A high-adhesion modified polyaniline composite material and its preparation method

Abstract

This invention relates to the field of polymer materials technology, and particularly to a high-adhesion modified polyaniline composite material and its preparation method, comprising the following steps: (1) washing glass fibers with acetone to obtain pretreated glass fibers; (2) preparing a silane hydrolysate; (3) immersing the pretreated glass fibers in the silane hydrolysate to obtain mercapto-modified glass fibers; (4) preparing compound (I) of formula I using mercaptoacetic acid and aniline as the starting point for synthesis; (5) preparing modified polyaniline by combining the compound of formula I with p-phenylenediamine and aniline; (6) crosslinking the mercapto-modified glass fibers and modified polyaniline through disulfide bonds to obtain the modified polyaniline composite material. The modified polyaniline composite material of this invention has good adhesion, resistance to damp heat, impact resistance, electrical conductivity, and self-healing ability.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a high-adhesion modified polyaniline composite material and its preparation method. Background Technology

[0002] Polyaniline (PANI) is one of the most widely studied conductive polymer materials, possessing significant advantages such as readily available raw materials, simple synthesis processes, excellent environmental stability, and tunable conductivity. It shows broad application prospects in fields such as metal anti-corrosion coatings, electromagnetic shielding materials, electrochemical sensors, and supercapacitor electrode materials. However, pure polyaniline has inherent defects: high molecular chain rigidity, high brittleness, poor mechanical properties, and extremely weak adhesion to substrates such as metals, glass, and ceramics. During use, it is prone to cracking and detachment, severely shortening its service life and limiting its large-scale industrial application.

[0003] To address the aforementioned shortcomings, publication number CN109207044A discloses a method for preparing modified polyaniline composite materials and anti-corrosion coatings, comprising the following steps: S1, mixing an acid solution and purified modified aniline monomers uniformly to obtain an intermediate mixture. S2, preparing a nano-zinc oxide solution. S3, adding the nano-zinc oxide solution to the intermediate mixture and mixing uniformly. S4, preparing an ammonium persulfate solution, a manganese dioxide solution, or a ferric chloride solution. S5, adding the solution prepared in step S4 to the solution obtained in step S3 and mixing uniformly to obtain a precursor reaction solution. S6, filtering, washing, and vacuum drying the precursor reaction solution to obtain the modified polyaniline composite material. The modified polyaniline composite material prepared by this method exhibits high corrosion resistance and strong adhesion to the surface of metal workpieces. However, this method uses inorganic and polymeric materials, and the poor compatibility between the two can easily lead to precipitation problems.

[0004] For example, CN117659758B discloses "a polyaniline nanocomposite material for anti-corrosion coatings and its preparation method, and a polyaniline composite anti-corrosion coating." This involves in-situ polymerization of polyaniline on graphene nanosheets, effectively inhibiting the aggregation of graphene nanosheets and polyaniline. Furthermore, the layered structure of the polyaniline nanocomposite material in the coating forms a mesh structure in the base material, further effectively blocking the diffusion of oxygen, water, chloride ions, etc., thus providing excellent shielding against corrosive gases and significantly improving the corrosion resistance of metal surfaces. However, when polyaniline is used as a coating, simply improving adhesion is no longer sufficient to meet higher requirements. The mechanical properties of the coating are also a key consideration. In addition, some coatings are often subjected to stress impacts during daily use, forming microcracks. Over time, these cracks can propagate, affecting the protection of the substrate.

[0005] Therefore, it is urgent to develop a modified polyaniline composite material with good adhesion and mechanical properties, as well as a certain degree of self-healing ability. Summary of the Invention

[0006] The purpose of this invention is to provide a high-adhesion modified polyaniline composite material and its preparation method, so as to solve the problems of poor adhesion and mechanical properties of polyaniline and its inability to repair micro-cracks on its own.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a method for preparing a high-adhesion modified polyaniline composite material, comprising the following steps: (1) Mix glass fiber with acetone, ultrasonically disperse for 25-45 min, filter, and vacuum dry to constant weight to obtain pretreated glass fiber; (2) Mix silane coupling agent, deionized water and ethanol, add dilute hydrochloric acid to adjust pH to 3-4, heat to 65-75℃ and stir for 30-40 min to obtain silane hydrolysate; (3) Under an inert protective gas atmosphere, the pretreated glass fiber obtained in step (1) is immersed in the silane hydrolysate obtained in step (2), heated to 40~50℃ and stirred for 3~4h, filtered, washed, and vacuum dried to obtain mercapto-modified glass fiber. (4) Under an inert protective gas atmosphere, mercaptoacetic acid and aniline were mixed, heated to 90-100℃ and stirred at a constant temperature for 5-8 hours. After the mixture was heated, dichloromethane was added, and the mixture was washed successively with dilute hydrochloric acid, deionized water and saturated brine. The mixture was then dried under vacuum to obtain the compound shown in Formula I. (I); (5) Mix the compound of formula I obtained in step (4) with p-phenylenediamine and aniline, add DMF, adjust the pH to 1-2 with dilute hydrochloric acid, add hydrochloric acid solution of ammonium persulfate, stir at room temperature for 24-26 h, filter after completion, wash with deionized water and acetone, and vacuum dry to obtain modified polyaniline; (6) Mix the mercapto-modified glass fiber obtained in step (3) with the modified polyaniline obtained in step (5), add a mixture of methylpyrrolidone and DMF, stir and disperse, add elemental iodine and stir at room temperature for 35-45 min, dry under reduced pressure, wash with sodium thiosulfate, wash with ethyl acetate, and dry under vacuum to obtain the modified polyaniline composite material.

[0008] This invention first washes the glass fiber to remove surface organic impurities and sizing agents, exposing surface hydroxyl groups. Then, it is immersed in a silane hydrolysis solution for surface modification. The silanol groups generated by the hydrolysis of the silane coupling agent react with the hydroxyl groups on the glass fiber surface through a dehydration reaction, forming stable Si-O-Si covalent bonds. This introduces a large number of high-density thiol active groups onto the glass fiber surface. Compared with traditional active groups such as amino and epoxy groups, thiol groups have higher reactivity and can undergo oxidative coupling reactions under mild conditions, providing sufficient reaction sites for subsequent interfacial covalent crosslinking. Subsequently, this application introduces thiol functional groups into the aniline monomer molecule by reacting thioglycolic acid with aniline. A mercapto-substituted aniline derivative (the compound shown in Formula I) was obtained. This derivative was then oxidatively copolymerized with p-phenylenediamine and aniline to obtain a polyaniline copolymer with mercapto-terminal groups without destroying the conjugated main chain of polyaniline. Finally, mercapto-modified glass fiber and modified polyaniline were covalently bonded through disulfide bonds to form a three-dimensional network structure, which improved the mechanical properties of the material. The bond energy of the disulfide covalent bond is higher than that of the hydrogen bond, resulting in stronger interfacial bonding ability. At the same time, the disulfide bond has a certain degree of dynamic reversibility, which can alleviate the stress concentration inside the composite material to a certain extent, further improving its adhesion and crack resistance, and also endowing the material with a certain degree of self-healing ability.

[0009] In some embodiments, the length of the glass fiber is 0.6 to 1 mm.

[0010] Preferably, the glass fiber has a length of 0.8 mm.

[0011] In some embodiments, in step (2), the silane coupling agent is any one or more of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and mercaptopropylmethyldimethoxysilane.

[0012] In some embodiments, the mass-to-volume ratio of the 3-mercaptopropyltriethoxysilane, deionized water, and anhydrous ethanol is 1 g:(3~5) ml:(15~18) ml.

[0013] Preferably, the mass-to-volume ratio of 3-mercaptopropyltriethoxysilane, deionized water, and anhydrous ethanol is 1 g: 4 ml: 16 ml.

[0014] In some embodiments, in step (3), the mass-to-volume ratio of the pretreated glass fiber to the silane hydrolysate is 1 g:(4~6) ml.

[0015] In some embodiments, in step (4), the molar ratio of mercaptoacetic acid and aniline is 1:(1.2~1.5).

[0016] Preferably, in step (4), the molar ratio of mercaptoacetic acid and aniline is 1:1.3.

[0017] In some embodiments, in step (5), the mass ratio of the compound represented by Formula I, p-phenylenediamine, and aniline is 1:(0.1~0.2):(0.4~0.6).

[0018] Preferably, in step (5), the mass ratio of the compound shown in Formula I, p-phenylenediamine, and aniline is 1:0.15:0.5.

[0019] In some embodiments, in step (5), the mass ratio of the compound represented by Formula I to ammonium persulfate is 1:(1.5~2).

[0020] Preferably, in step (5), the mass ratio of the compound represented by Formula I to ammonium persulfate is 1:1.7.

[0021] In some embodiments, in step (6), the mass ratio of the mercapto-modified glass fiber to the modified polyaniline is (0.1~0.5):1.

[0022] Preferably, in step (6), the mass ratio of the mercapto-modified glass fiber to the modified polyaniline is 0.3:1.

[0023] This application achieves superior mechanical properties by adjusting the mass ratio of mercapto-modified glass fiber to modified polyaniline. Mercapto-modified glass fiber can form a reinforcing skeleton with modified polyaniline, thereby giving the composite material excellent mechanical properties while balancing mechanical and electrical properties.

[0024] In some embodiments, in step (6), the amount of elemental iodine added is 0.4 to 0.6 times the total mass of mercapto-modified glass fiber and modified polyaniline.

[0025] Preferably, in step (6), the amount of elemental iodine added is 0.5 times the total mass of mercapto-modified glass fiber and modified polyaniline.

[0026] In another aspect, the present invention provides a modified polyaniline composite material prepared by any of the above methods.

[0027] Compared with the prior art, the present invention has the following beneficial effects: (1) In this invention, pretreated glass fibers are immersed in silane hydrolysis solution for surface modification. The silanol groups generated by the hydrolysis of silane coupling agent react with the hydroxyl groups on the surface of glass fibers to form stable Si-O-Si covalent bonds, thereby introducing a large number of high-density thiol active groups on the surface of glass fibers. Compared with traditional active groups such as amino and epoxy groups, thiol groups have higher reactivity and can undergo oxidative coupling reaction under mild conditions, providing sufficient reaction sites for subsequent interfacial covalent crosslinking. Subsequently, thiol functional groups are introduced into aniline monomer molecules by reacting thioglycolic acid with aniline to obtain the compound shown in Formula I. The compound is then oxidatively copolymerized with p-phenylenediamine and aniline. Finally, the thiol-modified glass fibers and modified polyaniline are covalently bonded through disulfide bonds to form a three-dimensional network structure, thereby improving the mechanical properties of the material.

[0028] (2) The disulfide covalent bond in the modified polyaniline composite material structure of the present invention has a higher bond energy than the hydrogen bond, and a stronger interfacial bonding ability. At the same time, the disulfide bond has a certain dynamic reversibility, which can alleviate the stress concentration inside the composite material to a certain extent, further improve its adhesion and crack resistance, and also endow the material with a certain self-healing ability. Detailed Implementation

[0029] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0030] Unless otherwise specified, those skilled in the art may select from the following post-processing operations, such as "mixing", "dispersing", "filtering", "heating", "stirring", "washing", "immersion", and "vacuum drying", according to actual conditions, without further limitation.

[0031] Example 1 A method for preparing a high-adhesion modified polyaniline composite material includes the following steps: (1) Mix 10g of glass fiber with a length of 0.8mm with 200mL of acetone, ultrasonically disperse for 35min, filter, and vacuum dry at 60℃ to constant weight to obtain pretreated glass fiber; (2) Mix 5g of 3-mercaptopropyltriethoxysilane, 20mL of deionized water and 80mL of anhydrous ethanol, add 1N dilute hydrochloric acid to adjust the pH to 3.5, heat to 70℃ and stir for 35min to obtain silane hydrolysate; (3) Under a nitrogen protective atmosphere, 10g of the pretreated glass fiber obtained in step (1) was impregnated into 50mL of silane hydrolysate obtained in step (2), heated to 45℃ and stirred for 3.5h, filtered, washed 3 times with anhydrous ethanol, and dried under vacuum at 80℃ to constant weight to obtain mercapto-modified glass fiber. (4) Under a nitrogen atmosphere, 9.2 g of mercaptoacetic acid and 12.1 g of aniline were mixed, heated to 95 °C and stirred for 6.5 h. After the mixture was heated, 150 mL of dichloromethane was added. The mixture was washed three times each with 0.5 N dilute hydrochloric acid, deionized water and saturated brine. The mixture was dried under vacuum with anhydrous sodium sulfate and the solvent was removed by vacuum distillation to obtain the compound shown in Formula I. (I); The NMR analysis of the compound shown in Formula I is as follows: 1 H NMR (400 MHz, DMSO-d6) δ 10.09 (s, 1H), 7.64-7.52 (m, 2H), 7.38-7.25 (m, 2H), 7.05 (tt, J = 7.0, 1.2 Hz, 1H), 3.56(d, J = 6.6 Hz, 2H), 3.08 (t, J = 6.5 Hz, 1H); (5) Mix 10g of the compound shown in Formula I obtained in step (4) with 1.5g of p-phenylenediamine and 5g of aniline, add 150mL of LDMF, adjust the pH to 1.5 with 2N dilute hydrochloric acid, add 100mL of 0.5N hydrochloric acid solution containing 17g of ammonium persulfate and add it dropwise over 1 hour. After the addition is complete, stir at room temperature for 25 hours. After the addition is complete, filter, wash with deionized water and acetone in sequence, and dry under vacuum at 60℃ to constant weight to obtain modified polyaniline; (6) Mix 3g of the mercapto-modified glass fiber obtained in step (3) with 10g of the modified polyaniline obtained in step (5), add 100mL of a mixture of N-methylpyrrolidone and DMF (volume ratio 1:1), stir and disperse, add 6.5g of elemental iodine, stir at room temperature for 40min, dry under reduced pressure, wash twice with 5wt% sodium thiosulfate, wash three times with ethyl acetate, and dry under vacuum at 80℃ to constant weight to obtain the modified polyaniline composite material.

[0032] Example 2 A method for preparing a high-adhesion modified polyaniline composite material includes the following steps: (1) Mix 10g of glass fiber with a length of 0.6mm with 200mL of acetone, ultrasonically disperse for 25min, filter, and vacuum dry at 60℃ to constant weight to obtain pretreated glass fiber; (2) Mix 5g of 3-mercaptopropyltriethoxysilane, 20mL of deionized water and 80mL of anhydrous ethanol, add 1N dilute hydrochloric acid to adjust the pH to 4, heat to 65℃ and stir for 40min to obtain silane hydrolysate. (3) Under a nitrogen protective atmosphere, 10g of the pretreated glass fiber obtained in step (1) was impregnated into 40mL of silane hydrolysate obtained in step (2), heated to 40℃ and stirred for 4h, filtered, washed 3 times with anhydrous ethanol, and dried under vacuum at 80℃ to constant weight to obtain mercapto-modified glass fiber. (4) Under a nitrogen atmosphere, 9.2 g of mercaptoacetic acid and 11.17 g of aniline were mixed, heated to 90 °C and stirred for 8 h. After the mixture was heated, 150 mL of dichloromethane was added. The mixture was washed three times each with 0.5 N dilute hydrochloric acid, deionized water and saturated brine. The mixture was dried under vacuum with anhydrous sodium sulfate and the solvent was removed by vacuum distillation to obtain the compound shown in Formula I. (I); (5) Mix 10g of the compound shown in Formula I obtained in step (4) with 1g of p-phenylenediamine and 4g of aniline, add 150mL of DMF, adjust the pH to 2 with 2N dilute hydrochloric acid, add 100mL of 0.5N hydrochloric acid solution containing 15g of ammonium persulfate and add it dropwise over 1 hour. After the addition is complete, stir at room temperature for 26 hours. After the addition is complete, filter, wash with deionized water and acetone in sequence, and dry under vacuum at 60℃ to constant weight to obtain modified polyaniline; (6) Mix 1g of the mercapto-modified glass fiber obtained in step (3) with 10g of the modified polyaniline obtained in step (5), add 100mL of a mixture of N-methylpyrrolidone and DMF (volume ratio 1:1), stir and disperse, add 4.4g of elemental iodine, stir at room temperature for 45min, dry under reduced pressure, wash twice with 5wt% sodium thiosulfate, wash three times with ethyl acetate, and dry under vacuum at 80℃ to constant weight to obtain the modified polyaniline composite material.

[0033] Example 3 A method for preparing a high-adhesion modified polyaniline composite material includes the following steps: (1) Mix 10g of glass fiber with a length of 1mm with 200mL of acetone, ultrasonically disperse for 45min, filter, and vacuum dry at 60℃ to constant weight to obtain pretreated glass fiber. (2) Mix 5g of 3-mercaptopropyltriethoxysilane, 20mL of deionized water and 80mL of anhydrous ethanol, add 1N dilute hydrochloric acid to adjust the pH to 3, heat to 75℃ and stir for 30min to obtain silane hydrolysate; (3) Under a nitrogen protective atmosphere, 10g of the pretreated glass fiber obtained in step (1) was impregnated into 60mL of silane hydrolysate obtained in step (2), heated to 50℃ and stirred for 3h, filtered, washed 3 times with anhydrous ethanol, and dried under vacuum at 80℃ to constant weight to obtain mercapto-modified glass fiber. (4) Under a nitrogen atmosphere, 9.2 g of mercaptoacetic acid and 14 g of aniline were mixed, heated to 100 °C and stirred for 5 h. After the mixture was heated, 150 mL of dichloromethane was added. The mixture was washed three times each with 0.5 N dilute hydrochloric acid, deionized water and saturated brine. The mixture was dried under vacuum with anhydrous sodium sulfate and the solvent was removed by vacuum distillation to obtain the compound shown in Formula I. (I); (5) Mix 10g of the compound shown in Formula I obtained in step (4) with 2g of p-phenylenediamine and 6g of aniline, add 150mL of DMF, adjust the pH to 1 with 2N dilute hydrochloric acid, add 100mL of 0.5N hydrochloric acid solution containing 20g of ammonium persulfate and add it dropwise over 1 hour. After the addition is complete, stir at room temperature for 24 hours. After the addition is complete, filter, wash with deionized water and acetone in sequence, and dry under vacuum at 60℃ to constant weight to obtain modified polyaniline; (6) Mix 5g of the mercapto-modified glass fiber obtained in step (3) with 10g of the modified polyaniline obtained in step (5), add 100mL of a mixture of N-methylpyrrolidone and DMF (volume ratio 1:1), stir and disperse, add 9g of elemental iodine, stir at room temperature for 35min, dry under reduced pressure, wash twice with 5wt% sodium thiosulfate, wash three times with ethyl acetate, and dry under vacuum at 80℃ to constant weight to obtain the modified polyaniline composite material.

[0034] Example 4 A method for preparing a high-adhesion modified polyaniline composite material, the specific implementation method is the same as in Example 1, except that in step (6), the amount of mercapto-modified glass fiber is 7g.

[0035] Comparative Example 1 A method for preparing a high-adhesion modified polyaniline composite material, the specific implementation method is the same as in Example 1, except that the pretreated glass fiber obtained in step (1) of equal mass is used instead of the mercapto-modified glass fiber in step (6).

[0036] Comparative Example 2 A method for preparing a high-adhesion modified polyaniline composite material, the specific implementation method is the same as in Example 1, except that an equal mass of polyaniline is used instead of the modified polyaniline in step (6).

[0037] Comparative Example 3 A method for preparing a high-adhesion modified polyaniline composite material, the specific implementation method is the same as in Example 1, except that p-phenylenediamine is not added in step (5).

[0038] Performance testing: The preparation method of the coating refers to the preparation method described in paragraphs

[0015] to

[0022] of the specification of CN105623497B, and the modified polyaniline composite material obtained in this application is used to replace the polyaniline of the prior art.

[0039] (1) Adhesion test: The test was conducted in accordance with GB / T 9286-1998 "Cross-cut test of paint and varnish film". The coating was applied to the surface of Q235 steel plate with a thickness of 50μm. After curing at room temperature for 24h, the cross-cut test was carried out. The adhesion grades were divided into 0 to 5, with grade 0 being the best and grade 5 being the worst.

[0040] (2) Adhesion test after damp heat cycle: The steel plate coated by method (1) was placed in a damp heat test chamber with a temperature of 40℃ and a relative humidity of 95%. After 100 cycles, the cross-cut test was performed again.

[0041] (3) Impact resistance test: The test shall be conducted in accordance with GB / T 1732-2020 standard, and the film thickness shall be in accordance with the dry film thickness specified in GB / T13452.2.

[0042] (4) Resistivity test: The steel plate coated by method (1) is tested according to GB / T 16906 standard.

[0043] (5) Self-healing test: Refer to method (1), the coating thickness is 200μm, and the test is carried out according to the standard T / CSCP0003-2023. The scratch length is 1cm and penetrates through the coating to the substrate. The distance between the scratch and each edge of the sample is greater than 20mm. Self-healing efficiency (%) = (initial scratch length - repaired scratch length) / initial scratch length × 100%.

[0044] The modified polyaniline composite materials obtained in each embodiment and comparative example were tested according to the above method, and the results are shown in Table 1.

[0045] Table 1 According to the data in Table 1, the coatings prepared from the modified polyaniline composite materials obtained in Examples 1-3 exhibit good adhesion, resistance to damp heat, impact resistance, conductivity, and self-healing ability. In Example 4, due to the altered mass ratio of mercapto-modified glass fiber to modified polyaniline, the coating prepared from the modified polyaniline composite material showed excessively high crosslinking density, decreased impact resistance, and a decrease in conductivity. In Comparative Example 1, the use of equal-mass pretreated glass fiber instead of mercapto-modified glass fiber resulted in a decrease in the adhesion of the coating prepared from the modified polyaniline composite material. Meanwhile, the crosslinking density decreased, and some glass fibers agglomerated, reducing the coating's impact resistance and self-healing ability. In Comparative Example 2, the use of equal mass of polyaniline instead of modified polyaniline also resulted in a decrease in the adhesion of the coating made from the modified polyaniline composite material. At the same time, the crosslinking density decreased, and glass fibers agglomerated, reducing the coating's impact resistance and self-healing ability. In Comparative Example 3, because p-phenylenediamine was not added in step 5, the coating could not form a crosslinked network structure, resulting in a decrease in impact resistance, and a slight decrease in conductivity and self-healing ability.

[0046] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing a high-adhesion modified polyaniline composite material, characterized in that, Includes the following steps: (1) Mix glass fiber with acetone, ultrasonically disperse for 25-45 min, filter, and vacuum dry to constant weight to obtain pretreated glass fiber; (2) Mix silane coupling agent, deionized water and ethanol, add dilute hydrochloric acid to adjust pH to 3-4, heat to 65-75℃ and stir for 30-40 min to obtain silane hydrolysate; (3) Under an inert protective gas atmosphere, the pretreated glass fiber obtained in step (1) is immersed in the silane hydrolysate obtained in step (2), heated to 40~50℃ and stirred for 3~4h, filtered, washed, and vacuum dried to obtain mercapto-modified glass fiber. (4) Under an inert protective gas atmosphere, mercaptoacetic acid and aniline were mixed, heated to 90-100℃ and stirred at a constant temperature for 5-8 hours. After the mixture was heated, dichloromethane was added, and the mixture was washed successively with dilute hydrochloric acid, deionized water and saturated brine. The mixture was then dried under vacuum to obtain the compound shown in Formula I. （Ⅰ）； (5) Mix the compound of formula I obtained in step (4) with p-phenylenediamine and aniline, add DMF, adjust the pH to 1-2 with dilute hydrochloric acid, add hydrochloric acid solution of ammonium persulfate, stir at room temperature for 24-26 h, filter after completion, wash with deionized water and acetone, and vacuum dry to obtain modified polyaniline; (6) Mix the mercapto-modified glass fiber obtained in step (3) with the modified polyaniline obtained in step (5), add a mixture of methylpyrrolidone and DMF, stir and disperse, add elemental iodine and stir at room temperature for 35-45 min, dry under reduced pressure, wash with sodium thiosulfate, wash with ethyl acetate, and dry under vacuum to obtain the modified polyaniline composite material.

2. The method for preparing the high-adhesion modified polyaniline composite material according to claim 1, characterized in that, The length of the glass fiber is 0.6~1mm.

3. The method for preparing the high-adhesion modified polyaniline composite material according to claim 1, characterized in that, In step (2), the silane coupling agent is any one or more of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and mercaptopropylmethyldimethoxysilane.

4. The method for preparing the high-adhesion modified polyaniline composite material according to claim 1, characterized in that, In step (3), the mass-to-volume ratio of 3-mercaptopropyltriethoxysilane, deionized water and anhydrous ethanol is 1 g:(3~5) ml:(15~18) ml.

5. The method for preparing the high-adhesion modified polyaniline composite material according to claim 1, characterized in that, In step (4), the molar ratio of mercaptoacetic acid and aniline is 1:(1.2~1.5).

6. The method for preparing the high-adhesion modified polyaniline composite material according to claim 1, characterized in that, In step (5), the mass ratio of the compound shown in Formula I, p-phenylenediamine, and aniline is 1:(0.1~0.2):(0.4~0.6).

7. The method for preparing the high-adhesion modified polyaniline composite material according to claim 1, characterized in that, In step (5), the mass ratio of the compound shown in Formula I to ammonium persulfate is 1:(1.5~2).

8. The method for preparing the high-adhesion modified polyaniline composite material according to claim 1, characterized in that, In step (6), the mass ratio of the mercapto-modified glass fiber to the modified polyaniline is (0.1~0.5):

1.

9. The method for preparing the high-adhesion modified polyaniline composite material according to claim 1, characterized in that, In step (6), the amount of elemental iodine added is 0.4 to 0.6 times the total mass of mercapto-modified glass fiber and modified polyaniline.

10. A modified polyaniline composite material prepared by the preparation method according to any one of claims 1 to 9.

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