A method for preparing polyaniline with nanotube structure by using alkali hydrolysis product of perylene imide as a template agent

Abstract

The application discloses a method for preparing polyaniline with nanotube structure by using an alkaline hydrolysis product of perylene imide as a template agent, and comprises the following steps: preparing perylene imide, preparing the alkaline hydrolysis product of perylene imide, and preparing polyaniline. The perylene imide is a product synthesized by using perylene-3,4,9,10-tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine as raw materials. After the perylene imide is subjected to alkaline hydrolysis treatment, on one hand, the hydrophilicity of the perylene imide can be increased, so that the perylene imide can be fully infiltrated by an aniline solution, and the oxidation polymerization process of the aniline on the perylene imide is promoted; on the other hand, the surface of the polyimide after the alkaline treatment carries a large number of -OH nucleation sites regularly distributed along the molecular axis, so that the polyaniline grown on the polyimide presents a regular micro-nano structure.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polyaniline preparation, and particularly relates to a method for preparing polyaniline with nanotube structure by using alkali hydrolysis product of perylene diimide as a template agent. BACKGROUND

[0002] Since the 1990s, bionic artificial muscle materials as a new type of smart materials have been continuously arousing research enthusiasm of scientists all over the world, and have an increasingly important application value in the fields of bionic robots and biomedical engineering.

[0003] The oriented structure of micro-nano scale is very important for artificial muscle fiber materials, which not only ensures the transmission and dissipation of pulling force through the endomysial connective tissue, thereby adjusting the stress distribution, but also enables the water and ions inside the fiber to move along a certain direction, ensuring the conductivity of the bionic muscle fiber.

[0004] The conductive polymers with π-conjugated structure such as polyaniline, polypyrrole and polythiophene exhibit significant structure stretching performance in the electrochemical oxidation-reduction process, and can directly convert electrical energy into mechanical work, so they have rapidly developed in the field of artificial muscles. Among them, polyaniline is considered to be the most potential conductive polymer material for preparing artificial muscles due to its easy availability and relatively mild reaction conditions.

[0005] However, it is difficult to obtain polyaniline with fiber orientation, and the polyaniline prepared by solution template method is prone to agglomeration, and usually spherical polyaniline particles with different morphologies (products without regular nano structure) are obtained. It is pointed out in some documents that the regular structure of polyaniline can significantly affect or determine the final performance and function of the material compared with irregular structure. The commonly used template agents such as PVP, PEG and CTAB are difficult to be used to prepare fiber or tubular polyaniline. Therefore, how to prepare polyaniline with fiber or tubular structure has gradually become a hot spot of people's attention. SUMMARY

[0006] The present application relates to the field of polyaniline preparation, and particularly relates to a method for preparing polyaniline with nanotube structure by using alkali hydrolysis product of perylene diimide as a template agent.

[0007] The perylene imide is synthesized by using perylene-3,4,9,10-tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine as raw materials. After the perylene imide is subjected to alkaline hydrolysis treatment, on one hand, the hydrophilicity of the perylene imide is increased, so that the perylene imide can be fully infiltrated by an aniline solution, and the oxidation polymerization process of the aniline on the perylene imide is promoted; on the other hand, the surface of the perylene imide after the alkaline treatment carries a large number of -OH nucleation sites regularly distributed along the molecular axis, so that the polyaniline grown on the surface of the perylene imide presents a regular micro-nano structure.

[0008] To achieve the above-mentioned purposes, the technical scheme of the present application is as follows:

[0009] A method for preparing polyaniline with a nanotube structure by using an alkaline hydrolysis product of perylene imide as a template agent, characterized in that the method comprises the following steps:

[0010] 1) preparing perylene imide:

[0011] (1.1) dispersing perylene tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine in DMAc to obtain a mixed solution A, the molar ratio of the perylene tetracarboxylic dianhydride and the 2,4-diamino-6-phenyl-1,3,5-triazine is 1:0.95-1.05, and the mass sum of the perylene tetracarboxylic dianhydride and the 2,4-diamino-6-phenyl-1,3,5-triazine is 20-30% of the mass of the mixed solution A;

[0012] (1.2) reacting the mixed solution A under a pressure of ≤0.1 MPa for 2-4 hours to obtain a reaction product, and then subjecting the reaction product to thermal imidization to obtain a perylene imide crude product B;

[0013] (1.3) dissolving the perylene imide crude product B in DMAc and performing recrystallization precipitation with ethanol, and then centrifuging and freeze-drying the recrystallization precipitation to obtain a perylene imide powder C;

[0014] Preparation of an alkaline hydrolysis product of perylene imide:

[0015] (2.1) dissolving NaOH in an ethanol aqueous solution with a volume fraction concentration of 40-60% to prepare a NaOH solution with a concentration of 0.9-1.1 mol / L;

[0016] (2.2) adding the perylene imide powder C into the NaOH solution and stirring until the solution appears transparent and uniform to obtain a solution D, and the mass ratio of the perylene imide powder C and the NaOH solution is 1:5-10;

[0017] (2.3) adding an ethanol solution with a volume fraction concentration of ≥70% into the solution D to generate white precipitates, and the white precipitates are an alkaline hydrolysis product E of perylene imide;

[0018] Preparation of polyaniline:

[0019] (3.1) sequentially adding the alkali hydrolysis product E of perylene bisimide, aniline and ammonium persulfate into deionized water to obtain a F solution; the concentration of the alkali hydrolysis product E in the F solution is 0.9-1.1 g / L, the concentration of aniline is 0.018-0.022 mol / L, and the concentration of ammonium persulfate is 0.018-0.022 mol / L;

[0020] (3.2) placing the F solution at 0-4 ℃ for reaction for more than 24 hours; then washing and suction-filtering the precipitate in the F solution with deionized water until the suction-filtered filtrate is neutral, obtaining a filter cake, and vacuum drying the filter cake to obtain a finished product.

[0021] Further, the alkali hydrolysis product E of perylene bisimide is dried in step (2.3).

[0022] The beneficial effects of the present application are:

[0023] 1. After the alkali hydrolysis treatment of perylene bisimide in the present application, on one hand, the hydrophilicity of perylene bisimide can be increased, so that it can be fully infiltrated by aniline solution, and the oxidation polymerization process of aniline on it can be promoted; on the other hand, the surface of perylene bisimide treated by alkali liquor carries a large number of -OH nucleation sites regularly distributed along the molecular axis, so that the polyaniline grown thereon presents a regular micro-nano structure; thus, polyaniline structure with certain orientation at the nano scale can be obtained.

[0024] After the hydrolysis of perylene bisimide with NaOH solution, the alkali hydrolysis product is collected as a template agent, then the alkali hydrolysis product template agent of perylene bisimide, aniline solution and hydrochloric acid solution containing an oxidation initiator (ammonium persulfate) are mixed under ice water bath, the polymerization of aniline on the structure of perylene bisimide is initiated, and the reaction is placed under ice water bath, thus the polyaniline material with nano-scale tubular structure can be obtained.

[0025] 2. The preparation process of the method of the present application is simple, environmentally friendly and reliable, the raw materials are widely available and low in cost, and the method is suitable for industrial production.

[0026] 3. The method of the present application utilizes the regularly distributed hydroxyl groups along the molecular axis of perylene bisimide after alkali hydrolysis treatment, which can combine with aniline molecules to prepare polyaniline with nano-tubular structure, and the regular nano structure can provide a good channel for the diffusion and movement of carriers, thus polyaniline material with good conductivity can be obtained. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The figure is a morphology diagram of perylene bisimide powder C under electron microscope.

[0028] Figure 2Morphology of the alkali hydrolysis product E of perylene imide under electron microscope.

[0029] Figure 3 Morphology of the prepared nanotube-structured polyaniline under electron microscope.

[0030] Figure 4 Morphology of the product prepared by Comparative Example 1 under electron microscope. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings.

[0032] Example 1: A method for preparing nanotube-structured polyaniline by using the alkali hydrolysis product of perylene imide as a template agent,

[0033] Preparation of perylene imide: Perylene tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine were dispersed in DMAc to obtain a mixed solution A, the molar ratio of perylene tetracarboxylic dianhydride to 2,4-diamino-6-phenyl-1,3,5-triazine was 1:0.95, and the total mass of perylene tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine was 20% of the mass of the mixed solution A; the mixed solution A was reacted for 2 hours under the condition of 0.1 MPa to obtain a reaction product, and then the reaction product was subjected to thermal imidization to obtain a crude product B of perylene imide; the crude product B of perylene imide was dissolved in DMAc and subjected to recrystallization precipitation with ethanol, and then the recrystallization precipitation was centrifuged and freeze-dried to obtain a perylene imide powder C;

[0034] Preparation of the alkali hydrolysis product of perylene imide: NaOH was dissolved in an ethanol aqueous solution with a volume fraction concentration of 40% to prepare a NaOH solution with a concentration of 0.9 mol / L; the perylene imide powder C was added to the NaOH solution and stirred until the solution appeared transparent and uniform to obtain a solution D, and the mass ratio of the perylene imide powder C to the NaOH solution was 1:5; an ethanol solution with a volume fraction concentration of 70% was added to the solution D to generate white precipitates, and the white precipitates were the alkali hydrolysis product E of perylene imide.

[0035] Preparation of polyaniline: the alkali hydrolysis product E of perylene imide, aniline and ammonium persulfate were sequentially added to deionized water to obtain a solution F; the concentration of the alkali hydrolysis product E in the solution F was 0.9 g / L, the concentration of aniline was 0.018 mol / L, and the concentration of ammonium persulfate was 0.018 mol / L; the solution F was statically reacted at 0°C for 12 hours; then the precipitates in the solution F were washed and suction-filtered with deionized water until the filtrate was neutral, and a filter cake was obtained; the filter cake was vacuum-dried to obtain a finished product.

[0036] Example 2: A method for preparing nanotube-structured polyaniline by using the alkali hydrolysis product of perylene imide as a template agent,

[0037] Preparation of perylene imide: perylene tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine are dispersed in DMAc to obtain a mixed solution A, the molar ratio of perylene tetracarboxylic dianhydride to 2,4-diamino-6-phenyl-1,3,5-triazine is 1:1, and the mass sum of perylene tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine is 25% of the mass of the mixed solution A; the mixed solution A is reacted for 3 hours under the condition of 0.08 MPa to obtain a reaction product, and then the reaction product is subjected to thermal imidization to obtain a perylene imide crude product B; the perylene imide crude product B is dissolved in DMAc and subjected to recrystallization precipitation with ethanol, and after centrifugation and freeze-drying of the crystalline precipitate, a perylene imide powder C is obtained;

[0038] Preparation of an alkaline hydrolysis product of perylene imide: NaOH is dissolved in an ethanol aqueous solution with a volume fraction concentration of 50% to prepare a NaOH solution with a concentration of 1.0 mol / L; the perylene imide powder C is added to the NaOH solution and stirred until the solution appears transparent and uniform to obtain a solution D, and the mass ratio of the perylene imide powder C to the NaOH solution is 1:7; an ethanol solution with a volume fraction concentration of 75% is added to the solution D to generate white precipitates, and the white precipitates are an alkaline hydrolysis product E of perylene imide.

[0039] Preparation of polyaniline: the alkaline hydrolysis product E of perylene imide, aniline and ammonium persulfate are sequentially added to deionized water to obtain a solution F; the concentration of the alkaline hydrolysis product E in the solution F is 1 g / L, the concentration of aniline is 0.02 mol / L, and the concentration of ammonium persulfate is 0.02 mol / L; the solution F is statically reacted for 18 hours at 2°C; then the precipitates in the solution F are washed and suction-filtered with deionized water until the filtrate is neutral, a filter cake is obtained, and the filter cake is vacuum-dried to obtain a finished product.

[0040] Example 3: a method for preparing polyaniline with a nanotube structure by using an alkaline hydrolysis product of perylene imide as a template agent,

[0041] Preparation of perylene imide: perylene tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine are dispersed in DMAc to obtain a mixed solution A, the molar ratio of perylene tetracarboxylic dianhydride to 2,4-diamino-6-phenyl-1,3,5-triazine is 1:1.05, and the mass sum of perylene tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine is 30% of the mass of the mixed solution A; the mixed solution A is reacted for 4 hours under the condition of 0.05 MPa to obtain a reaction product, and then the reaction product is subjected to thermal imidization to obtain a perylene imide crude product B; the perylene imide crude product B is dissolved in DMAc and subjected to recrystallization precipitation with ethanol, and after centrifugation and freeze-drying of the crystalline precipitate, a perylene imide powder C is obtained;

[0042] Preparation of the alkali hydrolysis product of perylene imide: NaOH is dissolved in an ethanol aqueous solution with a volume fraction concentration of 60% to prepare a NaOH solution with a concentration of 1.1 mol / L; perylene imide powder C is added to the NaOH solution and stirred until the solution is transparent and uniform, to obtain solution D, and the mass ratio of the perylene imide powder C and the NaOH solution is 1:10; an ethanol solution with a volume fraction concentration of 80% is added to the solution D to produce white precipitates, and the white precipitates are the alkali hydrolysis product E of perylene imide; and the alkali hydrolysis product E of perylene imide is dried.

[0043] Preparation of polyaniline: the dried alkali hydrolysis product E of perylene imide, aniline and ammonium persulfate are sequentially added to deionized water to obtain solution F; the concentration of the alkali hydrolysis product E in the solution F is 1.1 g / L, the concentration of aniline is 0.022 mol / L, and the concentration of ammonium persulfate is 0.022 mol / L; the solution F is placed at 4°C for 24 hours; then the precipitates in the solution F are washed and suction-filtered with deionized water until the filtrate is neutral, to obtain a filter cake, which is vacuum-dried to obtain a finished product.

[0044] Examples Resistivity (Ω-cm) 1 10.50 2 10.19 3 9.96

[0045] Reference Example 2: the process of preparing perylene imide and its alkali hydrolysis product is cancelled, and polyaniline is directly prepared by a template-free method; aniline and ammonium persulfate are sequentially added to deionized water to obtain solution F; the concentration of the alkali hydrolysis product E in the solution F is 1 g / L, the concentration of aniline is 0.02 mol / L, and the concentration of ammonium persulfate is 0.02 mol / L; the solution F is placed at 2°C for 18 hours; then the precipitates in the solution F are washed and suction-filtered with deionized water until the filtrate is neutral, to obtain a filter cake, which is vacuum-dried to obtain a finished product.

[0046] As can be seen from the reference example, the process of preparing perylene imide and its alkali hydrolysis product is cancelled, and polyaniline is directly prepared by a template-free method, and the obtained polyaniline has irregular morphology, as shown in FIG. 2. Figure 4

[0047] The described examples are only a part of the examples of the present application, but not all the examples. Based on the examples in the present application, all the other examples obtained by those skilled in the art without creative labor belong to the protection scope of the present application.​

Claims

1. A method for preparing polyaniline with a nanotube structure using the alkaline hydrolysis product of perylene imide as a template agent, characterized in that, The method comprises the following steps: 1) preparing perylene imide: (1.1) dispersing perylene tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine in DMAc to obtain a mixed solution A, the molar ratio of perylene tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine is 1:0.95~1.05, and the total mass of perylene tetracarboxylic dianhydride and 2,4-diamino-6-phenyl-1,3,5-triazine is 20~30% of the mass of the mixed solution A; (1.2) reacting the mixed solution A under a pressure of ≤0.1 MPa for 2~4 hours to obtain a reaction product, and then subjecting the reaction product to thermal imidization to obtain perylene imide crude product B; (1.3) dissolving the perylene imide crude product B in DMAc and subjecting the solution to recrystallization precipitation with ethanol, centrifuging and freeze-drying the crystalline precipitate to obtain perylene imide powder C; (2.1) dissolving NaOH in an ethanol aqueous solution with a volume fraction concentration of 40~60% to prepare a NaOH solution with a concentration of 0.9~1.1 mol / L; (2.2) adding the perylene imide powder C to the NaOH solution and stirring until the solution becomes transparent and uniform to obtain solution D, and the mass ratio of the perylene imide powder C and the NaOH solution is 1:5~10; (2.3) adding an ethanol solution with a volume fraction concentration of ≥70% to the solution D to produce white precipitate, and the white precipitate is the alkaline hydrolysis product E of perylene imide; (3.1) adding the alkaline hydrolysis product E of perylene imide, aniline and ammonium persulfate to deionized water in sequence to obtain solution F; the concentration of the alkaline hydrolysis product E in the solution F is 0.9~1.1 g / L, the concentration of aniline is 0.018~0.022 mol / L, and the concentration of ammonium persulfate is 0.018~0.022 mol / L; (3.2) placing the solution F at 0~4 ℃ for reaction for 24 hours or more; then washing and suction-filtering the precipitate in the solution F with deionized water until the suction-filtered filtrate is neutral to obtain a filter cake, and vacuum drying the filter cake to obtain a finished product. In the step (2.3), the alkaline hydrolysis product E of perylene imide is dried. ​ 2. The method of claim 1, wherein the method of preparing polyaniline having a nanotubular structure using an alkali hydrolysis product of perylenetetracarboxylic diimide as a template agent is characterized by, ​

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