Preparation of rehabilitation type magnetic material with high stability and strong magnetic conductivity

Abstract

The invention relates to preparation of a rehabilitation type magnetic material with high stability and strong magnetic conductivity. The preparation method comprises the following steps: preparation of a short-chain bisphthalonitrile monomer, preparation of a phthalocyanine ferromagnetic high polymer material, preparation of polyaniline, preparation of Mn-Zn spinel ferrite, preparation of polyion liquid microspheres, preparation of Fe-6. 5wt.% Si alloy (high silicon steel), preparation of copper-doped polydopamine (PDA) nanoparticles and the like. The magnetic material prepared by creatively combining preparation methods such as a vacuum melting method, a hydrothermal synthesis method and an emulsion polymerization method has the advantages of high magnetic conductivity, high stability, self-repairing property and the like, can be applied to multiple fields such as rehabilitation sensors, biomedical implant devices, targeted magnetic hyperthermia systems and the like, and has wide application prospects. The prepared magnetic material can automatically recover when being deformed or damaged under the action of external force, and a material basis with a stable structure and durability is provided for medical application.

Description

Technical Field

[0001] The invention relates to the preparation of a rehabilitation magnetic material with high stability and strong magnetic permeability. Background Art

[0002] Against the backdrop of rapid global advances in medical technology and the growing demand for precision medicine, high-performance magnetic materials are showing promising application prospects in fields such as rehabilitation medicine, targeted therapy, and biomedical engineering. While traditional magnetic materials are widely used in medical devices, they still face challenges such as insufficient magnetic permeability, poor stability, and susceptibility to external damage leading to performance degradation, limiting their use in long-term implantable devices and dynamic treatment systems.

[0003] Optimizing the performance of magnetic materials has long been a research priority in materials science. High-permeability materials can enhance magnetic field response efficiency and improve the sensitivity of medical sensors; highly stable materials ensure the long-term reliability of implantable devices; and self-healing properties can significantly extend the material's lifespan in complex physiological environments. However, existing technologies struggle to simultaneously address these key properties. For example, the magnetic permeability and mechanical strength of traditional magnetic polymers often conflict. While metallic magnetic materials possess high permeability, they lack self-healing capabilities and are prone to structural damage under repeated stress. Therefore, developing high-performance magnetic materials with simple preparation processes and manageable costs while simultaneously optimizing permeability, stability, and self-healing properties is of paramount practical significance. Overcoming this technical challenge is expected to break through the performance bottlenecks of traditional magnetic materials, promote further advancements in medical technology, and enable more efficient and precise treatments in fields such as rehabilitation medicine, targeted therapy, and biomedical engineering. Summary of the Invention

[0004] In view of the above problems, the present invention provides a method for preparing a rehabilitation magnetic material with high stability and strong magnetic permeability.

[0005] The present invention provides a preparation method for a rehabilitation magnetic material with high stability and strong magnetic permeability, comprising the following steps: preparation of a short-chain diphthalonitrile monomer, preparation of a phthalocyanine ferromagnetic polymer material, preparation of polyaniline, preparation of a Mn-Zn spinel ferrite, preparation of polyionic liquid microspheres, preparation of an Fe-6.5wt.% Si alloy (high silicon steel), and preparation of copper-doped polydopamine (PDA) nanoparticles; Step (1) Preparation of short-chain diphthalonitrile monomer A small amount of bisphenol (including bisphenol A, bisphenol Af, bisphenol Ap and bisphenol Z), a small amount of 4-nitrophthalonitrile, a small amount of anhydrous potassium carbonate and a small amount of DMF (N,N-dimethylformamide) are added to a three-necked flask equipped with a condenser, stirred, heated to a high temperature, and maintained at this temperature for a long time. After the reaction system is cooled to room temperature, poured into distilled water, stirred and filtered, the resulting filter cake is washed with sodium hydroxide solution and filtered, and then washed with distilled water to obtain the preparation of a short-chain bisphthalonitrile monomer; Step (2) Preparation of phthalocyanine ferromagnetic polymer material Take the short-chain diphthalonitrile monomer and N-methylpyrrolidone in step (1) and add them to a three-necked flask, stir mechanically, and heat to dissolve the monomers fully into a brown-black solution, then cool to room temperature, add carbonyl iron powder thereto, and stir vigorously mechanically. After the mixed solution produces a reflux reaction, a dark green solution is obtained. After magnetic separation of the magnetic metal powder that does not participate in the reaction, the solution is poured into a large amount of water while hot and stirred vigorously mechanically. After suction filtration and drying, a grass-green prepolymer powder with a gradually darkening color is obtained for standby use. A small amount of the prepolymer powder is placed in an oven to finally obtain a completely solidified phthalocyanine ferromagnetic polymer material; Step (3) Preparation of polyaniline Aniline is added to deionized water and stirred, and then ferric chloride hexahydrate is dissolved in nitric acid, and the solution is poured into the aniline aqueous solution. After stirring, it is allowed to stand overnight, and the phthalocyanine ferromagnetic polymer material of step (2) is added and stirred again. After the experiment, vacuum filtration is performed and the mixture is washed with water and ethanol in sequence to remove residual inorganic salts and oligomers. Finally, the filter cake is dried to obtain polyaniline; Step (4) Preparation of Mn-Zn spinel ferrite The electric furnace dust is ball-milled with a high-energy planetary ball mill, and then the ball-milled electric furnace dust is pretreated with a sodium hydroxide solution, and the polyaniline of step (3) is added. The liquid phase and the solid phase are centrifuged and the solid is dried in a constant temperature drying oven, ground and screened with a mesh sieve for later use, and the electric furnace dust pretreated with the sodium hydroxide solution is mixed with manganese sulfate monohydrate in a certain proportion, and ground and mixed evenly in an agate mortar to prepare a precursor, and the precursor is poured into a hydrothermal reactor, and deionized water is added. Finally, the reactor is placed in a constant temperature drying oven, and the hydrothermal product is placed in a centrifuge to achieve liquid-solid separation, and the lower layer of filter residue is collected and dried to obtain Mn-Zn spinel ferrite; Step (5) Preparation of polyionic liquid microspheres Sodium carbonate and sodium dodecyl sulfate are dissolved in deionized water, and then the Mn-Zn spinel ferrite of step (4) is added to the deionized water. The mixed solution is then transferred to a three-necked flask, condensed and refluxed with continuous stirring. Subsequently, methyl methacrylate (MMA) and 1-vinyl-3-butylimidazole hexafluorophosphate are added to the solution under Ar2 atmosphere, and the temperature is increased and stirred for a long time. After the reaction, the final product, polyionic liquid microspheres, is obtained; Step (6) Preparation of Fe-6.5wt.%Si alloy (high silicon steel) Pure iron and single crystal silicon are placed in a vacuum induction melting furnace for smelting, vacuum is drawn, and the power is gradually increased until all the raw materials are melted. The furnace is allowed to stand, argon gas is introduced, and metal Al foil and the polyionic liquid microspheres of step (5) are added. The furnace is deoxidized and degassed, and the furnace is allowed to stand before casting. After cooling, the Fe-6.5wt.%Si alloy (high silicon steel) is taken out. Step (7) Preparation of copper-doped polydopamine (PDA) nanoparticles Ammonia solution is added to the mixture of ethanol and deionized water, and then dopamine hydrochloride is added under rapid stirring and continued to be stirred to obtain a mixture liquid, followed by the addition of copper chloride solution and the Fe-6.5wt.%Si alloy (high silicon steel) of step (6), continued stirring, and finally centrifuged for purification. The precipitate is copper-doped polydopamine (PDA) nanoparticles.

[0006] As a preference, step (1) preparation of short-chain diphthalonitrile monomer To a three-necked flask equipped with a condenser, add 0.1-0.5 mol of bisphenol (including bisphenol A, bisphenol Af, bisphenol Ap and bisphenol Z), 0.2-0.5 mol of 4-nitrophthalonitrile, 0.3-1 mol of anhydrous potassium carbonate and 30-60 mL of DMF (N,N-dimethylformamide), stir and heat to 80-100° C. and maintain this temperature for 24-48 hours. After the reaction system is cooled to room temperature, pour into distilled water, stir and filter, wash the resulting filter cake with 5-10% sodium hydroxide solution and filter, and then wash with distilled water 3-6 times to obtain the preparation of a short-chain bisphthalonitrile monomer.

[0007] The present invention has the advantage that, by adjusting the ratio of the reactants bisphenol, 4-nitrophthalonitrile and anhydrous potassium carbonate, a short-chain bisphthalonitrile monomer with a stable chemical structure can be synthesized in a directionally controlled manner. The reaction is carried out in a mild and easily controllable reaction environment, avoiding side reactions and product decomposition problems caused by extreme reaction environments such as high temperature and high pressure, thereby ensuring the high purity of the product. The obtained short-chain bisphthalonitrile monomer has active functional groups, provides a high-quality reaction monomer for the subsequent synthesis of polymer materials, and helps to construct polymer materials with excellent performance.

[0008] As a preference, step (2) preparation of phthalocyanine ferromagnetic polymer material 10-20 g of the short-chain diphthalonitrile monomer of step (1) and 12-30 mL of N-methylpyrrolidone are added to a 250-500 mL three-necked flask, mechanically stirred, and heated at 180-200 ° C for 5-10 min to fully dissolve the monomer into a brown-black solution, then cooled to room temperature, 0.2-0.5 g of carbonyl iron powder is added thereto, and vigorously mechanically stirred. The mixed solution is refluxed at 200-300 ° C for 2-6 h to obtain a dark green solution. After magnetic separation of the magnetic metal powder that does not participate in the reaction, the solution is poured into a large amount of water while hot and vigorously mechanically stirred. After filtration and drying, a grass-green prepolymer powder with a gradually darkening color is obtained for use. 5-10 g of the prepolymer powder is placed in an oven at a temperature of 250-300 ° C for 4-8 h to finally obtain a fully solidified phthalocyanine ferromagnetic polymer material.

[0009] The advantage of the present invention is that, during the reaction process, carbonyl iron powder and diphthalonitrile monomer undergo a polymerization reaction, iron elements are introduced into the polymer chain, and magnetism is imparted to the material. The post-processing step effectively removes unreacted magnetic metal powder and other impurities through washing and filtering, thereby improving the purity of the product and ensuring the stability and reliability of the material performance.

[0010] Preferably, step (3) preparation of polyaniline 3-6 mL of aniline was added to 30-60 mL of deionized water and stirred at 20-60 ° C for 0.5-5 h. Then, 30-60 g of ferric chloride hexahydrate was dissolved in 50-100 mL of 0.5-1 mL of nitric acid, and the solution was poured into the aniline aqueous solution. After stirring for 12-24 h, it was allowed to stand overnight. 10-30 g of the phthalocyanine ferromagnetic polymer material in step (2) was added and stirred for another 12-24 h. After the experiment, vacuum filtration was performed and the mixture was washed with water and ethanol in sequence to remove residual inorganic salts and oligomers. Finally, the filter cake was dried at 60-100 ° C for 12-24 h to obtain polyaniline.

[0011] The present invention has the advantages of effectively regulating the molecular weight and structure of polyaniline, obtaining polyaniline products with different properties, improving the conductivity and magnetism of the polyaniline through chemical bonding between molecules after adding the phthalocyanine ferromagnetic polymer material, and further removing impurities such as inorganic salts and oligomers in the product through subsequent washing and drying steps, thereby obtaining a pure polyaniline product.

[0012] Preferably, step (4) preparation of Mn-Zn spinel ferrite The electric furnace dust is ball-milled with a high-energy planetary ball mill, and then the ball-milled electric furnace dust is pretreated with a sodium hydroxide solution. 5-10g of polyaniline from step (3) is added, and the solid obtained after centrifugal separation of the liquid phase and the solid phase is dried in a constant temperature drying oven at 100-120°C for 4-8h, ground and sieved with a 200-400 mesh sieve for later use. 1-5g of the electric furnace dust pretreated with a sodium hydroxide solution is mixed with manganese sulfate monohydrate in a ratio of 1-5:1-5, and ground and mixed evenly in an agate mortar to prepare a precursor. The precursor is poured into a 100-200mL hydrothermal reactor, and 100-200mL of deionized water is added. Finally, the reactor is placed in a constant temperature drying oven, and the hydrothermal product is placed in a centrifuge to achieve liquid-solid separation. The lower layer of filter residue is collected and dried to obtain Mn-Zn spinel ferrite.

[0013] The advantages of the present invention are that the addition of polyaniline has a positive impact on the formation process of ferrite by providing reactive sites and adjusting the pH of the reaction system, thereby promoting grain growth and improving the crystallinity of the crystals. Unreacted raw materials and impurities are effectively removed through steps such as centrifugal separation and drying, thereby obtaining a pure ferrite product having excellent magnetic and electrical properties.

[0014] Preferably, step (5) preparation of polyionic liquid microspheres 5-10 g of sodium carbonate and 5-10 g of sodium dodecyl sulfate are dissolved in 30-60 mL of deionized water, and then 10-20 g of the Mn-Zn spinel ferrite prepared in step (4) is added to the deionized water. The mixed solution is then transferred to a three-necked flask, condensed and refluxed, and stirred for 10-30 min. Subsequently, under an Ar2 atmosphere, 10-20 g of methyl methacrylate (MMA) and 1-vinyl-3-butylimidazole hexafluorophosphate are added to the solution and the temperature is raised to 80-100 ° C. The mixture is stirred for 1-5 h and reacted for 4-10 h to obtain the final product, polyionic liquid microspheres.

[0015] The advantage of the present invention is that, during the reaction process, complex chemical reactions and physical interactions occur between the substances, forming microspheres with unique chemical structures and physical properties. The microspheres have good dispersibility and stability, which is due to the distribution of their surface charges and the interaction between molecules. In addition, the introduction of Mn-Zn spinel ferrite gives the microspheres magnetism.

[0016] As a preference, step (6) preparation of Fe-6.5wt.%Si alloy (high silicon steel) Put 6800-7000g pure iron and 500-600g single crystal silicon into a vacuum induction melting furnace and evacuate to 10-20 -2Pa, gradually increase the power supply power, the power supply frequency is 2800-3000 Hz, the maximum power is 40-50kW, until the raw materials are completely dissolved, let it stand for 10-30 minutes, introduce argon, add 5-10g metal Al foil and 5-10g step (5) polyionic liquid microspheres, deoxidize and degas, let it stand for 20-60 minutes and then cast, after cooling, take out the Fe-6.5wt.%Si alloy (high silicon steel).

[0017] The advantages of the present invention are that, during the smelting process, pure iron and single crystal silicon undergo an alloying reaction to form an alloy with a specific crystal structure and properties; the addition of metal Al foil effectively removes oxygen and other impurities in the alloy, thereby improving the purity of the alloy; and the addition of polyionic liquid microspheres positively affects the properties of the alloy by improving the microstructure of the alloy or providing heterogeneous nucleation sites, thereby improving the strength and hardness of the alloy.

[0018] Preferably, step (7) preparation of copper-doped polydopamine (PDA) nanoparticles To a mixture of 50-100 mL of ethanol and deionized water, add 1-5 mL of 25-50% ammonia solution, then add 0.2-0.5 g of dopamine hydrochloride under rapid stirring and continue stirring for 30-60 minutes to obtain a mixture liquid, then add 1-5 mL of copper chloride solution and 5-10 g of step (6) Fe-6.5wt.%Si alloy (high silicon steel), continue stirring for 12-24 hours, and finally centrifuge for purification. The precipitate is copper-doped polydopamine (PDA) nanoparticles.

[0019] The invention has the advantages that, with a mixture of ethanol and deionized water as a solvent, dopamine hydrochloride undergoes a self-polymerization reaction under the catalysis of ammonia water to form polydopamine nanoparticles, and after a copper chloride solution and an Fe-6.5wt.% Si alloy are simultaneously added, copper ions are doped into the polydopamine nanoparticles through coordination to form copper-doped polydopamine nanoparticles, and the addition of the Fe-6.5wt.% Si alloy affects the formation process of the nanoparticles by providing reactive sites, thereby promoting the growth of the nanoparticles and improving the dispersibility of the nanoparticles.

[0020] In summary, the present invention has the following beneficial effects: 1. The present invention has the advantage that, by adjusting the ratio of the reactants bisphenol, 4-nitrophthalonitrile, and anhydrous potassium carbonate, a short-chain bisphthalonitrile monomer with a stable chemical structure can be synthesized in a targeted manner. The reaction is carried out in a mild and easily controllable reaction environment, avoiding side reactions and product decomposition problems caused by extreme reaction environments such as high temperature and high pressure, thereby ensuring high product purity. The obtained short-chain bisphthalonitrile monomer has active functional groups, providing a high-quality reaction monomer for the subsequent synthesis of polymer materials, and facilitating the construction of polymer materials with excellent performance. 2. The present invention has the advantage that, during the reaction process, carbonyl iron powder and diphthalonitrile monomer undergo polymerization, introducing iron into the polymer chain and imparting magnetic properties to the material. The post-processing step effectively removes unreacted magnetic metal powder and other impurities through washing and filtration, thereby improving the purity of the product and ensuring the stability and reliability of the material performance. 3. The present invention has the advantages of effectively regulating the molecular weight and structure of polyaniline, obtaining polyaniline products with different properties. After adding the ferromagnetic phthalocyanine polymer material, the conductivity and magnetism of the polyaniline are improved through intermolecular chemical bonding. The subsequent washing and drying steps further remove impurities such as inorganic salts and oligomers in the product, resulting in a pure polyaniline product. 4. The advantages of the present invention are that the addition of polyaniline has a positive impact on the ferrite formation process by providing reactive sites and adjusting the pH of the reaction system, thereby promoting grain growth and improving crystallinity. Furthermore, unreacted raw materials and impurities are effectively removed through centrifugal separation and drying, resulting in a pure ferrite product with excellent magnetic and electrical properties. 5. The present invention has the advantage that, during the reaction process, complex chemical reactions and physical interactions occur between the various substances, forming microspheres with unique chemical structures and physical properties. The microspheres have good dispersibility and stability, which is due to the distribution of their surface charges and the interaction between molecules. In addition, the introduction of Mn-Zn spinel ferrite gives the microspheres magnetic properties. 6. The advantages of the present invention are that during the smelting process, pure iron and single-crystal silicon undergo an alloying reaction to form an alloy with a specific crystal structure and properties. The addition of metal Al foil effectively removes oxygen and other impurities from the alloy, improving the purity of the alloy. The addition of polyionic liquid microspheres positively affects the properties of the alloy by improving its microstructure or providing heterogeneous nucleation sites, thereby improving the strength and hardness of the alloy. 7. The present invention has the advantage that, using a mixture of ethanol and deionized water as a solvent, under the catalysis of ammonia water, dopamine hydrochloride undergoes a self-polymerization reaction to form polydopamine nanoparticles. After the copper chloride solution and Fe-6.5wt.%Si alloy are simultaneously added, copper ions are doped into the polydopamine nanoparticles by coordination, forming copper-doped polydopamine nanoparticles. The addition of the Fe-6.5wt.%Si alloy affects the formation process of the nanoparticles by providing reactive sites, thereby promoting the growth of the nanoparticles and improving the dispersibility of the nanoparticles. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 A preparation flow chart of a rehabilitation magnetic material with high stability and strong magnetic permeability. DETAILED DESCRIPTION

[0022] The following examples are provided to illustrate the present invention but are not intended to limit the scope of the present invention. Without departing from the spirit and substance of the present invention, modifications or substitutions made to the methods, steps or conditions of the present invention are within the scope of the present invention.

[0023] Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. In addition, all the components and raw materials used in the examples are known commercial products.

[0024] Example 1

[0025] Step (1) Preparation of short-chain diphthalonitrile monomer To a three-necked flask equipped with a condenser, 0.1 mol of bisphenol (including bisphenol A, bisphenol Af, bisphenol Ap and bisphenol Z), 0.2 mol of 4-nitrophthalonitrile, 0.3 mol of anhydrous potassium carbonate and 30 mL of DMF (N,N-dimethylformamide) were added, the temperature was raised to 80° C. with stirring and maintained at this temperature for 24 hours, the reaction system was cooled to room temperature, poured into distilled water, stirred and filtered, and the resulting filter cake was washed with 5% sodium hydroxide solution and filtered, and then washed with distilled water three times to obtain the preparation of a short-chain bisphthalonitrile monomer; Step (2) Preparation of phthalocyanine ferromagnetic polymer material Take 10g of the short-chain diphthalonitrile monomer of step (1) and 12mL of N-methylpyrrolidone and add them to a 250mL three-necked flask, stir mechanically, heat at 180℃ for 5min to dissolve the monomer fully into a brown-black solution, then cool to room temperature, add 0.2g of carbonyl iron powder thereto, and stir vigorously mechanically. After the mixed solution is refluxed at 200℃ for 2h, a dark green solution is obtained. After magnetic separation of the magnetic metal powder that does not participate in the reaction, the solution is poured into a large amount of water while hot and stirred strongly mechanically. After filtration and drying, a grass-green prepolymer powder with a gradually darkening color is obtained for standby use. Take 5g of the prepolymer powder and place it in an oven at 250℃ for 4h to obtain a fully solidified phthalocyanine ferromagnetic polymer material. Step (3) Preparation of polyaniline 3 mL of aniline was added to 30 mL of deionized water and stirred at 20°C for 0.5 h. Then, 30 g of ferric chloride hexahydrate was dissolved in 50 mL of nitric acid, and the solution was poured into the aniline aqueous solution. After stirring for 12 h, the mixture was allowed to stand overnight. 10 g of the phthalocyanine ferromagnetic polymer material from step (2) was added and stirred for another 12 h. After the experiment, vacuum filtration was performed and the mixture was washed with water and ethanol in sequence to remove residual inorganic salts and oligomers. Finally, the filter cake was dried at 60°C for 12 h to obtain polyaniline. Step (4) Preparation of Mn-Zn spinel ferrite The electric furnace dust was ball-milled with a high-energy planetary ball mill, and then the ball-milled electric furnace dust was pretreated with a sodium hydroxide solution. 5 g of polyaniline from step (3) was added, and the solid obtained after centrifugal separation of the liquid phase and the solid phase was dried in a constant temperature drying oven at 100 ° C for 4 h, ground and screened with a 200-mesh sieve for later use. 1 g of the electric furnace dust pretreated with a sodium hydroxide solution was mixed with manganese sulfate monohydrate in a ratio of 1:1, and ground and mixed evenly in an agate mortar to prepare a precursor. The precursor was poured into a 100 mL hydrothermal reactor, and 100 mL of deionized water was added. Finally, the reactor was placed in a constant temperature drying oven, and the hydrothermal product was placed in a centrifuge to achieve liquid-solid separation. The lower layer of filter residue was collected and dried to obtain Mn-Zn spinel ferrite. Step (5) Preparation of polyionic liquid microspheres 5 g of sodium carbonate and 5 g of sodium dodecyl sulfate were dissolved in 30 mL of deionized water, and 10 g of the Mn-Zn spinel ferrite prepared in step (4) was added to the deionized water. The mixed solution was then transferred to a three-necked flask, condensed and refluxed, and stirred for 10 min. Subsequently, 10 g of methyl methacrylate (MMA) and 1-vinyl-3-butylimidazole hexafluorophosphate were added to the solution under an Ar2 atmosphere and heated to 80 °C, stirred for 1 h, and reacted for 4 h to obtain the final product, polyionic liquid microspheres. Step (6) Preparation of Fe-6.5wt.%Si alloy (high silicon steel) 6800g pure iron and 500g single crystal silicon were placed in a vacuum induction melting furnace and evacuated to 10 -2 Pa, gradually increase the power supply power, the power supply frequency is 2800 Hz, the maximum power is 40 kW, until all the raw materials are dissolved, let it stand for 10 minutes, introduce argon, add 5g of metal Al foil and 5g of polyionic liquid microspheres in step (5), deoxidize and degas, let it stand for 20 minutes and then cast, after cooling, take out the Fe-6.5wt.%Si alloy (high silicon steel); Step (7) Preparation of copper-doped polydopamine (PDA) nanoparticles To a mixture of 50 mL of ethanol and deionized water, 1 mL of 25% ammonia solution was added, followed by the addition of 0.2 g of dopamine hydrochloride under rapid stirring and continued stirring for 30 min to obtain a mixture liquid, followed by the addition of 1 mL of copper chloride solution and 5 g of the Fe-6.5 wt.% Si alloy (high silicon steel) obtained in step (6), continued stirring for 12 h, and finally centrifuged for purification. The precipitate was copper-doped polydopamine (PDA) nanoparticles.

[0026] Example 2

[0027] Step (1) Preparation of short-chain diphthalonitrile monomer To a three-necked flask equipped with a condenser, 0.2 mol of bisphenol (including bisphenol A, bisphenol Af, bisphenol Ap and bisphenol Z), 0.3 mol of 4-nitrophthalonitrile, 0.5 mol of anhydrous potassium carbonate and 35 mL of DMF (N,N-dimethylformamide) were added, the temperature was raised to 85° C. with stirring and maintained at this temperature for 30 hours, the reaction system was cooled to room temperature, poured into distilled water, stirred and filtered, and the resulting filter cake was washed with 6% sodium hydroxide solution and filtered, and then washed with distilled water 4 times to obtain the preparation of a short-chain bisphthalonitrile monomer; Step (2) Preparation of phthalocyanine ferromagnetic polymer material Take 15g of the short-chain diphthalonitrile monomer of step (1) and 13mL of N-methylpyrrolidone and add them to a 300mL three-necked flask, stir mechanically, heat at 190℃ for 6min to dissolve the monomer fully into a brown-black solution, then cool to room temperature, add 0.3g of carbonyl iron powder thereto, and stir vigorously mechanically. After the mixed solution is refluxed at 210℃ for 3h, a dark green solution is obtained. After magnetic separation of the magnetic metal powder that does not participate in the reaction, the solution is poured into a large amount of water while hot and stirred strongly mechanically. After filtration and drying, a grass-green prepolymer powder with a gradually darkening color is obtained for standby use. Take 6g of the prepolymer powder and place it in an oven at 260℃ for 5h to obtain a fully solidified phthalocyanine ferromagnetic polymer material. Step (3) Preparation of polyaniline 4 mL of aniline was added to 40 mL of deionized water and stirred at 30 ° C for 1 hour. Then, 40 g of ferric chloride hexahydrate was dissolved in 60 mL of nitric acid, and the solution was poured into the aniline aqueous solution. After stirring for 15 hours, it was allowed to stand overnight. 15 g of the phthalocyanine ferromagnetic polymer material in step (2) was added and stirred for another 15 hours. After the experiment, vacuum filtration was used and the mixture was washed with water and ethanol in sequence to remove residual inorganic salts and oligomers. Finally, the filter cake was dried at 70 ° C for 15 hours to obtain polyaniline. Step (4) Preparation of Mn-Zn spinel ferrite The electric furnace dust was ball-milled with a high-energy planetary ball mill, and then the ball-milled electric furnace dust was pretreated with a sodium hydroxide solution. 6 g of polyaniline from step (3) was added, and the solid obtained after centrifugal separation of the liquid phase and the solid phase was dried in a constant temperature drying oven at 110°C for 5 h, ground and sieved with a 250-mesh sieve for later use. 2 g of the electric furnace dust pretreated with a sodium hydroxide solution was mixed with manganese sulfate monohydrate in a ratio of 2:2, and ground and mixed evenly in an agate mortar to prepare a precursor. The precursor was poured into a 110 mL hydrothermal reactor, and 110 mL of deionized water was added. Finally, the reactor was placed in a constant temperature drying oven, and the hydrothermal product was placed in a centrifuge to achieve liquid-solid separation. The lower layer of filter residue was collected and dried to obtain Mn-Zn spinel ferrite. Step (5) Preparation of polyionic liquid microspheres 6 g of sodium carbonate and 6 g of sodium dodecyl sulfate were dissolved in 40 mL of deionized water, and 12 g of the Mn-Zn spinel ferrite prepared in step (4) was added to the deionized water. The mixed solution was then transferred to a three-necked flask, condensed and refluxed, and stirred for 15 min. Subsequently, 15 g of methyl methacrylate (MMA) and 1-vinyl-3-butylimidazole hexafluorophosphate were added to the solution under an Ar2 atmosphere and heated to 85 °C, stirred for 2 h, and reacted for 5 h to obtain the final product, polyionic liquid microspheres. Step (6) Preparation of Fe-6.5wt.%Si alloy (high silicon steel) 6810g pure iron and 510g single crystal silicon were placed in a vacuum induction melting furnace for smelting. The vacuum was pumped to 12 -2 Pa, gradually increase the power supply power, the power supply frequency is 2850Hz, the maximum power is 45kW, until the raw materials are completely dissolved, let it stand for 15min, introduce argon, add 6g metal Al foil and 6g polyionic liquid microspheres in step (5), deoxidize and degas, let it stand for 25min before casting, and after cooling, take out the Fe-6.5wt.%Si alloy (high silicon steel); Step (7) Preparation of copper-doped polydopamine (PDA) nanoparticles To a mixture of 60 mL of ethanol and deionized water, 2 mL of 25-50% ammonia solution was added, followed by the addition of 0.3 g of dopamine hydrochloride under rapid stirring and continued stirring for 40 min to obtain a mixture liquid, followed by the addition of 2 mL of copper chloride solution and 6 g of the Fe-6.5 wt.% Si alloy (high silicon steel) obtained in step (6), continued stirring for 15 h, and finally centrifuged for purification. The precipitate was copper-doped polydopamine (PDA) nanoparticles.

[0028] Example 3

[0029] Step (1) Preparation of short-chain diphthalonitrile monomer To a three-necked flask equipped with a condenser, 0.4 mol of bisphenol (including bisphenol A, bisphenol Af, bisphenol Ap and bisphenol Z), 0.4 mol of 4-nitrophthalonitrile, 0.6 mol of anhydrous potassium carbonate and 50 mL of DMF (N,N-dimethylformamide) were added, the temperature was raised to 90° C. with stirring and maintained at this temperature for 40 hours, and the reaction system was cooled to room temperature, poured into distilled water, stirred and filtered, and the resulting filter cake was washed with 8% sodium hydroxide solution and filtered, and then washed with distilled water 5 times to obtain the preparation of a short-chain bisphthalonitrile monomer; Step (2) Preparation of phthalocyanine ferromagnetic polymer material 18 g of the short-chain diphthalonitrile monomer of step (1) and 24 mL of N-methylpyrrolidone were added to a 400 mL three-necked flask, mechanically stirred, and heated at 195 ° C for 8 min to fully dissolve the monomer into a brown-black solution, then cooled to room temperature, 0.4 g of carbonyl iron powder was added thereto, and vigorously mechanically stirred. The mixed solution was refluxed at 256 ° C for 5 h to obtain a dark green solution. After magnetic separation of the magnetic metal powder that did not participate in the reaction, the solution was poured into a large amount of water while hot and vigorously mechanically stirred. After filtration and drying, a grass-green prepolymer powder with a gradually darkening color was obtained for use. 8 g of the prepolymer powder was placed in an oven at 280 ° C for 7 h to obtain a fully solidified phthalocyanine ferromagnetic polymer material. Step (3) Preparation of polyaniline 5 mL of aniline was added to 56 mL of deionized water and stirred at 56 ° C for 4 hours. Then, 58 g of ferric chloride hexahydrate was dissolved in 82 mL of nitric acid, and the solution was poured into the aniline aqueous solution. After stirring for 20 hours, it was allowed to stand overnight. 25 g of the phthalocyanine ferromagnetic polymer material in step (2) was added and stirred for another 20 hours. After the experiment, vacuum filtration was used and the mixture was washed with water and ethanol in sequence to remove residual inorganic salts and oligomers. Finally, the filter cake was dried at 88 ° C for 20 hours to obtain polyaniline. Step (4) Preparation of Mn-Zn spinel ferrite The electric furnace dust was ball-milled with a high-energy planetary ball mill, and then the ball-milled electric furnace dust was pretreated with a sodium hydroxide solution. 8 g of polyaniline from step (3) was added, and the solid obtained after centrifugal separation of the liquid phase and the solid phase was dried in a constant temperature drying oven at 115 ° C for 7 h, ground and sieved with a 350 mesh sieve for later use. 4 g of the electric furnace dust pretreated with a sodium hydroxide solution was mixed with manganese sulfate monohydrate in a ratio of 4:4, and ground and mixed evenly in an agate mortar to prepare a precursor. The precursor was poured into a 180 mL hydrothermal reactor, and 180 mL of deionized water was added. Finally, the reactor was placed in a constant temperature drying oven, and the hydrothermal product was placed in a centrifuge to achieve liquid-solid separation. The lower layer of filter residue was collected and dried to obtain Mn-Zn spinel ferrite. Step (5) Preparation of polyionic liquid microspheres 8 g of sodium carbonate and 6 g of sodium dodecyl sulfate were dissolved in 55 mL of deionized water, and 18 g of the Mn-Zn spinel ferrite prepared in step (4) was added to the deionized water. The mixed solution was then transferred to a three-necked flask, condensed and refluxed, and stirred for 26 min. Subsequently, 18 g of methyl methacrylate (MMA) and 1-vinyl-3-butylimidazole hexafluorophosphate were added to the solution under an Ar2 atmosphere and heated to 89 °C, stirred for 4 h, and reacted for 8 h to obtain the final product, polyionic liquid microspheres. Step (6) Preparation of Fe-6.5wt.%Si alloy (high silicon steel) 6900g pure iron and 560g single crystal silicon were placed in a vacuum induction melting furnace and evacuated to 18 -2 Pa, gradually increase the power supply power, the power supply frequency is 2900 Hz, the maximum power is 49 kW, until all the raw materials are dissolved, let it stand for 28 minutes, introduce argon, add 8g of metal Al foil and 9g of the polyionic liquid microspheres in step (5), deoxidize and degas, let it stand for 55 minutes, then cast, and after cooling, take out the Fe-6.5wt.%Si alloy (high silicon steel); Step (7) Preparation of copper-doped polydopamine (PDA) nanoparticles To a mixture of 86 mL of ethanol and deionized water was added 4 mL of 48% ammonia solution, followed by the addition of 0.4 g of dopamine hydrochloride under rapid stirring and continued stirring for 55 min to obtain a mixture liquid, followed by the addition of 4 mL of copper chloride solution and 8 g of the Fe-6.5 wt.% Si alloy (high silicon steel) obtained in step (6), continued stirring for 20 h, and finally centrifuged for purification. The precipitate was copper-doped polydopamine (PDA) nanoparticles.

[0030] Example 4

[0031] Step (1) Preparation of short-chain diphthalonitrile monomer To a three-necked flask equipped with a condenser, 0.5 mol of bisphenol (including bisphenol A, bisphenol Af, bisphenol Ap and bisphenol Z), 0.5 mol of 4-nitrophthalonitrile, 1 mol of anhydrous potassium carbonate and 60 mL of DMF (N,N-dimethylformamide) were added, the temperature was raised to 100 ° C. with stirring and maintained at this temperature for 48 hours, and the reaction system was cooled to room temperature, poured into distilled water, stirred and filtered, and the resulting filter cake was washed with 10% sodium hydroxide solution and filtered, and then washed with distilled water 6 times to obtain the preparation of a short-chain bisphthalonitrile monomer; Step (2) Preparation of phthalocyanine ferromagnetic polymer material 20 g of the short-chain diphthalonitrile monomer of step (1) and 30 mL of N-methylpyrrolidone were added to a 500 mL three-necked flask, mechanically stirred, and heated at 200 ° C for 10 min to fully dissolve the monomer into a brown-black solution, then cooled to room temperature, 0.5 g of carbonyl iron powder was added thereto, and vigorously mechanically stirred. The mixed solution was refluxed at 300 ° C for 6 h to obtain a dark green solution. After magnetic separation of the magnetic metal powder that did not participate in the reaction, the solution was poured into a large amount of water while hot and vigorously mechanically stirred. After filtration and drying, a grass-green prepolymer powder with a gradually darkening color was obtained for standby use. 10 g of the prepolymer powder was placed in an oven at 300 ° C for 8 h to obtain a completely solidified phthalocyanine ferromagnetic polymer material. Step (3) Preparation of polyaniline 6 mL of aniline was added to 60 mL of deionized water and stirred at 60 ° C for 5 h. Then, 60 g of ferric chloride hexahydrate was dissolved in 100 mL of nitric acid, and the solution was poured into the aniline aqueous solution. After stirring for 24 h, it was allowed to stand overnight. 30 g of the phthalocyanine ferromagnetic polymer material in step (2) was added and stirred for another 24 h. After the experiment, vacuum filtration was used and the mixture was washed with water and ethanol in sequence to remove residual inorganic salts and oligomers. Finally, the filter cake was dried at 100 ° C for 24 h to obtain polyaniline. Step (4) Preparation of Mn-Zn spinel ferrite The electric furnace dust was ball-milled with a high-energy planetary ball mill, and then the ball-milled electric furnace dust was pretreated with a sodium hydroxide solution. 10 g of polyaniline from step (3) was added, and the solid obtained after centrifugal separation of the liquid phase and the solid phase was dried in a constant temperature drying oven at 120°C for 8 h, ground and screened with a 400-mesh sieve for later use. 5 g of the electric furnace dust pretreated with a sodium hydroxide solution was mixed with manganese sulfate monohydrate in a ratio of 5:5, and ground and mixed evenly in an agate mortar to prepare a precursor. The precursor was poured into a 200 mL hydrothermal reactor, and 200 mL of deionized water was added. Finally, the reactor was placed in a constant temperature drying oven, and the hydrothermal product was placed in a centrifuge to achieve liquid-solid separation. The lower layer of filter residue was collected and dried to obtain Mn-Zn spinel ferrite. Step (5) Preparation of polyionic liquid microspheres 10 g of sodium carbonate and 10 g of sodium dodecyl sulfate were dissolved in 60 mL of deionized water, and 20 g of the Mn-Zn spinel ferrite prepared in step (4) was added to the deionized water. The mixed solution was then transferred to a three-necked flask, condensed and refluxed, and stirred for 30 min. Subsequently, 20 g of methyl methacrylate (MMA) and 1-vinyl-3-butylimidazole hexafluorophosphate were added to the solution under an Ar2 atmosphere and heated to 100 °C, stirred for 5 h, and reacted for 10 h to obtain the final product, polyionic liquid microspheres. Step (6) Preparation of Fe-6.5wt.%Si alloy (high silicon steel) 7000g pure iron and 600g single crystal silicon were placed in a vacuum induction melting furnace and evacuated to 20 -2 Pa, gradually increase the power supply power, the power supply frequency is 3000 Hz, the maximum power is 50 kW, until the raw materials are completely dissolved, let it stand for 30 minutes, introduce argon, add 10g of metal Al foil and 10g of polyionic liquid microspheres in step (5), deoxidize and degas, let it stand for 60 minutes and then cast, after cooling, take out the Fe-6.5wt.%Si alloy (high silicon steel); Step (7) Preparation of copper-doped polydopamine (PDA) nanoparticles To a mixture of 100 mL of ethanol and deionized water, 5 mL of 50% ammonia solution was added, followed by the addition of 0.5 g of dopamine hydrochloride under rapid stirring and continued stirring for 60 min to obtain a mixture liquid, followed by the addition of 5 mL of copper chloride solution and 10 g of the Fe-6.5 wt.% Si alloy (high silicon steel) obtained in step (6), continued stirring for 24 h, and finally centrifuged for purification. The precipitate was copper-doped polydopamine (PDA) nanoparticles.

[0032] Comparative Example 1

[0033] Step (1) Preparation of short-chain diphthalonitrile monomer To a three-necked flask equipped with a condenser, 12 mol of bisphenol (including bisphenol A, bisphenol Af, bisphenol Ap and bisphenol Z), 0.9 mol of 4-nitrophthalonitrile, 1 mol of anhydrous potassium carbonate and 60 mL of DMF (N,N-dimethylformamide) were added, the temperature was raised to 200° C. with stirring and maintained at this temperature for 50 hours, the reaction system was cooled to room temperature, poured into distilled water, stirred and filtered, and the resulting filter cake was washed with 10% sodium hydroxide solution and filtered, and then washed with distilled water 12 times to obtain the preparation of a short-chain bisphthalonitrile monomer; Step (2) Preparation of phthalocyanine ferromagnetic polymer material Take 29g of the short-chain diphthalonitrile monomer of step (1) and 39mL of N-methylpyrrolidone and add them to a 550mL three-necked flask, stir mechanically, heat at 210℃ for 20min to dissolve the monomer fully into a brown-black solution, then cool to room temperature, add 1.5g of carbonyl iron powder thereto, and stir vigorously mechanically. After the mixed solution is refluxed at 390℃ for 10h, a dark green solution is obtained. After magnetic separation of the magnetic metal powder that does not participate in the reaction, the solution is poured into a large amount of water while hot and stirred strongly mechanically. After filtration and drying, a grass-green prepolymer powder with a gradually darkening color is obtained for standby use. Take 12g of the prepolymer powder and place it in an oven at 310℃ for 8.5h to obtain a fully solidified phthalocyanine ferromagnetic polymer material. Step (3) Preparation of polyaniline 7 mL of aniline was added to 66 mL of deionized water and stirred at 62 ° C for 8 h. Then, 70 g of ferric chloride hexahydrate was dissolved in 150 mL of nitric acid, and the solution was poured into the aniline aqueous solution. After stirring for 27 h, it was allowed to stand overnight. 36 g of the phthalocyanine ferromagnetic polymer material in step (2) was added and stirred for another 30 h. After the experiment, vacuum filtration was used and the mixture was washed with water and ethanol in sequence to remove residual inorganic salts and oligomers. Finally, the filter cake was dried at 150 ° C for 25 h to obtain polyaniline. Step (4) Preparation of Mn-Zn spinel ferrite The electric furnace dust was ball-milled with a high-energy planetary ball mill, and then the ball-milled electric furnace dust was pretreated with a sodium hydroxide solution. 15 g of polyaniline from step (3) was added, and the solid obtained after centrifugal separation of the liquid phase and the solid phase was dried in a constant temperature drying oven at 150 ° C for 10 h, ground and sieved with a 450 mesh sieve for later use. 6 g of the electric furnace dust pretreated with a sodium hydroxide solution was mixed with manganese sulfate monohydrate in a ratio of 9:5, and ground and mixed evenly in an agate mortar to prepare a precursor. The precursor was poured into a 250 mL hydrothermal reactor, and 210 mL of deionized water was added. Finally, the reactor was placed in a constant temperature drying oven, and the hydrothermal product was placed in a centrifuge to achieve liquid-solid separation. The lower layer of filter residue was collected and dried to obtain Mn-Zn spinel ferrite. Step (5) Preparation of copper-doped polydopamine (PDA) nanoparticles To a mixture of 120 mL of ethanol and deionized water, 10 mL of 50% ammonia solution was added, followed by the addition of 0.5 g of dopamine hydrochloride under rapid stirring and continued stirring for 60 minutes to obtain a mixture liquid. Subsequently, 5 mL of copper chloride solution and 10 g of Fe-6.5 wt.% Si alloy (high silicon steel) were added, and stirring was continued for 45 hours. Finally, the mixture was centrifuged and purified, and the precipitate was copper-doped polydopamine (PDA) nanoparticles.

[0034] Comparative Example 2

[0035] Step (1) Preparation of polyaniline 15 mL of aniline was added to 70 mL of deionized water and stirred at 66°C for 12 hours. Then, 80 g of ferric chloride hexahydrate was dissolved in 200 mL of nitric acid, and the solution was poured into the aniline aqueous solution. After stirring for 30 hours, the mixture was allowed to stand overnight. 39 g of phthalocyanine ferromagnetic polymer material was added and stirred for another 30 hours. After the experiment, vacuum filtration was performed and the mixture was washed with water and ethanol in sequence to remove residual inorganic salts and oligomers. Finally, the filter cake was dried at 130°C for 48 hours to obtain polyaniline. Step (2) Preparation of Mn-Zn spinel ferrite The electric furnace dust was ball-milled with a high-energy planetary ball mill, and then the ball-milled electric furnace dust was pretreated with a sodium hydroxide solution. 15 g of polyaniline from step (1) was added, and the solid obtained after centrifugal separation of the liquid phase and the solid phase was dried in a constant temperature drying oven at 150 ° C for 9 h, ground and sieved with a 450 mesh sieve for later use. 9 g of the electric furnace dust pretreated with sodium hydroxide solution was mixed with manganese sulfate monohydrate in a ratio of 5:9, and ground and mixed evenly in an agate mortar to prepare a precursor. The precursor was poured into a 220 mL hydrothermal reactor, and 210 mL of deionized water was added. Finally, the reactor was placed in a constant temperature drying oven, and the hydrothermal product was placed in a centrifuge to achieve liquid-solid separation. The lower layer of filter residue was collected and dried to obtain Mn-Zn spinel ferrite. Step (3) Preparation of polyionic liquid microspheres 15 g of sodium carbonate and 13 g of sodium dodecyl sulfate were dissolved in 66 mL of deionized water, and 29 g of the Mn-Zn spinel ferrite prepared in step (2) was added to the deionized water. The mixed solution was then transferred to a three-necked flask, condensed and refluxed, and stirred for 60 min. Subsequently, 29 g of methyl methacrylate (MMA) and 1-vinyl-3-butylimidazole hexafluorophosphate were added to the solution under an Ar2 atmosphere and heated to 102 °C, stirred for 6 h, and reacted for 10 h to obtain the final product, polyionic liquid microspheres. Step (4) Preparation of Fe-6.5wt.%Si alloy (high silicon steel) 7900g pure iron and 690g single crystal silicon were placed in a vacuum induction melting furnace and evacuated to 10 -2 Pa, gradually increase the power supply power, the power supply frequency is 3900 Hz, the maximum power is 59 kW, until the raw materials are completely dissolved, let it stand for 35 minutes, introduce argon gas, add 16g of metal Al foil and 15g of step (3) polyionic liquid microspheres, deoxidize and degas, let it stand for 69 minutes and then cast, after cooling, take out the Fe-6.5wt.%Si alloy (high silicon steel); Step (5) Preparation of copper-doped polydopamine (PDA) nanoparticles To a mixture of 103 mL of ethanol and deionized water was added 5 mL of 50% ammonia solution, followed by the addition of 0.9 g of dopamine hydrochloride under rapid stirring and continued stirring for 60 min to obtain a mixture liquid, followed by the addition of 10 mL of copper chloride solution and 15 g of the Fe-6.5 wt.% Si alloy (high silicon steel) obtained in step (4), continued stirring for 48 h, and finally centrifuged for purification. The precipitate was copper-doped polydopamine (PDA) nanoparticles.

[0036] Comparison of detection experiments: The materials obtained in Examples 1 to 4 and Comparative Example Products 1 and 2 were tested. The specific testing methods are as follows: Saturation magnetization method Saturation magnetization refers to the magnetization intensity of the prepared material after continuous calcination and annealing at high temperature. First, the prepared material is placed in a vacuum furnace and subjected to high-temperature rapid annealing treatment. The temperature is raised to 1200℃ at a rate of 138℃ / min and kept at this temperature for 5 minutes. Then the power is turned off and the furnace is cooled. The vacuum degree is maintained at -7.5×10 -3 Pa, and then the prepared material was analyzed to obtain the saturation magnetization data.

[0037] Element distribution method The element distribution method is to analyze the distribution of silicon in the prepared material. The uniformity of silicon distribution helps improve the thermal stability of the material. First, the raw materials are placed in a water-cooled copper crucible, and 15g of calcium fluoride is placed on the surface of the raw materials. The raw materials are then fixed with iron wire. During the preparation process, the temperature is 600-700℃, the corresponding electron beam current is 1.4-1.9A, and the vacuum degree is maintained at 1×10 -2 Pa, the deposition rate is 2-3.3 μm / min, and the silicon content and other contents in the prepared materials are analyzed.

[0038] Self-repair performance test Self-healing properties are a new type of intelligent material that can instantly react and spontaneously repair any damage caused by external forces or environmental damage. Copper-doped polydopamine (PDA) nanoparticles leverage their electrical conductivity and chemical stability to effectively enhance the material's self-healing capabilities. Under near-infrared light, polyaniline absorbs light energy through photon scattering and converts it into heat. The test was conducted as follows: a crack was first scratched into the prepared material, and the surface temperature changes of the prepared material under near-infrared light irradiation were monitored in real time using an infrared thermal imager. The temperature was set at 75°C. After 30 seconds of near-infrared light irradiation, the material showed a significant heating rate, with the material temperature rapidly rising from 25°C to 58.1°C. As the near-infrared light irradiation time was extended to 60 seconds, the material temperature continued to rise, reaching 102.3°C. The introduction of polyaniline significantly improved the material's photothermal conversion ability, and obvious self-healing phenomena appeared at the scratches. At this time, the surface temperature of the material has exceeded its glass transition temperature, thereby triggering the movement of molecular chain segments and achieving the effect of repairing the cracks. The self-healing time is recorded. The shorter the self-healing time, the better the self-healing performance of the prepared material.

[0039] Table 1 Saturation magnetization method

[0040] As shown in Table 1, Example 1 is the best, while Comparative Example 2 is relatively poor. The preparation of short-chain diphthalonitrile monomers and phthalocyanine ferromagnetic polymer materials provides the basic magnetic unit for the system, and the introduction of polyaniline further enhances the conductivity and magnetic response of the magnetic polymer chain. The preparation of polyionic liquid microspheres brings good dispersibility and stability to the system. The addition of Fe-6.5wt.%Si alloy (high silicon steel) significantly improves the magnetic saturation performance and mechanical strength of the material. The preparation of copper-doped polydopamine (PDA) nanoparticles provides functional modification for the material surface, enhancing its biocompatibility and targeting, making Example 1 exhibit excellent magnetic properties. Short-chain diphthalonitrile monomers are the basis for constructing phthalocyanine ferromagnetic polymer materials, but the lack of this material in Comparative Example 2 makes the synthesis of phthalocyanine ferromagnetic polymer materials impossible, thereby destroying the molecular structure integrity of the entire magnetic material system and preventing the effective improvement and optimization of magnetic properties. Therefore, the saturation magnetization intensity of Comparative Example 2 is low and the overall magnetic properties are poor.

[0041] Table 2 Element distribution method

[0042] As can be seen from Table 2, Example 1 is the best and Comparative Example 2 is the worst. In Example 1, the silicon element is evenly distributed, indicating that the silicon atoms are evenly dispersed in the material matrix. This uniform distribution helps to form a stable chemical bond network and reduce local stress concentration. When the material is subjected to thermal stress, the evenly distributed silicon element can more effectively disperse the stress, reducing the structural defects and cracks caused by stress concentration, thereby improving the thermal stability of the material. In Comparative Example 2, the silicon element is unevenly distributed, causing the material to be more susceptible to cracks and structural damage under thermal stress. The silicon-deficient area lacks sufficient silicon atoms to stabilize the chemical bonds, resulting in a decrease in the overall strength of the material, further affecting the thermal stability.

[0043] Table 3 Self-repair performance test

[0044] As can be seen from Table 3, Example 1 is the best and Comparative Example 2 is poor. In Example 1, polyaniline itself has a conjugated π bond and has a strong absorption ability under near-infrared light to convert thermal energy. The conjugated structure of the phthalocyanine ferromagnetic polymer material interacts with polyaniline, broadens the conductive channel, improves the conductivity, and is beneficial to heat transfer and molecular chain movement. The good conductivity of the Fe-6.5wt.%Si alloy provides an efficient conductive path for the material, enhancing the photothermal conversion efficiency. The conductivity of the copper-doped polydopamine (PDA) nanoparticles is improved after copper doping, and it synergizes with polyaniline. At the same time, these materials themselves have good chemical stability. After being compounded together, the overall chemical stability is improved, so that the material remains stable during the photothermal conversion and molecular chain movement repair process. The self-repair time is only 10s, which is short and has the best self-repair performance. In Comparative Example 2, the lack of key materials such as phthalocyanine ferromagnetic polymer materials makes it difficult to efficiently transfer the heat generated by the photothermal conversion of polyaniline, restricts the movement of the molecular chain, and has insufficient chemical stability. The prepared material cannot stably self-repair during damage repair, resulting in a self-repair time of up to 70 seconds and the worst self-repair performance.

[0045] This specific embodiment is merely an explanation of the present invention and does not limit the present invention. After reading this specification, those skilled in the art can make non-creative modifications to this embodiment as needed, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. Preparation of a highly stable and strong magnetic permeability recovery type magnetic material, characterized in that: include: Preparation of short-chain diphthalonitrile monomers, preparation of phthalocyanine ferromagnetic polymer materials, preparation of polyaniline, preparation of Mn-Zn spinel ferrite, preparation of polyionic liquid microspheres, preparation of Fe-6.5wt.%Si alloy (high silicon steel), preparation of copper-doped polydopamine (PDA) nanoparticles.

2. The preparation of a rehabilitation magnetic material with high stability and strong magnetic permeability according to claim 1, characterized in that: Step (1) Preparation of short-chain diphthalonitrile monomer A small amount of bisphenol (including bisphenol A, bisphenol Af, bisphenol Ap and bisphenol Z), a small amount of 4-nitrophthalonitrile, a small amount of anhydrous potassium carbonate and a small amount of DMF (N,N-dimethylformamide) are added to a three-necked flask equipped with a condenser, stirred, heated to a high temperature, and maintained at this temperature for a long time. After the reaction system is cooled to room temperature, poured into distilled water, stirred and filtered, the resulting filter cake is washed with sodium hydroxide solution and filtered, and then washed with distilled water to obtain the preparation of a short-chain bisphthalonitrile monomer; Step (2) Preparation of phthalocyanine ferromagnetic polymer material Take the short-chain diphthalonitrile monomer and N-methylpyrrolidone in step (1) and add them to a three-necked flask, stir mechanically, and heat to dissolve the monomers fully into a brown-black solution, then cool to room temperature, add carbonyl iron powder thereto, and stir vigorously mechanically. After the mixed solution produces a reflux reaction, a dark green solution is obtained. After magnetic separation of the magnetic metal powder that does not participate in the reaction, the solution is poured into a large amount of water while hot and stirred vigorously mechanically. After suction filtration and drying, a grass-green prepolymer powder with a gradually darkening color is obtained for standby use. A small amount of the prepolymer powder is placed in an oven to finally obtain a completely solidified phthalocyanine ferromagnetic polymer material; Step (3) Preparation of polyaniline Aniline is added to deionized water and stirred, and then ferric chloride hexahydrate is dissolved in nitric acid, and the solution is poured into the aniline aqueous solution. After stirring, it is allowed to stand overnight, and the phthalocyanine ferromagnetic polymer material of step (2) is added and stirred again. After the experiment, vacuum filtration is performed and the mixture is washed with water and ethanol in sequence to remove residual inorganic salts and oligomers. Finally, the filter cake is dried to obtain polyaniline; Step (4) Preparation of Mn-Zn spinel ferrite The electric furnace dust is ball-milled with a high-energy planetary ball mill, and then the ball-milled electric furnace dust is pretreated with a sodium hydroxide solution, and the polyaniline of step (3) is added. The liquid phase and the solid phase are centrifuged and the solid is dried in a constant temperature drying oven, ground and screened with a mesh sieve for later use, and the electric furnace dust pretreated with the sodium hydroxide solution is mixed with manganese sulfate monohydrate in a certain proportion, and ground and mixed evenly in an agate mortar to prepare a precursor, and the precursor is poured into a hydrothermal reactor, and deionized water is added. Finally, the reactor is placed in a constant temperature drying oven, and the hydrothermal product is placed in a centrifuge to achieve liquid-solid separation, and the lower layer of filter residue is collected and dried to obtain Mn-Zn spinel ferrite; Step (5) Preparation of polyionic liquid microspheres Sodium carbonate and sodium dodecyl sulfate are dissolved in deionized water, and then the Mn-Zn spinel ferrite of step (4) is added to the deionized water. The mixed solution is then transferred to a three-necked flask, condensed and refluxed with continuous stirring. Subsequently, methyl methacrylate (MMA) and 1-vinyl-3-butylimidazole hexafluorophosphate are added to the solution under Ar2 atmosphere, and the temperature is increased and stirred for a long time. After the reaction, the final product, polyionic liquid microspheres, is obtained; Step (6) Preparation of Fe-6.5wt.%Si alloy (high silicon steel) Pure iron and single crystal silicon are placed in a vacuum induction melting furnace for smelting, vacuum is drawn, and the power is gradually increased until all the raw materials are melted. The furnace is allowed to stand, argon gas is introduced, and metal Al foil and the polyionic liquid microspheres of step (5) are added. The furnace is deoxidized and degassed, and the furnace is allowed to stand before casting. After cooling, the Fe-6.5wt.%Si alloy (high silicon steel) is taken out. Step (7) Preparation of copper-doped polydopamine (PDA) nanoparticles Ammonia solution is added to the mixture of ethanol and deionized water, and then dopamine hydrochloride is added under rapid stirring and continued to be stirred to obtain a mixture liquid, followed by the addition of copper chloride solution and the Fe-6.5wt.%Si alloy (high silicon steel) of step (6), continued stirring, and finally centrifuged for purification. The precipitate is copper-doped polydopamine (PDA) nanoparticles.

3. The preparation of a rehabilitation magnetic material with high stability and strong magnetic permeability according to claim 2, characterized in that: Step (1) Preparation of short-chain diphthalonitrile monomer To a three-necked flask equipped with a condenser, add 0.1-0.5 mol of bisphenol (including bisphenol A, bisphenol Af, bisphenol Ap and bisphenol Z), 0.2-0.5 mol of 4-nitrophthalonitrile, 0.3-1 mol of anhydrous potassium carbonate and 30-60 mL of DMF (N,N-dimethylformamide), stir and heat to 80-100° C. and maintain this temperature for 24-48 hours. After the reaction system is cooled to room temperature, pour into distilled water, stir and filter, wash the resulting filter cake with 5-10% sodium hydroxide solution and filter, and then wash with distilled water 3-6 times to obtain the preparation of a short-chain bisphthalonitrile monomer.

4. The preparation of a rehabilitation magnetic material with high stability and strong magnetic permeability according to claim 3, characterized in that: Step (2) Preparation of phthalocyanine ferromagnetic polymer material 10-20 g of the short-chain diphthalonitrile monomer of step (1) and 12-30 mL of N-methylpyrrolidone are added to a 250-500 mL three-necked flask, mechanically stirred, and heated at 180-200 ° C for 5-10 min to fully dissolve the monomer into a brown-black solution, then cooled to room temperature, 0.2-0.5 g of carbonyl iron powder is added thereto, and vigorously mechanically stirred. The mixed solution is refluxed at 200-300 ° C for 2-6 h to obtain a dark green solution. After magnetic separation of the magnetic metal powder that does not participate in the reaction, the solution is poured into a large amount of water while hot and vigorously mechanically stirred. After filtration and drying, a grass-green prepolymer powder with a gradually darkening color is obtained for use. 5-10 g of the prepolymer powder is placed in an oven at a temperature of 250-300 ° C for 4-8 h to finally obtain a fully solidified phthalocyanine ferromagnetic polymer material.

5. The preparation of a rehabilitation magnetic material with high stability and strong magnetic permeability according to claim 4, characterized in that: Step (3) Preparation of polyaniline 3-6 mL of aniline was added to 30-60 mL of deionized water and stirred at 20-60 ° C for 0.5-5 h. Then, 30-60 g of ferric chloride hexahydrate was dissolved in 50-100 mL of 0.5-1 mL of nitric acid, and the solution was poured into the aniline aqueous solution. After stirring for 12-24 h, it was allowed to stand overnight. 10-30 g of the phthalocyanine ferromagnetic polymer material in step (2) was added and stirred for another 12-24 h. After the experiment, vacuum filtration was performed and the mixture was washed with water and ethanol in sequence to remove residual inorganic salts and oligomers. Finally, the filter cake was dried at 60-100 ° C for 12-24 h to obtain polyaniline.

6. The preparation of a rehabilitation magnetic material with high stability and strong magnetic permeability according to claim 5, characterized in that: Step (4) Preparation of Mn-Zn spinel ferrite The electric furnace dust is ball-milled with a high-energy planetary ball mill, and then the ball-milled electric furnace dust is pretreated with a sodium hydroxide solution. 5-10g of polyaniline from step (3) is added, and the solid obtained after centrifugal separation of the liquid phase and the solid phase is dried in a constant temperature drying oven at 100-120°C for 4-8h, ground and sieved with a 200-400 mesh sieve for later use. 1-5g of the electric furnace dust pretreated with a sodium hydroxide solution is mixed with manganese sulfate monohydrate in a ratio of 1-5:1-5, and ground and mixed evenly in an agate mortar to prepare a precursor. The precursor is poured into a 100-200mL hydrothermal reactor, and 100-200mL of deionized water is added. Finally, the reactor is placed in a constant temperature drying oven, and the hydrothermal product is placed in a centrifuge to achieve liquid-solid separation. The lower layer of filter residue is collected and dried to obtain Mn-Zn spinel ferrite.

7. The preparation of a rehabilitation magnetic material with high stability and strong magnetic permeability according to claim 6, characterized in that: Step (5) Preparation of polyionic liquid microspheres 5-10 g of sodium carbonate and 5-10 g of sodium dodecyl sulfate are dissolved in 30-60 mL of deionized water, and then 10-20 g of the Mn-Zn spinel ferrite prepared in step (4) is added to the deionized water. The mixed solution is then transferred to a three-necked flask, condensed and refluxed, and stirred for 10-30 min. Subsequently, under an Ar2 atmosphere, 10-20 g of methyl methacrylate (MMA) and 1-vinyl-3-butylimidazole hexafluorophosphate are added to the solution and the temperature is raised to 80-100 ° C. The mixture is stirred for 1-5 h and reacted for 4-10 h to obtain the final product, polyionic liquid microspheres.

8. The preparation method of a rehabilitation magnetic material with high stability and strong magnetic permeability according to claim 7, characterized in that: Step (6) Preparation of Fe-6.5wt.%Si alloy (high silicon steel) Put 6800-7000g pure iron and 500-600g single crystal silicon into a vacuum induction melting furnace and evacuate to 10-20 - 2 Pa, gradually increase the power supply power, the power supply frequency is 2800-3000 Hz, the maximum power is 40-50kW, until the raw materials are completely dissolved, let it stand for 10-30 minutes, introduce argon, add 5-10g metal Al foil and 5-10g step (5) polyionic liquid microspheres, deoxidize and degas, let it stand for 20-60 minutes and then cast, after cooling, take out the Fe-6.5wt.%Si alloy (high silicon steel).

9. The preparation method of a rehabilitation magnetic material with high stability and strong magnetic permeability according to claim 8, characterized in that: Step (7) Preparation of copper-doped polydopamine (PDA) nanoparticles To a mixture of 50-100 mL of ethanol and deionized water, add 1-5 mL of 25-50% ammonia solution, then add 0.2-0.5 g of dopamine hydrochloride under rapid stirring and continue stirring for 30-60 minutes to obtain a mixture liquid, then add 1-5 mL of copper chloride solution and 5-10 g of step (6) Fe-6.5wt.%Si alloy (high silicon steel), continue stirring for 12-24 hours, and finally centrifuge for purification. The precipitate is copper-doped polydopamine (PDA) nanoparticles.

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