Amino aromatic compound containing a benzazepine structure, and preparation method and application thereof

Abstract

This invention provides an amino aromatic compound containing a benzo[a]azine heterocyclic structure, wherein the amino aromatic compound has the structure shown in Formula I. Polymers prepared from the amino aromatic compound containing the benzo[a]azine heterocyclic structure provided by this invention exhibit tensile strength above 100 MPa, elongation at break above 10%, and T0. d5％ At temperatures above 400℃, T g At temperatures above 450℃, it has significant application value in the preparation of high-performance polymers with benzo[a]azine heterocycles and other active substituents in the main chain.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to an amino aromatic compound containing a benzo[a]azine heterocyclic structure, its preparation method, and its application. Background Technology

[0002] Benzo[a]nitrogen heterocyclic structures such as benzimidazole, benzo[a]thiazole, and benzo[a]oxazole possess corresponding functionalities due to strong intermolecular hydrogen bonds and strong interfacial π-π interactions. Their corresponding polymers, such as polybenzimidazole, polybenzo[a]thiazole, and polybenzo[a]oxazole, have been widely used in gas separation, fuel cells, and aerospace applications. Introducing benzo[a]nitrogen heterocyclic structures into the backbones of other advantageous polymers, combining their strengths, can endow the corresponding polymers with many excellent properties. There have been many reports on this research, such as Zhuang et al. synthesizing homopolymers or copolymers of polyimides using benzo[a]aza-heterocyclic diamines, and studying the effects of introducing the benzo[a]aza-heterocyclic structure on the thermomechanical properties of the related polymers and their applications in gas separation ("Experimental and Modeling Study of Acrylamide Copolymerization with Quaternary Ammonium Salt in Aqueous Solution", Sabrina Jahn and Jacob Klein, Macromolecules 2015, 48, 15, 5059-5075., "Hyperbranched conjugated poly(tetraphenylethene): synthesis, aggregation-induced emission, fluorescent photopatterning, optical limiting and explosive detection", Rongrong Hu, Jacky W. Y. Lam, et al, Polym. Chem., 2012, 3, 1517).

[0003] CN105400173A discloses a method for preparing a high-surface-hardness polymer optical resin. The method is characterized by directly injecting a mixture of hydroxyl-containing olefin monomers and polyisocyanates into a mold, simultaneously completing the addition reaction of hydroxyl groups with isocyanates and the polymerization reaction of double bonds, thus obtaining a high-surface-hardness, transparent polymer optical resin in one step. The method features a simple synthesis process, with monomer synthesis and product obtained in one step, resulting in no pollution and low cost. The process has good controllability and repeatability, mild reaction conditions, and is applicable to various hydroxyl-containing monomers and polyisocyanates. The monomer sources are abundant, and the product quality is good. This polymer optical resin can be applied in various fields and is suitable for manufacturing various transparent devices, such as prisms, lenses, and plates. However, its tensile strength is not ideal.

[0004] Because existing polymers suffer from low tensile strength, this invention designs amino aromatic compound monomers containing benzo[a]azine heterocyclic structures and adds active substituents such as hydroxyl, methoxy, carboxyl, and sulfonic acid groups to the designed monomers. High-performance polymers containing benzo[a]azine heterocyclic units and active substituents in the main chain can be prepared using amino groups and these active groups, thereby improving the relevant properties of these polymer materials. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide an amino aromatic compound containing a benzo[a]azine heterocyclic structure, its preparation method, and its applications. The amino aromatic compound containing a benzo[a]azine heterocyclic structure has significant application value in the preparation of high-performance polymers with a main chain containing benzo[a]azine heterocyclic structures and other active substituents.

[0006] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides an amino aromatic compound containing a benzo[a]- ..."" W[a]-a]-a]-a]-a]-a]-a]"" W[a]-a]-a]-a]-a]"" W[a-a-a]-a]-a]-a]-a]-a]"" W[a-a-a]-a]-a]-a]-a]-a]-a]"" W[a-a-a]-a]-a]-a]-a]-a]-a]"" W[a-a-a]-a]-a]-a]-a]-a]-a]"" W[a-a-a"-a"-a"-a]-a Formula I R1-R5 are each independently selected from any one of -H, -OH, -OCH3, -COOH, -SO3H or -NH2, and at least one of R1-R5 is -NH2 (for example, it can be 1, 2, 3, 4 or 5). R6-R9 are each independently -H or -NH2, and at least one of R6-R9 is -NH2 (for example, it can be 1, 2, 3, or 4). X is selected from any one of NH, S, and O.

[0007] Preferably, one or two of R1-R5 are -NH2.

[0008] Preferably, 1 to 3 of R6-R9 are -NH2, for example, 1, 2, or 3.

[0009] Preferably, the amino aromatic compound containing a benzo[a]azine heterocyclic structure has the following structure: , , , , , , , , , , , , , , ; X is selected from any one of NH, S and O.

[0010] In a second aspect, the present invention provides a method for preparing an amino aromatic compound containing a benzo[a]azine heterocyclic structure as described in the first aspect, the method comprising: (1) Aromatic aldehyde compounds With aromatic compounds The reaction proceeds in the presence of a first catalyst to yield a nitroaromatic compound. ; (2) The nitro aromatic compound obtained in step (1) The reducing agent is reacted with a second catalyst to obtain the amino aromatic compound containing the benzo[a]azine heterocyclic structure; Wherein, X is selected from any one of NH, S and O; Y1-Y5 are each independently selected from -H, -OH, -OCH3, -COOH, -SO3H or -NO2, and at least one of Y1-Y5 is -NO2 (for example, it can be 1, 2, 3, 4 or 5).

[0011] Y6-Y9 are each independently -H or -NO2, and at least one of Y6-Y9 is -NO2 (for example, it can be 1, 2, 3, 4, or 5).

[0012] Preferably, the aromatic aldehyde compound in step (1) specifically includes: , , , , , , or Any one of them.

[0013] Preferably, the aromatic compound specifically includes any one of the following compounds: , , ; X is selected from any one of NH, S and O.

[0014] Preferably, the molar ratio of the aromatic aldehyde compound to the aromatic compound in step (1) is 1:(1-1.2), for example, it can be 1:1, 1:1.05, 1:1.1, 1:1.15, 1:2, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0015] Preferably, the mass ratio of the aromatic aldehyde compound to the first catalyst is 1:(0.1-0.2), for example, it can be 1:0.1, 1:0.13, 1:0.15, 1:0.18, 1:0.2, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0016] Preferably, the first catalyst comprises any one or a combination of at least two of potassium iodide, ammonium acetate, transition metals, imidazole hydrochloride, copper sulfate, ferric chloride, or polyphosphoric acid.

[0017] Preferably, the reaction in step (1) is carried out in the presence of a solvent.

[0018] Preferably, the solvent includes any one or a combination of at least two of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone.

[0019] Preferably, after the aromatic aldehyde compound and aromatic compound in step (1) are dissolved in a solvent, they are reacted in the presence of a first catalyst to obtain a nitro aromatic compound.

[0020] Preferably, the dissolution temperature is 10-30 ℃, for example, it can be 10 ℃, 12 ℃, 15 ℃, 20 ℃, 30 ℃, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0021] Preferably, the reaction temperature is 10-180 ℃, for example, it can be 10 ℃, 20 ℃, 50 ℃, 100 ℃, 150 ℃, 180 ℃, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0022] Preferably, the reaction time is 24-120 h, for example, it can be 24 h, 30 h, 50 h, 80 h, 100 h, 120 h, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0023] Preferably, the reaction in step (1) is followed by a post-processing step.

[0024] Preferably, the post-processing includes precipitation, filtration, washing, drying, and purification.

[0025] Preferably, precipitation is carried out in deionized water and / or ethanol.

[0026] Preferably, the molar ratio of the nitro aromatic compound to the reducing agent in step (2) is (1-4):(1-10), for example, it can be 1:1, 2:1, 3:1, 4:1, 1:2, 1:5, 1:10, 2:2, 2:5, 2:10, 3:2, 3:5, 3:10, 4:2, 4:5, 4:10, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0027] Preferably, the mass ratio of the nitro aromatic compound to the second catalyst is 1:(0.1-0.2), for example, it can be 1:0.1, 1:0.13, 1:0.15, 1:0.18, 1:0.2, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0028] Preferably, the reducing agent comprises hydrazine hydrate.

[0029] Preferably, the second catalyst comprises any one or a combination of at least two of palladium on carbon, platinum on carbon, or Raney nickel.

[0030] Preferably, the reaction in step (2) is carried out in the presence of a solvent.

[0031] Preferably, the solvent includes any one or a combination of at least two of methanol, ethanol, acetone or tetrahydrofuran.

[0032] Preferably, after the nitro aromatic compound in step (2) is dissolved in a solvent, it is reacted in the presence of a reducing agent and a second catalyst to obtain the amino aromatic compound containing the benzo[a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]"" nitro aromatic compound in step (2))")" )"" 2)" 2)"" 3'-a-a"-a]" 3'-a" 2'-a" 2'""'"'"'"'"'"'"'"" '""" "" ...

[0033] Preferably, the dissolution temperature is 10-30 ℃, for example, it can be 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0034] Preferably, the reaction temperature is 10-90 ℃, for example, it can be 10 ℃, 20 ℃, 50 ℃, 80 ℃, 90 ℃, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0035] Preferably, the reaction time is 10-48 h, for example, it can be 10 h, 15 h, 20 h, 25 h, 30 h, 35 h, 40 h, 45 h, 48 h, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0036] Preferably, the reaction in step (2) further includes post-processing.

[0037] Preferably, the post-processing includes rotary evaporation, washing, drying, separation, and purification.

[0038] Preferably, the drying time is 12-48 h, for example, it can be 12 h, 24 h, 36 h, 48 h and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0039] Preferably, the drying temperature is 70-90 ℃, for example, it can be 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0040] Preferably, the separation includes filtration.

[0041] Thirdly, the present invention provides an application of an amino aromatic compound containing a benzo[a]-azo heterocyclic structure as described in the first aspect in gas separation, fuel cells, or aerospace.

[0042] The synthesis of the amino aromatic compound containing the benzo[a]azine heterocyclic structure is a simple and easy-to-operate method, requiring only two reaction steps, with a simple post-processing and high yield. The amino aromatic compound monomer can be used to prepare related high-performance polymers with a main chain containing benzo[a]azine heterocyclic structures and other active functional groups.

[0043] Fourthly, the present invention provides a polymer, wherein the raw materials for preparing the polymer include amino aromatic compounds containing benzo[a]azine heterocyclic structures as described in the first aspect.

[0044] Preferably, the polymer is polyimide.

[0045] Compared with the prior art, the present invention has the following beneficial effects: The polymer prepared from the amino aromatic compound containing a benzo[a]azine heterocyclic structure provided by this invention has a tensile strength of over 100 MPa and an elongation at break of over 10%. d5% At temperatures above 400℃, T g At temperatures above 450°C, its permeability to H2 is more than three times that of the commercial membrane Matrimid (27), its permeability to CO2 is more than twice that of Matrimid (8.7), its selectivity for H2 / CH4 is more than three times that of Matrimid (130), and its selectivity for CO2 / CH4 is more than twice that of Matrimid (36). The gas separation performance is improved, and it has important application value in the preparation of high-performance polymers with benzo[a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a]-a-a]-a]""-a-a] ... Detailed Implementation

[0046] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention.

[0047] Example 1 This embodiment provides an amino aromatic compound containing a benzo[a]azine heterocyclic structure, specifically an aromatic tetraamine A containing benzimidazole and hydroxyl substituents, the structure of which is shown below: The synthesis reaction formula and specific method are as follows: At room temperature, 4.24 g (20 mmol) of aromatic compound A1 containing aldehyde, nitro and hydroxyl groups and 3.96 g (20 mmol) of diamine monomer a were added to a dry three-necked flask. Under a nitrogen atmosphere, 50 mL of DMF was added to the reaction flask and stirred to dissolve. Then, 2 mmol of potassium iodide (KI) was added, and the reaction was carried out at 150 °C for 24 h. After the reaction was completed, the mixture was poured into deionized water to precipitate, filtered, washed several times, dried at 80 °C, and then recrystallized from ethanol. After filtration and drying, tetranitro intermediate A2 (6.34 g, yield 81%) was obtained. Take 2 g (5.1 mmol) of the above nitro intermediate A2, add it to a dry three-necked flask under a nitrogen atmosphere, dissolve it in ethanol, add 0.2 g of Pd / C catalyst, stir, heat to reflux temperature, add 4-5 nitro equivalents of hydrazine hydrate dropwise, reflux for 12 h, cool, filter to remove catalyst, rotary evaporate, dry, and then recrystallize to obtain the target aromatic tetraamine A (1.18 g, yield 86%). NMR measurements were performed using a 600 MHz NMR spectrometer (Avance III 600 MHz spectrometer, Bruker, Switzerland). δ 12.83 (s, 1H, NH), 10.31 (s, 1H, OH), 7.38–6.46 (4H, Ar-H), 4.92 (s, 2H, NH2), 4.81 (s, 2H, NH2), 4.75 (s, 2H, NH2), 4.66 (s, 2H, NH2).

[0048] Example 2 This embodiment provides an amino aromatic compound containing a benzo[a]azine heterocyclic structure, specifically an aromatic diamine B containing benzimidazole, a hydroxyl substituent, and a methoxy substituent, the structure of which is shown below: The synthesis reaction formula and specific method are as follows: At room temperature, 3.94 g (20 mmol) of aromatic compound B1 containing aldehyde, nitro, hydroxyl and methoxy groups and 3.06 g (20 mmol) of diamine monomer b were added to a dry three-necked flask. Under a nitrogen atmosphere, 60 mL of DMF was added to the reaction flask and stirred to dissolve. Then, 2 mmol of ammonium acetate was added, and the reaction was carried out at 150 °C for 25 h. After the reaction was completed, the mixture was poured into a 1:1 deionized water:ethanol mixture to precipitate the compound. The precipitate was filtered, washed several times, dried at 80 °C, recrystallized from methanol, filtered, and dried to obtain dinitro intermediate B2 (5.53 g, yield 84%). 2 g (6.1 mmol) of the above-mentioned dinitro intermediate B2 was added to a dry three-necked flask under a nitrogen atmosphere, dissolved in methanol, and 0.2 g of Pd / C catalyst was added. The mixture was stirred, heated to reflux temperature, and then 5-6 nitro equivalents of hydrazine hydrate were added dropwise. The mixture was refluxed for 14 h, cooled, filtered to remove the catalyst, rotary evaporated, dried, and then purified by recrystallization to obtain the target aromatic diamine B (1.39 g, yield 86%). NMR was performed using a 600 MHz NMR spectrometer (Avance III 600 MHz spectrometer, Bruker, Switzerland). The NMR values ​​were δ 11.74 (s, 1H, NH), 9.27 (s, 1H, OH), 7.66-6.58 (5H, Ar-H), 4.62 (s, 2H, NH2), 4.48 (s, 2H, NH2), and 3.98 (s, 3H, OCH3).

[0049] Example 3 This embodiment provides an amino aromatic compound containing a benzo[a]azine heterocyclic structure, specifically an aromatic diamine C containing benzo[a]thiazole and a hydroxyl substituent, the structure of which is shown below: The synthesis reaction formula and specific method are as follows: At room temperature, 3.34 g (20 mmol) of aromatic compound C1 containing aldehyde, nitro and hydroxyl groups and 3.40 g (20 mmol) of monomer c were added to a dry three-necked flask. Under a nitrogen atmosphere, 50 mL of DMAC was added to the reaction flask and stirred to dissolve. Then, 2 mmol of imidazole hydrochloric acid was added, and the reaction was carried out at 180 °C for 24 h. After the reaction was completed, the mixture was poured into deionized water to precipitate, filtered, washed several times, dried at 80 °C, and then recrystallized from ethanol. After filtration and drying, the dinitro intermediate C2 (5.28 g, yield 83%) was obtained. 2 g (6.3 mmol) of the above-mentioned dinitro intermediate C2 was added to a dry three-necked flask under a nitrogen atmosphere, dissolved in ethanol, and 0.2 g of Pd / C catalyst was added. The mixture was stirred, heated to reflux temperature, and then 4-5 equivalents of hydrazine hydrate were added dropwise. After reflux for 14 h, the mixture was cooled, filtered to remove the catalyst, rotary evaporated, dried, and then purified by recrystallization to obtain the target aromatic diamine C (1.41 g, yield 87%). NMR was performed using a 600 MHz NMR spectrometer (Avance III 600 MHz spectrometer, Bruker, Switzerland), with δ 9.27 (s, 1H, OH), 7.89-6.44 (6H, Ar-H), 4.53 (s, 2H, NH2), and 4.46 (s, 2H, NH2).

[0050] Example 4 This embodiment provides an amino aromatic compound containing a benzo[a]- ...""" ]-a]-a]-a]"" situents:" 1,1-a]-a]-a]-a]-a]""" """ """""" The synthesis reaction formula and specific method are as follows: At room temperature, 4.80 g (20 mmol) of aromatic compound D1 containing aldehyde, nitro and carboxyl groups and 4.30 g (20 mmol) of monomer d were added to a dry three-necked flask. Under a nitrogen atmosphere, 60 mL of DMSO was added to the reaction flask and stirred to dissolve. Then, 2 mmol of copper sulfate was added, and the reaction was carried out at 150 °C for 30 h. After the reaction was completed, the mixture was poured into a 1:1 deionized water:ethanol mixture to precipitate the compound. The precipitate was filtered, washed several times, dried at 80 °C, and then recrystallized from tetrahydrofuran (THF). After filtration and drying, tetranitro intermediate D2 (7.55 g, yield 87%) was obtained. 2 g (4.5 mmol) of the above tetranitro intermediate D2 was added to a dry three-necked flask under a nitrogen atmosphere, dissolved in THF, and 0.2 g of Pd / C catalyst was added. The mixture was stirred, heated to reflux temperature, and then 5-6 equivalents of hydrazine hydrate were added dropwise. After reflux for 15 h, the mixture was cooled, filtered to remove the catalyst, rotary evaporated, dried, and then purified by recrystallization to obtain the target aromatic tetraamine D (1.3 g, 90% yield). NMR was performed using a 600 MHz NMR spectrometer (Avance III 600 MHz spectrometer, Bruker, Switzerland), with δ 7.57-6.12 (5H, Ar-H), 4.89 (s, 2H, NH2), 4.77 (s, 2H, NH2), 4.64 (s, 2H, NH2), and 4.45 (s, 2H, NH2).

[0051] Example 5 This embodiment provides an amino aromatic compound containing a benzo[a]azine heterocyclic structure, specifically an aromatic triamine E containing benzo[a]oxazole and sulfonic acid substituents, the structure of which is shown below: The synthesis reaction formula and specific method are as follows: At room temperature, 4.62 g (20 mmol) of aromatic compound E1 containing aldehyde, nitro and sulfonic acid groups and 3.98 g (20 mmol) of monomer e were added to a dry three-necked flask. Under a nitrogen atmosphere, 50 mL of DMF was added to the reaction flask and stirred to dissolve. Then, 2 mmol of imidazole hydrochloric acid was added, and the reaction was carried out at 150 °C for 24 h. After the reaction was completed, the mixture was poured into deionized water to precipitate, filtered, washed several times, dried at 80 °C, and then recrystallized from ethanol. After filtration and drying, trinitro intermediate E2 (6.92 g, yield 84%) was obtained. 2 g (4.9 mmol) of the above trinitro intermediate E2 was added to a dry three-necked flask under a nitrogen atmosphere, dissolved in ethanol, and 0.2 g of Pd / C catalyst was added. The mixture was stirred, heated to reflux temperature, and then 4-5 equivalents of hydrazine hydrate were added dropwise. The mixture was refluxed for 12 h, cooled, filtered to remove the catalyst, rotary evaporated, dried, and then purified by recrystallization to obtain the target aromatic triamine E (1.34 g, yield 86%). NMR was performed using a 600 MHz NMR spectrometer (Avance III 600 MHz spectrometer, Bruker, Switzerland). The NMR values ​​were δ 10.22 (1H, SO3H, 7.72-6.39 (5H, Ar-H), 4.81 (s, 2H, NH2), 4.70 (s, 2H, NH2), 4.55 (s, 2H, NH2).

[0052] Example 6 This embodiment provides an amino aromatic compound containing a benzo[a]azine heterocyclic structure, specifically an aromatic triamine F containing benzo[a]thiazole and methoxy substituents, the structure of which is shown below: The synthesis reaction formula and specific method are as follows: At room temperature, 4.52 g (20 mmol) of aromatic compound F1 containing aldehyde, nitro and methoxy groups and 3.08 g (20 mmol) of monomer f were added to a dry three-necked flask. Under a nitrogen atmosphere, 50 mL of DMF was added to the reaction flask and stirred to dissolve. Then, 2 mmol of ferric chloride was added, and the reaction was carried out at 150 °C for 24 h. After the reaction was completed, the mixture was poured into deionized water to precipitate, filtered, washed several times, dried at 80 °C, and then recrystallized from methanol. After filtration and drying, trinitro intermediate F2 (6.02 g, yield 84%) was obtained. 2 g (5.5 mmol) of the above trinitro intermediate F2 was added to a dry three-necked flask under a nitrogen atmosphere, dissolved in methanol, and 0.2 g of Pd / C catalyst was added. The mixture was stirred, heated to reflux temperature, and then 5-6 nitro equivalents of hydrazine hydrate were added dropwise. The mixture was refluxed for 15 h, cooled, filtered to remove the catalyst, rotary evaporated, dried, and then purified by recrystallization to obtain the target aromatic triamine F (1.33 g, yield 88%). NMR was performed using a 600 MHz NMR spectrometer (Avance III 600 MHz spectrometer, Bruker, Switzerland). The NMR values ​​were δ 7.72-6.39 (5H, Ar-H), 4.76 (s, 2H, NH2), 4.59 (s, 2H, NH2), 4.51 (s, 2H, NH2), and 4.01 (s, 3H, OCH3).

[0053] Example 7 This embodiment provides an amino aromatic compound containing a benzo[a]azine heterocyclic structure, specifically an aromatic diamine G containing benzo[a]oxazole, hydroxyl, and sulfonic acid substituents, the structure of which is shown below: The synthesis reaction formula and specific method are as follows: At room temperature, 4.94 g (20 mmol) of aromatic compound G1 containing aldehyde, nitro, hydroxyl and sulfonic acid groups and 3.08 g (20 mmol) of monomer g were added to a dry three-necked flask. Under a nitrogen atmosphere, 50 mL of DMF was added to the reaction flask and stirred to dissolve. Then, 2 mmol of imidazole hydrochloric acid was added, and the reaction was carried out at 150 °C for 24 h. After the reaction was completed, the mixture was poured into deionized water to precipitate, filtered, washed several times, dried at 80 °C, and then recrystallized from ethanol. After filtration and drying, the dinitro intermediate G2 (6.56 g, yield 86%) was obtained. 2 g (5.2 mmol) of the above-mentioned dinitro intermediate G2 was added to a dry three-necked flask under a nitrogen atmosphere, dissolved in ethanol, and 0.2 g of Pd / C catalyst was added. The mixture was stirred, heated to reflux temperature, and then 4-5 equivalents of hydrazine hydrate were added dropwise. After reflux for 12 h, the mixture was cooled, filtered to remove the catalyst, rotary evaporated, dried, and then purified by recrystallization to obtain the target aromatic diamine G (1.48 g, yield 88%). NMR was performed using a 600 MHz NMR spectrometer (Avance III 600 MHz spectrometer, Bruker, Switzerland). The NMR values ​​were δ 9.56 (s, 1H, OH), 8.45 (s, 1H, SO3H), 7.55-6.67 (5H, Ar-H), 5.34 (s, 2H, NH2), and 5.28 (s, 2H, NH2).

[0054] Application Example 1 This application example provides a polymer, which is a polyimide polymerized from an aromatic diamine B containing benzimidazole and hydroxyl substituents obtained in Example 2 and a commercially available dianhydride, having the following structure: The synthesis equation and specific method are as follows: At room temperature, 1.08116 g (4 mmol) of aromatic diamine B containing benzimidazole and hydroxyl substituents was added to a dry three-necked flask. Under a nitrogen atmosphere, 11 mL of N-methylpyrrolidone (NMP) was added to the reaction flask and stirred to dissolve. After complete dissolution, 1.77696 g (4 mmol) of dianhydride monomer BB was added, with a solid content of 25%. The mixture was stirred in an ice-water bath for 12 h, and then 17 mL of NMP was added (the solid content became 10%). 34 mL of toluene, a dehydrating agent, was added, and the reaction was carried out at 180 °C for 9 h. After the reaction was completed, the mixture was poured into deionized water to precipitate, filtered, washed several times with methanol, and dried in a vacuum drying oven at room temperature for 6 h, and then dried at 120 °C for 8 h to obtain polymer BBB (2.38 g, yield 85%).

[0055] The obtained polymer was used to prepare polymer films by conventional solvent drying method. The films were made into sizes of 0.5cm × 4cm and their tensile properties were tested by a dynamic mechanical analyzer Q800 (TA Instruments, USA). The results showed that the tensile strength was above 100MPa and the elongation at break was above 10%, indicating excellent mechanical properties. The obtained polymer was subjected to TGA testing to measure its thermal decomposition temperature T. d The instrument model is TG-DTA6300 (NSKLTD, Tokyo, Japan), and the results show that its T d5% Above 400°C; the resulting polymer was subjected to a DMA test to measure its glass transition temperature T. g The instrument model is DMA Q800 (TA Instruments, USA), and the results show T g Above 450℃; The obtained polymer membrane was tested for gas permeability using a gas permeation apparatus assembled in the laboratory. The results showed that its permeability to H2 was more than 3 times that of the commercial membrane Matrimid (27), its permeability to CO2 was more than 2 times that of Matrimid (8.7), its selectivity to H2 / CH4 was more than 3 times that of Matrimid (130), and its selectivity to CO2 / CH4 was more than 2 times that of Matrimid (36), thus improving its gas separation performance.

[0056] In summary, the synthesis of an amino aromatic compound containing a benzo[a]azine heterocyclic structure is a simple and easy-to-operate method, requiring only two reaction steps, with a simple post-processing and high yield. It can be used to prepare high-performance polymers with main-chain benzo[a]azine heterocyclic units and other active substituents, and to improve the relevant properties of these polymer materials.

[0057] The applicant declares that this invention illustrates an amino aromatic compound containing a benzo[a]azine heterocyclic structure, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

Claims

1. An amino aromatic compound containing a benzo[a]azine heterocyclic structure, characterized in that, The amino aromatic compound containing a benzo[a]azine heterocyclic structure has the structure shown in Formula I; Formula I Among them, R1 and R5 are selected from -H; R2 is selected from any one of -H, -OH, -OCH3, -COOH, -SO3H or -NH2; R3 is selected from -OH; and R4 is selected from -NH2. R6-R9 are each independently -H or -NH2, and at least one of R6-R9 is -NH2; X is selected from any one of NH, S, and O.

2. The amino aromatic compound containing a benzo[a]azine heterocyclic structure according to claim 1, characterized in that, One to three of R6-R9 are -NH2.

3. A method for preparing an amino aromatic compound containing a benzo[a]azine heterocyclic structure as described in claim 1 or 2, characterized in that, The preparation method includes: (1) Aromatic aldehyde compounds With aromatic compounds The reaction proceeds in the presence of a first catalyst to yield a nitroaromatic compound. ; (2) The nitro aromatic compound obtained in step (1) The reducing agent is reacted with a second catalyst to obtain the amino aromatic compound containing the benzo[a]azine heterocyclic structure; Wherein, X is selected from any one of NH, S and O; Y1 and Y5 are selected from -H; Y2 is selected from any one of -H, -OH, -OCH3, -COOH, -SO3H or -NO2, Y3 is -OH, Y4 is -NO2; Y6-Y9 are each independently -H or -NO2, and at least one of Y6-Y9 is -NO2.

4. The preparation method according to claim 3, characterized in that, The aromatic compound specifically includes any one of the following compounds: , , ; X is selected from any one of NH, S and O.

5. The preparation method according to claim 3, characterized in that, The molar ratio of the aromatic aldehyde compound to the aromatic compound in step (1) is 1:(1-1.2).

6. The preparation method according to claim 3, characterized in that, The mass ratio of the aromatic aldehyde compound to the first catalyst is 1:(0.1-0.2).

7. The preparation method according to claim 3, characterized in that, The first catalyst comprises any one or a combination of at least two of potassium iodide, ammonium acetate, imidazole hydrochloride, copper sulfate, ferric chloride, or polyphosphoric acid.

8. The preparation method according to claim 3, characterized in that, The reaction described in step (1) is carried out in the presence of a solvent.

9. The preparation method according to claim 8, characterized in that, The solvent includes any one or a combination of at least two of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone.

10. The preparation method according to claim 8, characterized in that, After the aromatic aldehydes and aromatic compounds in step (1) are dissolved in a solvent, they are reacted in the presence of a first catalyst to obtain nitro aromatic compounds.

11. The preparation method according to claim 10, characterized in that, The melting temperature is 10-30 ℃.

12. The preparation method according to claim 3, characterized in that, The reaction temperature in step (1) is 10-180℃.

13. The preparation method according to claim 3, characterized in that, The reaction time in step (1) is 24-120 hours.

14. The preparation method according to claim 3, characterized in that, The reaction described in step (1) also includes post-processing.

15. The preparation method according to claim 14, characterized in that, The post-processing includes precipitation, filtration, washing, drying, and purification.

16. The preparation method according to claim 15, characterized in that, The precipitation is carried out in deionized water and / or ethanol.

17. The preparation method according to claim 3, characterized in that, The mass ratio of the nitro aromatic compound to the reducing agent in step (2) is (1-4):(1-10).

18. The preparation method according to claim 3, characterized in that, The mass ratio of the nitro aromatic compound to the second catalyst is 1:(0.1-0.2).

19. The preparation method according to claim 3, characterized in that, The reducing agent includes hydrazine hydrate.

20. The preparation method according to claim 3, characterized in that, The second catalyst comprises any one or a combination of at least two of palladium on carbon, platinum on carbon, or Raney nickel.

21. The preparation method according to claim 3, characterized in that, The reaction described in step (2) is carried out in the presence of a solvent.

22. The preparation method according to claim 21, characterized in that, The solvent includes any one or a combination of at least two of methanol, ethanol, acetone or tetrahydrofuran.

23. The preparation method according to claim 21, characterized in that, After the nitro aromatic compound in step (2) is dissolved in a solvent, it is reacted in the presence of a reducing agent and a second catalyst to obtain the amino aromatic compound containing the benzo[a]azine heterocyclic structure.

24. The preparation method according to claim 23, characterized in that, The melting temperature is 10-30 ℃.

25. The preparation method according to claim 3, characterized in that, The reaction temperature in step (2) is 10-90℃.

26. The preparation method according to claim 3, characterized in that, The reaction time in step (2) is 10-48 h.

27. The preparation method according to claim 3, characterized in that, Step (2) includes post-processing after the reaction.

28. The preparation method according to claim 27, characterized in that, The post-processing includes rotary evaporation, washing, drying, separation, and purification.

29. The preparation method according to claim 28, characterized in that, The drying time is 12-48 h.

30. The preparation method according to claim 28, characterized in that, The drying temperature is 70-90 ℃.

31. The preparation method according to claim 28, characterized in that, The separation includes filtration.

32. The application of an amino aromatic compound containing a benzo[a]azine heterocyclic structure as described in claim 1 or 2 in H2 / CH4 gas separation or CO2 / CH4 gas separation.

33. A polymer, characterized in that, The raw materials for preparing the polymer include amino aromatic compounds containing benzo[a]azine heterocyclic structures as described in claim 1 or 2.

34. The polymer according to claim 33, characterized in that, The polymer is polyimide.

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