CN114478291A - Preparation method of monomer diamine compound of polyimide - Google Patents
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- CN114478291A CN114478291A CN202210234439.5A CN202210234439A CN114478291A CN 114478291 A CN114478291 A CN 114478291A CN 202210234439 A CN202210234439 A CN 202210234439A CN 114478291 A CN114478291 A CN 114478291A
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Abstract
The invention discloses a preparation method of a monomer diamine compound of polyimide, which comprises the following steps: adding o-chloro-p-nitrophenol and a first inorganic base into a mixed system of dioxane and water, and then adding a methylating reagent for reaction, extraction and liquid separation to obtain an o-chloro-p-nitroanisole solution; adding potassium carbonate, phenylboronic acid and tetrabutylammonium bromide into an o-chloro-p-nitrotoluene ether solution to perform Suzuki coupling reaction, adding a second inorganic base for alkaline hydrolysis, and performing deprotection reaction to obtain 2-hydroxy 5-nitrobiphenyl; carrying out esterification reaction on 2-hydroxy 5-nitrobiphenyl, triethylamine, an esterification catalyst and p-nitrobenzoyl chloride to obtain 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester; and (3) carrying out hydrogenation reaction on the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester and the second reaction solvent. The preparation process of the invention adopts classical reaction and conventional operation, the reaction is safe and simple, and the high selectivity and high quality synthesis of the product are realized.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of a monomer diamine compound of polyimide.
Background
Generally, Polyimide (PI) resins have excellent mechanical strength, abrasion resistance, dimensional stability, corrosion resistance and other excellent properties in addition to high heat resistance, and are widely used in the field of electronic materials such as flexible printed circuit boards, and are widely used in advanced technical fields such as aviation, aerospace, construction, automobiles, separation membranes, nano-meter and laser in addition to the field of electronic devices, and thus have been receiving wide attention from researchers.
The most important raw materials for polyimides are aromatic diamines and aromatic dianhydrides, of which 4,4' -diaminodiphenyl ether (ODA) and 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) are the most widely used.
One new class of polyimide monomeric diamine compounds is currently available: 4-aminobenzoic acid-5-aminobiphenyl-2-yl phenol ester (4-Amino-benzoic acid 5-Amino-phenyl-2-yl ester) has also received much attention, and the compound structure thereof is shown below:
the molecular formula of the compound is C19H16N2O2CAS No.: 2152614-82-7.
Studies have shown that this compound results in improvements in many properties of the polyimide product compared to conventional diamine ODA use: the introduction of ester bonds reduces the toxicity of diamine compounds, and has low thermal expansion coefficient and low water absorption; the introduction of the phenyl group leads to the improvement of the solubility and the melt-forming property of the final product.
Japanese technology introduces a synthesis method of the compound, which takes 2-phenylphenol (CAS NO.90-43-7) as a raw material to carry out nitration reaction, esterification and hydrogenation, the first step of the technical route adopts nitration reaction, the selectivity of the reaction is poor, the yield is low, the post-treatment is complex, the amount of three wastes is large, and the quality of the product obtained according to the process can hardly meet the actual requirement.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a monomer diamine compound of polyimide, which solves the problems of complex preparation process and low yield existing in the preparation method of the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing a monomeric diamine compound of polyimide, comprising the steps of:
step 1: adding o-chloro-p-nitrophenol and a first inorganic base into a mixed system of dioxane and water, then adding a methylating reagent for reaction, and extracting and separating liquid to obtain an o-chloro-p-nitroanisole solution;
step 2: adding potassium carbonate, phenylboronic acid and tetrabutylammonium bromide into the o-chloro-p-nitrotoluene ether solution prepared in the step 1, performing Suzuki coupling reaction under the catalysis of a palladium catalyst, adding a second inorganic base after the reaction is finished, performing alkaline hydrolysis, and performing deprotection reaction to obtain 2-hydroxy-5-nitrobiphenyl;
and step 3: carrying out esterification reaction on the 2-hydroxy 5-nitrobiphenyl prepared in the step 2, an esterification catalyst and p-nitrobenzoyl chloride to obtain 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester;
and 4, step 4: and (3) carrying out hydrogenation reaction on the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester prepared in the step (3) and a second reaction solvent under the catalysis of a catalyst to prepare 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester.
Further, in the step 1, the o-chloro-p-nitrophenol and the first inorganic base are added into a mixed system of dioxane and water, the temperature is raised to 40-50 ℃, then the methylating agent is added, and the temperature is raised to 80-90 ℃ for heat preservation reaction.
Furthermore, in the step 1, after the methylating agent is added for reaction, the temperature of the reaction solution is adjusted to 30-60 ℃, and toluene is added for extraction.
Illustratively, in the step 1, the methylating agent is one of methyl iodide, dimethyl carbonate and dimethyl sulfate, preferably methyl iodide; the first inorganic base is one of sodium hydroxide, potassium carbonate, potassium hydroxide and sodium hydride, preferably potassium carbonate.
Further, in the step 2, after the deprotection reaction is finished, removing the lower-layer water phase, washing with water, cooling to 0-5 ℃ after washing with water, crystallizing, and filtering to obtain the 2-hydroxy 5-nitrobiphenyl.
Illustratively, the palladium catalyst in step 2 is one of palladium on carbon, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) dichloride, dichloro-di-tert-butyl- (4-dimethylaminophenyl) palladium (II), preferably tetrakis (triphenylphosphine) palladium (0); the second inorganic base is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.
Further, in the step 3, the 2-hydroxy 5-nitrobiphenyl and the esterification catalyst are firstly dissolved in the first reaction solvent, and then the paranitrobenzoyl chloride is added for reaction. Illustratively, the esterification catalyst is triethylamine or pyridine, preferably triethylamine; the first reaction solvent is one of DCM, DCE, acetonitrile and THF, preferably acetonitrile.
Further, after the esterification reaction in the step 3 is finished, cooling to below 0 ℃ for filtering, then adding water for pulping, performing suction filtration to obtain a pulped product, then adding ethanol into the pulped product for boiling and washing, and performing suction filtration to obtain the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester.
Further, after the hydrogenation reaction in the step 4 is finished, filtering and negative pressure concentrating are carried out, methanol is added for pulping, the temperature is reduced to 0-5 ℃, filtering and drying are carried out, and the 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester is obtained.
Illustratively, the catalyst in the step 4 is one of palladium carbon, raney nickel and platinum carbon, preferably palladium carbon; the second reaction solvent is one of methanol, ethanol, isopropanol, DMAC, THF, ethyl acetate and acetonitrile, and preferably isopropanol.
Compared with the prior art, the invention has the following beneficial effects: the preparation method of the monomer diamine compound of the polyimide avoids the problems of nitration reaction with high pollution and high risk, troublesome post-treatment and low yield, adopts the classical reaction and the conventional operation in the preparation process, has safe and simple reaction, realizes the synthesis of products with high selectivity and high quality, has high solubility and melt formability in an organic solvent, and provides a new choice for realizing the performance improvement of the polyimide compound.
Drawings
FIG. 1 is an MS spectrum of 2-hydroxy-5-nitrobiphenyl as an intermediate in the preparation process of the present invention;
FIG. 2 is an MS spectrum of 4-aminobenzoic acid-5 aminobiphenyl 2 phenol ester prepared by the present invention;
FIG. 3 is an HPLC chromatogram of 4-aminobenzoic acid-5 aminobiphenyl 2 phenol ester prepared according to the present invention.
Detailed Description
The invention discloses a preparation method of a monomer diamine compound of polyimide, which comprises the following steps:
more specifically, the present invention discloses a method for preparing a monomeric diamine compound of polyimide, comprising the steps of:
step 1: adding o-chloro-p-nitrophenol and a first inorganic base into a mixed system of dioxane and water, then adding a methylating reagent for reaction, and extracting and separating liquid to obtain an o-chloro-p-nitroanisole solution;
further, the mol ratio of the o-chloro-p-nitrophenol to the first inorganic base is 1:1-1.5, preferably 1: 1.2; the molar ratio of the o-chloro-p-nitrophenol to the methylating agent is 1:1-1.5, preferably 1: 1.3. The dioxane and the water are used as solvents, can be determined according to the adding amount and the solubility of the o-chloro-p-nitrophenol and the first inorganic base, and can be arranged in an excessive amount.
Further, in the step 1, adding o-chloro-p-nitrophenol and first inorganic base into a mixed system of dioxane and water, heating to 40-50 ℃, adding a methylating agent, heating to 80-90 ℃, and carrying out heat preservation reaction.
Furthermore, in step 1, after the methylation reagent is added to complete the reaction, the temperature of the reaction solution is adjusted to 30-60 ℃, and toluene is added to perform extraction. Specifically, the mass-to-volume ratio of the o-chloro-p-nitrophenol to the toluene is (1:3-5) kg/L, and preferably (1:4) kg/L.
In step 1, the methylating agent may be one of methyl iodide, dimethyl carbonate and dimethyl sulfate, preferably methyl iodide; the first inorganic base is one of sodium hydroxide, potassium carbonate, potassium hydroxide and sodium hydride, preferably potassium carbonate.
Step 2: adding potassium carbonate, phenylboronic acid and tetrabutylammonium bromide into the o-chloro-p-nitrotoluene ether solution prepared in the step 1, performing Suzuki coupling reaction in the presence of a palladium catalyst, adding a second inorganic base for alkaline hydrolysis after the reaction is finished, and performing deprotection reaction to obtain 2-hydroxy-5-nitrobiphenyl;
further, the mol ratio of the o-chloro-p-nitroanisole to the potassium carbonate is 1:1-1.5, preferably 1: 1.2; the mol ratio of the o-chloro-p-nitroanisole to the phenylboronic acid is 1:1-1.3, preferably 1: 1.1; the mol ratio of the o-chloro-p-nitroanisole to the tetrabutylammonium bromide is 1:0.1-0.5, preferably 1: 0.3; the mol ratio of the o-chloro-p-nitroanisole to the palladium catalyst is 1:0.0005-0.0015, preferably 1: 0.001; the mol ratio of the o-chloro-p-nitroanisole to the second inorganic base is 1:1.5-3, preferably 1: 2.
And further, in the step 2, alkaline hydrolysis is carried out, after deprotection reaction is finished, a lower-layer water phase is removed, water washing is carried out again, the temperature is reduced to 0-5 ℃ after water washing, crystallization is carried out, and the 2-hydroxy 5-nitrobiphenyl is obtained after filtration.
Illustratively, the palladium catalyst in step 2 is one of palladium on carbon, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) dichloride, dichloro-di-tert-butyl- (4-dimethylaminophenyl) palladium (II), preferably tetrakis (triphenylphosphine) palladium (0); the second inorganic base is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.
And step 3: carrying out esterification reaction on the 2-hydroxy 5-nitrobiphenyl prepared in the step 2, an esterification catalyst and p-nitrobenzoyl chloride to obtain 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester;
further, the mass volume ratio of the 2-hydroxy 5-nitrobiphenyl to the esterification catalyst is (1:5-10) kg/L, preferably (1:8) kg/L; the molar ratio of 2-hydroxy 5-nitrobiphenyl to p-nitrobenzoyl chloride is 1:1 to 1.5, preferably 1: 1.2.
Further, in the step 3, the 2-hydroxy 5-nitrobiphenyl and the esterification catalyst are firstly dissolved in the first reaction solvent, and then the p-nitrobenzoyl chloride is added for reaction. Illustratively, the esterification catalyst is triethylamine or pyridine, preferably triethylamine; the first reaction solvent is one of DCM, DCE, acetonitrile and THF, and acetonitrile is preferred.
Further, after the esterification reaction in the step 3 is finished, cooling to below 0 ℃, filtering, adding water for pulping, performing suction filtration to obtain a pulped product, adding ethanol into the pulped product for boiling and washing, and performing suction filtration to obtain the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester.
And 4, step 4: and (3) carrying out hydrogenation reaction on the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester prepared in the step (3) and a second reaction solvent in the presence of a catalyst to prepare 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester, namely the monomer diamine compound of the polyimide to be prepared.
Further, the mass volume ratio of the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenol ester to the second reaction solvent is (1:5-10) kg/L, preferably (1:8) kg/L; the mass ratio of the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenol ester to the palladium carbon is 1:0.005-0.02, and preferably 0.01.
Further, after the hydrogenation reaction in the step 4 is finished, filtering and concentrating under negative pressure, adding methanol for pulping, cooling to 0-5 ℃, filtering and drying to obtain the 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester.
Illustratively, the catalyst in step 4 is one of palladium carbon, raney nickel and platinum carbon, preferably palladium carbon; the second reaction solvent is one of methanol, ethanol, isopropanol, DMAC, THF, ethyl acetate and acetonitrile, and preferably isopropanol.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The embodiment discloses a preparation method of a monomer diamine compound of polyimide, which specifically comprises the following steps:
step 1: adding 174ml of water, 348ml of dioxane, 173.6g of o-chloro-p-nitrophenol and 165.6g of potassium carbonate into a reaction device in sequence, heating the system to 43 ℃, then adding 184.6g of methyl iodide, heating the system to 80-90 ℃ for heat preservation reaction, cooling the system to 40 ℃ after the reaction is finished, adding 348ml of water into the system, extracting and washing with water by using 695ml of toluene, separating liquid to obtain an o-chloro-p-nitrophenol methyl ether solution, wherein the content is 98.5% by HPLC (high performance liquid chromatography) detection, and the yield is 100%;
step 2: adding the p-o-chloro-p-nitrotoluene ether solution prepared in the step 1, 165.5g of potassium carbonate, 134.2g of phenylboronic acid and 96.7g of tetrabutylammonium bromide into a reaction device in sequence, adding 1.16g of tetrakis (triphenylphosphine) palladium (0) and 348ml of purified water, starting stirring, heating the system to 80 ℃ for reaction, keeping the temperature for 5 hours, cooling the system to 55 ℃ after the reaction is finished, adding 80g of sodium hydroxide into the system, continuously keeping the temperature for 55 ℃ for reaction for 5 hours, separating a lower aqueous phase from the system after the reaction is finished, washing the organic phase twice, cooling to 4 ℃, filtering and drying to obtain 182.5g of 2-hydroxy-5-nitrobiphenyl, wherein the content is 99.2% by HPLC (high performance liquid chromatography), and the yield is 84.8%;
and step 3: then taking another reaction device, sequentially adding 1460ml of acetonitrile, 182.5g of 2-hydroxy 5-nitrobiphenyl, 111.6g of triethylamine and 188.9g of p-nitrobenzoyl chloride, starting stirring, controlling the temperature of the system to be 45 ℃, preserving heat for reaction for 4 hours, finishing the reaction, cooling the system to 0 ℃, filtering and drying to obtain 265.4g of refined 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester, wherein the content is 99.5% by HPLC (high performance liquid chromatography), and the yield is 85.9%;
and 4, step 4: and (2) adding 2123ml of isopropanol into a reaction device again, sequentially adding 265.4g of 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester and 2.65g of palladium carbon, starting stirring, replacing the system with hydrogen twice, controlling the temperature of the system to carry out hydrogenation reaction at 35 ℃, reacting for 24 hours, filtering the system to remove the palladium carbon after the reaction is finished, carrying out organic phase decompression concentration, adding methanol to precipitate a product, drying to obtain 210.6g of fine 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester, wherein the content is 99.8% by HPLC (high performance liquid chromatography), and the yield is 95%.
Example two
This example discloses a method for preparing a monomeric diamine compound of polyimide, which includes the steps of:
step 1: adding 174ml of water, 348ml of dioxane, 173.6g of o-chloro-p-nitrophenol and 40.0g of sodium hydroxide into a reaction device in sequence, adjusting the temperature of the system to 40 ℃, adding 126.1g of dimethyl sulfate, heating the system to 80 ℃ for heat preservation reaction, cooling the system to 40 ℃ after the reaction is finished, adding 348ml of water and 695ml of toluene into the system for extraction and water washing, separating liquid to obtain an o-chloro-p-nitrophenol methyl ether solution, wherein the content is 97.8 percent through HPLC detection, and the yield is 100 percent;
step 2: adding 165.5g of p-o-chloro-p-nitrotoluene ether solution prepared in the step 1, 165.5g of potassium carbonate, 134.2g of phenylboronic acid and 96.7g of tetrabutylammonium bromide into a reaction device in sequence, adding 1.06g of palladium catalyst bis (triphenylphosphine) palladium (II) dichloride and 348ml of purified water, starting stirring, heating the system to 84 ℃ for reaction, keeping the temperature for reaction for 4.5h, cooling the system to 51 ℃ after the reaction is finished, adding 80.0g of sodium hydroxide into the system, keeping the temperature for reaction for 5h at 52 ℃, separating a lower water phase from the system after the reaction is finished, washing an organic phase twice, cooling to 2 ℃, filtering and drying to obtain 172.5g of 2-hydroxy-5-nitrobiphenyl, wherein the content is 99.1% through HPLC (high performance liquid chromatography), and the yield is 80.2%;
and step 3: adding excessive DCM 1380ml into another reaction device, adding 172.5g of 2-hydroxy 5-nitrobiphenyl, 81.1g of triethylamine and 148.8g of paranitrobenzoyl chloride, starting stirring, controlling the system temperature at 48 ℃, preserving heat for reaction for 4 hours, finishing the reaction, cooling the system to 3 ℃, filtering, drying to obtain 240.9g of refined 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester, wherein the content is 99.3 percent through HPLC (high performance liquid chromatography), and the yield is 82.5 percent;
and 4, step 4: pouring 1927ml of isopropanol serving as a solvent into a reaction device again, adding 240.9g of 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester and 4.8g of raney nickel, starting stirring, replacing the system with hydrogen twice, controlling the temperature of the system to carry out hydrogenation reaction at 38 ℃, reacting for 24 hours, filtering the system to remove raney nickel after the reaction is finished, carrying out reduced pressure concentration on the organic phase, adding methanol to precipitate a product, and drying to obtain 190.2g of refined 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester, wherein the content is 99.7% through HPLC detection, and the yield is 94.5%.
EXAMPLE III
This example discloses a method for preparing a monomeric diamine compound of polyimide, which includes the steps of:
step 1: adding excessive water 174ml and dioxane 348ml into a reaction device, uniformly stirring, sequentially adding 173.5g of o-chloro-p-nitrophenol and 84.0g of potassium hydroxide, adjusting the temperature of the system to 50 ℃, then adding 117.0g of dimethyl carbonate, heating the system to 90 ℃ for heat preservation reaction, cooling the system to 50 ℃ after the reaction is finished, adding 348ml of water and 695ml of toluene for extraction and washing, separating liquid to obtain an o-chloro-p-nitroanisole solution, wherein the content is 98.3% by HPLC (high performance liquid chromatography), and the yield is 100%;
step 2: adding the p-o-chloro-p-nitrotoluene ether solution prepared in the step 1, 165.5g of potassium carbonate, 134.2g of phenylboronic acid and 96.7g of tetrabutylammonium bromide into a reaction device in sequence, adding 0.71g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphorus palladium (II) and 348ml of purified water, starting stirring, heating the system to 80 ℃ for reaction, keeping the temperature for 5 hours, cooling the system to 55 ℃ after the reaction is finished, adding 84.0g of potassium hydroxide into the system, continuing keeping the temperature for reaction at 52 ℃ for 6 hours, separating a lower water phase out of the system after the reaction is finished, washing the organic phase twice, cooling to 5 ℃, filtering and drying to obtain 181.9g of 2-hydroxy-5-nitrobiphenyl, wherein the content is 99.1% by HPLC (high performance liquid chromatography), and the yield is 84.5%;
and step 3: and adding 1455ml of DCE into another reaction device, and then adding 181.9g of 2-hydroxy 5-nitrobiphenyl, 128.3g of triethylamine and 235.3g of p-nitrobenzoyl chloride. Starting stirring, controlling the temperature of the system to be 47 ℃, preserving heat for reaction for 5 hours, after the reaction is finished, cooling the system to be 3 ℃, filtering and drying to obtain 264.1g of refined 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenol ester, wherein the content is 99.5 percent through HPLC detection, and the yield is 85.7 percent;
and 4, step 4: pouring 2113ml of ethyl acetate serving as a solvent into a reaction device again, adding 264.1g of 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester and 5.28g of platinum carbon, starting stirring, replacing the system with hydrogen twice, controlling the temperature of the system to carry out hydrogenation reaction at 37 ℃, reacting for 20 hours, filtering the system to remove the platinum carbon after the reaction is finished, carrying out reduced pressure concentration on the organic phase, adding methanol to precipitate a product, drying to obtain 209.1g of refined 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester, wherein the content is 99.8 percent through HPLC detection, and the yield is 94.8 percent.
The MS spectrum of the intermediate product 2-hydroxy 5-nitrobiphenyl in the preparation process of the embodiment of the invention is shown in figure 1, and can be seen from the following:
the fragment information of the molecular ion peak in the GC-MS spectrogram is consistent with the GC-MS characteristic peak of the 2-hydroxy 5-nitrobiphenyl, which indicates that the 2-hydroxy 5-nitrobiphenyl prepared by the synthesis method has an accurate structure.
The MS spectrum and the HPLC spectrum of the finally prepared product 4-aminobenzoic acid-5-aminobiphenyl 2 phenol ester of the present invention are shown in fig. 2 and 3, respectively, from which it can be known that:
the fragment information of the molecular ion peak in a GC-MS spectrogram is consistent with the GC-MS characteristic peak of the 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester, so that the 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester synthesized by the method has a correct structure, and the HPLC spectrogram shows that the content of the 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester synthesized by the method exceeds 99.8 percent, and the use requirement of the polyimide monomer is met.
It should be noted that, in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for producing a monomeric diamine compound of polyimide, characterized by comprising the steps of:
step 1: adding o-chloro-p-nitrophenol and a first inorganic base into a mixed system of dioxane and water, then adding a methylating reagent for reaction, and extracting and separating liquid to obtain an o-chloro-p-nitroanisole solution;
and 2, step: adding potassium carbonate, phenylboronic acid and tetrabutylammonium bromide into the o-chloro-p-nitrotoluene ether solution prepared in the step 1, performing Suzuki coupling reaction under the catalysis of a palladium catalyst, adding a second inorganic base for alkaline hydrolysis after the reaction is finished, and performing deprotection reaction to obtain 2-hydroxy 5-nitrobiphenyl;
and step 3: carrying out esterification reaction on the 2-hydroxy 5-nitrobiphenyl prepared in the step 2, an esterification catalyst and p-nitrobenzoyl chloride to obtain 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester;
and 4, step 4: and (3) carrying out hydrogenation reaction on the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester prepared in the step (3) and a second reaction solvent under the catalysis of a catalyst to prepare 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester.
2. The method according to claim 1, wherein in step 1, o-chloro-p-nitrophenol and the first inorganic base are added into a mixed system of dioxane and water, the temperature is raised to 40-50 ℃, the methylating agent is added, and the temperature is raised to 80-90 ℃ for the heat preservation reaction.
3. The method according to claim 1 or 2, wherein in the step 1, after the addition of the methylating agent is completed, the temperature of the reaction solution is adjusted to 30 to 60 ℃ and toluene is added for extraction.
4. The method of claim 1, wherein in step 1, the methylating agent is one of methyl iodide, dimethyl carbonate and dimethyl sulfate; the first inorganic base is one of sodium hydroxide, potassium carbonate, potassium hydroxide and sodium hydride.
5. The preparation method according to claim 1, wherein in the step 2, after the deprotection reaction is finished, the lower aqueous phase is removed, and then water washing is carried out, after the water washing is finished, the temperature is reduced to 0-5 ℃, crystallization is carried out, and the 2-hydroxy 5-nitrobiphenyl is obtained by filtering.
6. The method according to claim 1, wherein the palladium catalyst in step 2 is one of palladium on carbon, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) dichloride, dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphonium palladium (II); the second inorganic base is sodium hydroxide or potassium hydroxide.
7. The method according to claim 1, wherein in step 3, the 2-hydroxy-5-nitrobiphenyl and the esterification catalyst are dissolved in a first reaction solvent, and then p-nitrobenzoyl chloride is added to react, wherein the first reaction solvent is one of DCM, DCE, acetonitrile and THF.
8. The preparation method according to claim 1 or 7, wherein the esterification reaction in the step 3 is completed, the temperature is reduced to below 0 ℃, the filtration is performed, then water is added for pulping, the pumping filtration is performed to obtain a pulping product, ethanol is added into the pulping product for boiling and washing, and the pumping filtration is performed after the boiling and washing to obtain the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenol ester.
9. The preparation method according to claim 1, wherein the 4-aminobenzoic acid-5-aminobiphenyl 2 phenol ester is obtained by filtering, concentrating under negative pressure, pulping by adding methanol, cooling to 0-5 ℃, filtering and drying after the hydrogenation reaction in the step 4 is completed.
10. The method of claim 1 or 9, wherein the catalyst in step 4 is one of palladium on carbon, raney nickel, and platinum on carbon; the second reaction solvent is one of methanol, ethanol, isopropanol, DMAC, THF, ethyl acetate and acetonitrile.
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| CN104725303A (en) * | 2015-02-02 | 2015-06-24 | 西安近代化学研究所 | Synthetic method of 2-chloro-N-(4'-chlorodiphenyl-2-yl) nicotinamide |
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| CN110198926A (en) * | 2017-01-27 | 2019-09-03 | 胜高科技股份有限公司 | Diamine compound and the polyimide compound and molding for using it |
| CN110483225A (en) * | 2019-09-11 | 2019-11-22 | 陕西师范大学 | A kind of water phase Suzuki cross-coupling reaction of the palladium chtalyst without additional ligand |
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| CN104725303A (en) * | 2015-02-02 | 2015-06-24 | 西安近代化学研究所 | Synthetic method of 2-chloro-N-(4'-chlorodiphenyl-2-yl) nicotinamide |
| CN110198926A (en) * | 2017-01-27 | 2019-09-03 | 胜高科技股份有限公司 | Diamine compound and the polyimide compound and molding for using it |
| CN108191674A (en) * | 2018-02-11 | 2018-06-22 | 邵玉田 | A kind of synthetic method of benzidine compound |
| CN110483225A (en) * | 2019-09-11 | 2019-11-22 | 陕西师范大学 | A kind of water phase Suzuki cross-coupling reaction of the palladium chtalyst without additional ligand |
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