A method for preparing hyper-crosslinked polyaniline with high specific surface area

Abstract

The present invention relates to the technical field of polymer material synthesis, and in particular to a method for preparing a super-crosslinked polyaniline with a high specific surface area, wherein polystyrene@polyaniline composite microspheres are used as building units, and octavinylsilsesquioxane is used as a crosslinking agent to prepare super-crosslinked polyaniline by Friedel-Crafts alkylation reaction. The present invention uses acrylic acid functionalized polystyrene to prepare polystyrene@polyaniline composite microspheres, and in the synthesis process of polystyrene balls, a small amount of acrylic acid can play the role of a nucleating agent, and secondly, in the preparation process of polystyrene@polyaniline composite microspheres, the acid group derived from poly(styrene-acrylic acid) balls can also adsorb aniline through acid-base interaction, so that aniline can be well assembled on the surface of poly(styrene-acrylic acid) balls, and spherical polystyrene@polyaniline composite microspheres with uniform morphology are obtained, thereby obtaining super-crosslinked polyaniline with uniform void structure and high specific surface area.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material synthesis, and in particular relates to a method for preparing super-crosslinked polyaniline with a high specific surface area. Background Art

[0002] Hypercrosslinked polyaniline (HCPANI) is a new type of organic microporous material with a highly crosslinked structure. Since the American scientist Frantisek Svec prepared hypercrosslinked polyaniline in 2007, it has been widely used because of its large number of microporous structures and N heteroatoms, as well as the high molecular weight of HPANI. 2 and CO 2 It has shown good performance in applications such as adsorption and storage, and supercapacitors, and has been highly valued by scientific and technological workers. It is a current research hotspot in the field of new materials.

[0003] At present, the preparation methods of hyper-crosslinked polyaniline mainly include N-alkylation method and Frediel-Crafts alkylation method. Among them, N-alkylation method refers to the preparation of hyper-crosslinked polyaniline by N-alkylation reaction in high temperature solvent (N,N-dimethylformamide (DMF), N,N-dimethyl sulfoxide (DMSO) using intrinsic or reduced linear polyaniline as building unit and diiodomethane, diiodopropane and other highly reactive polyhalogenated alkanes or polyformaldehyde as crosslinking agent. For example, Sharma et al. used intrinsic polyaniline, anhydrous potassium carbonate, DMF, diiodomethane and the like as raw materials to prepare a series of hyper-crosslinked polyanilines by N-alkylation reaction (V. Sharma, A. Sahoo, Y. Sharma, P. Mohanty. RSC Adv., 2015, 5, 45749-45754; V. Sharma, S. Khilari, D. Pradhanb, P. Mohanty. RSC Adv., 2016, 6, 56421-56428). However, the preparation of hyper-crosslinked polyaniline by the above method has high reaction toxicity, low reaction efficiency, high temperature, long reaction time, harsh reaction conditions and high cost of polyaniline synthesis.

[0004] Chinese patent document CN 107629222 A (201711098012.2) discloses a method for preparing super-crosslinked polyaniline, which uses polyaniline as a building unit and octavinylsilsesquioxane as a crosslinking agent to prepare super-crosslinked polyaniline through Friedel-Crafts alkylation reaction. The method solves the problems of high reaction temperature, complex reaction operation, long reaction time, and high preparation cost in the existing method for preparing super-crosslinked polyaniline. However, the super-crosslinked polyaniline obtained by this method has uneven morphology, low specific surface area, and poor adsorption effect. Summary of the invention

[0005] In order to solve the problems of poor specific surface area and low adsorption performance of existing hyper-crosslinked polyaniline, the present invention provides a method for preparing hyper-crosslinked polyaniline with high specific surface area.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A method for preparing super-crosslinked polyaniline with a high specific surface area, using polystyrene@polyaniline composite microspheres as building units and octavinyl silsesquioxane as a crosslinking agent to prepare the super-crosslinked polyaniline through a Friedel-Crafts alkylation reaction.

[0008] Preferably, the Friedel-Crafts alkylation reaction comprises the following steps:

[0009] (1) Under argon protection, the catalyst, octaethylene POSS and dichloroethane (DCE) are quickly added into the reaction system and stirred;

[0010] (2) then adding polystyrene@polyaniline composite microspheres (PS@PANI) into the above reaction system, heating the mixture to react, and adding methanol or deionized water to terminate the reaction;

[0011] (3) Filter and recover the black powder, and wash until the pH of the filtrate reaches neutral (pH = 7.0 ± 0.2) to obtain a crude product;

[0012] (4) Purifying the crude product to remove unreacted octaethylene POSS, PS@PANI composite microspheres and catalyst; then vacuum drying to obtain hyper-crosslinked polyaniline (PS-HCPs for short).

[0013] Preferably, the catalyst in step (1) is anhydrous aluminum chloride, and the mass volume ratio (ml / g) of anhydrous aluminum chloride to octaethylene POSS is 1:35-45.

[0014] Preferably, the stirring time in step (1) is 0.5 to 1.5 h.

[0015] Preferably, in step (2), the mass ratio of polystyrene@polyaniline composite microspheres to octavinylsilsesquioxane (octaethylene POSS) is 1:0.1-1.5, preferably 1:0.6-1.2, and more preferably 1:0.95-1.05.

[0016] Preferably, in step (2), the reaction temperature is 60 to 120° C., more preferably 80 to 85° C., and the reaction time is 12 to 36 h, more preferably 22 to 26 h.

[0017] Preferably, in step (2), the mass ratio of polystyrene@polyaniline composite microspheres to anhydrous aluminum chloride is 1:1.5-2.5, more preferably 1:1.95-2.05.

[0018] Preferably, in step (2), the mass ratio of polystyrene to polyaniline in the polystyrene@polyaniline composite microspheres is 0.16-0.20: 1. The particle size of the polystyrene@polyaniline composite microspheres is 280-320 nm.

[0019] Further preferably, the polystyrene@polyaniline composite microspheres in step (2) are prepared by polymerizing aniline with acrylic acid functionalized polystyrene microspheres as templates, wherein the particle size of the acrylic acid functionalized polystyrene microspheres is 260 nm.

[0020] Further preferably, in step (2), the content of acrylic acid in the polystyrene@polyaniline composite microspheres is 1.6-1.8%.

[0021] The role of acrylic acid includes two aspects. In the synthesis process of polystyrene spheres, a small amount of acrylic acid can act as a nucleating agent. Secondly, in the preparation process of PS@PANI, the acid groups derived from poly(styrene-acrylic acid) spheres can also adsorb aniline through acid-base interactions, allowing aniline to be well assembled on the surface of poly(styrene-acrylic acid) spheres.

[0022] Preferably, in step (4), the crude product is purified by Soxhlet extraction using dichloroethane, DMF and methanol as solvents respectively.

[0023] Preferably, in step (4), the vacuum drying time is 18 to 30 hours, and the vacuum drying temperature is 55 to 65°C.

[0024] The present invention also provides the use of super-crosslinked polyaniline in adsorbing organic dyes in wastewater. The specific surface area of ​​the super-crosslinked polyaniline is 177 to 625 m 2 g -1 , preferably 530~625m 2 g -1 .

[0025] Beneficial effects of the present invention:

[0026] Compared with the prior art, one or more technical solutions provided by the specific embodiments of the present invention have at least the following beneficial effects:

[0027] (1) The present invention uses polystyrene@polyaniline composite microspheres as building units and octavinylsilsesquioxane as a crosslinking agent to prepare super-crosslinked polyaniline through Friedel-Crafts alkylation reaction, which solves the problems of high reaction temperature, complex reaction operation, long reaction time, high preparation cost, etc. in the existing super-crosslinked polyaniline preparation method, and provides a new idea for the preparation of super-crosslinked polyaniline.

[0028] (2) The specific surface area of ​​the super-crosslinked polyaniline prepared by the method of the present invention can be controlled by adjusting the mass ratio of octavinyl silsesquioxane to polystyrene@polyaniline composite microspheres; the specific surface area can reach 530-625 m 2 g -1 Under the following adsorption conditions: adsorbent dosage 100 mg / L, adsorption time 24 h, temperature 25 °C, initial concentration 200 mg / L, equilibrium adsorption capacity (Q e ) can reach 732mg g -1 and 1108 mg g -1 .

[0029] (3) The present invention does not require special reaction equipment, expensive catalysts, or special treatment of raw materials. The reaction is simple and the reaction conditions are mild. It has the advantages of low production cost, simple process, no pollution, and easy large-scale production.

[0030] (4) The present invention uses acrylic acid functionalized polystyrene to prepare polystyrene@polyaniline composite microspheres. The role of acrylic acid includes two aspects. In the synthesis process of polystyrene spheres, a small amount of acrylic acid can act as a nucleating agent. Secondly, in the preparation process of PS@PANI, the acid groups derived from poly(styrene-acrylic acid) spheres can also adsorb aniline through acid-base interactions, so that aniline can be well assembled on the surface of poly(styrene-acrylic acid) spheres, obtaining spherical polystyrene@polyaniline composite microspheres with uniform morphology, and then obtaining hyper-cross-linked polyaniline with uniform void structure and high specific surface area. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Schematic diagram of the synthesis route of hyper-crosslinked polyaniline PS-HCPs.

[0032] Figure 2 XRD spectra of hyper-crosslinked polyaniline obtained in different embodiments.

[0033] Figure 3 SEM images of hyper-crosslinked polyaniline obtained in different examples.

[0034] Figure 4 FI-IR spectra of hyper-crosslinked polyaniline obtained in different examples.

[0035] Figure 5 N is the N of the hyper-crosslinked polyaniline obtained in different embodiments 2 Adsorption isotherms and pore size distribution diagrams.

[0036] Figure 6 TGA curves of hyper-crosslinked polyaniline obtained in different examples. DETAILED DESCRIPTION

[0037] In order to further understand the present invention, the preferred embodiments of the present invention are further described below in conjunction with specific embodiments and drawings. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein.

[0038] The polystyrene@polyaniline composite microspheres (PS@PANI composite microspheres) used in the present invention can be prepared by the following method:

[0039] (1) Preparation of functionalized polystyrene microspheres:

[0040] In N 2 Under the atmosphere, acrylic acid and styrene (volume ratio of 1:9) are added to an aqueous solution containing 0.08-0.11% of the initiator by mass to obtain a mixed reaction solution; the mixture is rapidly stirred for 15-25 minutes, and the polymerization is carried out at 78-82°C. When the color of the mixture system shows a light blue, the stirring rate is reduced, and the reaction is maintained until the styrene smell disappears. Subsequently, the temperature is raised to 84-86°C, the reaction is carried out for 25-35 minutes, and the temperature is lowered to room temperature to obtain a functionalized polystyrene emulsion. The initiator is ammonium persulfate or potassium persulfate.

[0041] (2) Preparation of polystyrene@polyaniline composite microspheres:

[0042] At 0-5°C, functionalized polystyrene emulsion, deionized water and aniline were mixed and stirred for 45-75 minutes to evenly disperse functionalized polystyrene and aniline in the solution; dilute hydrochloric acid was added until the molar concentration of HCl in the system was 0.06-0.07 mol / L; then ammonium persulfate solution was dripped into the reaction system and reacted for 10-15 hours. The product was washed with deionized water several times and then filtered under reduced pressure. After drying, the product was PS@PANI composite microspheres.

[0043] The volume ratio of the functionalized polystyrene emulsion to aniline is 7.5-8.5:1; and the amount of ammonium persulfate added to the reaction system is 0.02-0.03 mol / L.

[0044] Specifically, the specific preparation method of the polystyrene@polyaniline composite microspheres (PS@PANI composite microspheres) used in the examples and comparative examples of the present invention is: 0.1 g K 2 S 2O 8 Add 95 mL of deionized water to a 250 mL single-necked flask and stir until K 2 S 2 O 8 Then in N 2 0.5 mL of acrylic acid and 4.5 mL of styrene were added to the solution under atmosphere, and the mixture was stirred rapidly for 20 min to fully emulsify the added monomers, and then polymerized at 80 ° C. When the color of the mixture system showed a slightly blue color, the stirring rate was reduced and the reaction was maintained until the styrene smell disappeared. Subsequently, the temperature was raised to 85 ° C, reacted for 0.5 h, and cooled to room temperature to obtain a functionalized polystyrene emulsion. At 0-5 ° C, 20 mL of the prepared functionalized polystyrene emulsion, 977.5 mL of deionized water and 2.5 mL of aniline were added to a 2000 mL beaker, and magnetically stirred for 1 h to uniformly disperse polystyrene and aniline in the solution. 500 mL of HCl solution (0.2 M) was added under stirring. Subsequently, 100 mL of 6.2 g of ammonium persulfate solution was dripped into the reaction system, and the reaction was terminated after 12 h of reaction. The product was washed with deionized water several times and then filtered under reduced pressure. After drying, the product was PS@PANI composite microspheres.

[0045] The octavinyl silsesquioxane of the present invention can be prepared by a conventional method by a person skilled in the art. In a preferred embodiment of the present invention, a method for preparing octavinyl silsesquioxane (OVS) is provided, and vinyl trimethoxysilane is placed in a mixed solution of acetone, hydrochloric acid and water for hydrolysis to prepare octavinyl silsesquioxane. Wherein, the hydrochloric acid is concentrated hydrochloric acid (mass fraction is 36%). The specific preparation method is as follows: 30 mL of vinyl trimethoxysilane is added to 150 mL of acetone, and then 80 mL of concentrated hydrochloric acid and 80 mL of water are added in sequence, reacted at room temperature for 72 hours, filtered, and the filter cake is washed with acetone and anhydrous ethanol for multiple times to obtain octavinyl silsesquioxane (OVS).

[0046] Using PS@PANI composite microspheres as building blocks and octaethylene POSS (OVS) as a crosslinking agent, hypercrosslinked polyaniline was prepared. The schematic diagram of the synthesis route is shown in Figure 1 shown.

[0047] Example 1

[0048] The method of preparing super-crosslinked polyaniline using polystyrene@polyaniline composite microspheres as building blocks comprises the following steps:

[0049] Under argon protection, 1.00 g of polystyrene@polyaniline composite microspheres, 0.60 g of octavinylsilsesquioxane, and 2.00 g of anhydrous AlCl 3and 40 mL of 1,2-dichloroethane, stirred magnetically for 1 h, heated to 80 °C and maintained at this temperature for 24 h, and methanol was added to terminate the reaction. Filtered, the product was washed with distilled water and anhydrous ethanol in turn, and then placed in a Soxhlet extractor, purified with methanol, dichloroethane and N-N-dimethylformamide as solvents for 48 h each, and vacuum dried at 60 °C for 24 h to obtain super-crosslinked polyaniline (denoted as PS-HCP-1).

[0050] Example 2

[0051] The method of preparing super-crosslinked polyaniline using polystyrene@polyaniline composite microspheres as building blocks comprises the following steps:

[0052] Under argon protection, 1.00 g of polystyrene@polyaniline composite microspheres, 0.80 g of octavinylsilsesquioxane, and 2.00 g of anhydrous AlCl 3 and 40mL 1,2-dichloroethane, stirred magnetically for 1h, heated to 80℃ and kept at this temperature for 24h, and methanol was added to terminate the reaction. Filtered, the product was washed with distilled water and anhydrous ethanol in turn, and then placed in a Soxhlet extractor, purified with methanol, dichloroethane and N-N-dimethylformamide as solvents for 48h each, and vacuum dried at 60℃ for 24h to obtain super cross-linked polyaniline (denoted as PS-HCP-2).

[0053] Example 3

[0054] The method of preparing super-crosslinked polyaniline using polystyrene@polyaniline composite microspheres as building blocks comprises the following steps:

[0055] Under argon protection, 1.00 g of polystyrene@polyaniline composite microspheres, 1.00 g of octavinylsilsesquioxane, and 2.00 g of anhydrous AlCl 3 and 40mL 1,2-dichloroethane, stirred magnetically for 1h, heated to 80℃ and kept at this temperature for 24h, and methanol was added to terminate the reaction. Filtered, the product was washed with distilled water and anhydrous ethanol in turn, and then placed in a Soxhlet extractor, purified with methanol, dichloroethane and N-N-dimethylformamide as solvents for 48h each, and vacuum dried at 60℃ for 24h to obtain super cross-linked polyaniline (denoted as PS-HCP-3), with a yield of 100%.

[0056] The hypercrosslinked polyaniline prepared in Examples 1 to 3 has a specific surface area of ​​177, 530 and 625 m2, respectively, when the mass ratio of polystyrene@polyaniline composite microspheres to octavinylsilsesquioxane is 1:0.6, 1:0.8 and 1:1, respectively. 2 g -1 .

[0057] Comparative Example 1

[0058] A method for preparing hyper-crosslinked polyaniline, which differs from Example 2 in that the building unit is different, and the building unit is hollow spherical polyaniline (HSPANI); chloroform is used as a solvent to Soxhlet extract the PS@PANI composite microspheres for 48 hours; finally, the hollow spherical polyaniline (HSPANI) is obtained by vacuum drying at 60°C for 12 hours, and the other conditions are the same as those in Example 2. The specific preparation method is: under Ar protection, 0.5g of hollow spherical polyaniline (HSPANI) and 0.4g of octaethylene POSS are added to a 100mL single-mouth flask containing 40mL of dichloroethane. After the mixture is stirred for 0.5h, 1.0g of anhydrous aluminum chloride is added. The reaction is terminated after reacting at 80°C for 24h. The product is collected by vacuum filtration. The product is Soxhlet extracted with methanol, dichloroethane and DMF as solvents for 48h to remove the catalyst, unreacted POSS and HSPANI. The purified product was wrapped with filter paper and dried with a hair dryer. After the solvent evaporated to trace amounts, it was dried in a vacuum drying oven at 60°C for 24 hours to finally obtain HCPP-3. Its specific surface area is 342m 2 g -1 .

[0059] Product performance test:

[0060] (1) Figure 2 The XRD spectra of PS@PANI composite microspheres, PS-HCP-1, PS-HCP-2 and PS-HCP-3 show that PS@PANI has two sharp diffraction peaks at 2θ=20.20° and 24.58°, indicating that PS@PANI is in a semi-crystalline state. After PS@PANI reacts with octaethylene POSS, the peak at 2θ=24.58° on the XRD of PS-HCP-1 to PS-HCP-3 disappears, and only a broad diffraction peak exists at about 2θ=21°, showing the amorphous nature of PS-HCPs; the results show that PS@PANI reacts with octaethylene POSS.

[0061] (2) Figure 3 The SEM images of PS@PANI, PS-HCP-1, PS-HCP-2, and PS-HCP-3 show that the PS@PANI composite microspheres ( Figure 3 , a) The surface is rough, the shape and structure are regular, and the size is relatively uniform. The particle size is about 300nm, and only a small part of it is aggregated together. Figure 3, b, c, and d are SEM images of PS-HCP-1, PS-HCP-2, and PS-HCP-3, respectively. It can be found that PS-HCPs have a rough surface morphology and are composed of many spherical particles stacked into a block structure to form a porous structure. In addition, the hollow structure of some particles may be caused by the removal of unreacted polystyrene balls after Soxhlet extraction. Combined with XRD analysis, PS-HCPs are amorphous non-crystalline polymers.

[0062] (3) Figure 4 Fourier transform infrared spectra (FI-IR) of PS@PANI, PS-HCP-1, PS-HCP-2, and PS-HCP-3. PS@PANI has the following peaks at 3400, 2912, 1565, 1486, 1301, 1274, 1144, 802, and 697 cm -1 The characteristic peaks at correspond to the stretching vibration of NH, polystyrene CH 2 The stretching vibration of CH on the carbonyl group, the stretching vibration of C=N quinone ring, the stretching vibration of C=C on the benzene ring, the stretching vibration of CN, the stretching vibration of CO on carboxyl functionalized polystyrene, the stretching vibration of quinone structure N=Q=N, the bending vibration of CH bond out of plane and the bending vibration of CH of monosubstituted benzene (five adjacent hydrogens) on the benzene ring of carboxyl functionalized polystyrene. For PS-HCPs, after PS@PANI reacted with octaethylene POSS, PS-HCPs had a peak at 1096 cm -1 The characteristic peak of Si-O-Si bond appears at about 2929 cm -1 The peak intensities at the 2 The increase in content indicates that the PS@PANI microspheres and octaethylene POSS successfully undergo Friedel-Crafts reaction and the extent of the reaction is different. -1 The characteristic peak at 697 cm is the stretching vibration peak of C=O and CO on the carboxyl functionalized polystyrene in the PS@PANI composite microspheres, and the original PS@PANI -1 The characteristic absorption peak of monosubstituted benzene disappeared after reacting with POSS, indicating that the benzene ring on PS@PANI polystyrene also participated in the Frediel-Crafts alkylation reaction.

[0063] (4) Figure 5 N of PS-HCPs 2 Results of adsorption-desorption test (77K, 1.0bar). As shown in Figure a, the PS-HCPs isotherm conforms to the characteristics of type IV isotherm. 0<0.001) the adsorption amount showed a vertical upward trend. At a higher specific pressure (P / P 0 =0.001-1.0), the adsorption amount increases slowly and has a hysteresis loop. Combined with the pore size distribution curve of PS-HCPs ( Figure 5 , b) It can be seen that PS-HCPs have micropores and mesopores. The micropores of PS-HCPs are concentrated at 1.4nm, and the mesopores are concentrated at 3-10nm. The pore parameters of PS-HCPs are shown in Table 1. From Table 1, it can be seen that the S BET 177, 530 and 625m respectively 2 g -1 In addition, PS-HCP-2 and PS-HCP-3 conform to H2 in the IV isotherm, indicating that there may be interstitial pores generated by the close packing of spherical particles, which is consistent with the results of SEM. PS-HCP-1 is more in line with H3 type, which may be due to the low crosslinking density and irregular pore structure. BET 342m 2 g -1 , which may be due to the fact that part of the polystyrene also participated in the reaction, resulting in a higher specific surface area.

[0064] Table 1 Porosity data of HCPPs

[0065]

[0066] (5) In N 2 Atmosphere, heating rate 10℃ min -1 , TGA test was carried out in the temperature range of 45-800℃, and the results are as follows Figure 6As shown. For PS@PANI, the weight loss is clearly divided into four stages. In the range of 45 and 100 °C, the loss here is mainly attributed to the evaporation of water. In the range of 240 and 350 °C, the loss here may be caused by the formation of polyacrylic anhydride and the decomposition of the side groups of the composite microspheres. In the range of 350 and 450 °C, the loss here is mainly due to the degradation of the functionalized polystyrene molecular chain and polyaniline. At 450 and 580 °C, the loss here is the further degradation of the polyaniline molecular chain. For PS-HCPs, the mass loss from 120 to 300 °C may be related to the detachment of the proton acid doped on the polyaniline main chain and the cleavage of the unreacted vinyl on POSS. The mass loss from 300 to 800 °C may be caused by the cleavage of the Si-O-Si bond on the POSS cage structure and the degradation of the polyaniline molecular chain. Compared with PS@PANI, the mass loss of PS-HCPs is less, which may be due to the hyper-crosslinked structure of PS-HCPs after the reaction of PS@PANI with POSS, which makes its structure not easily destroyed by high temperature. In addition, the carbon residue rate of PS-HCPs at 800 °C is still higher than 61%, indicating that PS-HCPs have excellent thermal stability.

[0067] (6) PS-HCP-1, PS-HCP-2 and PS-HCP-3 were used to carry out dye adsorption experiments. The equilibrium adsorption amount (Q) of PS-HCP-1 for rhodamine B (RhB) and malachite green (MG) was e ) is 452 and 520 mg g -1 ; PS-HCP-2 for MG and RhB Q e 556 and 932 mg g -1 ; PS-HCP-3 for MG and RhB e 732 and 1108 mg g -1 The hypercrosslinked polyaniline of Comparative Example 1 has a significant effect on the Q of MG and RhB. e 493.6 and 807.7 mg g -1 .

[0068] The embodiments described above provide a detailed description of the technical solutions and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, supplements and equivalent substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing hyper-crosslinked polyaniline with a high specific surface area, characterized in that: Hypercrosslinked polyaniline was prepared by Friedel-Crafts alkylation reaction using polystyrene@polyaniline composite microspheres as building blocks and octavinylsilsesquioxane as a crosslinking agent. The Friedel-Crafts alkylation reaction comprises the following steps: (1) Under argon protection, the catalyst, octavinylsilsesquioxane and ethylene dichloride are quickly added into the reaction system and stirred; (2) Then, polystyrene@polyaniline composite microspheres are added to the above reaction system, the mixture is heated for reaction, and methanol or deionized water is added to terminate the reaction; the mass ratio of polystyrene@polyaniline composite microspheres to octavinylsilsesquioxane is 1:0.95-1.05; the mass ratio of polystyrene to polyaniline in the polystyrene@polyaniline composite microspheres is 0.16-0.20:1; (3) Filter and recover the black powder, and wash until the pH of the filtrate reaches neutral to obtain a crude product; (4) Purifying the crude product to remove unreacted octavinylsilsesquioxane, polystyrene@polyaniline composite microspheres and catalyst; and then vacuum drying to obtain hyper-crosslinked polyaniline.

2. The method for preparing hyper-crosslinked polyaniline according to claim 1, characterized in that: The catalyst in step (1) is anhydrous aluminum chloride, and the mass volume ratio of anhydrous aluminum chloride to octavinylsilsesquioxane is 1:35-45 in ml / g; the stirring time is 0.5-1.5h.

3. The method for preparing hyper-crosslinked polyaniline according to claim 1, characterized in that: In step (2), the reaction temperature is 60-120 °C and the reaction time is 12-36 h.

4. The method for preparing hyper-crosslinked polyaniline according to claim 1, characterized in that: In step (2), the reaction temperature is 80-85°C and the reaction time is 22-26 h.

5. The method for preparing hyper-crosslinked polyaniline according to claim 2, characterized in that: In step (2), the mass ratio of polystyrene@polyaniline composite microspheres to anhydrous aluminum chloride is 1:1.5~2.

5.

6. The method for preparing hyper-crosslinked polyaniline according to claim 5, characterized in that: In step (2), the mass ratio of polystyrene@polyaniline composite microspheres to anhydrous aluminum chloride is 1:1.95-2.

05.

7. The method for preparing hyper-crosslinked polyaniline according to claim 1, characterized in that: In step (2), the particle size of the polystyrene@polyaniline composite microspheres is 280-320 nm.

8. The method for preparing hyper-crosslinked polyaniline according to claim 1, characterized in that: The polystyrene@polyaniline composite microspheres in step (2) are prepared by polymerizing aniline with acrylic acid functionalized polystyrene microspheres as templates; the content of acrylic acid in the polystyrene@polyaniline composite microspheres is 1.6-1.8%.

9. The method for preparing hyper-crosslinked polyaniline according to claim 8, characterized in that: In step (4), the crude product is purified by Soxhlet extraction using dichloroethane, DMF and methanol as solvents, respectively.

10. The method for preparing hyper-crosslinked polyaniline according to claim 1, characterized in that: In step (4), the vacuum drying time is 18 to 30 h, and the vacuum drying temperature is 55 to 65 °C.

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