CN111808028A - Synthesis method and application of aminobenzimidazole naphthalenesulfonic acid compound - Google Patents
Synthesis method and application of aminobenzimidazole naphthalenesulfonic acid compound Download PDFInfo
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- CN111808028A CN111808028A CN202010709639.2A CN202010709639A CN111808028A CN 111808028 A CN111808028 A CN 111808028A CN 202010709639 A CN202010709639 A CN 202010709639A CN 111808028 A CN111808028 A CN 111808028A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
Abstract
The invention relates to the technical field of preparation of amino naphthalene sulfonic acid compounds, in particular to a synthesis method and application of an amino benzimidazole naphthalene sulfonic acid compound. The method comprises the following steps: 1) dissolving 0.1mol of carboxyl naphthalene sulfonic acid and 0.15-0.25 mol of aminonitrobenzene in polyphosphoric acid to prepare a reaction solution; 2) placing the reaction solution in a reaction kettle, heating to 180-200 ℃, reacting for 1.5-10 hours, then adding water for precipitation, and filtering to obtain an intermediate product A; washing the intermediate product A with acid to obtain an intermediate product B; 3) and dissolving the intermediate product B in a solvent, and introducing hydrogen to reduce under the action of a catalyst to obtain the catalyst. According to the invention, through molecular design of reaction monomer raw materials and protection of amino groups and other groups in the reaction process, the aminobenzimidazole naphthalenesulfonic acid compound with high yield and purity is obtained, and a benzimidazole structure is successfully introduced into the diamine monomer, so that the polybenzimidazole and polyimide structures are fused together, and a novel material combining the advantages of the polybenzimidazole and polyimide is obtained.
Description
Technical Field
The invention relates to the technical field of preparation of amino naphthalene sulfonic acid compounds, in particular to a synthesis method and application of an amino benzimidazole naphthalene sulfonic acid compound.
Background
Polyimide, polyamide, etc. are also well-known high-performance materials, which have the advantages of high thermal stability, high mechanical strength and modulus, radiation resistance, good film forming property, excellent electrical properties, etc., many polyimides and polyamides have good solubility in aprotic organic solvents, so that the processability is good, but the acid resistance, alkali resistance and spinning property of the materials are poor, polybenzimidazole is a high-performance polymer material with excellent thermal stability, high mechanical strength and modulus, excellent chemical stability (especially acid resistance and alkali resistance), good flame retardance, good spinning and film forming properties, and the like, and has been widely researched and applied in the fields of aerospace, military, fire fighting, fuel cells, etc. However, polybenzimidazole is difficult to dissolve and infusible and has poor processability, thereby limiting the industrial application thereof. Therefore, a novel material combining the advantages of polybenzimidazole and polyimide is expected to be obtained by fusing the structures of both.
Imidazolyl polyimide or imidazolyl polyamide is generally prepared by condensation polymerization of aromatic dibasic acid anhydride and imidazolyl-containing diamine monomer, so that imidazolyl-containing diamine is a key monomer raw material for preparing the two materials, but the imidazolyl-containing diamine monomer is few in types so far, and development of imidazolyl-containing polymers is limited. There is therefore a need to develop imidazolyl diamine monomers that are suitable for combining polybenzimidazoles with polyimides.
Disclosure of Invention
In view of the above technical problems, a first aspect of the present invention provides a method for synthesizing aminobenzimidazole naphthalenesulfonic acid compounds, which comprises the following steps:
(1) dissolving 0.1mol of carboxyl naphthalene sulfonic acid and 0.15-0.25 mol of aminonitrobenzene in polyphosphoric acid to prepare 5-55 wt% solution;
(2) placing the reaction solution into a reaction kettle, raising the temperature of the reaction kettle to 180-200 ℃, reacting for 1.5-10 hours, adding water into the reaction kettle for precipitation, and filtering to obtain an intermediate product A; washing the intermediate product A with acid to obtain an intermediate product B;
(3) and dissolving the intermediate product B in an organic solvent, introducing hydrogen to reduce under the action of a catalyst, and carrying out post-treatment to obtain the aminobenzimidazole naphthalenesulfonic acid compound.
As a preferred technical scheme of the invention, the catalyst in the step (3) is a palladium carbon catalyst.
As a preferred technical solution of the present invention, the post-treatment in the step (3) includes the steps of: and filtering the reduced material, removing the catalyst, concentrating until solid is separated out, adding water to separate out precipitate, leaching a filter cake obtained after filtering with ethanol, draining, and drying in vacuum at 35-55 ℃ to obtain the catalyst.
As a preferable technical scheme of the invention, the acid in the step (2) is hydrochloric acid, and the concentration of the hydrochloric acid is 0.8-1.2 mol/L.
As a preferred technical scheme of the invention, the aminonitrobenzene has the following structural formula:
wherein: r1One selected from hydrogen atom, hydrocarbon group, carboxyl group, amino group, hydroxyl group, siloxane group and cyano group.
In a preferred embodiment of the present invention, the carboxynaphthalene sulfonic acid is a naphthalene sulfonate having a structure containing a carboxyl group.
As a preferred embodiment of the present invention, the carboxynaphthalene sulfonic acid has the following structure:
wherein: r2、R3、R4Is a substituent; the substituent groups are respectively and independently selected from one of hydrogen atoms, alkyl groups, carboxyl groups, amino groups, hydroxyl groups, siloxane groups and cyano groups.
As a preferable technical scheme of the invention, R is3And R4At least one of them is a carboxyl group.
As a preferred technical solution of the present invention, the aminobenzimidazole naphthalenesulfonic acid compound has the following structural formula:
the second aspect of the invention provides the application of the aminobenzimidazole naphthalenesulfonic acid compound synthesized by the above-mentioned method for synthesizing the aminobenzimidazole naphthalenesulfonic acid compound in the fields of polyamide and polyimide materials.
Has the advantages that: because the acidity of the sulfonic acid group influences the reactivity between the carboxyl group and the amino group to a certain extent, the carboxyl naphthalene sulfonic acid compound monomer is treated by alkaline solution, and then the sulfonic acid group is synthesized into sodium sulfonate and then reacts with the amino compound. In the invention, ortho amino and carboxyl are reacted in polyphosphoric acid solution at 180-200 ℃, and an imidazole structure is obtained through dehydration condensation, so that the bonding activity between naphthalene sulfonic acid and benzimidazole is ensured, and the total yield is improved. In addition, in the application, a diamine monomer containing nitro is adopted to react with carboxyl naphthalene sulfonic acid, and then the nitro is reduced under the action of a catalyst to obtain amino, so that random reaction between carboxyl in a carboxyl naphthalene sulfonic acid structure and all amino in the monomer is avoided, a three-dimensional cross-linked structure product is generated, or an imidazole structure is prevented from being generated, numerous byproducts are obtained, and the yield and the purity of a target product are seriously influenced. In conclusion, the invention obtains the aminobenzimidazole naphthalenesulfonic acid compound with high yield and purity by molecular design of reaction monomer raw materials and protection of amino groups and the like in the reaction process, successfully introduces the benzimidazole structure into diamine monomer for preparing polyimide and polyamide, and is beneficial to fusing the structures of polybenzimidazole, polyimide and the like to obtain a novel material combining the advantages of polybenzimidazole and polyimide.
Detailed Description
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent 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.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The term "prepared from" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The first aspect of the invention provides a method for synthesizing an aminobenzimidazole naphthalenesulfonic acid compound, which comprises the following steps:
(1) dissolving 0.1mol of carboxyl naphthalene sulfonic acid and 0.15-0.25 mol of aminonitrobenzene in polyphosphoric acid to prepare 5-55 wt% solution;
(2) placing the reaction solution into a reaction kettle, raising the temperature of the reaction kettle to 180-200 ℃, reacting for 1.5-10 hours, adding water into the reaction kettle for precipitation, and filtering to obtain an intermediate product A; washing the intermediate product A with acid to obtain an intermediate product B;
(3) and dissolving the intermediate product B in an organic solvent, introducing hydrogen to reduce under the action of a catalyst, and carrying out post-treatment to obtain the aminobenzimidazole naphthalenesulfonic acid compound.
The carboxyl naphthalene sulfonic acid and the amino nitrobenzene are dissolved in polyphosphoric acid, and after a solution of the carboxyl naphthalene sulfonic acid and the amino nitrobenzene is prepared, the reaction is carried out under the high-temperature condition. The polyphosphoric acid is colorless, transparent and viscous liquid, and is a protonic acid which is well known to those skilled in the art and can dissolve various low molecular and high molecular organic compounds, and the conventional polyphosphoric acid is used in the invention. In addition, the concentration of the carboxynaphthalene sulfonic acid and the aminonitrobenzene dissolved in the polyphosphoric acid is not particularly limited in the present invention, and in some embodiments, the concentration is independently 5 to 55 wt%. In addition, nitrogen gas can be adopted for protection during the reaction process of the step (1).
According to the invention, carboxyl naphthalene sulfonic acid and aminonitrobenzene react for 1.5-10 hours at 180-200 ℃, wherein carboxyl in a carboxyl naphthalene sulfonic acid structure and amino in aminonitrobenzene are subjected to dehydration condensation reaction, and two molecules of water are removed between every mole of aminonitrobenzene and carboxyl naphthalene sulfonic acid under high-temperature long-time reaction to form a benzimidazole structure, wherein the preferable reaction time is 2-6 hours. After the reaction, a large amount of water is used for separating out to obtain an intermediate product A, namely a product obtained by bonding the benzimidazole containing the nitro and the naphthalene sulfonate. Because the intermediate product A is insoluble in water, a large amount of water is added into a system after reaction, or the intermediate product A is separated out when the reacted material is poured into the large amount of water while the material is hot, and the solid intermediate product A is obtained after filtration for the next step.
The intermediate product a in the invention is washed with acid to obtain an intermediate product B, specifically, the intermediate product a on the filter cake after filtration is washed with acid for a plurality of times and then dried to obtain the intermediate product B, wherein the sulfonate in the intermediate product a is acidified after washing with acid to obtain the sulfonic acid group, the acid is not particularly limited, and various acids well known to those skilled in the art can be selected.
In some embodiments, the acid in step (2) is hydrochloric acid with a concentration of 0.8 to 1.2 mol/L; preferably, the concentration is 1.0 mol/L.
In the invention, under the action of a catalyst, hydrogen is introduced into the intermediate product B to reduce the nitro in the structure of the intermediate product B into amino to obtain a target product. The organic solvent is not particularly limited, and various solvents known to those skilled in the art can be selected, including but not limited to DMF, DMAc, DMSO, etc., preferably DMAc.
In some embodiments, the catalyst in step (3) is a palladium on carbon catalyst.
In some embodiments, the post-treatment in step (3) comprises the steps of: and filtering the reduced material, removing the catalyst, concentrating until solid is separated out, adding water to separate out precipitate, leaching a filter cake obtained after filtering with ethanol, draining, and drying in vacuum at 35-55 ℃ to obtain the catalyst. Further, filtering the reduced material, filtering out the catalyst, performing rotary evaporation and concentration until solid is separated out, then adding water to separate out a large amount of precipitate, and leaching the filter cake obtained after filtration with ethanol for 2-3 times. Filtering to dry, and vacuum drying at 40 deg.C.
In the step (3), the intermediate product B is dissolved in an organic solvent, and hydrogen is introduced to reduce under the action of a catalyst, wherein the specific operation of the reduction reaction is not particularly limited, the reaction can be carried out at normal temperature and normal pressure, a reaction kettle can be vacuumized to remove oxidizing gases such as oxygen and the like, then hydrogen is introduced, in order to ensure that the content of the oxidizing gases in the reaction kettle is reduced to a specific value, a multiple replacement mode can be adopted to remove the oxidizing gases in the reaction kettle, and then nitro groups in the intermediate product B are reduced into amino groups by hydrogen under the action of the catalyst, so that the target product is obtained.
Because the acidity of the sulfonic acid group influences the reactivity between the carboxyl group and the amino group to a certain extent, the carboxyl naphthalene sulfonic acid compound monomer is treated by alkaline solution, and then the sulfonic acid group is synthesized into sodium sulfonate and then reacts with the amino compound. In the invention, ortho amino and carboxyl are reacted in polyphosphoric acid solution at 180-200 ℃, and an imidazole structure is obtained through dehydration condensation, so that the bonding activity between naphthalene sulfonic acid and benzimidazole is ensured, and the total yield is improved. In addition, in the application, a diamine monomer containing nitro is adopted to react with carboxyl naphthalene sulfonic acid, and then the nitro is reduced under the action of a catalyst to obtain amino, so that random reaction between carboxyl in a carboxyl naphthalene sulfonic acid structure and all amino in the monomer is avoided, a three-dimensional cross-linked structure product is generated, or an imidazole structure is prevented from being generated, numerous byproducts are obtained, and the yield and the purity of a target product are seriously influenced.
In some embodiments, the aminonitrobenzene is a compound having both an amino group and a nitro group in the structure, and has the following structural formula:
wherein: r1One selected from hydrogen atom, hydrocarbon group, carboxyl group, amino group, hydroxyl group, siloxane group and cyano group.
The aminonitrobenzene in the invention is a compound containing both amino and nitro in the structure, wherein each aminonitrobenzene structure has at least two amino groups, and the two amino groups are on adjacent carbon atoms of a benzene ring. In addition, the position of the nitro group in the structure is not particularly limited, and may be any position having 4 carbons remaining on the benzene ring. The aminonitrobenzene in the invention also comprises a compound containing substituent groups in the structure, namely R in the structural formula1In the present invention, the structure and position of the substituent are not particularly limited, and may be one of a hydrogen atom, a hydrocarbon group, a carboxyl group, an amino group, a hydroxyl group, a siloxane group and a cyano group. Preferably, said R is1Is hydrogenAn atom.
In some preferred embodiments, the aminonitrobenzene has the following structural formula:
in some embodiments, the carboxynaphthalene sulfonic acid is a naphthalene sulfonate containing a carboxyl group in the structure.
Further, the carboxynaphthalene sulfonic acid has the following structure:
wherein: r2、R3、R4Is a substituent; the substituent groups are respectively and independently selected from one of hydrogen atoms, alkyl groups, carboxyl groups, amino groups, hydroxyl groups, siloxane groups and cyano groups. Further, said R3And R4At least one of them is a carboxyl group.
Each carboxynaphthalene sulfonic acid structure in the present invention contains at least one carboxyl group, and preferably contains two carboxyl groups. In addition, the position of the sulfonic acid group in the carboxynaphthalene sulfonic acid structure in the present application is not particularly limited, and it is preferable that the carboxyl group and the sulfonic acid group are on two different benzene rings, respectively. Further, the carboxynaphthalene sulfonic acid in the present invention includes the case where a group other than the carboxyl group and the sodium sulfonate group is substituted, that is, includes R2、R3、R4Is a substituent; the substituent groups are respectively and independently selected from one of hydrogen atoms, alkyl groups, carboxyl groups, amino groups, hydroxyl groups, siloxane groups and cyano groups. Preferred R2Is a hydrogen atom, R3And R4One of them is a carboxyl group and the other is a hydrogen atom.
Preferably, the carboxynaphthalene sulfonic acid has the following structural formula:
in one embodiment, the aminobenzimidazole naphthalenesulfonic acid compound has the following structural formula:
further, the synthesis equation of the aminobenzimidazole naphthalenesulfonic acid compound is as follows:
the second aspect of the invention provides the application of the aminobenzimidazole naphthalenesulfonic acid compound synthesized by the above-mentioned method for synthesizing the aminobenzimidazole naphthalenesulfonic acid compound in the fields of polyamide and polyimide materials.
The present invention will be specifically described below by way of examples. It is to be noted that the following examples are only intended to illustrate the present invention and should not be construed as limiting the scope of the present invention.
Examples
Example 1: the embodiment provides a synthesis method of an aminobenzimidazole naphthalenesulfonic acid compound, which comprises the following steps:
(1) dissolving 0.1mol of carboxyl naphthalene sulfonic acid and 0.2mol of aminonitrobenzene in 100g of polyphosphoric acid with the mass concentration of 86 percent to prepare a reaction solution;
(2) placing the reaction solution obtained in the step (1) into a reaction kettle, raising the temperature of the reaction kettle to 200 ℃, reacting for 6 hours under the protection of nitrogen, then pouring the materials in the reaction kettle into a large amount of water to precipitate solids, and filtering the precipitated solids to obtain an intermediate product A; then washing the intermediate product A with 1mol/L hydrochloric acid for 3 times to obtain an intermediate product B;
(3) and putting the intermediate product B into a 250ml three-necked bottle, adding 80ml DMAc, stirring and dissolving, adding 0.8g of palladium-carbon catalyst, stirring and mixing, introducing nitrogen to replace oxidizing gas in the three-necked bottle, vacuumizing, introducing hydrogen to perform reduction reaction for 4 hours, filtering the reduced material, filtering the catalyst, performing rotary evaporation and concentration until solid is separated out, adding water to separate out a large amount of precipitate, leaching the filter cake obtained after filtering for 3 times by using ethanol, and drying in vacuum at 40 ℃ after filtering to obtain the product with the total molar yield of 90% and the purity of 98.8%.
Wherein the aminonitrobenzene has the following structural formula (1), and the carboxyl naphthalene sulfonic acid has the following structural formula (2)
The synthesis equation of the aminobenzimidazole naphthalenesulfonic acid compound is as follows:
example 2: the embodiment provides a synthesis method of an aminobenzimidazole naphthalenesulfonic acid compound, which comprises the following steps:
(1) dissolving 0.1mol of carboxyl naphthalene sulfonic acid and 0.2mol of aminonitrobenzene in 100g of polyphosphoric acid with the mass concentration of 86 percent to prepare a reaction solution;
(2) placing the reaction solution obtained in the step (1) into a reaction kettle, raising the temperature of the reaction kettle to 200 ℃, reacting for 3 hours under the protection of nitrogen, then pouring the materials in the reaction kettle into a large amount of water to precipitate solids, and filtering the precipitated solids to obtain an intermediate product A; then washing the intermediate product A with 1mol/L hydrochloric acid for 3 times to obtain an intermediate product B;
(3) and putting the intermediate product B into a 250ml three-necked bottle, adding 80ml DMAc, stirring and dissolving, adding 0.8g of palladium-carbon catalyst, stirring and mixing, introducing nitrogen to replace oxidizing gas in the three-necked bottle, vacuumizing, introducing hydrogen to perform reduction reaction for 2.5 hours, filtering the reduced material, filtering the catalyst, performing rotary evaporation and concentration until solid is separated out, adding water to separate out a large amount of precipitate, leaching the filter cake obtained after filtering for 3 times by using ethanol, and drying in vacuum at 40 ℃ after filtering to obtain the product with the total molar yield of 83% and the purity of 99.2%.
Wherein the aminonitrobenzene has the following structural formula (1), and the carboxyl naphthalene sulfonic acid has the following structural formula (2)
Example 3: the embodiment provides a synthesis method of an aminobenzimidazole naphthalenesulfonic acid compound, which comprises the following steps:
(1) dissolving 0.1mol of carboxyl naphthalene sulfonic acid and 0.2mol of aminonitrobenzene in 100g of polyphosphoric acid with the mass concentration of 86 percent to prepare a reaction solution;
(2) placing the reaction solution obtained in the step (1) into a reaction kettle, raising the temperature of the reaction kettle to 180 ℃, reacting for 4 hours under the protection of nitrogen, then pouring the materials in the reaction kettle into a large amount of water to precipitate solids, and filtering the precipitated solids to obtain an intermediate product A; then washing the intermediate product A with 1mol/L hydrochloric acid for 3 times to obtain an intermediate product B;
(3) and putting the intermediate product B into a 250ml three-necked bottle, adding 80ml DMAc, stirring and dissolving, adding 0.8g of palladium-carbon catalyst, stirring and mixing, introducing nitrogen to replace oxidizing gas in the three-necked bottle, vacuumizing, introducing hydrogen to perform reduction reaction for 4 hours, filtering the reduced material, filtering the catalyst, performing rotary evaporation and concentration until solid is separated out, adding water to separate out a large amount of precipitate, leaching the filter cake obtained after filtering for 3 times by using ethanol, and drying in vacuum at 40 ℃ after filtering to obtain the product with the total molar yield of 78% and the purity of 98.5%.
Wherein the aminonitrobenzene has the following structural formula (1), and the carboxyl naphthalene sulfonic acid has the following structural formula (2)
Example 4: the embodiment provides a synthesis method of an aminobenzimidazole naphthalenesulfonic acid compound, which comprises the following steps:
(1) dissolving 0.1mol of carboxyl naphthalene sulfonic acid and 0.2mol of aminonitrobenzene in 150g of polyphosphoric acid with the mass concentration of 86 percent to prepare a reaction solution;
(2) placing the reaction solution obtained in the step (1) into a reaction kettle, raising the temperature of the reaction kettle to 200 ℃, reacting for 4 hours under the protection of nitrogen, then pouring the materials in the reaction kettle into a large amount of water to precipitate solids, and filtering the precipitated solids to obtain an intermediate product A; then washing the intermediate product A with 1mol/L hydrochloric acid for 3 times to obtain an intermediate product B;
(3) and putting the intermediate product B into a 250ml three-necked bottle, adding 80ml DMAc, stirring and dissolving, adding 0.8g of palladium-carbon catalyst, stirring and mixing, introducing nitrogen to replace oxidizing gas in the three-necked bottle, vacuumizing, introducing hydrogen to perform reduction reaction for 4 hours, filtering the reduced material, filtering the catalyst, performing rotary evaporation and concentration until solid is separated out, adding water to separate out a large amount of precipitate, leaching the filter cake obtained after filtering for 3 times by using ethanol, and drying in vacuum at 40 ℃ after filtering to obtain the product with the total molar yield of 81% and the purity of 98.4%.
Wherein the aminonitrobenzene has the following structural formula (1), and the carboxyl naphthalene sulfonic acid has the following structural formula (2)
Example 5: the embodiment provides a synthesis method of an aminobenzimidazole naphthalenesulfonic acid compound, which comprises the following steps:
0.1mol of carboxynaphthalene sulfonic acid (the structure is the same as the structural formula (2) in example 1) and 0.2mol of aminobenzene (1, 2, 4-triaminobenzene, CAS: 615-71-4) were dissolved in 100g of polyphosphoric acid having a mass concentration of 86% to prepare a reaction solution; putting the reaction solution in the steps into a reaction kettle, raising the temperature of the reaction kettle to 200 ℃, reacting for 6 hours under the protection of nitrogen, pouring the materials in the reaction kettle into a large amount of water, generating a certain amount of solid, filtering the precipitated solid, washing a filter cake for 3 times by using 1mol/L hydrochloric acid, and then drying in vacuum at 40 ℃ to obtain the aminobenzimidazole naphthalenesulfonic acid compound, wherein a plurality of components with different amino contents exist through nuclear magnetic and infrared structural characterization, but the components are not single compounds, and the applicant speculates that amino on 1, 2-position in 1, 2, 4-triaminobenzene reacts with carboxyl in carboxyl naphthalenesulfonic acid to obtain the aminobenzimidazole naphthalenesulfonic acid compound containing a benzimidazole structure, and simultaneously carboxyl in the carboxyl naphthalenesulfonic acid reacts with amino on 5-position to generate a product containing two amino groups in the structure, and other crosslinked products formed by dehydration condensation between a plurality of amino groups and carboxyl groups.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content disclosed above into an equivalent embodiment with equivalent changes, but all those simple modifications, equivalent changes and modifications made on the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. A method for synthesizing aminobenzimidazole naphthalenesulfonic acid compound is characterized by comprising the following steps:
(1) dissolving 0.1mol of carboxyl naphthalene sulfonic acid and 0.15-0.25 mol of aminonitrobenzene in polyphosphoric acid to prepare 5-55 wt% solution;
(2) placing the reaction solution into a reaction kettle, raising the temperature of the reaction kettle to 180-200 ℃, reacting for 1.5-10 hours, adding water into the reaction kettle for precipitation, and filtering to obtain an intermediate product A; washing the intermediate product A with acid to obtain an intermediate product B;
(3) and dissolving the intermediate product B in an organic solvent, introducing hydrogen to reduce under the action of a catalyst, and carrying out post-treatment to obtain the aminobenzimidazole naphthalenesulfonic acid compound.
2. The method for synthesizing an aminobenzimidazole naphthalenesulfonic acid compound according to claim 1, wherein the catalyst in step (3) is a palladium on carbon catalyst.
3. The method for synthesizing an aminobenzimidazole naphthalenesulfonic acid compound according to claim 1, wherein the post-treatment in step (3) includes the steps of: and filtering the reduced material, removing the catalyst, concentrating until solid is separated out, adding water to separate out precipitate, leaching a filter cake obtained after filtering with ethanol, draining, and drying in vacuum at 35-55 ℃ to obtain the catalyst.
4. The method for synthesizing an aminobenzimidazole naphthalenesulfonic acid compound according to claim 1, wherein the acid in step (2) is hydrochloric acid, and the concentration thereof is 0.8 to 1.2 mol/L.
5. The method of synthesizing an aminobenzimidazole naphthalenesulfonic acid compound according to claim 1, wherein the aminonitrobenzene has the following structural formula:
wherein: r1One selected from hydrogen atom, hydrocarbon group, carboxyl group, amino group, hydroxyl group, siloxane group and cyano group.
6. The method for synthesizing an aminobenzimidazole naphthalenesulfonic acid compound according to any one of claims 1 to 5, wherein the carboxynaphthalenesulfonic acid is a naphthalenesulfonate having a carboxyl group in its structure.
7. The method of synthesizing an aminobenzimidazole naphthalenesulfonic acid compound according to claim 6, wherein the carboxynaphthalenesulfonic acid has the following structure:
wherein: r2、R3、R4Is a substituent; the substituent groups are respectively and independently selected from one of hydrogen atoms, alkyl groups, carboxyl groups, amino groups, hydroxyl groups, siloxane groups and cyano groups.
8. The method for synthesizing an aminobenzimidazole naphthalenesulfonic acid compound according to claim 7,wherein R is3And R4At least one of them is a carboxyl group.
9. The method of synthesizing an aminobenzimidazole naphthalenesulfonic acid compound according to claim 1, wherein the aminobenzimidazole naphthalenesulfonic acid compound has the following structural formula:
10. the application of the aminobenzimidazole naphthalenesulfonic acid compound synthesized by the method for synthesizing an aminobenzimidazole naphthalenesulfonic acid compound according to any one of claims 1 to 9 in the fields of polyamide and polyimide materials.
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| CN109053582A (en) * | 2018-06-26 | 2018-12-21 | 同济大学 | Diamine monomer, heat-proof polyimide containing aromatic rings and glyoxaline structure and preparation method thereof |
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| CN109053582A (en) * | 2018-06-26 | 2018-12-21 | 同济大学 | Diamine monomer, heat-proof polyimide containing aromatic rings and glyoxaline structure and preparation method thereof |
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| Title |
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| 王小燕: "通过叠氮化合物固相反应制备高性能聚苯并咪唑质子交换膜", 《江西师范大学硕士研究生学位论文》 * |
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