenzoic acids；Wherein：
In step 1), heteropolyacid catalyst is polyacid parent or the parent that polyacid is modified；The molecular formula of the polyacid parent is used
[NH4]3[M1Mo6O18(OH)6] or [NH4]4[M2Mo6O18(OH)6] indicate, the molecular formula [N of the parent of the polyacid modification
(C4H9)4]3[M1Mo6O18(OH)3{(OCH2)3CR }] or [N (C4H9)4]4[M2Mo6O18(OH)3{(OCH2)3CR }] it indicates, wherein：
M1For Mn, Fe or Al, M2For Cu, Co or Ni, R NH2、CH2OH、CH3Or NO2。
2. according to the method described in claim 1, it is characterized in that, in step 1), heteropolyacid catalyst and paraxylene base ether
Molar ratio be 1:1000~1:50.
3. according to the method described in claim 1, it is characterized in that, in step 1), heteropolyacid catalyst and paraxylene methyl
The molar ratio of ether is 1:150~1:80.
4. according to the method described in claim 1, it is characterized in that, in step 1), additive be selected from sodium acetate, sodium hydroxide or
It is any in sodium carbonate；The molar ratio of additive and paraxylene base ether is 1:100~1:10.
5. method according to claim 1 or 4, which is characterized in that in step 1), additive and paraxylene base ether rub
You are than being 1:40~1:80.
6. according to the method described in claim 1, it is characterized in that, in step 1), solvent be selected from acetic acid, dimethyl succinate,
It is any one or several in diethyl succinate or diethyl malonate；The volume mass ratio of solvent and paraxylene base ether is 1:1
~50:1mL/g.
7. according to the method described in claim 1, it is characterized in that, in step 1), the temperature of oxidation reaction is 80-150 DEG C, oxygen
The gauge pressure for changing reaction is 1.0-5.0MPa, oxidation time 5-22h.
8. according to the method described in claim 1, it is characterized in that, in step 1), the temperature of oxidation reaction is 80-100 DEG C, oxygen
The gauge pressure for changing reaction is 1.0-2.0MPa, oxidation time 8-12h.
9. according to the method described in claim 1, it is characterized in that, in step 1), when oxidant is hydrogen peroxide, using 30%
The molar ratio of aqueous hydrogen peroxide solution, hydrogen peroxide and paraxylene base ether is 2:1~5:1.
10. according to the method described in claim 1, it is characterized in that, in step 3), purifying is using vacuum distillation or column chromatography
Mode.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292417A (en) * | 2021-05-24 | 2021-08-24 | 赣南医学院 | Process for producing carboxylic acid |
Citations (2)
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| 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 CN201810191963.2A patent/CN108484381A/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 |
Non-Patent Citations (1)
| Title |
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| HAN YU等: "An Efficient Iron(III)-Catalyzed Aerobic Oxidation of Aldehydes in Water for the Green Preparation of Carboxylic Acids", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292417A (en) * | 2021-05-24 | 2021-08-24 | 赣南医学院 | Process for producing carboxylic acid |
| CN113292417B (en) * | 2021-05-24 | 2023-05-23 | 赣南医学院 | Process for preparing carboxylic acids |
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