CN116803970A - A kind of 6,6`-disubstituted-3,3`,4,4`-biphenyltetracarboxylic acid and its dianhydride and its preparation method - Google Patents
A kind of 6,6`-disubstituted-3,3`,4,4`-biphenyltetracarboxylic acid and its dianhydride and its preparation method Download PDFInfo
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- CN116803970A CN116803970A CN202210267547.2A CN202210267547A CN116803970A CN 116803970 A CN116803970 A CN 116803970A CN 202210267547 A CN202210267547 A CN 202210267547A CN 116803970 A CN116803970 A CN 116803970A
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Abstract
The invention discloses 6,6 '-disubstituted-3, 3',4 '-biphenyl tetracarboxylic acid and dianhydride thereof and a preparation method thereof, wherein the structures of the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid and dianhydride thereof are respectively shown in a formula (I) and a formula (II), R is selected from alkyl, alkoxy, substituted alkyl or substituted alkoxy, and two R in the same structural formula are the same or different;
Description
Technical Field
The invention belongs to the field of organic aromatic acid anhydride, and particularly relates to synthesis of organic aromatic acid anhydride, in particular to 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid and dianhydride thereof and a preparation method thereof.
Background
With the increasing demand for 5G and transparent displays in recent years, the modification of polyimide materials to accommodate this evolving demand has become increasingly important. Polyimide (PI) is formed by polycondensation of diamines and dianhydrides, wherein polyimide materials based on 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) exhibit very good heat, water, mechanical and dielectric properties, being the heat resistant resins with the highest heat resistance temperatures to date. Therefore, the BPDA structure is modified and modified, and the BPDA with other substituent groups is developed, so that the related performance of the PI material can be further endowed and improved. Such as BPDA with cyano side chains can improve PI solubility (CN 102329290a, 2011); the dielectric and water absorption properties of PI can be further reduced by the BPDA modified with trifluoromethyl (CN 106699709a,2016; kr2017076114a, 2017); the use of large side groups such as phenyl and its derivatives to modify BPDA can reduce the birefringence of PI and the polarization loss during use (Macromolecules, 2003,36,2327; j. Mater. Chem.,2011,21,1810; cn 102086811 a, 2011); whereas simple methyl substituted BPDA, i.e. 6,6' -dialkyl-3, 3', 4' -biphenyltetracarboxylic dianhydride (DMPBDA), can reduce the expansion ratio of PI and increase the light transmittance of PI (EP 1013650a,2000; cn104513395a, 2015).
In reference to the preparation methods of 3,3', 4' -biphenyltetracarboxylic acid in the prior art and patent (JP 55020705, 1980;JP06122650, 1994;CN1228366C,2003; insulating material, 2011,44 (5), 24; CN110566788A, 2019, etc.), 3', 4' -biphenyltetracarboxylic acid can be obtained by first performing chlorination with phthalic anhydride to form chlorophthalic acid and then performing dehalogenation coupling with palladium-based metal catalyst in aqueous phase. For methyl phthalic anhydride, the first step of halogenation reaction is not easy to occur due to steric hindrance of methyl, the subsequent dehalogenation coupling reaction is difficult to occur due to methyl, and the competing side reaction dehalogenation reduction reaction mainly occurs, so that only methyl phthalic acid can be obtained.
So far, there is only one synthesis method disclosed (EP 1013650a, 2000), namely starting from 4-methylphthalic anhydride, first preparing 4-bromo-5-methylphthalic acid using potassium bromate under concentrated sulfuric acid, and then converting the dicarboxylic acid into dimethyl 4-bromo-5-methylphthalate using reagents such as thionyl chloride, methanol, etc. The 4-bromo-5-methyl phthalate dimethyl ester is coupled in the presence of zinc powder, nickel dichloride and a ligand to generate the 6,6' -dimethyl-3, 3', 4' -biphenyl tetracarboxylic acid dimethyl ester. The methyl ester is hydrolyzed and acidified to obtain the 6,6' -dimethyl-3, 3', 4' -biphenyl tetracarboxylic acid, and then the anhydride DMPBDA is obtained after dehydration. The method has the advantages of long route and total yield of about 25% after 5 steps of conversion process, which severely restricts the wide use of DMPBDA dianhydride in PI material preparation.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid and dianhydride thereof and a preparation method thereof. The 6,6 '-disubstituted-3, 3',4 '-biphenyl tetracarboxylic acid and dianhydride thereof have the advantages of high purity and high whiteness, the method firstly prepares 4-halogeno-5-substituted phthalic acid by halogen halogenation in the presence of quaternary ammonium salt, then carries out palladium catalytic coupling under the condition of visible light, can directly couple the 4-halogeno-5-substituted phthalic acid to generate 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid, and further dehydrates to obtain corresponding dianhydride. The method avoids the bromination method in EP1013650A by using concentrated sulfuric acid as an auxiliary reagent, and simultaneously adopts a palladium catalytic coupling technology to directly couple 4-halogeno-5-substituted phthalic acid, thereby avoiding complex reaction steps of ester formation and hydrolysis, and the obtained product is easy to separate. The method has the advantages of short route, higher yield, great improvement of preparation conditions and better industrialized prospect.
It is an object of the present invention to provide a 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid having a structure represented by formula (I), wherein R is selected from the group consisting of hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyl or substituted hydrocarbyloxy, and two R are the same or different (preferably two R are the same):
Wherein the purity of the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid is more than 95 percent, and the whiteness is more than 70.
Among these, the whiteness of the monomers has an important influence on the transparency of the subsequent polymers.
In the invention, the content of impurities such as 4-halogeno-5-substituted phthalic acid and 4-alkylphthalic acid in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is less than 5 percent.
In a preferred embodiment, the purity of the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is greater than 98%, preferably greater than 98.5%.
In a preferred embodiment, the total content of cations in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is less than 150ppm, preferably less than 100ppm, more preferably less than 50ppm.
In a preferred embodiment, the total content of anions in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is less than 150ppm, preferably less than 100ppm, more preferably less than 50ppm.
In a preferred embodiment, in formula (I), R is selected from alkyl, alkoxy, substituted alkyl (preferably halogen substituted alkyl) or substituted alkoxy (preferably halogen substituted alkoxy), the two R being the same or different.
In a further preferred embodiment, in formula (I), R is selected from C1-C10 alkyl, C1-C10 alkoxy, C1-C10 substituted alkyl or C1-C10 substituted alkoxy, the two R being identical or different.
In a further preferred embodiment, in formula (I), R is selected from C1-C4 alkyl, C1-C4 alkoxy, C1-C4 substituted alkyl or C1-C4 substituted alkoxy, the two R being identical or different. For example, R is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl or trifluoromethoxy.
In a preferred embodiment, the content of alkali metal ions in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is 20ppm or less, the content of alkaline earth metal ions is 20ppm or less, the content of transition metal ions is 5ppm or less, preferably, the alkali metal ions include sodium ions and/or potassium ions, the alkaline earth metal ions include calcium ions and/or magnesium ions, and the transition metal ions include at least one of copper ions, iron ions, manganese ions, nickel ions, cobalt ions, lead ions, and zinc ions.
In a preferred embodiment, the content of each anion in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is independently 30ppm or less, wherein the anion comprises at least one of chloride ion, sulfate ion, phosphate ion, silicate ion.
Another object of the present invention is to provide a method for preparing 6,6 '-disubstituted-3, 3',4 '-biphenyltetracarboxylic acid, preferably for preparing the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid according to one of the objects of the present invention, wherein the method comprises:
(1) Mixing 4-substituted phthalic acid and/or anhydride thereof, quaternary ammonium salt and strong alkali aqueous solution, adding halogen simple substance, reacting, adding reducing agent solution after the reaction is finished, and performing post-treatment to obtain an intermediate product I, namely 4-halogenated-5-substituted phthalic acid;
wherein in the step (1), the quaternary ammonium salt can form a compound with the halogen simple substance to promote the smooth and steady occurrence of the halogenation reaction, in particular, the halogenation reaction speed is improved by adopting the quaternary ammonium salt; in step (1), the reducing agent solution is added for the purpose of neutralizing the unreacted elemental halogen.
(2) And adding the intermediate product I into an inorganic alkaline water solution, adding a catalyst and a reducing agent, and carrying out reaction and post-treatment to obtain the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid.
Among them, the inventors have found through a number of experiments that the coupling of 4-halo-5-methylphthalic acid can be promoted under irradiation of visible light.
In a preferred embodiment, the substituents in the 4-substituted phthalic acid and/or anhydride thereof are selected from hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyl or substituted hydrocarbyloxy.
In a further preferred embodiment, the substituents in the 4-substituted phthalic acid and/or anhydride thereof are selected from alkyl, alkoxy, substituted alkyl or substituted alkoxy.
In a still further preferred embodiment, the substituents in the 4-substituted phthalic acid and/or anhydride thereof are selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, C1-C10 substituted alkyl or C1-C10 substituted alkoxy, preferably from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, C1-C4 substituted alkyl or C1-C4 substituted alkoxy.
The structure of the 4-substituted phthalic acid and/or the anhydride thereof is shown as a first structural formula on the left side in the figure 1, wherein R is a substituent group.
In a preferred embodiment, the quaternary ammonium salt has the formula (R 1 R 2 R 3 R 4 ) NY is shown, wherein R 1 、R 2 、R 3 、R 4 Each independently selected from one of C1-C20 alkyl, and Y is selected from one of halogen anions and acid radical anions.
In a further preferred embodiment, the quaternary ammonium salt has the formula (R 1 R 2 R 3 R 4 ) NY is shown, wherein R 1 、R 2 、R 3 、R 4 Each independently selected from one of C1-C10 alkyl groups, and Y is selected from one of halogen anions, and preferably accords with the element type of the halogen simple substance.
For example, (R) 1 R 2 R 3 R 4 ) N-may be selected from tetraethylammonium, tetrapropylammonium or tetrabutylammonium, and the anion Y is selected from chloride, bromide or iodide and is consistent with the subsequent addition of said elemental halogen.
In a preferred embodiment, in step (1), the strong base is selected from at least one of sodium hydroxide, potassium hydroxide, cesium hydroxide.
In a preferred embodiment, in step (1), the elemental halogen is selected from at least one of chlorine, bromine, and elemental iodine.
In a preferred embodiment, in step (1), the ratio by weight of the elemental halogen to 4-substituted phthalic acid and/or anhydride thereof is (0.4 to 1): 1.
For example, the elemental halogen to 4-substituted phthalic acid and/or anhydride is used in a weight ratio of 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1:1.
In a preferred embodiment, in step (1), the weight ratio of strong base to 4-substituted phthalic acid and/or anhydride thereof in the aqueous strong base is 1 (1-4), preferably 1 (1.8-3.2).
Wherein, when the weight ratio of the strong alkali to the 4-substituted phthalic acid and/or the anhydride thereof is more than 1:1, side reaction occurs, namely, the generated 4-halogeno-5-substituted phthalic acid is further hydrolyzed into 4 hydroxy-5-substituted phthalic acid.
For example, in step (1), the weight ratio of strong base to 4-substituted phthalic acid and/or anhydride in the aqueous strong base is 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, or 1:4.
In a preferred embodiment, in step (1), the ratio by weight of the aqueous alkali solution to the 4-substituted phthalic acid and/or anhydride thereof is from (5 to 20): 1.
For example, in step (1), the ratio of the aqueous strong base to the 4-substituted phthalic acid and/or anhydride thereof is 5:1, 6:1, 8:1, 10:1, 12:1, 14:1, 16:1, 18:1, or 20:1 by weight.
In a preferred embodiment, in step (1), the weight ratio of the quaternary ammonium salt to the 4-substituted phthalic acid and/or anhydride thereof is (0.1 to 0.5): 1.
Wherein, the quaternary ammonium salt has the function of promoting the halogenation reaction, and when the weight ratio of the quaternary ammonium salt to the 4-substituted phthalic acid and/or the anhydride thereof is higher than 0.5:1, the difficulty of subsequent separation and purification is increased, and the yield is reduced.
For example, in step (1), the weight ratio of quaternary ammonium salt to 4-substituted phthalic acid and/or anhydride thereof is 0.1:1, 0.2:1, 0.3:1, 0.4:1, or 0.5:1.
In a preferred embodiment, in step (1), the reaction is carried out at a temperature of from 0 to 100℃for a period of from 3 to 36 hours.
In a further preferred embodiment, in step (1), the reaction is carried out at a temperature of 25 to 80℃for a period of 6 to 24 hours.
For example, in step (1), the temperature of the reaction is 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃ for 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours.
In a preferred embodiment, in step (1), the reaction is completed and cooled to room temperature, and the reducing agent solution is added.
Wherein the reducing agent solvent is preferably an aqueous reducing agent solution
In a further preferred embodiment, in step (1), the reducing agent solution is selected from at least one of sodium sulfite solution, sodium bisulfite solution, sodium thiosulfate solution, sodium dithionite solution, hydrazine hydrate, hydroxylamine solution, preferably the weight concentration of the reducing agent solution is 10 to 25wt%, more preferably the weight ratio of the reducing agent solution to 4-substituted phthalic acid and/or its anhydride is (0.1 to 0.4): 1.
In a preferred embodiment, in step (1), the post-treatment comprises: (a) adjusting the pH of the reaction system to between 0 and 4, preferably between 1 and 2, (b) extracting the organic phase with an organic solvent, (c) drying the organic phase, optionally concentrating to obtain the intermediate product I.
In a further preferred embodiment, in step (a), the pH of the reaction system is adjusted with a strongly acidic substance, preferably selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid.
In a further preferred embodiment, in step (b), the organic solvent is selected from one or more of ethyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran.
In a further preferred embodiment, in step (c) the drying is performed with a drying agent, preferably selected from one or more of anhydrous sodium sulfate, anhydrous magnesium sulfate, 3A molecular sieve, 4A molecular sieve, silica gel drying agent.
In a preferred embodiment, in step (2), the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate.
In a further preferred embodiment, in step (2), the weight ratio of inorganic base to intermediate I is from (0.25 to 0.75): 1; and/or the weight ratio of the inorganic alkali aqueous solution to the intermediate product I is (5.0-10.0): 1.
For example, in step (2), the weight ratio of inorganic base to intermediate I (i.e., 4-halo-5-substituted phthalic acid) is 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, 0.65:1, 0.7:1, or 0.75:1; and/or the weight ratio of the inorganic aqueous base to the intermediate product I (i.e., 4-halo-5-substituted phthalic acid) is 5.0:1, 6.0:1, 7.0:1, 8.0:1, 9.0:1, or 10.0:1.
In a preferred embodiment, in step (2), the catalyst is selected from palladium on carbon catalysts and/or nickel palladium on carbon catalysts.
The carbon carrier in the palladium-carbon and/or nickel-palladium-carbon catalyst can absorb visible light, so that the catalytic efficiency of the catalyst is improved, and the smooth reaction is promoted.
In a further preferred embodiment, in the step (2), the palladium content in the palladium-carbon catalyst is 1 to 20% of the total mass of the palladium-carbon catalyst; and/or the palladium content in the nickel-palladium-carbon catalyst is 0.1-8% of the total mass of the nickel-palladium-carbon catalyst, and the mass ratio of palladium to nickel is 1:0.1-1:10.
For example, the palladium content in the palladium-carbon catalyst is 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18% or 20% of the total mass of the palladium-carbon catalyst; and/or the palladium content in the nickel palladium carbon catalyst is 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7% or 8% of the total mass of the nickel palladium carbon catalyst, and the mass ratio of palladium to nickel is 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:2, 1:4, 1:6, 1:8 or 1:10.
In a still further preferred embodiment, in step (2), the catalyst is used in an amount of 0.1 to 20% by weight of intermediate product I.
For example, in step (2), the catalyst is used in an amount of 0.1wt%, 0.5wt%, 0.8wt%, 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 15wt% or 20wt% of intermediate product I (i.e., 4-halo-5-substituted phthalic acid).
In a preferred embodiment, in step (2), the reducing agent is added under visible light irradiation and the reaction is carried out under visible light irradiation.
In a further preferred embodiment, the visible light irradiation light source is one or more of an incandescent lamp, a xenon lamp, a halogen lamp, a tungsten lamp, an LED lamp, and sunlight.
In a preferred embodiment, in step (2), the reducing agent is selected from one or more of hydroxylamine hydrochloride, hydroxylamine sulfate, hydrazine hydrate, hydrazine hydrochloride, hydrazine sulfate, glycerol, glucose, sodium formate, potassium formate, ammonium formate, isopropanol.
In a further preferred embodiment, in step (2), the weight ratio of the reducing agent to the intermediate product I (i.e. 4-halo-5-substituted phthalic acid) is 1 (1-6).
For example, in step (2), the weight ratio of the reducing agent to intermediate I (i.e., 4-halo-5-substituted phthalic acid) is 1:1, 1:2, 1:3, 1:4, 1:5, or 1:6.
In a further preferred embodiment, the reducing agent is added dropwise as an aqueous solution for a period of time ranging from 4 to 24 hours, preferably from 6 to 8 hours, and the incubation period is from 0 to 6 hours, preferably from 2 to 3 hours.
In a preferred embodiment, in step (2), the temperature of the reaction is 40 to 120 ℃.
For example, in step (2), the temperature of the reaction is 40 ℃, 60 ℃, 80 ℃, 100 ℃ or 120 ℃.
In a preferred embodiment, in step (2), the post-treatment comprises: firstly, centrifugally separating, then adding a strong acid substance into supernatant to generate a coarse product precipitate of the 6,6 '-disubstituted-3, 3',4 '-biphenyl tetracarboxylic acid, and finally, washing with water to obtain a pure product of the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid.
In a further preferred embodiment, in the post-treatment of step (2), the strongly acidic substance is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid.
In a still further preferred embodiment, in the post-treatment of step (2), a strongly acidic substance is added to adjust the pH of the reaction system to 1 to 4.
For example, in the post-treatment of step (2), a strongly acidic substance is added to adjust the pH of the reaction system to 1, 2, 3 or 4.
It is still another object of the present invention to provide a 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride having a structure represented by formula (II), wherein R is selected from the group consisting of a hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon group and a substituted hydrocarbon oxy group, and two R are the same or different (preferably, two R are the same):
wherein the purity of the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic dianhydride is more than 95 percent, and the whiteness is more than 70.
In the invention, the content of impurities such as 4-halogeno-5-substituted phthalic acid and 4-alkylphthalic acid in the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic dianhydride is less than 5 percent.
In a preferred embodiment, the purity of the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride is greater than 98%, preferably greater than 98.5%.
In a preferred embodiment, the total content of cations in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride is less than 150ppm, preferably less than 100ppm, more preferably less than 50ppm.
In a preferred embodiment, the total content of anions in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride is less than 150ppm, preferably less than 100ppm, more preferably less than 50ppm.
In a preferred embodiment, in formula (II), R is selected from alkyl, alkoxy, substituted alkyl (preferably halogen substituted alkyl) or substituted alkoxy (preferably halogen substituted alkoxy), the two R being the same or different.
In a further preferred embodiment, in formula (II), R is selected from C1-C10 alkyl, C1-C10 alkoxy, C1-C10 substituted alkyl or C1-C10 substituted alkoxy, the two R being identical or different.
In a further preferred embodiment, in formula (II), R is selected from C1-C4 alkyl, C1-C4 alkoxy, C1-C4 substituted alkyl or C1-C4 substituted alkoxy, the two R being identical or different. For example, R is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl or trifluoromethoxy.
In a preferred embodiment, the content of alkali metal ions in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride is 20ppm or less, the content of alkaline earth metal ions is 20ppm or less, the content of transition metal ions is 5ppm or less, preferably, the alkali metal ions include sodium ions and/or potassium ions, the alkaline earth metal ions include calcium ions and/or magnesium ions, and the transition metal ions include at least one of copper ions, iron ions, manganese ions, nickel ions, cobalt ions, lead ions, and zinc ions.
In a preferred embodiment, the content of each anion in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride is independently 30ppm or less, wherein the anion comprises at least one of chloride ion, sulfate ion, phosphate ion, silicate ion.
Wherein the 6,6 '-disubstituted-3, 3',4 '-biphenyl tetracarboxylic dianhydride is used for an electronic grade polyimide monomer, and the polymer has strict requirements on ion content, so that the ion content in the obtained 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic dianhydride needs to be controlled within a reasonable range.
The fourth object of the present invention is to provide a process for producing 6,6 '-disubstituted-3, 3',4 '-biphenyltetracarboxylic dianhydride, preferably for producing three of the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydrides of the object of the present invention, wherein the process comprises: the preparation method for the 6,6 '-disubstituted-3, 3',4 '-biphenyl tetracarboxylic acid is adopted to obtain the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid, and then the 6,6 '-disubstituted-3, 3',4 '-biphenyl tetracarboxylic acid is dehydrated and washed to obtain the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic dianhydride.
In a preferred embodiment, the dehydration treatment is performed with a dehydrating agent selected from one or more of acetyl chloride, propionyl chloride, acetic anhydride, propionic anhydride, oxalyl chloride, thionyl chloride, di-tert-butyl dicarbonate.
In a further preferred embodiment, the dehydration treatment is carried out with a dehydrating agent selected from one or more of acetic anhydride, propionic anhydride, di-tert-butyl dicarbonate.
In a still further preferred embodiment, the mass ratio of the dehydrating agent to 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is (4 to 15): 1.
For example, the mass ratio of the dehydrating agent to 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is 4:1, 6:1, 8:1, 10:1, 12:1, 14:1, or 15:1.
In a preferred embodiment, the dehydration treatment is performed as follows: refluxing for 2-8 hours in the presence of a dehydrating agent.
In a preferred embodiment, the washing is performed with an aprotic solvent, preferably selected from one or more of methyl tert-butyl ether, diethyl ether, 1, 4-dioxane, acetone, methyl isopropyl ketone, ethylene glycol dimethyl ether, tetrahydrofuran, methyl tetrahydrofuran.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention prepares the 4-halogenated 5-alkylphthalic acid under alkaline condition, avoids the bromination method using concentrated sulfuric acid as auxiliary reagent in the prior art (such as EP 1013650A), and has mild reaction condition;
2. the palladium catalytic coupling technology is adopted to directly couple halogenated alkylated phthalic acid, so that complicated reaction steps of ester formation and hydrolysis are avoided, and the process route is simplified;
3. the product obtained by the method is easy to separate, has short route and higher yield, greatly improves the preparation conditions, and has better industrialized prospect.
Drawings
FIG. 1 shows a schematic representation of the chemical reaction process of the method of the present invention;
FIG. 2 shows a nuclear magnetic resonance hydrogen spectrum of 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid prepared in example 1 of the present invention;
FIG. 3 shows a mass spectrum of 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid prepared as example 1 of the present invention.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Whiteness testing was performed as follows: the obtained product powder is pressed into tablets, and a whiteness meter is adopted to directly measure a sample and calculate the whiteness value of the sample.
[ example 1 ]
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid:
(1) Distilled water 2000g,162g of 4-methylpentanoic anhydride and 16.2g of tetraethylammonium chloride dissolved with 90g of sodium hydroxide are sequentially added into a reaction tank, 82g of chlorine is introduced under stirring at room temperature, then stirring is carried out at 80 ℃ for 6 hours, after cooling to room temperature, 30g of 25wt% sodium bisulphite aqueous solution is added, then concentrated hydrochloric acid is used for neutralization until the pH value is=1, ethyl acetate is used for extracting aqueous phase for 3 times, an organic phase is dried by anhydrous sodium sulfate, and the obtained crude product is directly used as a next step after concentration to obtain 204g of white powdery crude product 4-chloro-5-methylphthalic acid.
(2) 1020g of aqueous solution containing 132g of sodium hydroxide, 204g of 4-chloro-5-methylphthalic acid and 2.04g of 20% palladium-carbon catalyst are sequentially added into a reaction kettle, the temperature is raised to 100 ℃, 312g of aqueous solution containing 78g of hydroxylamine sulfate is dropwise added under sunlight irradiation, the dropwise addition time of the temperature is kept for 8 hours, and then the temperature is kept for 2 hours; after centrifugation, 50% sulfuric acid was added to the supernatant to adjust the ph=2, to obtain white crystals, and 160g of a crude 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid product was obtained by filtration. The crude product is washed by deionized water for several times and then dried to obtain the pure 6,6' -dimethyl-3, 3', 4' -biphenyl tetracarboxylic acid product with the purity of 98.8 percent and the whiteness of 76.8. Wherein, the sodium ion is 16.6ppm, and the potassium ion, the calcium ion, the magnesium ion and other transition metal ions are not detected, and anions such as chloride ion, sulfate ion and the like are not detected.
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride:
(3) 132g of the 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid obtained above was refluxed in 1500g of acetic anhydride for 3 hours, and the crude product was obtained by filtration. The crude product was slurried with methyl tert-butyl ether, followed by filtration, and the filter cake was washed with methyl tert-butyl ether for 2 times, and dried to give 113g of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride in 95% yield and 99.0% purity, with a whiteness of 73.6, wherein sodium ion of 15.1ppm, potassium ion, calcium ion, magnesium ion and other transition metal ions were not detected, and anions such as chloride ion, sulfate ion were not detected.
[ example 2 ]
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid:
(1) Distilled water 2000g,208g of 4-isopropyl phthalic acid and 50g of tetrabutylammonium bromide dissolved with 65g of sodium hydroxide are sequentially added into a reaction tank, 180g of liquid bromine is introduced under stirring at room temperature, then the mixture is heated to 80 ℃ and stirred for 12 hours, 36g of 20wt% sodium sulfite aqueous solution is added after the temperature is reduced to room temperature, then concentrated sulfuric acid is used for neutralization until the pH value is=2, ethyl acetate is used for extracting the water phase for 3 times, an organic phase is dried by anhydrous magnesium sulfate, and the obtained product is concentrated to obtain 240g of white powdery crude product 4-bromo-5-isopropyl phthalic acid, and the obtained crude product can be directly used as the next step.
(2) 2000g of aqueous solution containing 127g of potassium hydroxide, 240g of 4-bromo-5-isopropyl phthalic acid and 2.5g of 10% palladium-carbon catalyst are sequentially added into a reaction kettle, the temperature is raised to 120 ℃, 210g of aqueous solution containing 70g of hydroxylamine sulfate is dropwise added under the irradiation of a xenon lamp, the dropwise addition time of the temperature is kept for 8 hours, and then the temperature is kept for 2 hours; after centrifugal separation, concentrated hydrochloric acid is added into the supernatant to adjust the pH to be 3, white crystals are obtained, 163g of crude 6,6 '-diisopropyl-3, 3',4 '-biphenyl tetracarboxylic acid product is obtained through filtration, and the crude product is washed by deionized water for a plurality of times and then dried, thus obtaining the pure 6,6' -diisopropyl-3, 3', 4' -biphenyl tetracarboxylic acid product with the purity of 98.5 percent and the whiteness of 75.8. Wherein, the potassium ion is 17.2ppm, the sodium ion is 20.1ppm, the calcium ion, the magnesium ion and other transition metal ions are not detected, the chloride ion is 30.0ppm, the sulfate ion is 23.0ppm, and other anions are not detected.
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride:
(3) 135g of the 6,6' -diisopropyl-3, 3', 4' -biphenyltetracarboxylic acid obtained above was refluxed in 1700g of propionyl chloride for 2 hours, and the crude product 121g was obtained by filtration. The crude product was slurried with diethyl ether, then filtered, the filter cake was washed 2 times with diethyl ether and dried to give 115g of 6,6' -diisopropyl-3, 3', 4' -biphenyltetracarboxylic dianhydride in 93% yield, 98.8% purity and 72.3% whiteness. Wherein, the potassium ion is 15.1ppm, the sodium ion is 18.7ppm, the calcium ion, the magnesium ion and other transition metal ions are not detected, the chloride ion is 28.0ppm, the sulfate ion is 22.0ppm, and other anions are not detected.
[ example 3 ]
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid:
(1) Adding 900g of distilled water dissolved with 90g of sodium hydroxide, 180g of 4-methylphthalic acid and 45g of tetrabutylammonium chloride into a reaction tank in sequence, introducing 80g of chlorine gas under stirring at room temperature, and then stirring for 12 hours at 25 ℃; after cooling to room temperature, 72g of a 10wt% aqueous sodium thiosulfate solution was added, followed by neutralization with phosphoric acid to ph=3, extraction of the aqueous phase with methyl tert-butyl ether 3 times, drying of the organic phase with a 3A molecular sieve and concentration to give 192g of 4-chloro-5-methylphthalic acid as a white powdery crude product, which was used directly as the next step.
(2) 1000g of aqueous solution containing 144g of sodium hydroxide, 192g of 4-chloro-5-methylphthalic acid and 2.68g of 5% palladium-carbon catalyst are sequentially added into a reaction kettle, the temperature is raised to 60 ℃, 231g of aqueous solution containing 77g of hydroxylamine hydrochloride is dropwise added under the irradiation of a halogen lamp, the dropwise addition time of the temperature is kept for 4 hours, and then the temperature is kept for 6 hours; after centrifugation, phosphoric acid was added to the supernatant to adjust ph=2 to give white crystals, and the white crystals were filtered to give 142g of a crude 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid. The crude product is washed by deionized water for several times and then dried to obtain the pure 6,6' -dimethyl-3, 3', 4' -biphenyl tetracarboxylic acid product with the purity of 98.5 percent and the whiteness of 81.2. Wherein, the sodium ion is 22.8ppm, the potassium ion, the calcium ion, the magnesium ion and other transition metal ions are not detected, the phosphate ion is 21.7ppm, and other anions are not detected.
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride:
(3) 130g of the 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid obtained above was refluxed in 1500g of acetic anhydride for 4 hours, and the crude product 116g was obtained by filtration. The crude product was slurried with chloroform, then filtered, and the cake was washed with chloroform 2 times and dried to give 111g of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride in 95% yield. The purity was 99.5% and the whiteness was 78.5. Wherein, the sodium ion is 20.1ppm, the potassium ion, the calcium ion, the magnesium ion and other transition metal ions are not detected, the phosphate ion is 20.0ppm, and other anions are not detected.
[ example 4 ]
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid:
(1) Adding 3240g of distilled water dissolved with 90g of sodium hydroxide, 162g of 4-methyl phthalic anhydride and 81g of tetrabutylammonium iodide into a reaction tank in sequence, adding 130g of iodine simple substance under stirring at room temperature, and then heating to 90 ℃ and stirring for 9 hours; after cooling to room temperature 36g of 15wt% aqueous sodium sulfite solution was added, followed by neutralization with concentrated hydrochloric acid to ph=4, extraction of the aqueous phase 3 times with ethyl acetate, drying of the organic phase with silica gel and concentration to give 235g of 4-iodo-5-methylphthalic acid as a white powdery crude product, which was used directly as the next step.
(2) Sequentially adding 1630g of aqueous solution containing 123g of sodium hydroxide, 235g of 4-iodo-5-methylphthalic acid and 12g of nickel-palladium-carbon catalyst (wherein the palladium content is 1 percent and the nickel content is 1 percent) into a reaction kettle, heating to 50 ℃, dropwise adding 175g of aqueous solution containing 75g of glycerol under the irradiation of a tungsten lamp, keeping the temperature dropwise adding time for 5 hours, and then preserving the heat for 5 hours; after centrifugation, concentrated hydrochloric acid was added to the supernatant to adjust ph=2 to obtain white crystals, and the white crystals were filtered to obtain 120g of a crude 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid product. The crude product is washed by deionized water for several times and then dried to obtain the pure product of 6,6' -dimethyl-3, 3', 4' -biphenyl tetracarboxylic acid with the purity of 99.5 percent and the whiteness of 79.4. Wherein, the sodium ion is 11.5ppm, the potassium ion, the calcium ion, the magnesium ion and other transition metal ions are not detected, the chloride ion is 10.8ppm, and other anions are not detected.
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride:
(3) 111g of the 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid obtained above was refluxed in 1620g of propionic anhydride for 5 hours, and filtered to obtain 100g of a crude product. The crude product was slurried with acetone, then filtered, the filter cake was washed 2 times with acetone, and dried to give 92g of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride in 92% yield. The purity was 99.3% and the whiteness was 78.2. Wherein, the sodium ion is 10.1ppm, the potassium ion, the calcium ion, the magnesium ion and other transition metal ions are not detected, the chloride ion is 10.0ppm, and other anions are not detected.
[ example 5 ]
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid:
(1) 2000g of distilled water dissolved with 90g of sodium hydroxide, 176g of 4-ethyl phthalic anhydride and 34g of tetrapropyl ammonium bromide are sequentially added into a reaction tank, 168g of liquid bromine is added under stirring at room temperature, and then the mixture is heated to 50 ℃ and stirred for 3 hours; after cooling to room temperature, 40g of 10wt% aqueous sodium dithionite solution was added, followed by neutralization with concentrated hydrochloric acid to ph=0, extraction of the aqueous phase with diethyl ether 3 times, drying of the organic phase with anhydrous sodium sulfate, and concentration to give 238g of 4-bromo-5-ethylphthalic acid as a white powdery crude product, which was used as such in the next step.
(2) Sequentially adding 1750g of aqueous solution containing 110g of potassium hydroxide, 238g of 4-bromo-5-ethylphthalic acid and 47g of nickel-palladium-carbon catalyst (wherein the palladium content is 0.1% and the nickel content is 1%) into a reaction kettle, heating to 40 ℃, dropwise adding 180g of aqueous solution containing 60g of sodium formate under the irradiation of an incandescent lamp, keeping the temperature dropwise adding time for 7 hours, and then preserving heat for 3 hours; after centrifugation, concentrated hydrochloric acid was added to the supernatant to adjust ph=2 to obtain white crystals, and the white crystals were filtered to obtain 141g of a crude 6,6' -diethyl-3, 3', 4' -biphenyltetracarboxylic acid product. The crude product is washed by deionized water for several times and then dried to obtain the pure 6,6' -diethyl-3, 3', 4' -biphenyl tetracarboxylic acid product with the purity of 99.0% and the whiteness of 74.1. Wherein, the potassium ion is 12.5ppm, the sodium ion, the calcium ion, the magnesium ion and other transition metal ions are not detected, the chloride ion is 12.9ppm, and other anions are not detected.
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride:
(3) 135g of the above-obtained 6,6' -diethyl-3, 3', 4' -biphenyltetracarboxylic acid was refluxed in 900g of oxalyl chloride for 6 hours, and then filtered to obtain 118g of a crude product. The crude product is pulped by ethylene glycol dimethyl ether, then filtered, the filter cake is washed by the ethylene glycol dimethyl ether for 2 times, and 111g of 6,6' -diethyl-3, 3', 4' -biphenyl tetracarboxylic dianhydride is obtained by drying, the yield is 91%, the purity is 98.9%, and the whiteness is 72.3. Wherein, the potassium ion is 11.1ppm, the sodium ion, the calcium ion, the magnesium ion and other transition metal ions are not detected, the chloride ion is 12.0ppm, and other anions are not detected.
[ example 6 ]
6,6 '-dimethyl-3, 3',preparation of 4,4' -biphenyltetracarboxylic acid:
(1) Distilled water 2000g,246g of 4-trifluoromethyl phthalic anhydride and 25g of tetrabutylammonium bromide dissolved with 90g of sodium hydroxide are added into a reaction tank in sequence, 198g of liquid bromine is added under stirring at room temperature, and then the mixture is stirred for 12 hours at 35 ℃; after cooling to room temperature, 30g of 20wt% aqueous sodium sulfite solution was added, followed by neutralization with concentrated sulfuric acid to ph=1, extraction of the aqueous phase with methyl tert-butyl ether 3 times, drying of the organic phase with 4A molecular sieve, and concentration to give 282g of 4-bromo-5-trifluoromethylphthalic acid as a white powdery crude product, which was used directly as the next step.
(2) 1800g of aqueous solution containing 70.5g of sodium hydroxide, 282g of 4-bromo-5-trifluoromethyl phthalic acid and 28g of 1% palladium-carbon catalyst are sequentially added into a reaction kettle, the temperature is raised to 70 ℃, 400g of aqueous solution containing 170g of glucose is dropwise added under the irradiation of an LED lamp, the dropwise adding time of the temperature is kept for 6 hours, and then the temperature is kept for 4 hours; after centrifugation, 50% sulfuric acid was added to the supernatant to adjust the ph=2, to obtain white crystals, and the white crystals were filtered to obtain 170g of a crude 6,6' -bistrifluoromethyl-3, 3', 4' -biphenyltetracarboxylic acid. The crude product is washed by deionized water for several times and then dried to obtain the pure product of 6,6' -bistrifluoromethyl-3, 3', 4' -biphenyl tetracarboxylic acid, wherein the purity is 99.0 percent and the whiteness is 73.2. Wherein, the sodium ion is 4.8ppm, and the calcium ion, the magnesium ion and other transition metal ions are not detected, and the anions are not detected.
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride:
(3) 161g of the 6,6' -bistrifluoro-3, 3', 4' -biphenyltetracarboxylic acid obtained above was refluxed in 840g of oxalyl chloride for 7 hours, and filtered to obtain 152g of crude product. The crude product was slurried with 1,4 dioxane, then filtered, and the filter cake was washed 2 times with 1,4 dioxane, and dried to give 140g of 6,6' -bistrifluoro-3, 3', 4' -biphenyltetracarboxylic dianhydride in 94% yield, 98.7% purity and 70.9% whiteness. Wherein, the sodium ion is 4.1ppm, and the calcium ion, the magnesium ion and other transition metal ions are not detected, and the anions are not detected.
[ example 7 ]
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid:
(1) 2000g of distilled water dissolved with 65g of potassium hydroxide, 204g of 4-butylphthalic anhydride and 25g of tetraethylammonium chloride are sequentially added into a reaction tank, 86g of chlorine is introduced under stirring at room temperature, and then the mixture is heated to 30 ℃ and stirred for 24 hours; after cooling to room temperature 20.4g of 20wt% hydrazine hydrate solution was added, followed by neutralization with phosphoric acid to ph=2, extraction of the aqueous phase with diethyl ether 3 times, drying of the organic phase with anhydrous sodium sulfate and concentration to give 206g of 4-chloro-5-butylphthalic acid as a white powdery crude product, which was used directly as the next step.
(2) Sequentially adding 1030g of an aqueous solution containing 133g of potassium hydroxide, 206g of the 4-chloro-5-butylphthalic acid and 30g of a nickel-palladium-carbon catalyst (wherein the palladium content is 0.5 percent and the nickel content is 3 percent) into a reaction kettle, heating to 85 ℃, dropwise adding 164g of an aqueous solution containing 41g of isopropanol under the irradiation of a xenon lamp, keeping the temperature dropwise adding time for 8 hours, and then keeping the temperature for 0.5 hour; then, centrifugal separation was performed, concentrated hydrochloric acid was added to the supernatant to adjust the ph=1, white crystals were obtained, and 168g of a crude 6,6' -dibutyl-3, 3', 4' -biphenyltetracarboxylic acid product was obtained by filtration. The crude product is washed by deionized water for several times and then dried to obtain the pure product of 6,6' -dibutyl-3, 3', 4' -biphenyl tetracarboxylic acid with the purity of 99.1 percent and the whiteness of 77.6. Wherein, the potassium ion is 5.1ppm, and sodium ion, calcium ion, magnesium ion and other transition metal ions are not detected, and anions are not detected.
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride:
(3) 159g of the 6,6' -dibutyl-3, 3', 4' -biphenyltetracarboxylic acid obtained above was refluxed in 1140g of acetyl chloride for 8 hours, and the crude product was obtained by filtration. The crude product was slurried with methyltetrahydrofuran, followed by filtration, and the cake was washed with methyltetrahydrofuran 2 times and dried to give 136g of 6,6' -dibutyl-3, 3', 4' -biphenyltetracarboxylic dianhydride in 95% yield. The purity was 98.9% and the whiteness was 74.2. Wherein, the potassium ion is 4.1ppm, and sodium ion, calcium ion, magnesium ion and other transition metal ions are not detected, and anions are not detected.
[ example 8 ]
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid:
(1) 2000g of distilled water dissolved with 90g of sodium hydroxide, 162g of 4-methyl phthalic anhydride and 55g of tetrapropyl ammonium iodide are sequentially added into a reaction tank, 162g of iodine simple substance is added under stirring at room temperature, and then the mixture is heated to 60 ℃ and stirred for 36 hours; after cooling to room temperature, 30g of 25wt% aqueous sodium bisulphite solution was added, followed by neutralization with concentrated hydrochloric acid to ph=1, extraction of the aqueous phase with ethyl acetate 3 times, drying of the combined organic phase with anhydrous magnesium sulfate, and concentration to give 201g of the crude product 4-iodo-5-methylphthalic acid as a white powder, which was used as such for the next step.
(2) Sequentially adding 2010g of aqueous solution containing 100g of sodium hydroxide, 201g of the 4-iodo-5-methylphthalic acid and 18g of nickel-palladium-carbon catalyst (wherein the palladium content is 8 percent and the nickel content is 0.8 percent) into a reaction kettle, heating to 95 ℃, dropwise adding 132g of aqueous solution containing 33g of hydrazine hydrate under the irradiation of an LED lamp, keeping the dropwise adding time at the temperature for 4 hours, and then preserving the heat for 1 hour; after centrifugation, concentrated hydrochloric acid was added to the supernatant to adjust ph=2 to give white crystals, and the crystals were filtered to give 133g of a crude 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid. The crude product is washed by deionized water for several times and then dried to obtain the pure 6,6' -dimethyl-3, 3', 4' -biphenyl tetracarboxylic acid product with the purity of 98.9 percent and the whiteness of 76.3. Wherein, the sodium ion is 12.3ppm, and the calcium ion, the magnesium ion and other transition metal ions are not detected, and the anions are not detected.
Preparation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride:
(3) 125g of the above-obtained 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid was refluxed in 900g of oxalyl chloride for 2 hours, and the crude product 110g was obtained by filtration. The crude product was slurried with tetrahydrofuran, followed by filtration, and the cake was washed with tetrahydrofuran 2 times and dried to give 105g of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic dianhydride in 93% yield. The purity was 98.9% and the whiteness was 73.1. Wherein, the sodium ion is 9.1ppm, and the calcium ion, the magnesium ion and other transition metal ions are not detected, and the anions are not detected.
Comparative example 1
Referring to the method described in the prior document (patent CN1526710A, 2003), 49g of 4-methylphthalic acid monosodium salt and 170g of water are added into a three-port reaction bottle, the mixture is heated to 90 ℃ until the mixture is dissolved and then cooled to 70 ℃, chlorine gas is introduced into the bottom of the reaction liquid at a speed of 0.127g/min, the reaction temperature is controlled to be 70 ℃ and the reaction is carried out for 1 hour, naHCO is added in the reaction process 3 The solution is neutralized with byproduct hydrogen chloride to ensure that the pH value of a reaction system is basically unchanged, then the chlorine speed is changed to 0.082g/min, the reaction is carried out for 3 hours at 50 ℃, 30g of concentrated hydrochloric acid is added for acidification for 2 hours, then the reaction is cooled to room temperature, 45g of crude product is obtained by extraction and spin drying with diethyl ether, the purity of 4-chloro-5-methylphthalic acid is 36 percent by HPLC determination, and a large amount of unreacted 4-methylphthalic acid exists in the crude product.
Comparative example 2
Referring to the method described in the prior art, 60g of water and 76g (32% concentration) of liquid alkali are added to a four-necked flask equipped with a thermometer, a stirrer, a dropping device and a reflux device, 37g of purified 4-chloro-5-methylphthalic acid monosodium salt and 0.4g of nickel palladium carbon catalyst (dry basis) are added under stirring, the temperature is raised to reflux, a mixed liquid of 16g of hydroxylamine hydrochloride and 60g of water is dropped, the dropping speed is controlled, the liquid level is kept stable, the reflux state is kept, and the dropping time is about 6 hours. The temperature is kept for 1.5 hours after the dripping. Cooling to 85 ℃, and filtering while the mixture is hot to obtain filtrate for standby.
100g of water and 35g of sulfuric acid (98% concentration) are added into a four-mouth bottle provided with a thermometer, a stirrer, a dripping device and a reflux device, the temperature is raised to reflux, the filtrate is dripped, the reflux is kept for 4 hours, and the reflux is kept for 2 hours. Cooling to 85 ℃, filtering while the mixture is hot to obtain 13g of product solid, and analyzing the main component of the crude product to be 4-methylphthalic acid, wherein the formation of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid is not detected.
[ Experimental example ]
1. Nuclear magnetic resonance characterization
The results of nuclear magnetic resonance hydrogen spectrum characterization of the 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid prepared in example 1 are shown in fig. 2, in which a single peak of about δ=7.85 ppm is attributed to carbon number 6 between carbonyl group and biphenyl bond on benzene ring, which is affected by carbonyl group to move toward low field; the single peak at δ=7.65 ppm is attributed to carbon number 3 between carbonyl and methyl groups, which, together with methyl electron donating and carbonyl electron withdrawing, affects hydrogen on carbon number 6 with a chemical shift less than that of carbon number 6; δ=2.50 ppm is the solvent peak of deuterated dimethyl sulfoxide; the single peak of delta=2.41 ppm is attributed to hydrogen on methyl, indicating that 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid was prepared. And the obtained nuclear magnetic spectrum is pure, no other obvious signal peaks are found, and the content of other impurities in the sample is less than 5%.
The 6,6 '-dimethyl-3, 3',4 '-biphenyltetracarboxylic acid prepared in examples 2 to 8 was also characterized by nuclear magnetic resonance hydrogen spectrum, and it was confirmed that 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid was obtained.
2. Mass spectrometry characterization
The mass spectrum of 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid prepared in example 1 was characterized, and the results are shown in FIG. 3, wherein [ M-H ]] － (C 8 H 13 O 8 ) The m/z theory of (2) is 357.0610, the actual measurement is 357.060; [ M-2H] 2- /2(C 9 H 6 O 4 ) The m/z theory of (2) is 178.0266, the actual measurement is 178.0260; [ M-2H+Na ]] － (C 18 H 12 NaO 8 ) Is 379.0430 and the actual value is 379.0422. The above description is that 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid was prepared.
Mass spectrometry was performed in the same manner as for 6,6 '-dimethyl-3, 3',4 '-biphenyltetracarboxylic acid prepared in examples 2 to 8, and it was confirmed that 6,6' -dimethyl-3, 3', 4' -biphenyltetracarboxylic acid was obtained.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (16)
1. The structure of the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid is shown as a formula (I), wherein R is selected from hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyl or substituted hydrocarbyloxy, and two R are the same or different:
wherein the purity of the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid is more than 95 percent, and the whiteness is more than 70.
2. The 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid as claimed in claim 1, wherein in formula (I), R is selected from alkyl, alkoxy, substituted alkyl or substituted alkoxy, and two R are the same or different;
preferably, in formula (I), R is selected from C1-C10 alkyl, C1-C10 alkoxy, C1-C10 substituted alkyl or C1-C10 substituted alkoxy, two R being the same or different;
more preferably, in formula (I), R is selected from C1-C4 alkyl, C1-C4 alkoxy, C1-C4 substituted alkyl or C1-C4 substituted alkoxy, and two R are the same or different.
3. The 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid as claimed in claim 1, wherein,
the purity of the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is greater than 98%, preferably greater than 98.5%; and/or the number of the groups of groups,
the total content of cations in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is less than 150ppm, preferably less than 100ppm; and/or the number of the groups of groups,
The total content of anions in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is less than 150ppm, preferably less than 100ppm.
4. The 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid as claimed in claim 3,
the content of alkali metal ions in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is less than or equal to 20ppm, the content of alkaline earth metal ions is less than or equal to 20ppm, the content of transition metal ions is less than or equal to 5ppm, preferably, the alkali metal ions comprise sodium ions and/or potassium ions, the alkaline earth metal ions comprise calcium ions and/or magnesium ions, and the transition metal ions comprise at least one of copper ions, iron ions, manganese ions, nickel ions, cobalt ions, lead ions and zinc ions; and/or the number of the groups of groups,
the content of each anion in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is independently less than or equal to 30ppm, wherein the anion comprises at least one of chloride ion, sulfate ion, phosphate ion and silicate ion.
5. A process for the preparation of 6,6 '-disubstituted-3, 3',4 '-biphenyltetracarboxylic acid, preferably for the preparation of 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid according to any one of claims 1 to 4, wherein said process comprises:
(1) Mixing 4-substituted phthalic acid and/or anhydride thereof, quaternary ammonium salt and strong alkali aqueous solution, adding halogen simple substance, reacting, adding reducing agent solution after the reaction is finished, and performing post-treatment to obtain an intermediate product I;
(2) And adding the intermediate product I into an inorganic alkaline water solution, adding a catalyst and a reducing agent, and carrying out reaction and post-treatment to obtain the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid.
6. The process according to claim 5, wherein in step (1),
the substituent in the 4-substituted phthalic acid and/or anhydride thereof is selected from the group consisting of a hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon group, and a substituted hydrocarbon oxy group, preferably from an alkyl group, an alkoxy group, a substituted alkyl group, or a substituted alkoxy group, more preferably from a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C1 to C10 substituted alkyl group, or a C1 to C10 substituted alkoxy group; and/or the number of the groups of groups,
the structural formula of the quaternary ammonium salt is shown as (R) 1 R 2 R 3 R 4 ) NY is shown, wherein R 1 、R 2 、R 3 、R 4 Each independently selected from one of C1-C20 alkyl, and Y is selected from one of halogen anions and acid radical anions; and/or the number of the groups of groups,
the strong base is at least one of sodium hydroxide, potassium hydroxide and cesium hydroxide; and/or the number of the groups of groups,
the halogen simple substance is at least one selected from chlorine, bromine and iodine simple substances.
7. The process according to claim 5, wherein in step (1),
the weight ratio of the quaternary ammonium salt to the 4-substituted phthalic acid and/or the anhydride thereof is (0.1-0.5): 1; and/or the number of the groups of groups,
the weight ratio of the halogen simple substance to the 4-substituted phthalic acid and/or the anhydride thereof is (0.4-1): 1; and/or the number of the groups of groups,
the weight ratio of the strong alkali to the 4-substituted phthalic acid and/or the anhydride thereof in the strong alkali aqueous solution is 1 (1-4), preferably 1 (1.8-3.2); and/or the number of the groups of groups,
the weight ratio of the strong alkali aqueous solution to the 4-substituted phthalic acid and/or the anhydride thereof is (5-20): 1.
8. The method according to claim 5, wherein,
in the step (1), the reaction temperature is 0-100 ℃ and the reaction time is 3-36 hours;
and/or the number of the groups of groups,
in the step (1), cooling to room temperature after the reaction is finished, and adding a reducing agent solution; preferably, the reducing agent solution is selected from at least one of sodium sulfite solution, sodium bisulfite solution, sodium thiosulfate solution, sodium dithionite solution, hydrazine hydrate and hydroxylamine solution, preferably, the weight concentration of the reducing agent solution is 10-25 wt%, more preferably, the weight-to-weight ratio of the reducing agent solution to 4-substituted phthalic acid and/or anhydride thereof is (0.1-0.4): 1;
And/or the number of the groups of groups,
in step (1), the post-processing includes: (a) adjusting the pH of the reaction system to between 0 and 4, preferably between 1 and 2, (b) extracting the organic phase with an organic solvent, (c) drying the organic phase, optionally concentrating to obtain the intermediate product I.
9. The process according to any one of claims 5 to 8, wherein,
in the step (2), the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate; preferably, the weight ratio of the inorganic base to the intermediate product I is (0.25-0.75): 1; and/or, preferably, the weight ratio of the inorganic alkaline aqueous solution to the intermediate product I is (5.0-10.0): 1;
and/or the number of the groups of groups,
in step (2), the catalyst is selected from palladium on carbon catalyst and/or nickel palladium on carbon catalyst;
preferably, the palladium content in the palladium-carbon catalyst is 1-20% of the total mass of the palladium-carbon catalyst; and/or the palladium content in the nickel-palladium-carbon catalyst is 0.1-8% of the total mass of the nickel-palladium-carbon catalyst, and the mass ratio of palladium to nickel is 1:0.1-1:10; more preferably, the catalyst is used in an amount of 0.1 to 20wt% of intermediate I.
10. The method according to claim 9, wherein,
In step (2), the reducing agent is added under visible light irradiation, and the reaction is performed under visible light irradiation; preferably, the reducing agent is selected from one or more of hydroxylamine hydrochloride, hydroxylamine sulfate, hydrazine hydrate, hydrazine hydrochloride, hydrazine sulfate, glycerol, glucose, sodium formate, potassium formate, ammonium formate, isopropanol; more preferably, the weight ratio of the reducing agent to the intermediate product I is 1 (1-6); more preferably, the reducing agent is added dropwise in the form of an aqueous solution for a period of 4 to 24 hours, preferably 6 to 8 hours, and the incubation period is 0 to 6 hours, preferably 2 to 3 hours;
and/or the number of the groups of groups,
in the step (2), the temperature of the reaction is 40-120 ℃;
and/or the number of the groups of groups,
in step (2), the post-processing includes: firstly, centrifugally separating, adding a strong acid substance into supernatant to generate a coarse product precipitate of the 6,6 '-disubstituted-3, 3',4 '-biphenyl tetracarboxylic acid, and finally, washing with water to obtain a pure product of the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid; preferably, in the post-treatment of step (2), a strongly acidic substance is added to adjust the pH of the reaction system to 1 to 4.
11. The structure of the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic dianhydride is shown as a formula (II), wherein R is selected from hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyl or substituted hydrocarbyloxy, and two R are the same or different:
Wherein the purity of the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic dianhydride is more than 95 percent, and the whiteness is more than 70.
12. The 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride according to claim 11 wherein in formula (II) R is selected from alkyl, alkoxy, substituted alkyl or substituted alkoxy, two R being the same or different; preferably, R is selected from C1-C10 alkyl, C1-C10 alkoxy, C1-C10 substituted alkyl or C1-C10 substituted alkoxy, and two R are the same or different.
13. The 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride as claimed in claim 11 or 12,
the purity of the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride is greater than 98%, preferably greater than 98.5%; and/or the number of the groups of groups,
the total content of cations in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride is less than 150ppm, preferably less than 100ppm; and/or the number of the groups of groups,
the total content of anions in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride is less than 150ppm, preferably less than 100ppm.
14. The 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride as set forth in claim 13,
the content of alkali metal ions in the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride is 20ppm or less, the content of alkaline earth metal ions is 20ppm or less, the content of transition metal ions is 5ppm or less, preferably, the alkali metal ions comprise sodium ions and/or potassium ions, the alkaline earth metal ions comprise calcium ions and/or magnesium ions, and the transition metal comprises at least one selected from copper ions, iron ions, manganese ions, nickel ions, cobalt ions, lead ions and zinc ions; and/or the number of the groups of groups,
The content of each anion in the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic dianhydride is independently less than or equal to 30ppm, wherein the anion comprises at least one of chloride ion, sulfate ion, phosphate ion and silicate ion.
15. A process for the preparation of 6,6 '-disubstituted-3, 3',4 '-biphenyltetracarboxylic dianhydride, preferably for the preparation of 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride as claimed in any one of claims 11 to 14, wherein the process comprises: the preparation method of one of claims 5 to 10 is adopted to obtain 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid, and the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic acid is dehydrated and washed to obtain the 6,6' -disubstituted-3, 3', 4' -biphenyltetracarboxylic dianhydride.
16. The method according to claim 15, wherein,
the dehydration treatment is carried out by adopting a dehydrating agent, wherein the dehydrating agent is one or more selected from acetyl chloride, propionyl chloride, acetic anhydride, propionic anhydride, oxalyl chloride, thionyl chloride and di-tert-butyl dicarbonate; and/or the number of the groups of groups,
the mass ratio of the dehydrating agent to the 6,6' -disubstituted-3, 3', 4' -biphenyl tetracarboxylic acid is (4-15) 1; and/or the number of the groups of groups,
The dehydration treatment is performed as follows: refluxing for 2-8 hours in the presence of a dehydrating agent; and/or the number of the groups of groups,
the washing is performed with an aprotic solvent, preferably selected from one or more of methyl tert-butyl ether, diethyl ether, 1, 4-dioxane, acetone, methyl isopropyl ketone, ethylene glycol dimethyl ether, tetrahydrofuran, methyl tetrahydrofuran.
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