CN105330633A - Preparation method for biphenyltetracarboxylic dianhydride mixture - Google Patents
Preparation method for biphenyltetracarboxylic dianhydride mixture Download PDFInfo
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Abstract
The invention relates to a preparation method for a biphenyltetracarboxylic dianhydride mixture. The preparation method comprises the following steps: with phthalic acid as a starting raw material, carrying out an electrophilic substitution reaction so as to produce a phthalic acid derivative; then subjecting the derivative to esterification so as to produce phthalate; further catalyzing phthalate and carrying out a coupling reaction so as to produce a biphenyl tetraformate mixture; and finally, successively carrying out saponification and acidification so as to produce the product biphenyltetracarboxylic dianhydride mixture. The method provided by the invention uses cheap and easily phthalic acid as the starting raw material and is a novel low-cost easily-operatable environment-friendly production method for biphenyltetracarboxylic dianhydride; moreover, isomeric compounds of all the biphenyltetracarboxylic dianhydride are synthesized at one time in the invention, so efficiency is improved and the cost is reduced.
Description
Technical field
The present invention relates to biphenyl dianhydride preparing technical field, particularly a kind of method preparing biphenyl dianhydride mixture.
Background technology
Also known as BPDA, there are three kinds of isomer in biphenyl dianhydride, and namely 3,3 '; 3,4; 4,4 ’ – BPDA that is 3,4,3 ', 4 '-BPDA, 2,3,2 ', 3 '-BPDA and 2,3,3 ' 4 '-BPDA.Biphenyl dianhydride is the important monomer of synthesis heat-proof macromolecule material polyimide, can be polymerized, thus prepare polyimide with many kinds of substance.Polyimide has superior over-all properties in current industrialized macromolecular material, and at film, coating, plastics, matrix material, tackiness agent, porous plastics, fiber, separatory membrane, the field such as liquid crystal aligning agent and photoresist material is widely used.Therefore biphenyl dianhydride is as the important monomer of high-performance polyimide, and its synthesis and application are subject to extensive concern both domestic and external.
Biphenyl dianhydride is generally corresponding bibenzene tetracarboxylic and is dehydrated into acid anhydride and obtains, and the synthetic method of bibenzene tetracarboxylic all can use oxidizing reaction, and not only cost is high but also to the extremely disagreeableness oxygenant of environment to use some, such as potassium permanganate.
The preparation method of a Chinese patent application CN201110202366.3 biphenyl dianhydride, disclose a kind of preparation method of biphenyl dianhydride, comprise the following steps: take acetic acid as solvent, cobalt source compound is catalyzer, bromine source compound is promotor, by the gas reaction of tetramethyl biphenyl and molecule-containing keto, obtain bibenzene tetracarboxylic, then dehydration reaction, obtains biphenyl dianhydride; Chinese patent CN200810051688.0, discloses in a kind of 2,3, the preparation method of 3 ', 4 '-biphenyl dianhydride and derivative thereof.By phthalic esters different for two kinds of chloro positions or phthalic imidine, under nickel catalysis, cross-coupling reaction obtains 2,3,3 ', 4 '-biphenyl dianhydride.The reaction scheme product that aforesaid method is single all only has a kind of isomer, and efficiency is low, and cost is high.
Summary of the invention
The object of the invention is: solve the deficiencies in the prior art, provide a kind of low-cost and easy-to to operate environmentally friendly, disposable generation 3 biphenyl dianhydride mixtures prepare the method for biphenyl dianhydride mixture efficiently.
The technical scheme realizing the object of the invention is: a kind of method preparing biphenyl dianhydride mixture, and the method, for adopting phthalic acid to be starting raw material, carries out electrophilic substitution reaction, generates phthalic acid derivatives; Then carry out esterification, generate phthalic ester; Further catalysis is carried out to phthalic ester, linked reaction occurs, generate biphenyl tetracarboxylic acid ester mixtures; Finally carry out saponification reaction, and after acidifying, generate product biphenyl dianhydride mixture.
The above-mentioned method preparing biphenyl dianhydride mixture, specifically comprises the steps: that (1) adopts phthalic acid to carry out electrophilic substitution reaction, obtains the phthalic acid derivatives that ortho position and a position as general formula (I) replace,
Wherein R
1for one of in bromine, chlorine, iodine, nitro;
Phthalic acid is dissolved in the aqueous solution of acid or alkali, after stirring, drips electrophilic reagent, after dropwising, stoichiometric number hour, drains all solvents, adds organic solvent, gained solution saturated common salt washes 3 times, after organic phase is separated, and aqueous phase organic solvent extraction twice.Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the phthalic acid derivatives (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.One of aforementioned organic solvents can be ethyl acetate, methylene dichloride, ether, in sherwood oil.
(2) phthalic acid derivatives that the ortho position of front step and a position replace is carried out esterification, obtains the ester as general formula (II),
Wherein R
1for one of in bromine, chlorine, iodine, nitro, R
2for one of in methyl, ethyl, sec.-propyl, the tertiary butyl;
Be dissolved in by phthalic acid derivatives in esterifying reagent, add alkaline solution, after stirring, drain all solvents, add organic solvent, gained solution saturated common salt washes 3 times, after organic phase is separated, and aqueous phase organic solvent extraction twice.Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the phthalate derivatives (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.One of aforementioned organic solvents can be ethyl acetate, methylene dichloride, ether, in sherwood oil.
(3) under the catalysis of metal, there is linked reaction, generate biphenyl tetracarboxylic acid ester mixtures (III) in the phthalic ester (II) replaced in front step ortho position and a position,
Wherein R
2for one of in methyl, ethyl, sec.-propyl, the tertiary butyl,
Described metal is one of in nickel, zinc, copper, iron;
Respectively by organic solvent, metal-powder and dilute acid soln add and are warming up to 60 DEG C after stirring at room temperature in the three-necked flask with condensing works and continue to stir a few hours, reacted by TLC tracing detection, until stopped reaction when reaction substrate no longer reduces, reaction solution is cooled, cross and filter metal catalyst, solvent evaporated.Add organic solvent, gained solution saturated common salt washes 3 times, after organic phase is separated, and aqueous phase organic solvent extraction twice.Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, to corresponding biphenyl tetracarboxylic acid ester mixtures (yield 80-99%, GC purity (three isomer) 85-95%).But aforementioned organic solvents tetrahydrofuran (THF), ether, Isosorbide-5-Nitrae-dioxane, DMF.
(4) biphenyl tetracarboxylic acid ester mixtures (III) saponification under the effect of alkali, then acidifying, can generate biphenyl dianhydride mixture (IV);
Biphenyl tetracarboxylic acid ester mixtures is dissolved in the aqueous solution of alkali, after stirring, dropping acid solution neutralizes, drop to when pH value is less than 2 and stop dripping, stirred for several hour, drains all solvents, add organic solvent, gained solution saturated common salt washes 3 times, after organic phase is separated, and aqueous phase organic solvent extraction twice.Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the adjacent benzene dianhydride mixture (yield 80-95%, GC purity (three isomer) 85-95%) of corresponding ortho position and a position replacement.Aforementioned siccative can be magnesium sulfate, sodium sulfate, magnesium chloride, calcium chloride
The above-mentioned method preparing biphenyl dianhydride mixture, in the described electrophilic substitution reaction process of described step (1), electrophilic reagent is halogen, Cl
2, Br
2, I
2, a kind of in nitric acid, preferentially use chlorine, the usage quantity of electrophilic reagent be the 1.1-1.5 of phthalic acid substrate doubly mole, preferably 1.1,1.2,1.3,1.4,1.5 times moles.
The above-mentioned method preparing biphenyl dianhydride mixture, in described step (2) esterification reaction process, esterifying reagent is methyl alcohol, ethanol, Virahol, a kind of in the trimethyl carbinol, preferentially select methyl alcohol, the usage quantity of esterifying reagent is 2.1-3.0 times mole of phthalic acid substrate, preferably 2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3.0 times moles.
The above-mentioned method preparing biphenyl dianhydride mixture, in described step (3) metal catalysed reaction process, metal catalyst is nickel, zinc, copper, a kind of in iron, its usage quantity is 0.1-1.0 times mole of phthalic ester substrate, preferably 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0 times mole.
The above-mentioned method preparing biphenyl dianhydride mixture, in described step (4) saponification reaction process, alkali used is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium methylate, a kind of in potassium methylate.
The above-mentioned method preparing biphenyl dianhydride mixture, in described saponification reaction process, the usage quantity of alkali is 0.1-10 times mole of phthalic ester substrate, preferably 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0 times mole.
The above-mentioned method preparing biphenyl dianhydride mixture, in described acidification reaction process, acid used is dilute sulphuric acid or dilute hydrochloric acid, and its usage quantity is 1.0-2.0 times mole of phthalic acid substrate, preferably 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0 times moles.
The present invention has positive effect: (1) the present invention adopts the phthalic acid be cheaply easy to get to be starting raw material, is the production method of the environment amenable new biphenyl dianhydride of a kind of low-cost and easy-to operation; (2) isomeric compound of all biphenyl dianhydrides of the disposable synthesis of the present invention, efficiency improves, and cost declines.
Embodiment
(embodiment 1)
Phthalic acid (1mmol) is dissolved in 20 milliliters of aqueous acids, stir after 1.5 hours, pass into chlorine, react 3 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the phthalic acid muriate (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.
Phthalic acid muriate (1mmol) is dissolved in 20 ml methanol, add alkaline solution, stir after 1.5 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the Methyl Benzene-o-dicarboxylate mixture (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.
Respectively by 50mLDMF, the above-mentioned Methyl Benzene-o-dicarboxylate mixture of 10mmol, 10mmol metallic nickel powder and 10mL1mol/L dilute hydrochloric acid solution add and are warming up to 60 DEG C after stirring at room temperature 0.5h in the 250mL three-necked flask with condensing works and continue to stir 5h, reacted by TLC tracing detection, until stopped reaction when reaction substrate no longer reduces, reaction solution is cooled, crosses and filter metal catalyst, solvent evaporated.Add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, to corresponding biphenyl tetracarboxylic acid ester mixtures (yield 90%, GC purity (three isomer) 95%).
Bibenzene tetracarboxylic mixtures of methyl esters (1mmol) is dissolved in the aqueous solution of 20 milliliters of alkali, stir after 1.5 hours, dropping acid solution neutralizes, drop to when pH value is less than 2 and stop dripping, stir 3 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, the adjacent benzene dianhydride mixture (yield 90%, GC purity (three isomer) 90%) replaced to corresponding ortho position and position.
(embodiment 2)
Phthalic acid (1mmol) is dissolved in 20 milliliters of aqueous acids by 1, stir after 1.5 hours, pass into bromine gas, react 3 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, after organic phase is separated, aqueous phase extracted with diethyl ether twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the phthalic acid muriate (yield 100%, GC purity (two isomer) 98%) of corresponding ortho position and a position replacement.
Phthalic acid muriate (1mmol) is dissolved in 22 milliliters of Virahols, add alkaline solution, stir after 1.5 hours, drain all solvents, add ether 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase ether is got twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the Methyl Benzene-o-dicarboxylate mixture (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.
Respectively by 50mL1,4-dioxane, the above-mentioned Methyl Benzene-o-dicarboxylate mixture of 10mmol, 1mmol metallic copper powder and 10mL1mol/L dilute hydrochloric acid solution add and are warming up to 60 DEG C after stirring at room temperature 0.5h in the 250mL three-necked flask with condensing works and continue to stir 5h, reacted by TLC tracing detection, until stopped reaction when reaction substrate no longer reduces, reaction solution is cooled, cross and filter metal catalyst, solvent evaporated.Add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, to corresponding biphenyl tetracarboxylic acid ester mixtures (yield 91%, GC purity (three isomer) 95%).
Bibenzene tetracarboxylic mixtures of methyl esters (1mmol) is dissolved in the aqueous solution of 23 milliliters of alkali sodium hydroxide, stir after 1.5 hours, dropping acid solution neutralizes, drop to when pH value is less than 2 and stop dripping, stir 3 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase is merged, siccative dried over sodium sulfate, filtering siccative, solvent evaporated, the adjacent benzene dianhydride mixture (yield 90%, GC purity (three isomer) 90%) replaced to corresponding ortho position and position.
(embodiment 3)
Phthalic acid (1mmol) is dissolved in 20 milliliters of aqueous acids, stir after 1.5 hours, pass into bromine gas, react 3 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, after organic phase is separated, aqueous phase dichloromethane extraction twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the phthalic acid muriate (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.
Phthalic acid muriate (1mmol) is dissolved in 25 milliliters of ethanol, add alkaline solution, stir after 1.5 hours, drain all solvents, add methylene dichloride 50 milliliters, gained solution saturated common salt washes 3 times, after organic phase is separated, and aqueous phase dichloromethane extraction twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the Methyl Benzene-o-dicarboxylate mixture (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.
Respectively by 50mL ether, the above-mentioned Methyl Benzene-o-dicarboxylate mixture of 10mmol, 5mmol metallic zinc powder and 10mL1mol/L dilute hydrochloric acid solution add and are warming up to 60 DEG C after stirring at room temperature 0.5h in the 250mL three-necked flask with condensing works and continue to stir 5h, reacted by TLC tracing detection, until stopped reaction when reaction substrate no longer reduces, reaction solution is cooled, crosses and filter metal catalyst, solvent evaporated.Add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, to corresponding biphenyl tetracarboxylic acid ester mixtures (yield 90%, GC purity (three isomer) 94%).
Bibenzene tetracarboxylic mixtures of methyl esters (1mmol) is dissolved in the aqueous solution of 25 milliliters of alkali potassium hydroxide, stir after 1.5 hours, dropping acid solution neutralizes, drop to when pH value is less than 2 and stop dripping, stir 3 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase is merged, siccative dried over mgso, filtering siccative, solvent evaporated, the adjacent benzene dianhydride mixture (yield 90%, GC purity (three isomer) 92%) replaced to corresponding ortho position and position.
(embodiment 4)
Phthalic acid (1mmol) is dissolved in 20 milliliters of aqueous acids, stir after 1.5 hours, pass into nitric acid, react 3 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, after organic phase is separated, aqueous phase petroleum ether extraction twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the phthalic acid muriate (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.
Phthalic acid muriate (1mmol) is dissolved in 26 milliliters of trimethyl carbinols, add alkaline solution, stir after 1.5 hours, drain all solvents, add sherwood oil 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase sherwood oil is got twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the Methyl Benzene-o-dicarboxylate mixture (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.
Respectively by 50mLN, dinethylformamide, the above-mentioned Methyl Benzene-o-dicarboxylate mixture of 10mmol, 8mmol metallic iron powder and 10mL1mol/L dilute hydrochloric acid solution add and are warming up to 60 DEG C after stirring at room temperature 0.5h in the 250mL three-necked flask with condensing works and continue to stir 5h, reacted by TLC tracing detection, until stopped reaction when reaction substrate no longer reduces, reaction solution is cooled, cross and filter metal catalyst, solvent evaporated.Add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, to corresponding biphenyl tetracarboxylic acid ester mixtures (yield 90%, GC purity (three isomer) 95%).
Bibenzene tetracarboxylic mixtures of methyl esters (1mmol) is dissolved in the aqueous solution of 27 milliliters of alkali calcium hydroxides, stir after 1.5 hours, dropping acid solution neutralizes, drop to when pH value is less than 2 and stop dripping, stir 3 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase merged, siccative calcium chloride is dry, filtering siccative, solvent evaporated, the adjacent benzene dianhydride mixture (yield 90%, GC purity (three isomer) 93%) replaced to corresponding ortho position and a position.
(embodiment 5)
Phthalic acid (1mmol) is dissolved in 20 milliliters of aqueous acids, stir after 1.5 hours, pass into iodine gas, react 3 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, after organic phase is separated, aqueous phase petroleum ether extraction twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the phthalic acid muriate (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.
Phthalic acid muriate (1mmol) is dissolved in 20 ml methanol, add alkaline solution, stir after 1.5 hours, drain all solvents, add sherwood oil 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase sherwood oil is got twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, obtain the Methyl Benzene-o-dicarboxylate mixture (yield 100%, GC purity (two isomer) 99%) of corresponding ortho position and a position replacement.
Respectively by 50mLDMF, the above-mentioned Methyl Benzene-o-dicarboxylate mixture of 10mmol, 6mmol metallic nickel powder and 10mL1mol/L dilute hydrochloric acid solution add and are warming up to 60 DEG C after stirring at room temperature 0.5h in the 250mL three-necked flask with condensing works and continue to stir 5h, reacted by TLC tracing detection, until stopped reaction when reaction substrate no longer reduces, reaction solution is cooled, crosses and filter metal catalyst, solvent evaporated.Add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase is merged, desiccant dryness, filtering siccative, solvent evaporated, to corresponding biphenyl tetracarboxylic acid ester mixtures (yield 90%, GC purity (three isomer) 93%).
Bibenzene tetracarboxylic mixtures of methyl esters (1mmol) is dissolved in the aqueous solution of 20 milliliters of alkali sodium methylates, stir after 1.5 hours, dropping acid solution neutralizes, drop to when pH value is less than 2 and stop dripping, stir 3 hours, drain all solvents, add ethyl acetate 50 milliliters, gained solution saturated common salt washes 3 times, and after organic phase is separated, aqueous phase is extracted with ethyl acetate twice (50mL).Organic phase merged, siccative calcium chloride is dry, filtering siccative, solvent evaporated, the adjacent benzene dianhydride mixture (yield 90%, GC purity (three isomer) 90%) replaced to corresponding ortho position and a position.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. prepare a method for biphenyl dianhydride mixture, the method, for adopting phthalic acid to be starting raw material, carries out electrophilic substitution reaction, generates phthalic acid derivatives; Then carry out esterification, generate phthalic ester; Further catalysis is carried out to phthalic ester, linked reaction occurs, generate biphenyl tetracarboxylic acid ester mixtures; Finally carry out saponification reaction, and after acidifying, generate product biphenyl dianhydride mixture.
2. the method preparing biphenyl dianhydride mixture according to claim 1, is characterized in that: specifically comprise the steps:
(1) adopt phthalic acid to carry out electrophilic substitution reaction, obtain the phthalic acid derivatives that ortho position and a position as general formula (I) replace,
Wherein R
1for one of in bromine, chlorine, iodine, nitro;
(2) phthalic acid derivatives that the ortho position of front step and a position replace is carried out esterification, obtains the ester as general formula (II),
Wherein R
1for one of in bromine, chlorine, iodine, nitro, R
2for one of in methyl, ethyl, sec.-propyl, the tertiary butyl;
(3) under the catalysis of metal, there is linked reaction, generate biphenyl tetracarboxylic acid ester mixtures (III) in the phthalic ester (II) replaced in front step ortho position and a position,
Wherein R
2for one of in methyl, ethyl, sec.-propyl, the tertiary butyl,
Described metal is one of in nickel, zinc, copper, iron;
(4) biphenyl tetracarboxylic acid ester mixtures (III) saponification under the effect of alkali, then acidifying, can generate biphenyl dianhydride mixture (IV);
3. prepare the method for biphenyl dianhydride mixture according to claim 2, it is characterized in that: in the described electrophilic substitution reaction process of described step (1), electrophilic reagent is halogen, Cl
2, Br
2, I
2, a kind of in nitric acid.
4. prepare the method for biphenyl dianhydride mixture according to claim 3, it is characterized in that: in described cationoid reaction process, the usage quantity of electrophilic reagent is 1.1-1.5 times mole of phthalic acid substrate.
5. prepare the method for biphenyl dianhydride mixture according to claim 2, it is characterized in that: in described step (2) esterification reaction process, esterifying reagent is methyl alcohol, ethanol, Virahol, a kind of in the trimethyl carbinol.
6. prepare the method for biphenyl dianhydride mixture according to claim 5, it is characterized in that: in described esterification reaction process, the usage quantity of esterifying reagent is 2.1-3.0 times mole of phthalic acid substrate.
7. prepare the method for biphenyl dianhydride mixture according to claim 2, it is characterized in that: in described metal catalysed reaction process, metal catalyst is nickel, zinc, copper, a kind of in iron, its usage quantity is 0.1-1.0 times mole of phthalic ester substrate.
8. prepare the method for biphenyl dianhydride mixture according to claim 2, it is characterized in that: in described step (4) saponification reaction process, alkali used is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium methylate, a kind of in potassium methylate.
9. prepare the method for biphenyl dianhydride mixture according to claim 8, it is characterized in that: in described saponification reaction process, the usage quantity of alkali is 0.1-10 times mole of phthalic ester substrate.
10. prepare the method for biphenyl dianhydride mixture according to claim 2, it is characterized in that: in described acidification reaction process, acid used is dilute sulphuric acid or dilute hydrochloric acid, and its usage quantity is 1.0-2.0 times mole of phthalic acid substrate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699709A (en) * | 2016-11-28 | 2017-05-24 | 江苏尚莱特医药化工材料有限公司 | Preparation method of 2,2'-bis (trifluoromethyl)-4,4',5,5'-diphenyl dianhydride |
| CN112321550A (en) * | 2020-11-05 | 2021-02-05 | 吉林省亚安新材料有限公司 | Preparation method of aromatic diether dianhydride |
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| JPH07109245A (en) * | 1993-07-30 | 1995-04-25 | Nippon Steel Chem Co Ltd | Production of 4,5-dichlorophthalic acid or salt thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699709A (en) * | 2016-11-28 | 2017-05-24 | 江苏尚莱特医药化工材料有限公司 | Preparation method of 2,2'-bis (trifluoromethyl)-4,4',5,5'-diphenyl dianhydride |
| CN112321550A (en) * | 2020-11-05 | 2021-02-05 | 吉林省亚安新材料有限公司 | Preparation method of aromatic diether dianhydride |
| CN112321550B (en) * | 2020-11-05 | 2023-05-23 | 吉林省亚安新材料有限公司 | Preparation method of aromatic diether dianhydride |
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