CN113461646A - Preparation and separation method of biphenyl dianhydride isomer - Google Patents
Preparation and separation method of biphenyl dianhydride isomer Download PDFInfo
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Abstract
The invention discloses a method for preparing and separating biphenyl dianhydride isomer, which mainly comprises the steps of using nickel salt as a catalyst, using zinc as a reducing agent, in an aprotic solvent system, the mixture of aliphatic 3-chlorophthalimide and aryl 4-chlorophthalimide is used as raw materials for coupling to generate the mixture of the biphenyl dianhydride derivatives, the solubility of the mixture of the aliphatic 3-chlorophthalimide and the aryl 4-chlorophthalimide is utilized to separate the mixture to respectively obtain 3,4 ' -, 3 ' -and 4,4 ' -biphenyl derivatives, the method is characterized in that a simple method for separating the three biphenyl tetracid isomer dianhydride intermediates is established, the problem that three biphenyl tetracid mixtures or three biphenyl dianhydride mixtures are difficult to separate is solved, and pure biphenyl dianhydride isomers are respectively obtained.
Description
Technical Field
The invention relates to a preparation and separation method of biphenyl dianhydride isomer, belonging to the field of synthetic chemistry.
Background
Biphenyltetracarboxylic dianhydride, BPDA for short, is one of the marked dianhydride monomers for synthesizing polyimide materials and is expensive. At present, biphenyl tetracarboxylic dianhydride is industrially prepared mainly by a noble metal palladium catalytic coupling method, related research reports such as patents JP7352749, US5243067, CN201310049837 and the like are high in cost, while asymmetric biphenyl dianhydride 3,4 '-BPDA required by low-viscosity processing characteristics is more than 10 times higher in price than a conventional product 4, 4' -BPDA, and the asymmetric biphenyl dianhydride 3,4 '-BPDA' mainly requires separation from three biphenyl dianhydride mixtures by a traditional synthesis method, and various properties of the 3,4-BPDA 'monomer of the asymmetric biphenyl dianhydride, such as boiling point and solubility, are extremely similar to the isomer 3, 3' of an isomer mixture thereof, so that separation and purification from the isomer mixture cannot be realized, and the application of the asymmetric biphenyl dianhydride is greatly limited. Therefore, the development of a cheap catalytic coupling reaction system for preparing and separating the asymmetric biphenyl dianhydride isomer has important significance.
The preparation of asymmetric biphenyl dianhydride must be carried out by cross-coupling two structurally asymmetric monomers, such as CN1436780A using mixed dimethyl 3-and 4-chlorophthalates or mixed 3-and 4-chlorophthalimides as starting materials to prepare biphenyl dianhydride isomers. In addition to the formation of 3,4 '-biphenyltetracarboxylic acid tetramethyl ester (or 3, 4' -biphenyldiimine), a large number of isomer mixtures of 3,3 '-biphenyltetracarboxylic acid tetramethyl ester (or 3, 3' -biphenyldiimine) and 4,4 '-biphenyltetracarboxylic acid tetramethyl ester (or 4, 4' -biphenyldiimine) are simultaneously produced as symmetrical coupling products. As noted above, both the 3, 4' -and 3, 3-intermediate isomers, and the final dianhydride isomer, are difficult to separate. The reaction system of the method can not obtain the pure products of the three isomers at all, so the method of CN1436780A can not realize industrial production so far.
It is known that 3,3 ', 4, 4' -biphenyltetracarboxylic acid among three isomeric biphenyltetracarboxylic acids is difficult to dissolve in water, and 2,3 ', 3, 4' -biphenyltetracarboxylic acid and 2,2 ', 3, 3' -biphenyltetracarboxylic acid have similar solubility in water and are difficult to separate. And the three kinds of isomeric biphenyl dianhydrides after dehydration have similar solubility and are more difficult to separate and purify. The preparation of the isomeric biphenyl dianhydride pure product by adopting the mixed halogenated phthalic anhydride derivative as the raw material is not carried out on the premise of generating a mixture of 2,3 ', 3, 4' -biphenyltetracarboxylic acid and 2,2 ', 3, 3' -biphenyltetracarboxylic acid, namely, the separation of the preparation intermediates of the two is required to be realized.
Disclosure of Invention
In order to overcome the defects of the existing preparation method of isomeric biphenyl dianhydride, the invention provides a new scheme for preparing and separating the isomer of biphenyl dianhydride, namely, a mixture of aliphatic 3-halogenated phthalimide and aryl 4-halogenated phthalimide is adopted to carry out coupling reaction through molecular design to generate three intermediate mixtures of diphenyl-4, 4 ' -biphenyl diimine (a), 3,4 ' -biphenyl diimine (b) and 3,3 ' -biphenyl diimine (c). The invention discovers that the 3,3 '-biphenyl diimine terminated by the bis-aliphatic amine is very easy to dissolve in aromatic hydrocarbon, and the generated biphenyl diimine a and b with single end and double end protected by aniline are difficult to dissolve in aromatic hydrocarbon, so that the 3, 3' -biphenyl diimine (c) is separated from three intermediates; the mixture a and b which are difficult to dissolve in aromatic hydrocarbon is directly hydrolyzed, the obtained 4,4 '-biphenyl tetracarboxylic acid d is difficult to dissolve in water, and the 3, 4' -biphenyl tetracarboxylic acid e is soluble in hot water, so that the separation of two biphenyl tetracarboxylic acids d and e is realized, and then the mixture is dehydrated into anhydride, and three biphenyl dianhydride isomers are obtained, wherein the purity of the biphenyl dianhydride isomers is more than 98%.
In order to realize the invention task, the invention adopts the following technical scheme:
a method for preparing and separating biphenyl derivatives, which is characterized in that the preparation process is as follows 1:
wherein, the adopted reaction raw materials are shown as the following formulas 2 and 3:
wherein the molar ratio of the two halogenated phthalimide reaction raw materials 2 and 3 is 0.1-1: 0.2-1, the halogen atom of the substituent group is chlorine or bromine, R is a linear chain or branched chain aliphatic hydrocarbon group with the carbon number of 3-5, and R is1Is phenyl;
the catalyst is nickel salt;
the reducing agent is metal zinc;
the additive is one or a mixture of several of the following formulas 4-11:
the preparation and separation method specifically comprises the following steps:
under inert atmosphere, mixing a nickel salt catalyst, a ligand additive, a mixed halogenated phthalimide monomer and a reducing agent such as zinc according to the weight ratio of 0.01-0.02: 0.01-0.28: 1: feeding materials according to a molar ratio of 0.5-1, adding an anhydrous oxygen-free aprotic solvent, controlling the concentration to be 20-30%, stirring at 50-100 ℃ for coupling reaction for 1-10 hours, tracking by thin-layer chromatography, filtering to remove insoluble substances after the reaction is completed, recovering the solvent such as DMAc under reduced pressure, adding aromatic hydrocarbon with the mass more than 4 times that of a reaction monomer into the system, heating and refluxing for 30 minutes, filtering while hot, and collecting insoluble mixtures which are biphenyl diimine a and biphenyl diimine b; cooling the filtrate, collecting precipitate 3,3 '-biphenyl diimine c, performing reflux hydrolysis for 2-24 hours by using 10-20% excess NaOH aqueous solution (concentration-20%), filtering insoluble substances, acidifying by using concentrated hydrochloric acid, adjusting the pH value to be 1, cooling to generate 2, 2', 3,3 '-biphenyl tetracid precipitate, filtering and collecting 2, 2', 3,3 '-biphenyl tetracid, and performing reflux water-carrying by using trimethylbenzene or dehydrating for 4 hours at 200 ℃ to obtain 2, 2', 3,3 '-biphenyl dianhydride (3, 3' -BPDA), wherein the purity is more than 98%. Adding 10-20% excess NaOH aqueous solution (concentration-20%) into insoluble mixture biphenyl diimines a and b, refluxing and hydrolyzing for 2-24 hours, filtering insoluble substances, cooling, acidifying with concentrated hydrochloric acid, adjusting pH to 1, heating to boil, filtering to collect 3,3 ', 4, 4' -biphenyl tetracid (d) insoluble in boiling water, cooling filtrate, precipitating 2,3 ', 3, 4' -biphenyl tetracid (e), filtering to collect 2,3 ', 3, 4' -biphenyl tetracid, dehydrating the obtained 3,3 ', 4, 4' -biphenyl tetracid and 2,3 ', 3, 4' -biphenyl tetracid at 200 ℃ for 4 hours to obtain 3,3 ', 4, 4' -biphenyl dianhydride (4,4 '-BPDA) and 2, 3', 3,4 '-biphenyl dianhydride (3, 4' -BPDA).
Further, the nickel salt is one or a mixture of nickel chloride, nickel bromide, nickel acetate and nickel sulfate, and the molar ratio of the nickel salt to the reactant halophthalimide is 0.01-0.02: 1; the reducing agent is metal zinc, and the molar ratio of the reducing agent to the halophthalimide is (0.5-1): 1.
further, in the molecular structural formula of the additive, R is shown in 4-112～R6Is an alkane having a carbon number of from 0 to 4, R7～R16Is an alkane having a carbon number of from 1 to 6 or a phenyl group; the molar ratio of the nickel salt to the additive is 1: 1 to 7.
Further, a solvent used for the coupling reaction comprises one or a mixture of several of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and N, N-Dimethylacetamide (DMF), and the using amount of the solvent is 3-6 times of the mass of the reaction monomers; the aromatic hydrocarbon refers to xylene, trimethylbenzene or chloro-o-xylene.
The invention has the advantages that:
the invention is characterized in that biphenyl dianhydride intermediates with different solubility properties are prepared by adopting different reaction raw materials through molecular design, and novel methods for preparing and separating the three biphenyl dianhydride intermediates are established, so that compared with the disclosed patent method, the preparation cost of asymmetric biphenyl dianhydride is reduced by more than 50%, and the novel method has important significance for preparing 3, 4' -BPDA pure products.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be described in detail with reference to examples, but the present invention is not limited to the scope of the examples.
Example 1
A500 mL three-necked flask was charged with N-phenyl-4-chlorophthalimide (25.7g, 0.1moL), N-isopropyl-3-chlorophthalimide (22.3g, 0.1moL), zinc powder (6.5g, 0.1moL), and anhydrous NiCl2(255mg, 2mmoL) and triphenylphosphine (0.5g, 2mmoL) were mixed under a nitrogen atmosphere, 140mL of anhydrous DMAc was added, the reaction was stirred at 50 ℃ for 24 hours, insoluble matter was filtered, and 120mL of DMAc as a solvent was recovered from the filtrate under reduced pressure in a round-bottomed flask. 144g of xylene was added to the system and refluxed for 30 minutes, and insoluble N-phenyl-N '-isopropyl-2, 3', 3,4 '-biphenyldiimine (hereinafter, referred to as 3, 4' -biphenyldiimine) and N-phenyl-N '-phenyl-3, 3', 4,4 '-biphenyldiimine (hereinafter, referred to as 4, 4' -biphenyldiimine) were filtered off while hot, and dried at 100 ℃ for 10 hours to obtain 29.5g of a mixture of the two. The filtrate was concentrated to 30mL, cooled to generate a precipitate, collected by filtration, and dried at 100 ℃ for 10 hours to obtain 9g of N-isopropyl-N '-isopropyl-2, 2', 3,3 '-biphenyldiimine (hereinafter collectively referred to as 3, 3' -biphenyldiimine).
Taking 9g of the 3,3 ' -biphenyl diimine, adding 22g of 20% sodium hydroxide aqueous solution, heating and refluxing for 24 hours, filtering out insoluble substances, cooling, adjusting the pH to 1 by concentrated hydrochloric acid, cooling to obtain 2,2 ', 3,3 ' -biphenyl tetracarboxylic acid precipitate, filtering the precipitate, washing for three times by cold water, and dehydrating at 200 ℃ for 4 hours to obtain 6.50g of white 2,2 ', 3,3 ' -biphenyl dianhydride (3,3 ' -BPDA), wherein the white 2,2 ', 3,3 ' -biphenyl dianhydride (3,3 ' -BPDA) accounts for 22% of the total yield of theoretical biphenyl dianhydride isomers, and the melting point 268 and 270 ℃ are respectively adopted.
Taking 29.5g of the mixture of the 4,4 ' -biphenyl diimine and the 3,4 ' -biphenyl diimine, adding 45g of 20% sodium hydroxide aqueous solution, heating and refluxing for 24 hours, filtering out insoluble substances, cooling, adjusting the pH value to be 1 by concentrated hydrochloric acid to obtain 3,3 ', 4,4 ' -biphenyl tetracarboxylic acid and 2,3 ', 3,4 ' -biphenyl tetracarboxylic acid, adding the 3,3 ', 4,4 ' -biphenyl tetracarboxylic acid to be boiled in water, filtering and collecting the insoluble 3,3 ', 4,4 ' -biphenyl tetracarboxylic acid, washing the 3,3 ', 4,4 ' -biphenyl tetracarboxylic acid with water for three times, dehydrating the mixture at 200 ℃ for 4 hours to obtain 6.8g of white 3,3 ', 4,4 ' -biphenyl dianhydride (4,4 ' -BPDA), accounting for 23% of the total yield of the biphenyl dianhydride isomers and having the melting point of 298-; the filtrate containing 2,3 ', 3,4 ' -biphenyltetracarboxylic acid was cooled, filtered, precipitated, washed three times with cold water, and then dehydrated at 200 ℃ for 4 hours to obtain 13.4g of white 2,3 ', 3,4 ' -biphenyldianhydride (3,4 ' -BPDA) in a total yield of 45.5% from the theoretical biphenyldianhydride isomer, and a melting point of 194 and 196 ℃.
Example 2
A500 mL three-necked flask was charged with N-phenyl-4-chlorophthalimide (38.55g, 0.15moL), N-propyl-3-chlorophthalimide (11.2g, 0.05moL), zinc powder (6.5g, 0.1moL), and anhydrous NiCl2(255mg, 2mmoL) and triphenylphosphine (3.5g, 14mmoL) were mixed under a nitrogen atmosphere, 160mL of anhydrous DMAc was added, the reaction was stirred at 100 ℃ for 5 hours, insoluble matter was filtered, and the resulting filtrate was subjected to vacuum recovery of 140mL of the solvent DMAc in a round-bottomed flask. 154g of chloro-o-xylene was added to the system and refluxed for 30 minutes, and the insoluble N-phenyl-N '-butyl-2, 3', 3,4 '-biphenyldiimine (hereinafter collectively referred to as 3, 4' -biphenyldiimine) and N-phenyl-N '-phenyl-3, 3', 4,4 '-biphenyldiimine (hereinafter collectively referred to as 4, 4' -biphenyldiimine) were filtered off while hot, and dried at 100 ℃ for 10 hours to obtain 40g of a mixture of the two. The filtrate was concentrated to 6mL, cooled to generate a precipitate, collected by filtration, and dried at 100 ℃ for 10 hours to obtain 2.1g of N-butyl-N '-butyl-2, 2', 3,3 '-biphenyldiimine (hereinafter collectively referred to as 3, 3' -biphenyldiimine).
Taking 2.1g of the 3,3 '-biphenyl diimine, adding 5g of 20% sodium hydroxide aqueous solution, heating and refluxing for 24 hours, filtering out insoluble substances, cooling, adjusting the pH value to be 1 by concentrated hydrochloric acid, cooling to obtain 2, 2', 3,3 '-biphenyl tetracarboxylic acid precipitate, filtering the precipitate, washing for three times by cold water, refluxing and dehydrating for 4 hours by trimethylbenzene to obtain 1.4g of white 2, 2', 3,3 '-biphenyl dianhydride (3, 3' -BPDA), wherein the yield accounts for 4.7% of the total yield of the biphenyl dianhydride isomers, and the melting point 268 and 270 ℃.
Taking 40g of the mixture of the 4,4 ' -biphenyl diimine and the 3,4 ' -biphenyl diimine, adding 72g of 20% sodium hydroxide aqueous solution, heating and refluxing for 24 hours, filtering out insoluble substances, cooling, adjusting the pH value to be 1 by concentrated hydrochloric acid to obtain 3,3 ', 4,4 ' -biphenyl tetracarboxylic acid and 2,3 ', 3,4 ' -biphenyl tetracarboxylic acid, adding the 3,3 ', 4,4 ' -biphenyl tetracarboxylic acid to be boiled in water, filtering and collecting the insoluble 3,3 ', 4,4 ' -biphenyl tetracarboxylic acid, washing the obtained solution for three times by water, dehydrating the obtained solution at 200 ℃ for 4 hours to obtain 15.5g of white 3,3 ', 4,4 ' -biphenyl dianhydride (4,4 ' -BPDA), wherein the yield accounts for 52.7% of the total isomers of the biphenyl dianhydride, and the melting point is 298-; the filtrate containing 2,3 ', 3,4 ' -biphenyltetracarboxylic acid was cooled, precipitated by filtration, washed three times with cold water, and then dehydrated at 200 ℃ for 4 hours to obtain 10.4g of white 2,3 ', 3,4 ' -biphenyldianhydride (3,4 ' -BPDA) in a total yield of 35.3% based on the biphenyldianhydride isomer, a melting point of 194-.
Example 3
A500 mL three-necked flask was charged with N-phenyl-4-chlorophthalimide (25.7g, 0.1moL), N-propyl-3-chlorophthalimide (22.3g, 0.1moL), zinc powder (13g, 0.2moL), and anhydrous NiCl2(510mg, 4mmoL) and 2, 2-bipyridine (2.18g, 14mmoL) were mixed under a nitrogen atmosphere, 140mL of anhydrous NMP was added thereto, the reaction was stirred at 90 ℃ for 8 hours, insoluble matter was filtered, and 120mL of NMP as a solvent was recovered from the filtrate under reduced pressure in a round-bottomed flask. 144g of trimethylbenzene was added to the system and refluxed for 30 minutes, and insoluble N-phenyl-N '-isopropyl-2, 3', 3,4 '-biphenyldiimine (hereinafter, referred to as 3, 4' -biphenyldiimine) and N-phenyl-N '-phenyl-3, 3', 4,4 '-biphenyldiimine (hereinafter, referred to as 4, 4' -biphenyldiimine) were filtered off while hot, and the mixture was dried at 100 ℃ for 10 hours to obtain 30.5g of a mixture of the two. The filtrate was concentrated to 40mL, cooled to generate a precipitate, collected by filtration, and dried at 100 ℃ for 10 hours to obtain 9.1g of N-isopropyl-N '-isopropyl-2, 2', 3,3 '-biphenyldiimine (hereinafter collectively referred to as 3, 3' -biphenyldiimine).
Taking 9.1g of the 3,3 '-biphenyl diimine, adding 22g of 20% sodium hydroxide aqueous solution, heating and refluxing for 24 hours, filtering out insoluble substances, cooling, adjusting the pH value to be 1 by concentrated hydrochloric acid, cooling to obtain 2, 2', 3,3 '-biphenyl tetracarboxylic acid precipitate, filtering the precipitate, washing for three times by cold water, dehydrating for 4 hours at 200 ℃ to obtain 6.6g of white 2, 2', 3,3 '-biphenyl dianhydride (3, 3' -BPDA), wherein the yield accounts for 22.3% of the total theoretical biphenyl dianhydride isomer, and the melting point is 268 and 270 ℃.
Taking 30.5g of the mixture of the 4,4 '-biphenyl diimine and the 3, 4' -biphenyl diimine, adding 45g of 20% sodium hydroxide aqueous solution, heating and refluxing for 24 hours, filtering out insoluble substances, cooling, adjusting the pH value to be 1 by concentrated hydrochloric acid to obtain 3,3 ', 4, 4' -biphenyl tetracarboxylic acid and 2,3 ', 3, 4' -biphenyl tetracarboxylic acid, adding the 3,3 ', 4, 4' -biphenyl tetracarboxylic acid to be boiled in water, filtering and collecting the insoluble 3,3 ', 4, 4' -biphenyl tetracarboxylic acid, washing the 3,3 ', 4, 4' -biphenyl tetracarboxylic acid with water for three times, dehydrating the mixture at 200 ℃ for 4 hours to obtain 6.9g of white 3,3 ', 4, 4' -biphenyl dianhydride (4,4 '-BPDA), wherein the white 3,4, 4' -biphenyl dianhydride accounts for 23.3% of the total yield of biphenyl dianhydride isomers, and the melting point of 298-; the filtrate containing 2,3 ', 3,4 ' -biphenyltetracarboxylic acid was cooled, filtered, precipitated, washed three times with cold water, and then dehydrated at 200 ℃ for 4 hours to obtain 13.8g of white 2,3 ', 3,4 ' -biphenyldianhydride (3,4 ' -BPDA) in a percentage of 46.5% of the total yield of theoretical biphenyldianhydride isomers, and a melting point of 194 and 196 ℃.
The preparation and separation methods of a biphenyl dianhydride isomer provided by the present invention are described in detail above, and the principle and the embodiments of the present invention are illustrated herein by using specific examples, and the above description of the examples is only for helping understanding the method of the present invention and the core concept thereof, and it should be noted that, for those skilled in the art, many modifications and modifications can be made without departing from the principle of the present invention, and the modifications and modifications also belong to the full protection scope of the present invention.
Claims (4)
1. A method for preparing and separating biphenyl dianhydride isomer is characterized in that the preparation process is as the following formula 1:
wherein, the adopted reaction raw materials are shown as the following formulas 2 and 3:
wherein the molar ratio of the two halophthalimide reaction raw materials 2 and 3 is 0.1-1: 0.2-1, the substituent halogen atom (X) is chlorine or bromine, R is a linear or branched aliphatic hydrocarbon group with 3-5 carbons, R is1Is phenyl;
the catalyst is nickel salt;
the reducing agent is metal zinc;
the additive is one or a mixture of several of the following formulas 4-11:
the preparation and separation method specifically comprises the following steps: under the protection of nitrogen, stirring amino halogenated phthalimide monomer, nickel salt catalyst, aprotic solvent and additive reducing agent at 50-100 ℃ for coupling reaction for 1-10 hours, filtering to remove insoluble substances, decompressing and recovering solvent such as DMAc, adding aromatic hydrocarbon with the mass more than 4 times of that of the reaction monomer into the system, heating and refluxing for 30 minutes, filtering while hot, and collecting insoluble mixture as biphenyl diimine a and b; cooling the filtrate, collecting precipitate 3,3 '-biphenyl diimine c, performing reflux hydrolysis for 2-24 hours by using 10-20% excess NaOH aqueous solution (concentration-20%), filtering insoluble substances, acidifying by using concentrated hydrochloric acid, adjusting the pH value to be 1, cooling to generate 2, 2', 3,3 '-biphenyl tetracid precipitate, filtering and collecting 2, 2', 3,3 '-biphenyl tetracid, and performing reflux water-carrying by using trimethylbenzene or dehydrating for 4 hours at 200 ℃ to obtain 2, 2', 3,3 '-biphenyl dianhydride (3, 3' -BPDA), wherein the purity is more than 98%. Adding 10-20% excess NaOH aqueous solution (concentration-20%) into insoluble mixture biphenyl diimines a and b, refluxing and hydrolyzing for 2-24 hours, filtering insoluble substances, cooling, acidifying with concentrated hydrochloric acid, adjusting pH to 1, heating to boil, filtering to collect 3,3 ', 4, 4' -biphenyl tetracid (d) insoluble in boiling water, cooling filtrate, precipitating 2,3 ', 3, 4' -biphenyl tetracid (e), filtering to collect 2,3 ', 3, 4' -biphenyl tetracid, dehydrating the obtained 3,3 ', 4, 4' -biphenyl tetracid and 2,3 ', 3, 4' -biphenyl tetracid at 200 ℃ for 4 hours to obtain 3,3 ', 4, 4' -biphenyl dianhydride (4,4 '-BPDA) and 2, 3', 3,4 '-biphenyl dianhydride (3, 4' -BPDA).
2. The method for preparing and separating the isomers of biphenyl dianhydride according to claim 1, wherein the nickel salt is one or a mixture of nickel chloride, nickel bromide, nickel acetate and nickel sulfate, and the molar ratio of the nickel salt to the reactant halophthalimide is 0.01-0.02: 1; the reducing agent is metal zinc, and the molar ratio of the reducing agent to the halophthalimide is (0.5-1): 1.
3. the method for preparing and separating biphenyl dianhydride isomers according to claim 1, wherein R in the molecular structural formula 4-11 of the additive is2～R6Is an alkane having a carbon number of from 0 to 4, R7～R16Is an alkane having a carbon number of from 1 to 6 or a phenyl group; the molar ratio of the nickel salt to the additive is 1: 1 to 7.
4. The method for preparing and separating the biphenyl dianhydride isomer according to claim 1, wherein the solvent used in the coupling reaction comprises one or a mixture of several of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and N, N-Dimethylacetamide (DMF), and the amount of the solvent is 3-6 times of the mass of the reaction monomers; the aromatic hydrocarbon refers to xylene, trimethylbenzene or chloro-o-xylene.
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| US5384413A (en) * | 1992-07-10 | 1995-01-24 | Hoechst Aktiengesellschaft | Process for the preparation of tetrafluorophthalic acid and/or tetrafluorophthalic anhydride |
| CN1436780A (en) * | 2003-03-03 | 2003-08-20 | 中国科学院长春应用化学研究所 | Prepn process of 2,3,3',4'-diphenyl tetraformic dianhydride and its derivative |
| CN101481366A (en) * | 2008-12-29 | 2009-07-15 | 中国科学院长春应用化学研究所 | Preparation of 2,3,3',4'-biphenyl-tetracarboxylic acid dianhydride and derivatives thereof |
| CN104262234A (en) * | 2014-09-18 | 2015-01-07 | 哈尔滨工业大学（威海） | Preparation method of biphenyl derivatives |
| US20200290945A1 (en) * | 2017-11-22 | 2020-09-17 | Exxonmobil Chemical Patents Inc. | Preparation and Purification of Biphenyldicarboxylic Acids |
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2021
- 2021-08-03 CN CN202110888553.5A patent/CN113461646B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5384413A (en) * | 1992-07-10 | 1995-01-24 | Hoechst Aktiengesellschaft | Process for the preparation of tetrafluorophthalic acid and/or tetrafluorophthalic anhydride |
| CN1436780A (en) * | 2003-03-03 | 2003-08-20 | 中国科学院长春应用化学研究所 | Prepn process of 2,3,3',4'-diphenyl tetraformic dianhydride and its derivative |
| CN101481366A (en) * | 2008-12-29 | 2009-07-15 | 中国科学院长春应用化学研究所 | Preparation of 2,3,3',4'-biphenyl-tetracarboxylic acid dianhydride and derivatives thereof |
| CN104262234A (en) * | 2014-09-18 | 2015-01-07 | 哈尔滨工业大学（威海） | Preparation method of biphenyl derivatives |
| US20200290945A1 (en) * | 2017-11-22 | 2020-09-17 | Exxonmobil Chemical Patents Inc. | Preparation and Purification of Biphenyldicarboxylic Acids |
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