CN113461646B - 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 preparation and separation method of biphenyl dianhydride isomers, which mainly comprises the steps of taking nickel salt as a catalyst, taking zinc as a reducing agent, coupling aliphatic 3-chlorophthalimide and aryl 4-chlorophthalimide mixture as raw materials in an aprotic solvent system to generate a biphenyl dianhydride derivative mixture, separating by utilizing the difference of the solubility of the three to respectively obtain 3,4' -, 3' -and 4,4' -biphenyl derivatives, and respectively obtaining three biphenyl dianhydride isomers after hydrolysis and dehydration.
Description
Technical Field
The invention relates to a preparation and separation method of biphenyl dianhydride isomer, belonging to the category of synthetic chemistry.
Background
The biphenyl tetracarboxylic dianhydride is called BPDA for short, is one of the marked dianhydride monomers for synthesizing polyimide materials, and has high price. At present, the biphenyl tetracarboxylic dianhydride is industrially prepared by mainly adopting a noble metal palladium catalytic coupling method, related researches report that the cost is high as in patent JP7352749, US5243067, CN201310049837 and the like, and the asymmetric biphenyl dianhydride 3,4'-BPDA required by the low-viscosity processing characteristic is more than 10 times more than that of the conventional product 4,4' -BPDA, and the conventional synthesis method mainly needs to separate the asymmetric biphenyl dianhydride 3,4-BPDA 'from a three-biphenyl dianhydride mixture, and various properties of the asymmetric biphenyl dianhydride 3,4-BPDA' monomer, such as boiling point and solubility, are extremely similar to those of the isomer mixture 3,3', so that the separation and purification of the asymmetric biphenyl dianhydride 3,4' -BPDA 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 the unsymmetrical biphenyl dianhydride must be carried out by cross-coupling of two structurally unsymmetrical monomers, such as CN1436780a, using mixed dimethyl 3-and 4-chlorophthalide or mixed 3-and 4-chlorophthalimide as starting materials to prepare the biphenyl dianhydride isomer. In addition to the formation of tetramethyl 3,4 '-biphenyltetracarboxylic acid (or 3,4' -biphenylbisimine), a large number of two isomer mixtures of symmetrical coupling products, tetramethyl 3,3 '-biphenyltetracarboxylic acid (or 3,3' -biphenylbisimine) and tetramethyl 4,4 '-biphenyltetracarboxylic acid (or 4,4' -biphenylbisimine), are produced. As described above, both the 3,4' -and 3, 3-intermediate isomers, as well as the final dianhydride isomer, are difficult to separate. The reaction system of the method cannot obtain pure products of three isomers at all, so the method of CN1436780A cannot realize industrial production to date.
It is known that among three isomeric biphenyltetracarboxylic acids, 3', 4' -biphenyltetracarboxylic acid is difficult to dissolve in water, and 2,3',3,4' -biphenyltetracarboxylic acid and 2,2', 3' -biphenyltetracarboxylic acid have similar solubilities in water, and are difficult to separate. And the three isomerism biphenyl dianhydrides after dehydration have similar solubility, and are more difficult to separate and purify. The precondition of preparing pure product of isomerism biphenyl dianhydride by adopting mixed halogenated phthalic anhydride derivative as raw material can not generate mixture of 2,3',3,4' -biphenyl tetracarboxylic acid and 2,2', 3' -biphenyl tetracarboxylic acid, that is, separation of the two preparation intermediates must be realized.
Disclosure of Invention
In order to overcome the defects in the existing preparation method of the isomerism biphenyl dianhydride, the invention provides a new scheme for preparing and separating biphenyl dianhydride isomers, namely, a mixture of aliphatic 3-halophthalimide and aryl 4-halophthalimide is adopted for coupling reaction through molecular design, and the generated mixture of three intermediates, namely, biphenyl-4, 4' -biphenyl bisimine (a), 3,4' -biphenyl bisimine (b) and 3,3' -biphenyl bisimine (c). The invention discovers that 3,3 '-biphenyl bisimine blocked by the double fatty amine is very easy to dissolve in aromatic hydrocarbon, and the generated single end and double end contain biphenyl bisimine a and b with aniline protection are difficult to dissolve in aromatic hydrocarbon, so that the separation of 3,3' -biphenyl bisimine (c) from three intermediates is realized; the mixture a and b which is 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 dissolved in hot water, so that the separation of the two biphenyl tetracarboxylic acids d and e is realized, and then the dehydration is carried out to form anhydride, thereby obtaining three biphenyl dianhydride isomers, and the purity reaches more than 98 percent.
In order to realize the task of the invention, the invention adopts the following technical scheme:
a preparation and separation method of biphenyl derivatives, which is characterized in that the preparation process is as follows in formula 1:
wherein the following reaction materials are used:
wherein the mol ratio of the two halophthalimide reaction raw materials 2 and 3 is 0.1-1:0.2-1, the substituent halogen atom is chlorine or bromine, R is straight-chain or branched-chain aliphatic hydrocarbon group with 3-5 carbon atoms, R 1 Is phenyl;
the catalyst is nickel salt;
the reducing agent is metallic 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, nickel salt catalyst, ligand additive, mixed halogenated phthalimide monomer and reducing agent such as zinc according to the proportion of 0.01-0.02: 0.01 to 0.28:1: adding 0.5-1 mol ratio, adding anhydrous anaerobic 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 solvent such as DMAc under reduced pressure, adding aromatic hydrocarbon with the mass of more than 4 times of that of a reaction monomer into a system, heating and refluxing for 30 minutes, filtering while the mixture is hot, and collecting the insoluble mixture as biphenylbisimine a and b; and cooling the filtrate to collect and precipitate 3,3' -biphenylbisimine c, carrying out reflux hydrolysis on the 3,3' -biphenylbisimine c for 2-24 hours by using 10-20% excess NaOH aqueous solution (the concentration is 20%), filtering insoluble matters, acidifying by using concentrated hydrochloric acid, adjusting the pH value to be 1, cooling to generate 2,2', 3' -biphenyltetracarboxylic acid precipitate, filtering and collecting 2,2', 3' -biphenyltetracarboxylic acid, carrying out water by trimethyl benzene reflux or dehydrating at 200 ℃ for 4 hours, and obtaining the 2,2', 3' -biphenyldianhydride (3, 3' -BPDA) with the purity of more than 98%. Adding 10-20% NaOH aqueous solution (concentration-20%) into the insoluble mixture of biphenylbisimine a and b, carrying out reflux hydrolysis for 2-24 hours, filtering insoluble matters, cooling, acidifying with concentrated hydrochloric acid, adjusting pH to be 1, heating and boiling, filtering and collecting 3,3', 4' -biphenyltetracarboxylic acid (d) insoluble in boiling water, cooling filtrate, separating out 2,3',3,4' -biphenyltetracarboxylic acid (e), filtering and collecting 2,3',3,4' -biphenyltetracarboxylic acid, respectively dehydrating the obtained 3,3', 4' -biphenyltetracarboxylic acid and 2,3',3,4' -biphenyltetracarboxylic acid at 200 ℃ for 4 hours to obtain 3,3', 4' -biphenyldianhydride (4, 4 '-BPDA) and 2,3',3,4 '-biphenyldianhydride (3, 4' -BPDA).
Further, the nickel salt is one or a mixture of a plurality 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, a step of; the reducer is metallic zinc, and the mol ratio of the reducer to the halophthalimide is 0.5-1: 1.
further, in the molecular structural formulas 4-11 of the additive, R 2 ～R 6 Is an alkane of carbon number from 0 to 4, R 7 ～R 16 Is an alkane or phenyl group having from 1 to 6 carbon atoms; the molar ratio of the nickel salt to the additive is 1:1 to 7.
Further, the solvent used in the coupling reaction comprises one or a mixture of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and N, N-Dimethylacetamide (DMF), and the use amount of the solvent is 3-6 times of the mass of the reaction monomers; the arene refers to dimethylbenzene, trimethylbenzene or chloro-o-xylene.
The invention has the advantages that:
the invention is characterized in that different reaction raw materials are adopted to prepare biphenyl dianhydride intermediates with different dissolution properties, a new preparation and separation method for three biphenyl dianhydride intermediates is established, the preparation cost of the asymmetric biphenyl dianhydride is reduced by more than 50% compared with the disclosed patent method, the method has important significance for the preparation of 3,4' -BPDA pure products, the invention provides a new preparation and separation method for biphenyl dianhydride isomers, and the total yield of the three isomers is 85% -95%, and the yield is high.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be specifically described with reference to examples, but the present invention is not limited to the scope of the examples.
Example 1
Taking 500mL three-necked flask, and carrying out N-phenyl-4-chloroPhthalimide (25.7 g,0.1 mL), N-isopropyl-3-chlorophthalimide (22.3 g,0.1 mL), zinc powder (6.5 g,0.1 mL), anhydrous NiCl 2 (255 mg,2 mmol) and triphenylphosphine (0.5 g,2 mmol) were mixed under nitrogen, 140mL of anhydrous DMAc was added, the reaction was stirred at 50℃for 24 hours, the insoluble matter was filtered, and the resulting filtrate was recovered under reduced pressure in a round-bottomed flask as 120mL of solvent DMAc. 144g of xylene was added to the system and refluxed for 30 minutes, and insoluble matters N-phenyl-N '-isopropyl-2, 3',3,4 '-biphenylbisimine (collectively: 3,4' -biphenylbisimine) and N-phenyl-N '-phenyl-3, 3',4 '-biphenylbisimine (collectively: 4,4' -biphenylbisimine) were filtered off while they were still hot, and dried at 100℃for 10 hours, to obtain 29.5g of a mixture of both. The filtrate was concentrated to 30mL, cooled to form a precipitate, collected by filtration, and dried at 100℃for 10 hours to obtain 9g of N-isopropyl-N '-isopropyl-2, 2',3 '-biphenylbisimine (collectively: 3,3' -biphenylbisimine).
9g of the 3,3 '-biphenylbisimine is taken, 22g of 20% sodium hydroxide aqueous solution is added, heated and refluxed for 24 hours, insoluble matters are filtered, cooled, pH=1 is regulated by concentrated hydrochloric acid, 2',3 '-biphenyltetracarboxylic acid precipitate is obtained by cooling, the precipitate is filtered and washed three times by cold water, and dehydration is carried out at 200 ℃ for 4 hours, thus obtaining 6.50g of white 2,2',3 '-biphenyldianhydride (3, 3' -BPDA) which accounts for 22% of the total yield of the theoretical biphenyldianhydride isomer, and the melting point is 268-270 ℃.
29.5g of the mixture of the 4,4' -biphenylbisimine and the 3,4' -biphenylbisimine is taken, 45g of 20 percent aqueous sodium hydroxide solution is added, heated and refluxed for 24 hours, insoluble matters are filtered out, cooled, the pH=1 is regulated by concentrated hydrochloric acid to obtain 3,3', 4' -biphenyltetracarboxylic acid and 2,3',3,4' -biphenyltetracarboxylic acid, the 3,3', 4' -biphenyltetracarboxylic acid and the insoluble 3,3', 4' -biphenyltetracarboxylic acid are added into water for boiling, filtered and collected, washed for three times, dehydrated for 4 hours at 200 ℃, and 6.8g of white 3,3', 4' -biphenyldianhydride (4, 4' -BPDA) is obtained, the total yield of the biphenyldianhydride isomer is 23 percent, and the melting point is 298-300 ℃; the filtrate containing 2,3',3,4' -biphenyltetracarboxylic acid was cooled, filtered and precipitated, washed three times with cold water, and dehydrated at 200℃for 4 hours to obtain 13.4g of white 2,3',3,4' -biphenyldianhydride (3, 4' -BPDA) in 45.5% of the total yield of the theoretical biphenyldianhydride isomer and a melting point of 194-196 ℃.
Example 2
500mL of a three-necked flask was used to obtain N-phenyl-4-chlorophthalimide (38.55 g,0.15 mol), N-propyl-3-chlorophthalimide (11.2 g,0.05 mol), zinc powder (6.5 g,0.1 mol), and anhydrous NiCl 2 (255 mg,2 mmol) and triphenylphosphine (3.5 g,14 mmoL) were mixed under nitrogen, 160mL of anhydrous DMAc was added thereto, the reaction was stirred at 100℃for 5 hours, the insoluble matter was filtered, and 140mL of the solvent DMAc was recovered under reduced pressure from the obtained filtrate in a round-bottomed flask. 154g of chloro-o-xylene is added to the system and refluxed for 30 minutes, and insoluble N-phenyl-N '-butyl-2, 3',3,4 '-biphenylbisimine (collectively: 3,4' -biphenylbisimine) and N-phenyl-N '-phenyl-3, 3',4 '-biphenylbisimine (collectively: 4,4' -biphenylbisimine) are filtered out while they are 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 form a precipitate, collected by filtration, and dried at 100℃for 10 hours to obtain 2.1g of N-butyl-N '-butyl-2, 2',3 '-biphenylbisimine (collectively: 3,3' -biphenylbisimine).
Taking 2.1g of the 3,3 '-biphenylbisimine, adding 5g of 20% sodium hydroxide aqueous solution, heating and refluxing for 24 hours, filtering insoluble matters, cooling, regulating the pH value to be 1 by concentrated hydrochloric acid, cooling to obtain 2,2',3 '-biphenyltetracarboxylic acid precipitate, filtering the precipitate, washing the precipitate with cold water for three times, refluxing and dehydrating trimethylbenzene for 4 hours to obtain 1.4g of white 2,2',3 '-biphenyldianhydride (3, 3' -BPDA) accounting for 4.7% of total yield of biphenyldianhydride isomer, and melting point of 268-270 ℃.
Taking 40g of the mixture of the 4,4' -biphenylbisimine and the 3,4' -biphenylbisimine, adding 72g of 20% sodium hydroxide aqueous solution, heating and refluxing for 24 hours, filtering insoluble substances, cooling, regulating the pH value to be 1 by concentrated hydrochloric acid to obtain 3,3', 4' -biphenyltetracarboxylic acid and 2,3',3,4' -biphenyltetracarboxylic acid, adding the 3,3', 4' -biphenyltetracarboxylic acid into water for boiling, filtering and collecting insoluble 3,3', 4' -biphenyltetracarboxylic acid, washing for three times, dehydrating at 200 ℃ for 4 hours to obtain 15.5g of white 3,3', 4' -biphenyldianhydride (4, 4' -BPDA), wherein the total yield of the biphenyldianhydride isomer is 52.7%, and the melting point is 298-300 ℃; the filtrate containing 2,3',3,4' -biphenyltetracarboxylic acid was cooled, filtered and precipitated, washed with cold water three times, and dehydrated at 200℃for 4 hours to obtain 10.4g of white 2,3',3,4' -biphenyldianhydride (3, 4' -BPDA) accounting for 35.3% of the total yield of biphenyldianhydride isomers, melting point 194-196 ℃.
Example 3
500mL three-necked flask was used to obtain N-phenyl-4-chlorophthalimide (25.7 g,0.1 mL), N-propyl-3-chlorophthalimide (22.3 g,0.1 mL), zinc powder (13 g,0.2 mL), and anhydrous NiCl 2 (510 mg,4 mmoL) and 2, 2-bipyridine (2.18 g,14 mmoL) were mixed under a nitrogen atmosphere, 140mL of anhydrous NMP was then added, the mixture was stirred at 90℃for 8 hours, the insoluble matter was filtered, and the resulting filtrate was recovered under reduced pressure in a round-bottomed flask as 120mL of NMP solvent. 144g of trimethylbenzene was added to the system and refluxed for 30 minutes, and insoluble matters N-phenyl-N '-isopropyl-2, 3',3,4 '-biphenylbisimine (collectively: 3,4' -biphenylbisimine) and N-phenyl-N '-phenyl-3, 3',4 '-biphenylbisimine (collectively: 4,4' -biphenylbisimine) were filtered out while they were still hot, and dried at 100℃for 10 hours, to obtain 30.5g of a mixture of both. The filtrate was concentrated to 40mL, cooled to form a precipitate, collected by filtration, and dried at 100℃for 10 hours to give 9.1g of N-isopropyl-N '-isopropyl-2, 2',3 '-biphenylbisimine (collectively: 3,3' -biphenylbisimine).
Taking 9.1g of the 3,3 '-biphenylbisimine, adding 22g of 20% sodium hydroxide aqueous solution, heating and refluxing for 24 hours, filtering insoluble matters, cooling, regulating the pH value to be 1 by concentrated hydrochloric acid, cooling to obtain 2,2',3 '-biphenyltetracarboxylic acid precipitate, filtering the precipitate, washing the precipitate with cold water for three times, and dehydrating the precipitate at 200 ℃ for 4 hours to obtain 6.6g of white 2,2',3 '-biphenyldianhydride (3, 3' -BPDA) with the total yield of theoretical biphenyldianhydride isomer of 22.3 percent and the melting point of 268-270 ℃.
Taking 30.5g of the mixture of the 4,4' -biphenylbisimine and the 3,4' -biphenylbisimine, adding 45g of 20% sodium hydroxide aqueous solution, heating and refluxing for 24 hours, filtering insoluble substances, cooling, regulating the pH value to be 1 by concentrated hydrochloric acid to obtain 3,3', 4' -biphenyltetracarboxylic acid and 2,3',3,4' -biphenyltetracarboxylic acid, adding the mixture into water for boiling, filtering and collecting insoluble 3,3', 4' -biphenyltetracarboxylic acid, washing for three times, dehydrating at 200 ℃ for 4 hours to obtain 6.9g of white 3,3', 4' -biphenyldianhydride (4, 4' -BPDA) accounting for 23.3% of total yield of biphenyldianhydride isomer and having a melting point of 298-300 ℃; the filtrate containing 2,3',3,4' -biphenyltetracarboxylic acid was cooled, filtered and precipitated, washed three times with cold water, and dehydrated at 200℃for 4 hours to obtain 13.8g of white 2,3',3,4' -biphenyldianhydride (3, 4' -BPDA) in 46.5% of the total yield of the theoretical biphenyldianhydride isomer, and a melting point of 194-196 ℃.
The preparation and separation method of the biphenyl dianhydride isomer provided by the invention are described in detail, and specific examples are used herein to illustrate the principles and embodiments of the invention, and the above examples are only for aiding in understanding of the method and core idea of the invention, and it should be pointed out that, for those skilled in the art, several improvements and modifications can be made to the invention without departing from the scope of the invention.
Claims (4)
1. A preparation and separation method of biphenyl dianhydride isomer comprises the following preparation process of formula 1:
the reaction materials used are of the following formulas 2 and 3:
the molar ratio of the two halophthalimide reaction raw materials 2 and 3 is 0.1-1:0.2-1, the substituent X is chlorine or bromine, R is straight-chain or branched-chain aliphatic hydrocarbon group with 3-5 carbons, R 1 Is phenyl;
the catalyst is nickel salt;
the reducing agent is metallic zinc;
the aprotic solvent is one or a mixture of several of N, N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP);
the additive is one or a mixture of several of the following formulas 4-11:
in the molecular structural formulas 4-11 of the additive, R 2 ～R 6 Is an alkyl group having from 0 to 4 carbon atoms, R 7 ～R 16 Is an alkyl group having 1 to 6 carbon atoms or a phenyl group;
the preparation and separation process is as follows: under the protection of nitrogen, stirring a halophthalimide monomer, a nickel salt catalyst, an aprotic solvent, an additive and a reducing agent at 50-100 ℃ for coupling reaction for 1-10 hours, filtering to remove insoluble substances, recovering the solvent under reduced pressure, adding aromatic hydrocarbon with the mass of more than 4 times that of the halophthalimide monomer into a system, wherein the aromatic hydrocarbon is any one of dimethylbenzene, trimethylbenzene or chloro-o-xylene, heating and refluxing for 30 minutes, filtering while the mixture is hot, and collecting insoluble mixtures of biphenyl diimine a and biphenyl diimine b; cooling the filtrate to collect precipitate 3,3 '-biphenylbisimine c, refluxing and hydrolyzing the 3,3' -biphenylbisimine c for 2-24 hours by using an aqueous solution of NaOH with an excessive amount of 10-20% and a concentration of 20%, filtering insoluble matters, acidifying the insoluble matters by using concentrated hydrochloric acid, adjusting the pH value to be 1, cooling to generate 2,2', 3' -biphenyltetracarboxylic acid precipitate, filtering and collecting the 2,2', 3' -biphenyltetracarboxylic acid, and dehydrating the 2,2', 3' -biphenyldianhydride (3, 3 '-BPDA) for 4 hours by using trimethylbenzene to carry water or at 200 ℃ to obtain the 2,2',3 '-biphenyldianhydride (3, 3' -BPDA) with the purity of more than 98%; adding 10-20% excess NaOH aqueous solution with concentration of 20% into the insoluble mixture biphenyl bisimine a and b, refluxing and hydrolyzing for 2-24 hours, filtering insoluble matters, cooling, acidifying with concentrated hydrochloric acid, adjusting to pH=1, heating and boiling, filtering and collecting 3,3', 4' -biphenyl tetraoic acid shown in a formula d insoluble in boiling water, cooling filtrate, separating out 2,3',3,4' -biphenyl tetraoic acid shown in a formula e, and filtering and collecting 2,3',3,4' -biphenyl tetraoic acid; the obtained 3,3', 4' -biphenyltetracarboxylic acid and 2,3',3,4' -biphenyltetracarboxylic acid were dehydrated at 200℃for 4 hours to obtain 3,3', 4' -biphenyldianhydride (4, 4 '-BPDA) and 2,3',3,4 '-biphenyldianhydride (3, 4' -BPDA), respectively.
2. The preparation and separation method of biphenyl dianhydride isomer 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, a step of; the mol ratio of the reducing agent to the halogenated phthalimide is 0.5-1: 1.
3. the method for preparing and separating biphenyl dianhydride isomer according to claim 1, wherein the molar ratio of the nickel salt to the additive is 1:1 to 7.
4. The method for preparing and separating biphenyl dianhydride isomer according to claim 1, wherein the aprotic solvent used in the coupling reaction is 3-6 times of the mass of the halogenated phthalimide reaction monomer.
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| CN1215068C (en) * | 2003-03-03 | 2005-08-17 | 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 |
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