CN113582954A - Method for preparing biphenyl dianhydride based on metal coordination halogenated phthalimide monomer coupling - Google Patents
Method for preparing biphenyl dianhydride based on metal coordination halogenated phthalimide monomer coupling Download PDFInfo
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- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
The invention discloses a method for preparing biphenyl dianhydride by coupling halogenated phthalimide monomers based on metal coordination. The main content includes using halogenated phthalimide with complexing coordination capacity as raw material, zinc or magnesium as reducing agent, nickel salt as catalyst, coupling reaction in non-proton solvent system to produce biphenyl derivative, hydrolysis and dewatering to produce anhydride. The invention adopts halogenated monomer with coordination function, and the halogenated monomer and the byproduct zinc halide generated by the reaction form organic metal complex which is dissolved in a reaction system, thereby avoiding the reduction capability reduction caused by the deposition of the halogenated monomer on the metal surface of the reducing agent. Compared with the traditional preparation reaction of the same kind of biphenyl dianhydride, the reducing agent of the invention is close to quantitative reaction and is more suitable for industrialization.
Description
Technical Field
The invention relates to a method for preparing biphenyl dianhydride by coupling halogenated phthalimide monomers based on metal coordination, belonging to the technical field of synthetic chemistry.
Background
Biphenyltetracarboxylic dianhydride, BPDA for short, is one of the marked dianhydride monomers for synthesizing polyimide materials with heat resistance, insulation, high strength and stable dimension. At present, biphenyl tetracarboxylic dianhydride is mainly prepared by a noble metal catalytic coupling method, and the cost is high, so that the application market of biphenyl polyimide materials is greatly limited. Therefore, the development of a cheap catalytic coupling reaction system for preparing the biphenyl dianhydride has important significance.
The industrial production of biphenyl dianhydride mainly adopts metal palladium (Pd) and salts thereof as catalysts, and the catalyst of the synthetic route is expensive and large in dosage, and has high pressure reaction, low yield and high cost. Relevant research reports are as in patents JP7352749, US5243067, US 363636168, CN201310049837, etc.
The biphenyl dianhydride can be prepared by using Ni (0) or Pd (0) as a catalyst, using organic phosphine or nitrogen compound ligand and zinc powder as a reducing agent and through the processes of coupling halogenated phthalic acid derivatives, hydrolysis, acidification, dehydration and the like, and related research reports are more, including patents US 5081281, CN1189597, CN101481366, CN102020622B, CN201110202366 and the like. Inorganic salt byproducts such as zinc halide and the like generated in the reaction process of the method are adsorbed on the surface of metal zinc serving as a reducing agent in a large amount, so that the full contact between a catalyst and solid active reducing agent zinc powder is influenced, and the reduction coupling reaction is further influenced, therefore, the reaction system generally needs to use the catalyst with more than 5 percent of mole of raw materials and 400 percent of the feeding amount of the reducing agent to generate a large amount of solid waste residues; after the reaction is finished, the waste residue mixed with the excessive activated metal reducing agent is easy to cause fire when encountering oxygen, influences the safety production and has no industrial value, so that the problem of adsorption of inorganic byproducts on the surface of the reducing agent in the method is solved, and the key factor for realizing the industrial application of the method is realized.
Patents US7893306, US7425650, JP61-22045, CN201310234457, CN201310302428, CN201310050630 and the like use tetrahydrofuran or diethyl ether with low boiling point and high toxicity as a solvent to prepare a grignard reagent, an aromatic halide is prepared into the grignard reagent, then the polymetaphenylene is prepared by a coupling method, and then the biphenyl dianhydride is prepared by oxidation. As is well known, tetrahydrofuran or diethyl ether is a highly flammable and explosive organic solvent, is difficult to recover, is easy to cause safety accidents, and is unfavorable for industrial production.
Disclosure of Invention
In order to overcome the defects in the preparation method of the biphenyl dianhydride, the invention provides a new preparation technology of the biphenyl dianhydride, which adopts amino halogenated phthalimide as a monomer for the first time, realizes the complex coordination of amino and a byproduct metal halide in a reaction system, generates a metal organic complex as shown in the following formula 1,
the organic complex in the formula 1 is dissolved in a reaction system, so that ZnCl is effectively relieved2The difficult problem that the reaction efficiency is influenced by the adsorption on the surface of the active metal reducing agent is solved, so that the use efficiency of the reducing agent is improved, the use amount of the catalyst is reduced, and the efficiency of preparing the biphenyl dianhydride derivative by the coupling reaction is improved.
The invention provides a preparation method of biphenyl dianhydride, which comprises the following steps:
1) coupling reaction: carrying out catalytic coupling on the amino halogenated phthalimide to generate a biphenyl compound, wherein the reaction temperature is 50-100 ℃, and the reaction time is 1-24 hours;
2) purifying the benzidine tetracarboximide: purifying by a recrystallization mode, wherein the yield is 90-95% and the purity is 95-99%;
3) hydrolysis to anhydride: the diamine biphenyl tetracarboximide is hydrolyzed and dehydrated to obtain biphenyl tetracarboxylic dianhydride, and the yield is 90-98%.
In order to realize the invention task, the invention adopts the following technical scheme:
a method for preparing biphenyl dianhydride by coupling halogenated phthalimide monomers based on metal coordination is characterized by comprising the following reaction processes:
wherein, the adopted reaction raw material is amino halogenated phthalimide in the following formula:
the halogen atom in the raw material is chlorine or bromine, the position of the halogen atom can be 3-position of an aromatic ring or 4-position of the aromatic ring, R is a saturated aliphatic group with 2-5 carbons or a group with more than 6 carbons and containing aromatic hydrocarbon;
the catalyst is nickel salt;
the reducing agent is metal zinc or magnesium;
the additive is one or a mixture of more of triphenylphosphine, 2' -bipyridyl or sodium bromide;
the preparation method comprises the following steps: under the protection of nitrogen, an amino halogenated phthalimide monomer, nickel salt are catalytically mixed, an aprotic solvent and an additive reducing agent are stirred at 50-100 ℃ to carry out coupling reaction for 1-24 hours, the solvent is recovered under reduced pressure, toluene or xylene which is 3-4 times the mass of the reaction monomer is added into the system, heating and refluxing are carried out until organic matters are dissolved, hot filtration is carried out, filtrate is cooled to collect precipitated bis-amino biphenyl diimine, then the biphenyl diimine is refluxed and hydrolyzed for 2-24 hours by 10-20% of excessive NaOH aqueous solution (concentration is 20%), insoluble matters are filtered, concentrated hydrochloric acid is used for acidification to generate biphenyl tetracid precipitate, the biphenyl tetracid is filtered and collected, and 3,3 ', 4, 4' -biphenyl dianhydride or 2,2 ', 3, 3' -biphenyl dianhydride is obtained by carrying water through trimethylbenzene reflux.
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 amino halophthalimide is 0.005-0.02: 1; the reducing agent is metal zinc or magnesium, and the molar ratio of the reducing agent to the amino halophthalimide is 0.5-0.7: 1; the additive is one or a mixture of more of triphenylphosphine, 2' -bipyridine or sodium bromide, and the molar ratio of the additive to the nickel salt is 1-7: 1.
furthermore, the solvent used in the coupling reaction comprises one or a mixture of several of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMF) and dimethyl sulfoxide (DMSO), and the using amount of the solvent is 2.5-4 times of the mass of the reaction monomers.
The invention has the advantages that: the invention is characterized in that amino halogen phthalimide with complexing action with metal ions is used as a raw material, the solubility of the amino halogen phthalimide in an organic solvent is increased by complexing the contained amino and a byproduct halogen metal salt, and the influence of the metal salt on the surface of reduction metal to the catalytic reduction process is avoided, so that the catalytic coupling reaction efficiency of the halogen o-xylene derivative can be improved, the catalyst usage amount is greatly reduced, the usage amount of a reducing agent is reduced to be close to quantitative reaction from 4 times of the usage amount of a literature formula, the post-treatment difficulty is reduced, the preparation cost of the biphenyl dianhydride is reduced, and the method is suitable for industrial production.
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
N- (3-N, N-dimethylamino-propyl) -4-chlorophthalimide (26.65g, 0.1moL), zinc powder (3.25g, 0.05moL), anhydrous NiCl were added to a 500mL reaction flask under a nitrogen atmosphere2(127.5mg, 1mmoL), triphenylphosphine (250mg, 1mmoL) and 70mL of anhydrous DMAc, and the reaction was stirred at 50 ℃ for 24 hours, and 55mL of the solvent DMAc was recovered under reduced pressure. Adding 80g of dimethylbenzene into the system for refluxing (recrystallization), filtering out inorganic matters, cooling the clear filtrate to generate precipitate, filtering, and drying in vacuum for 10 hours to obtain 21.8g of 3,3 ', 4, 4' -biphenyl diimine with the yield of 94%.
In a 100mL reaction flask, 4.62g (0.01mol) of the above 3,3 ', 4, 4' -biphenyldiimine and 9g of 20% aqueous sodium hydroxide solution were charged, heated under reflux for 24 hours, filtered, adjusted to pH 1 with concentrated hydrochloric acid to give 3,3 ', 4, 4' -biphenyltetracarboxylic acid, washed three times after filtration, refluxed with water with 20mL of trimethylbenzene to give 2.85g of white 3,3 ', 4, 4' -biphenyldianhydride, yield 97%, melting point 298 at 300 ℃.
Example 2
In a 500mL reaction flask, N- (3-N, N-dimethylamino-propyl) -3-chlorophthalimide (26.65g, 0.1moL), zinc powder (3.25g, 0.05moL), anhydrous NiBr were added under nitrogen atmosphere2(216mg, 1mmoL), triphenylphosphine (1.75g, 7mmoL) and 110mL of anhydrous DMAc were added, the reaction was stirred at 100 ℃ for 12 hours, and 99mL of DMAc was recovered under reduced pressure. 106g of toluene (recrystallization) is added into the system for reflux, inorganic matters are filtered out, the clear filtrate is cooled to generate precipitate, and the precipitate is filtered and vacuum-dried for 10 hours to obtain 21.2g of 2,2 ', 3, 3' -biphenyl diimine with the yield of 92 percent.
In a 100mL reaction flask, 4.62g (0.01mol) of the above 2,2 ', 3, 3' -biphenyldiimine was added, 9.9g of a 20% aqueous solution of sodium hydroxide was added, the mixture was refluxed for 12 hours, filtered, the pH was adjusted to 1 with concentrated hydrochloric acid to obtain 2,2 ', 3, 3' -biphenyltetracarboxylic acid, and after the filtration, the mixture was washed with cold water three times, and refluxed with 20mL of trimethylbenzene to obtain 2.79g of white 2,2 ', 3, 3' -biphenyldianhydride, with a yield of 95% and a melting point of 268 and 270 ℃.
Example 3
To a 500mL reaction flask, N- (3-N, N-dimethylamino-pentyl) -4-chlorophthalimide (28.05g, 0.1moL), zinc powder (4.55g, 0.07moL), anhydrous NiCl were added under a nitrogen atmosphere2(255mg, 2mmoL), triphenylphosphine (3.5g, 14mmoL) and 70mL of anhydrous DMF were stirred at 85 ℃ for 4 hours, and 55mL of the solvent DMAc was recovered under reduced pressure. Adding 80g of dimethylbenzene (recrystallization) into the system for refluxing, filtering out inorganic matters, cooling the clear filtrate to generate precipitate, filtering and drying in vacuum for 10 hours to obtain 25.4g of 3,3 ', 4, 4' -biphenyl diimine with the yield of 98 percent.
In a 100mL reaction flask, 5.18g (0.01mol) of the above 3,3 ', 4, 4' -biphenyldiimine was added, 9g of a 20% aqueous solution of sodium hydroxide was added, the mixture was refluxed for 24 hours, filtered, the pH was adjusted to 1 with concentrated hydrochloric acid to obtain 3,3 ', 4, 4' -biphenyltetracarboxylic acid, the filtrate was washed with water three times, and refluxed with 20mL of trimethylbenzene to obtain 2.82g of white 3,3 ', 4, 4' -biphenyldianhydride, the yield was 96%, and the melting point was 298 ℃ at 300 ℃.
Example 4
N- (3-N, N-dimethylamino-propyl) -4-chlorophthalimide (26.65g, 0.1moL), zinc powder (4.55g, 0.07moL), anhydrous NiCl were added to a 500mL reaction flask under a nitrogen atmosphere2(255mg, 2mmoL), 2-bipyridine (2.18g, 7mmoL) and 70mL of anhydrous NMP, and the reaction was stirred at 85 ℃ for 4 hours, and 55mL of the solvent DMAc was recovered under reduced pressure. Adding 80g of dimethylbenzene (recrystallization) into the system for refluxing, filtering out inorganic matters, cooling the clear filtrate to generate precipitate, filtering and drying in vacuum for 10 hours to obtain 21.9g of 3,3 ', 4, 4' -biphenyl diimine with the yield of 95%.
In a 100mL reaction flask, 4.62g (0.01mol) of the above 3,3 ', 4, 4' -biphenyldiimine was added, 9g of a 20% aqueous solution of sodium hydroxide was added, the mixture was refluxed for 15 hours, filtered, the pH was adjusted to 1 with concentrated hydrochloric acid to obtain 3,3 ', 4, 4' -biphenyltetracarboxylic acid, the filtrate was washed with water three times, and refluxed with 20mL of trimethylbenzene to obtain 2.82g of white 3,3 ', 4, 4' -biphenyldianhydride, the yield was 96%, and the melting point was 298 ℃ at 300 ℃.
The preparation method of biphenyl derivative and biphenyl dianhydride isomer provided by the present invention is described in detail above, and the principle and the embodiment of the present invention are illustrated herein by using specific examples, and the description of the above examples is only for helping to understand the method of the present invention and the core concept thereof, and it should be noted that, for those skilled in the art, the present invention can be modified and modified without departing from the principle of the present invention, and the modified and modified are also within the full protection scope of the present invention.
Claims (3)
1. A method for preparing biphenyl dianhydride by coupling halogenated phthalimide monomers based on metal coordination is characterized by comprising the following reaction processes:
wherein, the adopted reaction raw material is amino halogenated phthalimide in the following formula:
the halogen atom (X) in the raw material is chlorine or bromine, the position of the halogen atom (X) can be 3-position of an aromatic ring or 4-position of the aromatic ring, R is a saturated aliphatic group with 2-5 carbons or a group with more than 6 carbons and containing aromatic hydrocarbon;
the catalyst is nickel salt;
the reducing agent is metal zinc or magnesium;
the additive is one or a mixture of more of triphenylphosphine, 2' -bipyridyl or sodium bromide;
the preparation method specifically comprises the following steps: under the protection of nitrogen, mixing an amino halogenated phthalimide monomer, a nickel salt catalyst, an aprotic solvent, an additive and a reducing agent, stirring at 50-100 ℃ to perform a coupling reaction for 1-24 hours, recovering the solvent under reduced pressure, adding toluene or xylene which is 3-4 times the mass of the reaction monomer into the system, heating and refluxing until organic matters are dissolved, filtering while hot, cooling filtrate to collect precipitated bis-amino biphenyl diimine, then refluxing and hydrolyzing the biphenyl diimine for 2-24 hours by using 10-20% of excessive NaOH aqueous solution (concentration-20%), filtering insoluble substances, acidifying by using concentrated hydrochloric acid to generate biphenyl tetracid precipitate, filtering and collecting the biphenyl tetracid, and obtaining 3,3 ', 4, 4' -biphenyl dianhydride or 2,2 ', 3, 3' -biphenyl dianhydride by carrying water through trimethylbenzene reflux.
2. The method for preparing the biphenyl dianhydride by coupling the halogenated phthalimide monomer based on the metal coordination effect 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 amino halogenated phthalimide is 0.005-0.02: 1; the molar ratio of the reducing agent to the amino halophthalimide is 0.5-0.7: 1; the molar ratio of the additive to the nickel salt is 1-7: 1.
3. the method for preparing the biphenyl dianhydride by coupling the halogenated phthalimide monomer based on the metal coordination effect according to claim 1, wherein a solvent used in the coupling reaction comprises one or a mixture of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMF) and dimethyl sulfoxide (DMSO), and the amount of the solvent is 2.5-4 times of the mass of the reaction monomer.
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| CN115073761A (en) * | 2022-07-07 | 2022-09-20 | 西安交通大学 | Metal organic framework adsorbent for xylene separation and preparation method and application thereof |
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