Hypercrosslinked polyamide-imide polymer and preparation method thereof

Abstract

The invention discloses a super-crosslinked polyamide-imide polymer and a preparation method thereof, and relates to a polymer and a preparation method thereof, the polymer has a plurality of active adsorption sites such as carbonyl, imide ring and amide, and provides rich nitrogen and oxygen heteroatoms and a regular polymer network structure. Due to the fact that the super-crosslinked polyamide-imide polymer carries a large number of positive charges and a regular polymer network structure, the electrostatic interaction with anions is enhanced, bromine, iodine and dye anions can be evenly fixed to the adsorbent, and meanwhile the adsorption capacity of the adsorbent is improved. The carried oxygen-containing functional group, nitrogen-containing functional group and fluorine-containing functional group can be used as Lewis alkaline sites to be combined with bromine, iodine and organic dye; the preparation method is simple, and the cost is reduced. The super-crosslinked polyamide-imide polymer is widely applied to preparation of pollutant adsorption materials and has a wide application prospect in the field of pollutant adsorption materials.

Description

Technical Field

[0001] The invention relates to an organic polymer and a preparation method thereof, in particular to a hyper-crosslinked polyamide-imide polymer and a preparation method thereof. Background Art

[0002] Hypercrosslinked polyamide-imide is a high-performance specialty polymer material. It is widely used in aerospace, electronics and other fields due to its excellent high and low temperature resistance, excellent mechanical properties and excellent dielectric properties. In the field of environmental science, the application of hypercrosslinked polyamide-imide is mainly concentrated in waste liquid treatment and pollutant separation.

[0003] Due to its good solvent resistance and thermal stability, hyper-crosslinked polyamide-imide can remain stable in a variety of solvents, which makes it perform well in treating waste solutions containing organic pollutants. However, traditional hyper-crosslinked polyamide-imide only has amide and imide groups, with fewer active sites, lower heteroatom content, and fewer functional groups that can effectively adsorb and fix pollutants. And with the development of chemical technology, the environment has higher and higher requirements for adsorbents, so hyper-crosslinked polyamide-imide with multiple active sites and high heteroatom content has attracted widespread attention from academia and environmentalists.

[0004] In the prior art, due to the fast kinetics of the Lewis acid catalyzed reaction, the network structure of the hyper-crosslinked polyamide-imide polymer is highly irregular, which limits the ability to synthesize hyper-crosslinked polyamide-imide with a precise pore structure. Summary of the invention

[0005] The purpose of the present invention is to provide a hyper-crosslinked polyamide-imide polymer and a preparation method thereof. The polymer has multiple active adsorption sites such as carbonyl, imide ring and amide, and provides abundant nitrogen and oxygen heteroatoms. Moreover, the hyper-crosslinked polyamide-imide polymer carries a large amount of positive charge, which enhances the electrostatic interaction with anions, so that bromine, iodine and dye anions are fixed on the adsorbent. At the same time, the oxygen-containing functional groups, nitrogen-containing functional groups and fluorine-containing functional groups carried by the polymer can be combined with bromine, iodine and organic dyes as Lewis basic sites.

[0006] The objective of the present invention is achieved through the following technical solutions:

[0007] The first object of the present invention is to provide a novel hyper-crosslinked polyamide-imide polymer, wherein the hyper-crosslinked polyamide-imide polymer has a structural formula as shown in formula (I):

[0008]

[0009] Among them, AR is

[0010]

[0011] Any one of .

[0012] The second object of the present invention is to provide a novel method for preparing a hyper-crosslinked polyamide-imide polymer, which comprises: placing 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), a diamine monomer and dry calcium chloride in a reaction bottle, adding a mixture of pyridine, triphenyl phosphite and N-methylpyrrolidone as a solvent into the reaction bottle, placing the reaction bottle on a magnetic stirrer, heating and stirring, and waiting for 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) to form a crosslinked polyamide-imide polymer. After (1,3-dioxoisoindoline-5-carboxylic acid) is dissolved, N-methylpyrrolidone is added dropwise to dissolve the residual diamine monomer, and the mixture is reacted at 100-180°C for 3-84 hours and then cooled naturally. The yellow precipitate is washed with methanol and anhydrous acetone for 6-8 times until the filtrate is colorless, and then Soxhlet extraction is performed with acetone at 45-85°C for 12-48 hours. The obtained polymer is placed in a vacuum drying oven at 40-80°C for 12 hours, and finally a new type of hyper-crosslinked polyamide-imide polymer is prepared. The specific reaction equation is as follows:

[0013]

[0014] In order to better realize the above technical solution, the structural formula of the diamine monomer in the preparation method of a novel hyper-crosslinked polyamide-imide polymer of the present invention is shown in formula (II):

[0015] H2N-RA-NH2 formula (II), wherein AR is

[0016]

[0017] Any one of .

[0018] In order to better realize the above technical scheme, in a novel method for preparing a hyper-crosslinked polyamide-imide polymer of the present invention, the molar mass ratio of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) to diamine monomer is 1:(1 ～ 5.8).

[0019] In order to better realize the above technical scheme, the volume ratio of pyridine, triphenyl phosphite and N-methylpyrrolidone in the preparation method of a novel hyper-crosslinked polyamide-imide polymer of the present invention is 1:(2 ～ 8.5):(6 ～ 11.5).

[0020] In order to better realize the above technical scheme, the preparation method of 2,2',2"-((benzene-1,3,5-triyltri(oxy))tris(3-(trifluoromethyl)benzene-4,1-diyl))tris(1,3-dioxyisoindole-5-carboxylic acid) in the preparation method of a novel hyper-crosslinked polyamide-imide polymer of the present invention is as follows:

[0021] Step 1, reduction reaction: under nitrogen atmosphere, tri(4-nitrophenyl)amine and catalyst are dispersed in ethanol in a three-necked round-bottom flask in turn, placed in an oil bath and stirred, the sample is mixed evenly and heated, and when the reaction temperature is balanced and stable, hydrazine hydrate is added dropwise to the reaction system using a constant pressure funnel, and the drop rate is controlled to be 4-5s per drop to obtain a mixture A, and the mixture is reacted under reflux for 1 ～ 3 days, click the plate regularly, observe the reduction of the sample, wait for the reaction to be completed, take a sand core funnel to filter and remove the catalyst in the solution, concentrate the filtrate by rotary evaporator to remove excess hydrazine hydrate to obtain mixture B, add mixture B to ice-water mixture under stirring to obtain a light yellow precipitate, wash the light yellow precipitate thoroughly with distilled water to remove the solvent and reducing agent, dry in vacuo, and elute with dichloromethane column chromatography to obtain a white solid powder, namely tris(4-aminophenyl)amine. The specific reaction is as follows:

[0022]

[0023] Step 2, buckling reaction: tris(4-aminophenyl)amine and trimellitic anhydride are dispersed in 20-60 mL of glacial acetic acid in a three-necked round-bottom flask under a nitrogen atmosphere, and mechanically stirred for 1-5 hours at room temperature. After the sample in the flask is evenly mixed, the reaction is heated for 12-60 hours, the product is filtered, washed with methanol 3-5 times, and then dried in a vacuum drying oven at 60° C. for 24 hours to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), and the specific reaction equation is as follows:

[0024]

[0025] In order to better realize the above technical scheme, in the preparation method of a novel hyper-crosslinked polyamide-imide polymer of the present invention, the mass volume ratio of tri(4-nitrophenyl)amine, catalyst and ethanol in the above step 1 is (1.9-18) g: (0.1-2) g: (25-250) mL.

[0026] In order to better realize the above technical solution, in the preparation method of a novel hyper-crosslinked polyamide-imide polymer of the present invention, the above catalyst is palladium carbon.

[0027] In order to better realize the above technical scheme, in the preparation method of a novel hyper-crosslinked polyamide-imide polymer of the present invention, the temperature is slowly raised to 75-100°C in the above step 1, and the reflux time is 1-2h, and then hydrazine hydrate is added dropwise and reacted at 75-100°C for 15-30h, and the temperature is lowered to 20-40°C after the reaction is completed.

[0028] In order to better realize the above technical scheme, in the preparation method of a novel hyper-crosslinked polyamide-imide polymer of the present invention, the mass volume ratio of tri(4-aminophenyl)amine, trimellitic anhydride and glacial acetic acid in the above step 2 is (1-7.5) g: (3-22) g: (20-100) mL.

[0029] The third object of the present invention is to provide an application of preparing a hyper-crosslinked poly(amide-imide) polymer, wherein the hyper-crosslinked poly(amide-imide) polymer is used for the adsorption of bromine, iodine and dyes, and the process is as follows: first, 0.01-0.1 mol / L bromine and iodine cyclohexane solutions and 10-80 mg / L Congo red and methylene blue dyes are respectively prepared; 5.0 mg of the hyper-crosslinked polyamide-imide polymer is placed in a dry glass bottle, and 2-50 mL of bromine or iodine or dye solution is added to the bottle; at a fixed time, the solution in the glass bottle is drawn and the absorbance is tested with an ultraviolet spectrophotometer; the residual amount of bromine, iodine and dye in the solution is determined according to the absorbance curve of the solution containing bromine, iodine and dye, and then the absorption amount of the adsorbent is calculated by subtracting the residual amount of bromine, iodine and dye from the initial amount of bromine, iodine and dye in the solution.

[0030] The advantages and positive effects of the present invention are:

[0031] 1. The polymer of the present invention has multiple active adsorption sites such as carbonyl, imide ring and amide, providing abundant nitrogen\oxygen heteroatoms and regular polymer network structure. Because the hyper-crosslinked polyamide-imide polymer carries a large amount of positive charge and regular polymer network structure, it enhances the electrostatic interaction with anions, and can evenly fix bromine, iodine and dye anions on the adsorbent. At the same time, the oxygen-containing functional groups, nitrogen-containing functional groups and fluorine-containing functional groups it carries can be combined with bromine, iodine and organic dyes as Lewis basic sites. Therefore, the new hyper-crosslinked polyamide-imide polymer can be widely used in the preparation of pollutant adsorbent materials, and has broad application prospects in the field of pollutant adsorbent materials.

[0032] 2. The preparation method of the novel hyper-crosslinked polyamide-imide polymer of the present invention uses tri(4-nitrophenyl)amine as a raw material to prepare a triamino monomer tri(4-aminophenyl)amine through a reduction reaction, and then uses the triamino monomer and trimellitic anhydride to prepare a tridentate imidic acid monomer 2,2',2"-(nitrile tri(phenyl-4,1-diyl)tri(1,3-dioxoisoindoline-5-carboxylic acid) through a thermal buckling reaction, and uses the triacid monomer and four diamine monomers to prepare a series of novel hyper-crosslinked polyamide-imide polymers with different functional groups. The synthesis route of the present invention is simpler and reduces the cost. The hyper-crosslinked polyamide-imide polymer has multiple active adsorption sites and abundant nitrogen\oxygen heteroatoms. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The drawings described herein are used to provide a further understanding of the present invention and constitute a part of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0034] Figure 1 IR spectra of novel hyper-crosslinked polyamide-imide polymers 1-4 of Examples 1, 6, 11, and 16 of the present invention;

[0035] Figure 2 It is the XPS spectra of the novel hyper-crosslinked polyamide-imide polymers 1-4 of Examples 1, 6, 11, and 16 of the present invention. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention and the corresponding drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0037] A novel hyper-crosslinked polyamide-imide polymer, wherein the hyper-crosslinked polyamide-imide polymer has a structural formula as shown in formula (I):

[0038]

[0039] in, Any one of the above, the polymer of the present invention is introduced into the main chain, and the stacking ability of the molecular chain is improved by hydrogen bonding to produce a mesoporous structure; the side groups such as trifluoromethyl and methyl are introduced to destroy the coplanarity of the electron cloud in the benzene ring and inhibit the generation of a conjugated structure. At the same time, the trifluoromethyl group has a large free volume, thereby increasing the specific surface area and porosity of the polymer; the nitrogen\oxygen heteroatoms, fluorine-containing groups and imide rings contained in the molecular chain provide ion exchange capacity, promote intramolecular and intermolecular charge transfer, and form a good interaction between the new hyper-crosslinked polyamide-imide polymer and the pollutants; the new hyper-crosslinked polyamide-imide polymer is widely used in the preparation of pollutant adsorbent materials, and has broad application prospects in the field of pollutant adsorbent materials.

[0040] The preparation method of the novel hyper-crosslinked polyamide-imide polymer comprises the following steps: placing 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), diamine monomer and dry calcium chloride in a reaction bottle, adding a mixture of pyridine, triphenyl phosphite and N-methylpyrrolidone as a solvent into the reaction bottle, placing the reaction bottle on a magnetic stirrer, heating and stirring, and after observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) is dissolved, then adding N-methylpyrrolidone dropwise to dissolve the residual diamine monomer, and heating at 100 °C. ～ Reaction at 180℃ ～ After 84 hours of natural cooling, the yellow precipitate was washed 6-8 times with methanol and anhydrous acetone until the filtrate was colorless, and then heated at 45 ～ Soxhlet extraction with acetone at 85°C for 12 ～ 48h, the obtained polymer was placed in 40 ～ The reaction mixture was placed in a vacuum drying oven at 80°C for 12 hours to prepare a novel hyper-crosslinked polyamide-imide polymer. The specific reaction equation is as follows:

[0041]

[0042] Furthermore, the structural formula of the diamine monomer in the preparation method of a novel hyper-crosslinked polyamide-imide polymer of the present invention is as shown in formula (II): H2N-RA-NH2 formula (II), wherein AR is

[0043]

[0044] In any one of the above, different monomers can be replaced in the process of preparing the new hyper-crosslinked polyamide-imide polymer, and polymers with different structures can be prepared by replacing different monomers, and different types of new hyper-crosslinked polyamide-imide polymers can be prepared by changing the type of polymer.

[0045] Furthermore, in the preparation method of the novel hyper-crosslinked polyamide-imide polymer of the present invention, the molar mass ratio of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) to diamine monomer is 1:(1 ～ 5.8), preferably, the molar mass ratio of 2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) to the diamine monomer is 1:(1 ～ 5.6).

[0046] Furthermore, in the preparation method of the novel hyper-crosslinked polyamide-imide polymer of the present invention, the volume ratio of pyridine, triphenyl phosphite and N-methylpyrrolidone is 1:(2 ～ 8.5):(6 ～ 11.5), preferably, the volume ratio of pyridine, triphenyl phosphite and N-methylpyrrolidone is 1:(2 ～ 8):(6 ～ 11).

[0047] The preparation method of 2,2',2"-((benzene-1,3,5-triyltri(oxy))tris(3-(trifluoromethyl)benzene-4,1-diyl))tris(1,3-dioxyisoindole-5-carboxylic acid) in a novel method for preparing a hyper-crosslinked polyamide-imide polymer is as follows:

[0048] Step 1, reduction reaction: under a nitrogen atmosphere, tri(4-nitrophenyl)amine and a catalyst are dispersed in ethanol in a three-necked round-bottom flask in turn, placed in an oil bath and stirred, the sample is mixed evenly and then heated, and when the reaction temperature is balanced and stable, hydrazine hydrate is added dropwise to the reaction system using a constant pressure funnel, and the dripping rate is controlled to be 4-5s per drop to obtain a mixture A, wherein the mass volume ratio of tri(4-nitrophenyl)amine, catalyst, and ethanol is (1.9-18) g: (0.1-2) g: (25-250) mL. Preferably, the mass volume ratio of tri(4-nitrophenyl)amine, catalyst, and ethanol of the present invention is The reaction mixture is (1.9-16.2) g: (0.1-1.9) g: (25-85) mL, and the mixture is reacted under reflux for 1-3 days. The plate is pressed at regular intervals to observe the reduction of the sample. After the reaction is completed, a sand core funnel is used to filter and remove the catalyst in the solution. The filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate to obtain a mixture B. Under stirring conditions, the mixture B is added to an ice-water mixture to obtain a light yellow precipitate. The light yellow precipitate is thoroughly washed with distilled water to remove the undistilled solvent and reducing agent. After vacuum drying, the mixture is eluted by dichloromethane column chromatography to obtain a white solid powder, namely tris(4-aminophenyl)amine. The specific reaction is as follows:

[0049]

[0050] Step 2, buckling reaction: tris(4-aminophenyl)amine and trimellitic anhydride are dispersed in 20-60 mL of glacial acetic acid in a three-necked round-bottom flask under a nitrogen atmosphere, and mechanically stirred for 1-5 h at room temperature. After the sample in the flask is evenly mixed, the reaction is heated for 12-60 h, wherein the mass volume ratio of tris(4-aminophenyl)amine, trimellitic anhydride and glacial acetic acid is (1-7.5) g: (3-22) g: (20-100) mL, as a preferred , the mass volume ratio of tri(4-aminophenyl)amine, trimellitic anhydride and glacial acetic acid is (1-7.3) g: (3-21.8) g: (20-85) mL, the product is filtered and washed with methanol 3-5 times, and then placed in a vacuum drying oven at 60°C for 24 hours to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), the specific reaction equation is as follows:

[0051]

[0052] The application of a novel hyper-crosslinked polyamide-imide polymer prepared according to the above method in the adsorption of bromine, iodine and dyes is as follows: first, cyclohexane solutions of bromine and iodine with a concentration of 0.01-0.1 mol / L and 10-80 mg / L of Congo red and methylene blue dyes are respectively prepared. 5.0 mg of the novel hyper-crosslinked polyamide-imide polymer is placed in a dry glass bottle, and 2-50 mL of bromine or iodine or dye solution is added to the bottle. At a fixed time, the solution in the glass bottle is drawn and the absorbance is tested with an ultraviolet spectrophotometer. The residual amount of bromine, iodine and dye in the solution is determined according to the absorbance curve of the solution containing bromine, iodine and dye, and then the absorption amount of the adsorbent is calculated by subtracting the residual amount of bromine, iodine and dye from the initial amount of bromine, iodine and dye in the solution.

[0053] The technical solutions provided by various embodiments of the present invention are described in detail below in conjunction with the accompanying drawings.

[0054] Example 1

[0055] 1. Synthesis of tris(4-aminophenyl)amine

[0056] Tris(4-nitrophenyl)amine (3.8g, 10mmol) and palladium / carbon (10%, 0.21g) were dispersed in ethanol (55mL), and the sample was mixed evenly and heated to 75°C. When the reaction temperature was balanced and stable, hydrazine hydrate was slowly dripped under nitrogen protection. After that, the mixture was refluxed for 1 day, and the plate was tapped at regular intervals to observe the reduction of the sample. After the reflux was completed, the palladium carbon was removed by a sand core funnel, and the filtrate was concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture was added to an ice-water mixture to obtain a light yellow precipitate. The formed product was collected by filtration, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tris(4-aminophenyl)amine, 2.47g.

[0057] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0058] Tris(4-aminophenyl)amine (2.4 g, 8.27 mmol) and trimellitic anhydride (15.23 g, 79.26 mmol) were dispersed in 60 mL of glacial acetic acid under a nitrogen atmosphere and mechanically stirred for 3 h at room temperature. After the sample in the flask was evenly mixed, the reaction was heated for 24 h. The product was filtered and washed with methanol for 3-5 times, and then dried in a vacuum drying oven at 60°C for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 12.138 g.

[0059] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 1

[0060] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindolin-5-carboxylic acid) (0.16 g, 0.5 mmol), o-toluidine (0.169 g, 0.8 mmol) and 0.2 g of dry calcium chloride were placed in a reaction bottle, and 0.5 mL of pyridine, 1.5 mL of triphenyl phosphite and 3.5 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated and stirred. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 100°C for 12 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 12 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.2214 g of a novel hyper-crosslinked polyamide-imide polymer 1 was prepared.

[0061] Example 2

[0062] 1. Synthesis of tris(4-aminophenyl)amine

[0063] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (11.76g, 30.9mmol), palladium / carbon is changed to (10%, 0.517g) and dispersed in ethanol (150mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 1 day, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is filtered and collected, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 8.82g.

[0064] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0065] The method is the same as that of Example 1. Under a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (6.32 g, 21.76 mmol) and trimellitic anhydride is replaced with (19.28 g, 100 mmol) and dispersed in 75 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 32 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 17.88 g.

[0066] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 1

[0067] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindolin-5-carboxylic acid) (0.2 g, 0.65 mmol), o-toluidine (0.255 g, 1.2 mmol) and 0.4 g of dry calcium chloride were placed in a reaction flask, and 1.0 mL of pyridine, 4.0 mL of triphenyl phosphite and 8.0 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated and stirred. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 110°C for 14 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 12 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.315 g of a novel hyper-crosslinked polyamide-imide polymer 1 was prepared.

[0068] Example 3

[0069] 1. Synthesis of tris(4-aminophenyl)amine

[0070] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (18.79 g, 49 mmol) and palladium / carbon is changed to (10%, 1 g) and dispersed in ethanol (250 mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 1 day, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is filtered and collected, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 14.09 g.

[0071] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0072] The method is the same as that of Example 1. Under a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (7.5 g, 25.83 mmol) and trimellitic anhydride is replaced with (22.5 g, 117 mmol) and dispersed in 90 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 32 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 18.03 g.

[0073] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 1

[0074] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.256 g, 0.8 mmol), o-toluidine (0.286 g, 1.35 mmol) and 0.4 g of dry calcium chloride were placed in a reaction bottle, and 1.4 mL of pyridine, 8 mL of triphenyl phosphite and 12 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated and stirred. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 120°C for 20 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 16 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.323g of a novel hyper-crosslinked polyamide-imide polymer 1 was prepared.

[0075] Example 4

[0076] 1. Synthesis of tris(4-aminophenyl)amine

[0077] The method is the same as Example 1, except that tri(4-nitrophenyl)amine is changed to (22.36 g, 58.8 mmol), palladium / carbon is changed to (10%, 1.2 g) and dispersed in ethanol (290 mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 2 days, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, the palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring conditions, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is collected by filtration, thoroughly washed with distilled water, dried in vacuo, and eluted by dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 16.77 g.

[0078] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0079] The method is the same as that of Example 1. In a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (8.3 g, 28.5 mmol) and trimellitic anhydride is replaced with (23.7 g, 123 mmol) and dispersed in 80 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 54 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 19.2 g.

[0080] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 1

[0081] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.304 g, 0.95 mmol), o-toluidine (0.318 g, 1.5 mmol) and 0.8 g of dry calcium chloride were placed in a reaction bottle, and 1.8 mL of pyridine, 12 mL of triphenyl phosphite and 15 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated and stirred. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 140°C for 24 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 18 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.372g of a novel hyper-crosslinked polyamide-imide polymer 1 was prepared.

[0082] Example 5

[0083] 1. Synthesis of tris(4-aminophenyl)amine

[0084] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (24.32g, 64mmol) and palladium / carbon is changed to (10%, 2g) and dispersed in ethanol (320mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 2 days, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, the palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring conditions, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is collected by filtration, thoroughly washed with distilled water, dried in vacuo, and eluted by dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 18.19g.

[0085] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0086] The method is the same as that of Example 1. In a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (10.15 g, 35 mmol) and trimellitic anhydride is replaced with (26.88 g, 140 mmol) and dispersed in 100 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 54 h. The product is filtered and washed with methanol for 3-5 times, and then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 23.6 g.

[0087] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 1

[0088] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.352 g, 1.1 mmol), o-toluidine (0.3604 g, 1.7 mmol) and 1.2 g of dry calcium chloride were placed in a reaction bottle, and 2 mL of pyridine, 15 mL of triphenyl phosphite and 18 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 160°C for 24 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 24 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.413g of a novel hyper-crosslinked polyamide-imide polymer 1 was prepared.

[0089] Example 6

[0090] 1. Synthesis of tris(4-aminophenyl)amine

[0091] Tris(4-nitrophenyl)amine (3.8g, 10mmol) and palladium / carbon (10%, 0.21g) were dispersed in ethanol (55mL), and the sample was mixed evenly and heated to 75°C. When the reaction temperature was balanced and stable, hydrazine hydrate was slowly dripped under nitrogen protection. After that, the mixture was refluxed for 1 day, and the plate was tapped at regular intervals to observe the reduction of the sample. After the reflux was completed, the palladium carbon was removed by a sand core funnel, and the filtrate was concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture was added to an ice-water mixture to obtain a light yellow precipitate. The formed product was collected by filtration, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tris(4-aminophenyl)amine, 2.47g.

[0092] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0093] Tris(4-aminophenyl)amine (2.4 g, 8.27 mmol) and trimellitic anhydride (15.23 g, 79.26 mmol) were dispersed in 60 mL of glacial acetic acid under a nitrogen atmosphere and mechanically stirred for 3 h at room temperature. After the sample in the flask was evenly mixed, the reaction was heated for 24 h. The product was filtered and washed with methanol for 3-5 times, and then dried in a vacuum drying oven at 60°C for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 12.138 g.

[0094] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 2

[0095] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindolin-5-carboxylic acid) (0.16 g, 0.5 mmol), p-phenylenediamine (0.086 g, 0.8 mmol) and 0.2 g of dry calcium chloride were placed in a reaction bottle, and 0.5 mL of pyridine, 1.5 mL of triphenyl phosphite and 3.5 mL of A mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated and stirred. After the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was observed to be dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 100°C for 12 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 12 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.147 g of a novel hyper-crosslinked polyamide-imide polymer 2 was prepared.

[0096] Example 7

[0097] 1. Synthesis of tris(4-aminophenyl)amine

[0098] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (11.76g, 30.9mmol), palladium / carbon is changed to (10%, 0.517g) and dispersed in ethanol (150mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 1 day, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is filtered and collected, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 8.82g.

[0099] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0100] The method is the same as that of Example 1. Under a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (6.32 g, 21.76 mmol) and trimellitic anhydride is replaced with (19.28 g, 100 mmol) and dispersed in 75 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 32 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 17.88 g.

[0101] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 2

[0102] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindolin-5-carboxylic acid) (0.2 g, 0.65 mmol), p-phenylenediamine (0.13 g, 1.2 mmol) and 0.4 g of dry calcium chloride were placed in a reaction flask, and 1.0 mL of pyridine, 4.0 mL of triphenyl phosphite and 8.0 mL of A mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 110°C for 14 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 12 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.188 g of a novel hyper-crosslinked polyamide-imide polymer 2 was prepared.

[0103] Example 8

[0104] 1. Synthesis of tris(4-aminophenyl)amine

[0105] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (18.79 g, 49 mmol) and palladium / carbon is changed to (10%, 1 g) and dispersed in ethanol (250 mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 1 day, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is filtered and collected, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 14.09 g.

[0106] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0107] The method is the same as that of Example 1. Under a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (7.5 g, 25.83 mmol) and trimellitic anhydride is replaced with (22.5 g, 117 mmol) and dispersed in 90 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 32 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 18.03 g.

[0108] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 2

[0109] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindolin-5-carboxylic acid) (0.256 g, 0.8 mmol), p-phenylenediamine (0.1458 g, 1.35 mmol) and 0.4 g of dry calcium chloride were placed in a reaction bottle, and 1.4 mL of pyridine, 8 mL of triphenyl phosphite and 12 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated and stirred. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 120°C for 20 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 16 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.236g of a novel hyper-crosslinked polyamide-imide polymer 2 was prepared.

[0110] Example 9

[0111] 1. Synthesis of tris(4-aminophenyl)amine

[0112] The method is the same as Example 1, except that tri(4-nitrophenyl)amine is changed to (22.36 g, 58.8 mmol), palladium / carbon is changed to (10%, 1.2 g) and dispersed in ethanol (290 mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 2 days, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, the palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring conditions, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is collected by filtration, thoroughly washed with distilled water, dried in vacuo, and eluted by dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 16.77 g.

[0113] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0114] The method is the same as that of Example 1. In a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (8.3 g, 28.5 mmol) and trimellitic anhydride is replaced with (23.7 g, 123 mmol) and dispersed in 80 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 54 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 19.2 g.

[0115] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 2

[0116] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindolin-5-carboxylic acid) (0.304 g, 0.95 mmol), p-phenylenediamine (0.162 g, 1.5 mmol) and 0.8 g of dry calcium chloride were placed in a reaction bottle, and 1.8 mL of pyridine, 12 mL of triphenyl phosphite and 15 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was observed to be dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 140°C for 24 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 18 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.278 g of a novel hyper-crosslinked polyamide-imide polymer 2 was prepared.

[0117] Example 10

[0118] 1. Synthesis of tris(4-aminophenyl)amine

[0119] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (24.32g, 64mmol), palladium / carbon is changed to (10%, 2g) and dispersed in ethanol (320mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 2 days, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, the palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is filtered and collected, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 18.19g.

[0120] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0121] The method is the same as that of Example 1. In a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (10.15 g, 35 mmol) and trimellitic anhydride is replaced with (26.88 g, 140 mmol) and dispersed in 100 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 54 h. The product is filtered and washed with methanol for 3-5 times, and then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 23.6 g.

[0122] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 2

[0123] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.352 g, 1.1 mmol), p-phenylenediamine (0.1836 g, 1.7 mmol) and 1.2 g of dry calcium chloride were placed in a reaction flask, and 2 mL of pyridine, 15 mL of triphenyl phosphite and 18 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 160°C for 24 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 24 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.332 g of a novel hyper-crosslinked polyamide-imide polymer 2 was prepared.

[0124] Embodiment 11

[0125] 1. Synthesis of tris(4-aminophenyl)amine

[0126] Tris(4-nitrophenyl)amine (3.8g, 10mmol) and palladium / carbon (10%, 0.21g) were dispersed in ethanol (55mL), and the sample was mixed evenly and heated to 75°C. When the reaction temperature was balanced and stable, hydrazine hydrate was slowly dripped under nitrogen protection. After that, the mixture was refluxed for 1 day, and the plate was tapped at regular intervals to observe the reduction of the sample. After the reflux was completed, the palladium carbon was removed by a sand core funnel, and the filtrate was concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture was added to an ice-water mixture to obtain a light yellow precipitate. The formed product was collected by filtration, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tris(4-aminophenyl)amine, 2.47g.

[0127] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0128] Tris(4-aminophenyl)amine (2.4 g, 8.27 mmol) and trimellitic anhydride (15.23 g, 79.26 mmol) were dispersed in 60 mL of glacial acetic acid under a nitrogen atmosphere and mechanically stirred for 3 h at room temperature. After the sample in the flask was evenly mixed, the reaction was heated for 24 h. The product was filtered and washed with methanol for 3-5 times, and then dried in a vacuum drying oven at 60°C for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 12.138 g.

[0129] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 3

[0130] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.16 g, 0.5 mmol), m-phenylenediamine (0.086 g, 0.8 mmol) and 0.2 g of dry calcium chloride were placed in a reaction bottle, and 0.5 mL of pyridine, 1.5 mL of triphenyl phosphite and 3.5 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated and stirred. After the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was observed to be dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 100°C for 12 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 12 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.244 g of a novel hyper-crosslinked polyamide-imide polymer 3 was prepared.

[0131] Example 12

[0132] 1. Synthesis of tris(4-aminophenyl)amine

[0133] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (11.76g, 30.9mmol), palladium / carbon is changed to (10%, 0.517g) and dispersed in ethanol (150mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 1 day, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is filtered and collected, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 8.82g.

[0134] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0135] The method is the same as that of Example 1. Under a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (6.32 g, 21.76 mmol) and trimellitic anhydride is replaced with (19.28 g, 100 mmol) and dispersed in 75 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 32 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 17.88 g.

[0136] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 3

[0137] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.2 g, 0.65 mmol), m-phenylenediamine (0.13 g, 1.2 mmol) and 0.4 g of dry calcium chloride were placed in a reaction flask, and 1.0 mL of pyridine, 4.0 mL of triphenyl phosphite and 8.0 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was observed to be dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 110°C for 14 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless, and then Soxhlet extraction was carried out with acetone at 65°C for 12 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours, and finally 0.341g of a novel hyper-crosslinked polyamide-imide polymer 3 was prepared.

[0138] Example 13

[0139] 1. Synthesis of tris(4-aminophenyl)amine

[0140] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (18.79 g, 49 mmol) and palladium / carbon is changed to (10%, 1 g) and dispersed in ethanol (250 mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 1 day, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is filtered and collected, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 14.09 g.

[0141] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0142] The method is the same as that of Example 1. Under a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (7.5 g, 25.83 mmol) and trimellitic anhydride is replaced with (22.5 g, 117 mmol) and dispersed in 90 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 32 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 18.03 g.

[0143] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 3

[0144] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.256 g, 0.8 mmol), m-phenylenediamine (0.1458 g, 1.35 mmol) and 0.4 g of dry calcium chloride were placed in a reaction bottle, and 1.4 mL of pyridine, 8 mL of triphenyl phosphite and 12 mL of The mixture of N-methylpyrrolidone is used as a solvent and is put into the reaction bottle. The reaction bottle is placed on a magnetic stirrer and heated and stirred. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) is dissolved, N-methylpyrrolidone is added dropwise to dissolve the residual diamine monomer. The reaction is carried out at a temperature of 120°C for 20 hours and then naturally cooled. The obtained yellow precipitate is washed with methanol and anhydrous acetone for 6-8 times until the filtrate is colorless, and then Soxhlet extraction is carried out with acetone at 65°C for 16 hours. The obtained polymer is placed in a vacuum drying oven at 50°C for 12 hours, and finally 0.247g of a novel hyper-crosslinked polyamide-imide polymer is prepared.

[0145] Embodiment 14

[0146] 1. Synthesis of tris(4-aminophenyl)amine

[0147] The method is the same as Example 1, except that tri(4-nitrophenyl)amine is changed to (22.36 g, 58.8 mmol), palladium / carbon is changed to (10%, 1.2 g) and dispersed in ethanol (290 mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 2 days, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, the palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring conditions, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is collected by filtration, thoroughly washed with distilled water, dried in vacuo, and eluted by dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 16.77 g.

[0148] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0149] The method is the same as that of Example 1. In a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (8.3 g, 28.5 mmol) and trimellitic anhydride is replaced with (23.7 g, 123 mmol) and dispersed in 80 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 54 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 19.2 g.

[0150] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 3

[0151] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.304 g, 0.95 mmol), m-phenylenediamine (0.162 g, 1.5 mmol) and 0.8 g of dry calcium chloride were placed in a reaction flask, and 1.8 mL of pyridine, 12 mL of triphenyl phosphite and 15 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 140°C for 24 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 18 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.293g of a novel hyper-crosslinked polyamide-imide polymer 3 was prepared.

[0152] Embodiment 15

[0153] 1. Synthesis of tris(4-aminophenyl)amine

[0154] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (24.32g, 64mmol), palladium / carbon is changed to (10%, 2g) and dispersed in ethanol (320mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 2 days, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is filtered and collected, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 18.19g.

[0155] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0156] The method is the same as that of Example 1. In a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (10.15 g, 35 mmol) and trimellitic anhydride is replaced with (26.88 g, 140 mmol) and dispersed in 100 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 54 h. The product is filtered and washed with methanol for 3-5 times, and then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 23.6 g.

[0157] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 3

[0158] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.352 g, 1.1 mmol), m-phenylenediamine (0.1836 g, 1.7 mmol) and 1.2 g of dry calcium chloride were placed in a reaction flask, and 2 mL of pyridine, 15 mL of triphenyl phosphite and 18 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 160°C for 24 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 24 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.347 g of a novel hyper-crosslinked polyamide-imide polymer 3 was prepared.

[0159] Example 16

[0160] 1. Synthesis of tris(4-aminophenyl)amine

[0161] Tris(4-nitrophenyl)amine (3.8g, 10mmol) and palladium / carbon (10%, 0.21g) were dispersed in ethanol (55mL), and the sample was mixed evenly and heated to 75°C. When the reaction temperature was balanced and stable, hydrazine hydrate was slowly dripped under nitrogen protection. After that, the mixture was refluxed for 1 day, and the plate was tapped at regular intervals to observe the reduction of the sample. After the reflux was completed, the palladium carbon was removed by a sand core funnel, and the filtrate was concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture was added to an ice-water mixture to obtain a light yellow precipitate. The formed product was collected by filtration, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tris(4-aminophenyl)amine, 2.47g.

[0162] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0163] Tris(4-aminophenyl)amine (2.4 g, 8.27 mmol) and trimellitic anhydride (15.23 g, 79.26 mmol) were dispersed in 60 mL of glacial acetic acid under a nitrogen atmosphere and mechanically stirred for 3 h at room temperature. After the sample in the flask was evenly mixed, the reaction was heated for 24 h. The product was filtered and washed with methanol for 3-5 times, and then dried in a vacuum drying oven at 60°C for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 12.138 g.

[0164] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 4

[0165] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.16 g, 0.5 mmol), 2,2-bis(trifluoromethyl)diaminobiphenyl (0.256 g, 0.8 mmol) and 0.2 g of dry calcium chloride were placed in a reaction bottle, and 0.5 mL of pyridine, 1.5 mL of triphenyl phosphite and 3.5 mL of The mixture of N-methylpyrrolidone is used as a solvent and is put into the reaction bottle. The reaction bottle is placed on a magnetic stirrer and heated and stirred. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) is dissolved, N-methylpyrrolidone is added dropwise to dissolve the residual diamine monomer. The reaction is carried out at 100°C for 12 hours and then naturally cooled. The yellow precipitate is washed with methanol and anhydrous acetone for 6-8 times until the filtrate is colorless, and then Soxhlet extraction is carried out with acetone at 65°C for 12 hours. The obtained polymer is placed in a vacuum drying oven at 50°C for 12 hours, and finally 0.271g of a novel hyper-crosslinked polyamide-imide polymer 4 is prepared.

[0166] Embodiment 17

[0167] 1. Synthesis of tris(4-aminophenyl)amine

[0168] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (11.76g, 30.9mmol), palladium / carbon is changed to (10%, 0.517g) and dispersed in ethanol (150mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 1 day, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is filtered and collected, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 8.82g.

[0169] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0170] The method is the same as that of Example 1. Under a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (6.32 g, 21.76 mmol) and trimellitic anhydride is replaced with (19.28 g, 100 mmol) and dispersed in 75 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 32 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 17.88 g.

[0171] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 4

[0172] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindolin-5-carboxylic acid) (0.2 g, 0.65 mmol), 2,2-bis(trifluoromethyl)diaminobiphenyl (0.384 g, 1.2 mmol) and 0.4 g of dry calcium chloride were placed in a reaction bottle, and 1.0 mL of pyridine, 4.0 mL of triphenyl phosphite and 8.0 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 110°C for 14 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 12 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.335 g of a novel hyper-crosslinked polyamide-imide polymer 4 was prepared.

[0173] Embodiment 18

[0174] 1. Synthesis of tris(4-aminophenyl)amine

[0175] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (18.79 g, 49 mmol) and palladium / carbon is changed to (10%, 1 g) and dispersed in ethanol (250 mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 1 day, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is filtered and collected, thoroughly washed with distilled water, vacuum dried, and eluted with dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 14.09 g.

[0176] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0177] The method is the same as that of Example 1. Under a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (7.5 g, 25.83 mmol) and trimellitic anhydride is replaced with (22.5 g, 117 mmol) and dispersed in 90 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 32 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 18.03 g.

[0178] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 1

[0179] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindolin-5-carboxylic acid) (0.256 g, 0.8 mmol), 2,2-bis(trifluoromethyl)diaminobiphenyl (0.432 g, 1.35 mmol) and 0.4 g of dry calcium chloride were placed in a reaction bottle, and 1.4 mL of pyridine, 8 mL of triphenyl phosphite and 12 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 120°C for 20 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 16 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.688g of a novel hyper-crosslinked polyamide-imide polymer 4 was prepared.

[0180] Embodiment 19

[0181] 1. Synthesis of tris(4-aminophenyl)amine

[0182] The method is the same as Example 1, except that tri(4-nitrophenyl)amine is changed to (22.36 g, 58.8 mmol), palladium / carbon is changed to (10%, 1.2 g) and dispersed in ethanol (290 mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 2 days, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, the palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring conditions, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is collected by filtration, thoroughly washed with distilled water, dried in vacuo, and eluted by dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 16.77 g.

[0183] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0184] The method is the same as that of Example 1. Under a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (8.3 g, 28.5 mmol) and trimellitic anhydride is replaced with (23.7 g, 123 mmol) and dispersed in 80 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 54 h. The product is filtered and washed with methanol for 3-5 times. The product is then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 19.2 g.

[0185] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 4

[0186] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.304 g, 0.95 mmol), 2,2-bis(trifluoromethyl)diaminobiphenyl (0.48 g, 1.5 mmol) and 0.8 g of dry calcium chloride were placed in a reaction bottle, and 1.8 mL of pyridine, 12 mL of triphenyl phosphite and 15 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 140°C for 24 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 18 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.509 g of a novel hyper-crosslinked polyamide-imide polymer 4 was prepared.

[0187] Embodiment 20

[0188] 1. Synthesis of tris(4-aminophenyl)amine

[0189] The method is the same as in Example 1, except that tri(4-nitrophenyl)amine is changed to (24.32g, 64mmol) and palladium / carbon is changed to (10%, 2g) and dispersed in ethanol (320mL). After the sample is mixed evenly, it is heated to 75°C. When the reaction temperature is balanced and stable, hydrazine hydrate is slowly dripped under nitrogen protection. After that, the mixture is refluxed for 2 days, and the plate is tapped at regular intervals to observe the reduction of the sample. After the reflux is completed, the palladium carbon is removed by a sand core funnel, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate. Under stirring conditions, the mixture is added to an ice-water mixture to obtain a light yellow precipitate. The formed product is collected by filtration, thoroughly washed with distilled water, dried in vacuo, and eluted by dichloromethane column chromatography to obtain a white solid powder, i.e., tri(4-aminophenyl)amine, 18.19g.

[0190] 2. Synthesis of 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid)

[0191] The method is the same as that of Example 1. Under a nitrogen atmosphere, tri(4-aminophenyl)amine is replaced with (10.15 g, 35 mmol) and trimellitic anhydride is replaced with (26.88 g, 140 mmol) and dispersed in 100 mL of glacial acetic acid. The mixture is mechanically stirred for 3 h at room temperature. After the sample in the flask is evenly mixed, the mixture is heated for reaction for 54 h. The product is filtered and washed with methanol for 3-5 times, and then dried in a vacuum drying oven at 60° C. for 24 h to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), 23.6 g.

[0192] 3. Preparation of novel hyper-crosslinked polyamide-imide polymer 1

[0193] 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) (0.352 g, 1.1 mmol), 2,2-bis(trifluoromethyl)diaminobiphenyl (0.544 g, 1.7 mmol) and 1.2 g of dry calcium chloride were placed in a reaction bottle, and 2 mL of pyridine, 15 mL of triphenyl phosphite and 18 mL of The mixture of N-methylpyrrolidone was used as a solvent and put into the reaction bottle. The reaction bottle was placed on a magnetic stirrer and heated with stirring. After observing that 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) was dissolved, N-methylpyrrolidone was added dropwise to dissolve the residual diamine monomer. The reaction was carried out at 160°C for 24 hours and then naturally cooled. The yellow precipitate was washed with methanol and anhydrous acetone for 6-8 times until the filtrate was colorless. Then, Soxhlet extraction was carried out with acetone at 65°C for 24 hours. The obtained polymer was placed in a vacuum drying oven at 50°C for 12 hours. Finally, 0.582g of a novel hyper-crosslinked polyamide-imide polymer 4 was prepared.

[0194] from Figure 1 It can be seen from the infrared spectra that the infrared characteristic absorption peaks of the four hyper-crosslinked polyamide-imide polymers are extremely similar. The stretching vibration peaks of C=O were observed at 1689, 1705, and 1712 cm-1, respectively, the stretching vibration peaks of the benzene ring carbon skeleton in polyamide-imide were observed at 1589, 1511, and 1380 cm-1, and the stretching vibration peak of CN was at 1332 cm-1. The structures of these four polymers are basically similar, but polymer 4 has its unique CF stretching vibration peak at 1249 cm-1, which confirms that polymer 4 contains trifluoromethyl. The results prove the successful synthesis of target polymers 1-4.

[0195] from Figure 2The XPS spectra of the four hyper-crosslinked polyamide-imide polymers show the C1s spectra, which show three types of carbon, corresponding to CC sp2 carbon (284.41eV), CN (285.66eV), and C=O (287.83eV), while polymer 4 also shows a unique CF (292.05eV). In the N1s spectrum, there is only one binding energy, which is the binding energy peak belonging to CN (399.98eV), which is formed by the nitrogen in the triphenylamine unit (CN) and the nitrogen in the amide unit (CN). The high-resolution spectrum of O1s was observed at 530.9eV, which belongs to the oxygen of C=O in the amide unit. In the unique F1s spectrum of polymer 4, there are two peaks belonging to trifluoromethyl (-CF3), corresponding to the semi-ionic CF bond (687.9eV) and the covalent CF bond (689.7eV). These results indicate that the elements and functional groups of the polymers are exactly as expected, which is consistent with the FT-IR spectrum of the polymers, further proving that the polymers have multiple active adsorption sites such as carbonyl, imide ring, and amide, and provide N\O heteroatoms.

[0196] The above description is only an embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A hyper-crosslinked polyamide-imide polymer, characterized in that: The structural formula of the hyper-crosslinked polyamide-imide polymer is shown in formula (I): in, Any one of .

2. A method for preparing a hyper-crosslinked polyamide-imide polymer, characterized in that: The method comprises placing 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), a diamine monomer and dry calcium chloride in a reaction bottle, adding a mixture of pyridine, triphenyl phosphite and N-methylpyrrolidone as a solvent into the reaction bottle, placing the reaction bottle on a magnetic stirrer, heating and stirring, and waiting for 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) to be observed. After dissolution, N-methylpyrrolidone is added dropwise to dissolve the residual diamine monomer, and the mixture is reacted at a temperature of 100 to 180°C for 3 to 84 hours and then cooled naturally. The yellow precipitate is washed with methanol and anhydrous acetone for 6 to 8 times until the filtrate is colorless, and then Soxhlet extraction is performed with acetone at 45 to 85°C for 12 to 48 hours. The obtained polymer is placed in a vacuum drying oven at 40 to 80°C for 12 hours, and finally a new type of hyper-crosslinked polyamide-imide polymer is prepared. The specific reaction equation is as follows:

3. The method for preparing a hyper-crosslinked polyamide-imide polymer according to claim 2, characterized in that: The structural formula of the diamine monomer is shown in formula (II): H2N-RA-NH2 formula (II), wherein AR is Any one of .

4. The method for preparing a hyper-crosslinked polyamide-imide polymer according to claim 2, characterized in that: The molar mass ratio of the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid) to the diamine monomer is 1:(1-5.8).

5. The method for preparing a hyper-crosslinked polyamide-imide polymer according to claim 2, characterized in that: The volume ratio of pyridine, triphenyl phosphite and N-methylpyrrolidone is 1:(2-8.5):(6-11.5).

6. The method for preparing a hyper-crosslinked polyamide-imide polymer according to claim 2, characterized in that: The method contains a fluorine-containing linear long-chain transparent polyamide-imide polymer, wherein the 2,2',2"-((benzene-1,3,5-triyl tris(oxygen)) The preparation method of tris(3-(trifluoromethyl)benzene-4,1-diyl))tris(1,3-dioxoisoindole-5-carboxylic acid) is as follows: Step 1, reduction reaction: under nitrogen atmosphere, tri(4-nitrophenyl)amine and catalyst are dispersed in ethanol in a three-necked round-bottom flask in turn, placed in an oil bath and stirred, the sample is mixed evenly and then heated, when the reaction temperature is balanced and stable, hydrazine hydrate is added dropwise to the reaction system using a constant pressure funnel, and the drop rate is controlled to be 4-5s per drop to obtain a mixture A, and reacted under reflux for 1 to 3 days, and the plate is pressed at regular intervals to observe the reduction of the sample. After the reaction is completed, a sand core funnel is used to filter and remove the catalyst in the solution, and the filtrate is concentrated by a rotary evaporator to remove excess hydrazine hydrate to obtain a mixture B. Under stirring conditions, the mixture B is added to an ice-water mixture to obtain a light yellow precipitate, and the light yellow precipitate is thoroughly washed with distilled water to remove the unevaporated solvent and reducing agent, and after vacuum drying, dichloromethane column chromatography is performed to obtain a white solid powder, namely tri(4-aminophenyl)amine. The specific reaction is as follows: Step 2, buckling reaction: tris(4-aminophenyl)amine and trimellitic anhydride are dispersed in 20-60 mL of glacial acetic acid in a three-necked round-bottom flask under a nitrogen atmosphere, and mechanically stirred for 1-5 hours at room temperature. After the sample in the flask is evenly mixed, the reaction is heated for 12-60 hours, the product is filtered, washed with methanol 3-5 times, and then dried in a vacuum drying oven at 60° C. for 24 hours to obtain the 2,2',2"-(nitrile tris(phenyl-4,1-diyl)tris(1,3-dioxoisoindoline-5-carboxylic acid), and the specific reaction equation is as follows:

7. The method for preparing a hyper-crosslinked polyamide-imide polymer according to claim 6, characterized in that: In the preparation step 1 of the fluorine-containing linear long-chain transparent polyamide-imide polymer, the mass volume ratio of tri(4-nitrophenyl)amine, catalyst and ethanol is (1.9-18) g: (0.1-2) g: (25-250) mL.

8. The method for preparing a hyper-crosslinked polyamide-imide polymer according to claim 6, characterized in that: The catalyst is palladium on carbon.

9. The method for preparing a hyper-crosslinked polyamide-imide polymer according to claim 6, characterized in that: In the step 1, the temperature is slowly raised to 75-100° C., the reflux time is 1-2 hours, hydrazine hydrate is added dropwise, the reaction is carried out at 75-100° C. for 15-30 hours, and the temperature is lowered to 20-40° C. after the reaction is completed; in the step 2, the mass volume ratio of tri(4-aminophenyl)amine, trimellitic anhydride and glacial acetic acid is (1-7.5) g: (3-22) g: (20-100) mL.

10. A hyper-crosslinked polyamide-imide polymer and a preparation method thereof according to claim 1 or 2, characterized in that: The hyper-crosslinked poly(amide-imide) polymer is used for adsorption of bromine, iodine and dyes, and the process is as follows: first, cyclohexane solutions of bromine and iodine with a concentration of 0.01-0.1 mol / L and 10-80 mg / L of Congo red and methylene blue dyes are respectively prepared; 5.0 mg of the hyper-crosslinked polyamide-imide polymer is put into a dry glass bottle, and 2-50 mL of bromine or iodine or dye solution is added into the bottle; at a fixed time, the solution in the glass bottle is sucked, and the absorbance is tested by an ultraviolet spectrophotometer; the residual amount of bromine, iodine and dye in the solution is determined according to the absorbance curve of the solution containing bromine, iodine and dye, and then the absorption amount of the adsorbent is calculated by subtracting the residual amount of bromine, iodine and dye from the initial amount of bromine, iodine and dye in the solution.

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