Preparation process and application of a biomagnetic composite material

Abstract

This invention relates to the field of magnetic nanomaterials technology, specifically to a preparation process and application of a biomagnetic composite material, comprising the following preparation steps: S1, first, permanent magnet spheres and silane coupling agent are mixed uniformly at room temperature, then nano-PEG / Fe3O4 magnetic fluid, polyurethane, polyethylene glycol, dispersant and crosslinking agent are added at 81-90℃, an external magnetic field is applied and ultrasonic stirring is performed; S2, granulation, washing with water, and drying; S3, first, modified nano-sized natural minerals are added to a polymer emulsion, ultrasonically dispersed to obtain a mixed emulsion, then stabilizers, inorganic fillers and additives are added to the mixed emulsion, stirred uniformly to obtain a functional coating; S4, physical coating and drying; S5, magnetization. This invention has a reasonable process and simple preparation. By leaving complex three-dimensional channels on the surface of the permanent magnet spheres, sufficient channels are provided for loading natural mineral nanoparticles, resulting in a good composite effect between the permanent magnet spheres and natural mineral nanoparticles.

Description

Technical Field

[0001] This invention relates to the field of magnetic nanomaterials technology, specifically to a preparation process and application of a biomagnetic composite material. Background Technology

[0002] According to the "Guiding Principles for Technical Review of Registration of Magnetotherapy Products" issued by the State Food and Drug Administration of China, the mechanism of action of magnetotherapy is defined as follows: magnetic fields can regulate the biomagnetic field in the body, generate induced microcurrents, change cell membrane permeability, change the activity of certain enzymes, and dilate blood vessels and accelerate blood flow, thereby achieving auxiliary therapeutic effects such as pain relief and swelling reduction.

[0003] Biomagnetic medicine studies the physiological effects of magnetic fields on the human body and utilizes the mechanism of the body's response to magnetic fields to unblock and balance magnetic circuits, thereby achieving the effects of magnetic therapy and health maintenance. Currently, products based on biomagnetic medicine are becoming increasingly popular, and their inherent magnetic health benefits have been recognized, such as magnetic health pillows and magnetic therapy patches.

[0004] Chinese invention patent CN110127860B discloses a method for preparing a novel biomagnetic suspension packing for water treatment. In this invention, the pore-forming agent inside the molded packing is removed, making the interior of the molded packing porous. The pore-forming agent is the main factor affecting the size and shape of the surface pores. However, the pore-forming agents currently used are mainly cationic quaternary ammonium salts represented by hexadecyl ammonium bromide, which are generally used for pore formation on the surface of thin film materials. The pore shape is relatively simple and the pore size is small, which is not conducive to loading functional materials. Summary of the Invention

[0005] The purpose of this invention is to provide a preparation process and application of biomagnetic composite materials to solve the problems mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a preparation process for a biomagnetic composite material, comprising the following preparation steps:

[0007] S1. Weigh the following raw materials A according to the following mass percentages: 10-20 parts of permanent magnet spheres with a working temperature of 70-80℃, 1-2 parts of nano-PEG / Fe3O4 magnetic fluid, 10-20 parts of silane coupling agent, 100-120 parts of polyurethane, 10-12 parts of polyethylene glycol, 6-10 parts of dispersant, and 2-4 parts of crosslinking agent. First, mix the permanent magnet spheres and silane coupling agent evenly at room temperature. Then, add the nano-PEG / Fe3O4 magnetic fluid, polyurethane, polyethylene glycol, dispersant, and crosslinking agent at 81-90℃. Apply an external magnetic field of 6.5-8.5mT and stir ultrasonically for 1-2 hours to obtain a mixture.

[0008] S2. The mixture is fed into a kneading granulator and granulated at 81-90°C. After granulation, it is washed with deionized water and then placed in a dryer and dried continuously at 100°C for 8 hours to obtain a porous material.

[0009] S3. Weigh the following raw materials B according to the following mass percentages: 50-84 parts polymer emulsion, 0.1-0.5 parts stabilizer, 10-30 parts modified nano-grade natural mineral, 5-10 parts inorganic filler, and 0.9-5 parts additives. First, add the modified nano-grade natural mineral to the polymer emulsion and disperse it ultrasonically to obtain a mixed emulsion. Then, add the stabilizer, inorganic filler, and additives to the mixed emulsion and stir evenly to obtain the functional coating.

[0010] S4. Physically coat the porous material with functional coating and dry it to obtain a composite material with functional coating on the outer surface.

[0011] S5. The composite material is placed in a magnetizer for magnetization to obtain a biomagnetic composite material.

[0012] Optionally, the permanent magnet sphere is a neodymium iron boron magnet, and the particle size of the permanent magnet sphere is 1-6 mm, and the particle size of the nano PEG / Fe3O4 magnetic fluid is 500-800 nm.

[0013] Optionally, the polyurethane is obtained by copolymerization modification of a silicone emulsion and a polyurethane, wherein the silicone emulsion comprises an emulsifier and phenyltrichlorosilane in a mass ratio of (2-2.5):1.

[0014] Optionally, the dispersant is any one of polyether polysiloxane copolymer, polyacrylate, and polyoxyethylene alkylphenol.

[0015] Optionally, the crosslinking agent is any one of alkyl isocyanate, phthalic anhydride, and polyisocyanate.

[0016] Optionally, the polymer emulsion is formed by dissolving polyurethane or polyamide in water, and the stabilizer is polyvinyl alcohol or polyethylene glycol.

[0017] Optionally, the modified nano-sized natural mineral is a natural mineral nanoparticle modified with a titanate coupling agent, and the natural mineral nanoparticle is any one or a mixture of more than one of maifanite, tourmaline and taiji stone.

[0018] Optionally, the additives include a leveling agent and a curing agent in a mass ratio of 1:(1 to 4).

[0019] On the other hand, the present invention also provides the following technical solution: an application of a biomagnetic composite material, wherein the biomagnetic composite material is embedded in the surface of a massage device using the above-mentioned preparation process of the biomagnetic composite material.

[0020] Compared with the prior art, the present invention has the following beneficial effects: the process of the present invention is reasonable and the preparation is simple. By leaving complex three-dimensional channels on the surface of the permanent magnet sphere, sufficient channels are provided for loading natural mineral nanoparticles. The composite effect of the permanent magnet sphere and the natural mineral nanoparticles is good, the binding is tight, and the slow release effect is excellent. Attached Figure Description

[0021] Figure 1 This is a flowchart illustrating the preparation process of the biomagnetic composite material in this invention. Detailed Implementation

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. 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.

[0023] Example 1: This invention provides a preparation process for a biomagnetic composite material, comprising the following preparation steps:

[0024] S1. Weigh the following raw materials A according to the following mass proportions: 10 parts of permanent magnet spheres with a working temperature of 70-80℃, 1 part of nano PEG / Fe3O4 magnetic fluid, 10 parts of silane coupling agent, 100 parts of polyurethane, 10 parts of polyethylene glycol, 6 parts of dispersant and 2 parts of crosslinking agent. First, mix the permanent magnet spheres and silane coupling agent evenly at room temperature. Then, add nano PEG / Fe3O4 magnetic fluid, polyurethane, polyethylene glycol, dispersant and crosslinking agent at 81℃. Apply an external magnetic field of 6.5mT and stir ultrasonically for 1h to obtain a mixture.

[0025] S2. The mixture is fed into a kneading granulator and granulated at 81°C. After granulation, it is washed with deionized water and then placed in a dryer and dried continuously at 100°C for 8 hours to obtain a porous material.

[0026] S3. Weigh the following raw materials B according to the following mass percentages: 50 parts polymer emulsion, 0.1 parts stabilizer, 10 parts modified nano-grade natural mineral, 5 parts inorganic filler, and 0.9 parts additives. First, add the modified nano-grade natural mineral to the polymer emulsion and disperse it by ultrasonication to obtain a mixed emulsion. Then, add the stabilizer, inorganic filler, and additives to the mixed emulsion and stir evenly to obtain the functional coating.

[0027] S4. Physically coat the porous material with functional coating and dry it to obtain a composite material with functional coating on the outer surface.

[0028] S5. The composite material is placed in a magnetizer for magnetization to obtain a biomagnetic composite material.

[0029] In Example 1, the permanent magnet spheres are neodymium iron boron magnets with a particle size of 1 mm, and the nano-PEG / Fe3O4 magnetic fluid has a particle size of 500 nm. The polyurethane is obtained by copolymerizing and modifying a silicone emulsion with polyurethane, and the silicone emulsion includes an emulsifier and phenyltrichlorosilane in a 2:1 mass ratio. The dispersant is a polyether polysiloxane copolymer. The crosslinking agent is an alkyl isocyanate. The polymer emulsion is formed by dissolving polyurethane or polyamide in water, and the stabilizer is polyvinyl alcohol. The modified nano-sized natural mineral is a mixture of maifanite, tourmaline, and taiji stone modified with a titanate coupling agent. Additives include a leveling agent and a curing agent in a 1:1 mass ratio.

[0030] Example 2: This invention provides a preparation process for a biomagnetic composite material, comprising the following preparation steps:

[0031] S1. Weigh the following raw materials A according to the following mass percentages: 14 parts of permanent magnet spheres with a working temperature of 70-80℃, 1.2 parts of nano PEG / Fe3O4 magnetic fluid, 15 parts of silane coupling agent, 105 parts of polyurethane, 11 parts of polyethylene glycol, 8 parts of dispersant and 3 parts of crosslinking agent. First, mix the permanent magnet spheres and silane coupling agent evenly at room temperature. Then, add the nano PEG / Fe3O4 magnetic fluid, polyurethane, polyethylene glycol, dispersant and crosslinking agent at 84℃. Apply an external magnetic field of 7.5mT and stir ultrasonically for 1h to obtain a mixture.

[0032] S2. The mixture is fed into a kneading granulator and granulated at 84°C. After granulation, it is washed with deionized water and then placed in a dryer and dried continuously at 100°C for 8 hours to obtain a porous material.

[0033] S3. Weigh the following raw materials B according to the following mass percentages: 60 parts polymer emulsion, 0.2 parts stabilizer, 15 parts modified nano-grade natural mineral, 7 parts inorganic filler, and 2 parts additives. First, add the modified nano-grade natural mineral to the polymer emulsion and disperse it ultrasonically to obtain a mixed emulsion. Then, add the stabilizer, inorganic filler, and additives to the mixed emulsion and stir evenly to obtain the functional coating.

[0034] S4. Physically coat the porous material with functional coating and dry it to obtain a composite material with functional coating on the outer surface.

[0035] S5. The composite material is placed in a magnetizer for magnetization to obtain a biomagnetic composite material.

[0036] In Example 2, the permanent magnet spheres are neodymium iron boron magnets with a particle size of 2 mm, and the nano-PEG / Fe3O4 magnetic fluid has a particle size of 600 nm. The polyurethane is obtained by copolymerizing and modifying a silicone emulsion with polyurethane, and the silicone emulsion includes an emulsifier and phenyltrichlorosilane in a mass ratio of 2.2:1. The dispersant is polyacrylate. The crosslinking agent is phthalic anhydride. The polymer emulsion is formed by dissolving polyurethane in water, and the stabilizer is polyvinyl alcohol. The modified nano-sized natural mineral is natural mineral nanoparticles modified with a titanate coupling agent; the natural mineral nanoparticles are a mixture of maifanite, tourmaline, and taiji stone. Additives include a leveling agent and a curing agent in a mass ratio of 1:2.

[0037] Example 3: This invention provides a preparation process for a biomagnetic composite material, comprising the following preparation steps:

[0038] S1. Weigh the following raw materials A according to the following mass percentages: 10-16 parts of permanent magnet spheres with a working temperature of 70-80℃, 1.8 parts of nano PEG / Fe3O4 magnetic fluid, 18 parts of silane coupling agent, 115 parts of polyurethane, 11 parts of polyethylene glycol, 9 parts of dispersant, and 3 parts of crosslinking agent. First, mix the permanent magnet spheres and silane coupling agent evenly at room temperature. Then, add the nano PEG / Fe3O4 magnetic fluid, polyurethane, polyethylene glycol, dispersant, and crosslinking agent at 88℃. Apply an external magnetic field of 7.5mT and stir ultrasonically for 2 hours to obtain a mixture.

[0039] S2. The mixture is fed into a kneading granulator and granulated at 88°C. After granulation, it is washed with deionized water and then placed in a dryer and dried continuously at 100°C for 8 hours to obtain a porous material.

[0040] S3. Weigh the following raw materials B according to the following mass percentages: 72 parts polymer emulsion, 0.4 parts stabilizer, 25 parts modified nano-grade natural mineral, 9 parts inorganic filler, and 4 parts additives. First, add the modified nano-grade natural mineral to the polymer emulsion and disperse it by ultrasonication to obtain a mixed emulsion. Then, add the stabilizer, inorganic filler, and additives to the mixed emulsion and stir evenly to obtain the functional coating.

[0041] S4. Physically coat the porous material with functional coating and dry it to obtain a composite material with functional coating on the outer surface.

[0042] S5. The composite material is placed in a magnetizer for magnetization to obtain a biomagnetic composite material.

[0043] In Example 3, the permanent magnet spheres are neodymium iron boron magnets with a particle size of 4 mm, and the nano-PEG / Fe3O4 magnetic fluid has a particle size of 700 nm. The polyurethane is obtained by copolymerizing and modifying a silicone emulsion with polyurethane, and the silicone emulsion includes an emulsifier and phenyltrichlorosilane in a mass ratio of 2.4:1. The dispersant is polyacrylate. The crosslinking agent is phthalic anhydride. The polymer emulsion is formed by dissolving polyamide in water, and the stabilizer is polyethylene glycol. The modified nano-sized natural mineral is natural mineral nanoparticles modified with a titanate coupling agent; the natural mineral nanoparticles are a mixture of maifanite, tourmaline, and taiji stone. Additives include a leveling agent and a curing agent in a mass ratio of 1:3.

[0044] Example 4: This invention provides a preparation process for a biomagnetic composite material, comprising the following preparation steps:

[0045] S1. Weigh the following raw materials A according to the following mass percentages: 20 parts of permanent magnet spheres with a working temperature of 70-80℃, 2 parts of nano PEG / Fe3O4 magnetic fluid, 20 parts of silane coupling agent, 120 parts of polyurethane, 112 parts of polyethylene glycol, 10 parts of dispersant and 4 parts of crosslinking agent. First, mix the permanent magnet spheres and silane coupling agent evenly at room temperature. Then, add the nano PEG / Fe3O4 magnetic fluid, polyurethane, polyethylene glycol, dispersant and crosslinking agent at 890℃. Apply an external magnetic field of 8.5mT and stir ultrasonically for 2 hours to obtain a mixture.

[0046] S2. The mixture is fed into a kneading granulator and granulated at 90°C. After granulation, it is washed with deionized water and then placed in a dryer and dried continuously at 100°C for 8 hours to obtain a porous material.

[0047] S3. Weigh the following raw materials B according to the following mass parts: 84 parts polymer emulsion, 0.5 parts stabilizer, 30 parts modified nano-grade natural mineral, 10 parts inorganic filler and 5 parts additives. First, add the modified nano-grade natural mineral to the polymer emulsion and disperse it by ultrasonication to obtain a mixed emulsion. Then, add the stabilizer, inorganic filler and additives to the mixed emulsion and stir evenly to obtain the functional coating.

[0048] S4. Physically coat the porous material with functional coating and dry it to obtain a composite material with functional coating on the outer surface.

[0049] S5. The composite material is placed in a magnetizer for magnetization to obtain a biomagnetic composite material.

[0050] In Example 4, the permanent magnet spheres are neodymium iron boron magnets with a particle size of 6 mm, and the nano-PEG / Fe3O4 magnetic fluid has a particle size of 800 nm. The polyurethane is obtained by copolymerizing and modifying a silicone emulsion with polyurethane, and the silicone emulsion includes an emulsifier and phenyltrichlorosilane in a mass ratio of 2.5:1. The dispersant is polyoxyethylene alkylphenol. The crosslinking agent is polyisocyanate. The polymer emulsion is formed by dissolving polyurethane or polyamide in water, and the stabilizer is polyethylene glycol. The modified nano-sized natural mineral is natural mineral nanoparticles modified with a titanate coupling agent; the natural mineral nanoparticles are a mixture of maifanite, tourmaline, and taiji stone. Additives include a leveling agent and a curing agent in a mass ratio of 1:4.

[0051] In S1 of Examples 1-4, permanent magnet spheres and silane coupling agents are mixed uniformly at room temperature to obtain silane coupling agent modified permanent magnet spheres. Neodymium iron boron magnets, as the material for the permanent magnet spheres, have the advantages of high remanence, high coercivity, and high energy product. Under an external magnetic field of 6.5-8.5 mT and an environment of 81-90°C, the permanent magnet spheres lose their magnetic force, while the nano-PEG / Fe3O4 magnetic fluid gains magnetic force due to its superparamagnetism. The nano-PEG / Fe3O4 magnetic fluid is polyethylene glycol-encapsulated nano-Fe3O4, with polyethylene glycol acting as a pore-forming agent. The nano-PEG / Fe3O4 magnetic fluid and polyethylene glycol combine more easily. Under ultrasonic stirring, the nano-PEG / Fe3O4 magnetic fluid can aggregate with polyurethane and polyethylene glycol on the surface of the permanent magnet spheres, that is, the outer periphery of the permanent magnet spheres has multiple layers of nano-PEG / Fe3O4 magnetic fluid, and the gaps between adjacent nano-PEG / Fe3O4 magnetic fluids are filled with polyethylene glycol and polyurethane.

[0052] After granulation and washing, the surface polyethylene glycol and nano-PEG / Fe3O4 magnetic fluid dissolve in water due to the good water solubility of polyethylene glycol, detaching from the permanent magnet spheres. This leaves complex three-dimensional channels on the surface of the permanent magnet spheres, providing ample pores for loading natural mineral nanoparticles. The natural mineral nanoparticles can combine with the polyurethane on the permanent magnet spheres to form a complex three-dimensional connection, resulting in a tight bond and excellent slow-release effect. Furthermore, fragrant plant essential oils can be added to the natural mineral nanoparticles, giving the biomagnetic composite material both disease-preventing, health-promoting, and therapeutic functions.

[0053] Biomagnetic composite materials, based on the effects of magnetotherapy, have the following benefits: 1. Improve microcirculation and promote blood circulation; 2. Cut water molecules, promote cell metabolism, and balance endocrine function; 3. Enhance the oxygen-carrying capacity of red blood cells and reduce blood viscosity; 4. Improve lipid metabolism and lower cholesterol; 5. Eliminate inflammation, swelling, and pain; 6. Regulate blood pressure, especially lowering hypertension; 7. Enhance and improve the body's immunity and disease resistance; 8. Improve sleep, eliminate fatigue, and promote physical recovery; 9. Anti-aging, skin-brightening, and free radical scavenging effects; 10. Calm the nervous system and eliminate insomnia and mental tension.

[0054] On the other hand, the present invention also provides the following technical solution: an application of a biomagnetic composite material, which uses the above-mentioned preparation process of the biomagnetic composite material to embed the biomagnetic composite material on the surface of a massage device, so that raised massage magnetic beads are formed on the surface of the massage device. The wearing time of the biomagnetic composite material is controlled at 6 to 8 hours, and the single use time of the massage magnetic beads is controlled at 1 to 2 hours.

[0055] Experimental Example 1:

[0056] Test content: According to the test methods disclosed in GB / T 3217-1992 "Magnetic Test Methods for Permanent Magnet (Hard Magnet) Materials", the magnetic field strength of the biomagnetic composite materials prepared in Examples 1 to 4 was measured, as shown in Table 1. The air gap d between the biomagnetic composite material and the magnetic field detector tip, and the diameter l of the biomagnetic composite material, satisfy d / l = 0.005.

[0057] Table 1

[0058] Magnetic field strength / GS Example 1 0.552 Example 2 0.567 Example 3 0.573 Example 4 0.586

[0059] As shown in Table 1, the magnetic field strength of the biomagnetic composite materials prepared in Examples 1 to 4 is close to that of the Bama geomagnetic field (magnetic field strength of about 0.58GS). Therefore, the massage magnetic beads prepared from the biomagnetic composite material can simulate the Bama geomagnetic environment and improve blood circulation in the human body.

[0060] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A preparation process for a biomagnetic composite material, characterized in that, The preparation steps include the following: S1. Weigh the following raw materials A according to the following mass percentages: 10-20 parts of permanent magnet spheres with a working temperature of 70-80℃, 1-2 parts of nano-PEG / Fe3O4 magnetic fluid, 10-20 parts of silane coupling agent, 100-120 parts of polyurethane, 10-12 parts of polyethylene glycol, 6-10 parts of dispersant, and 2-4 parts of crosslinking agent. First, mix the permanent magnet spheres and silane coupling agent evenly at room temperature. Then, add the nano-PEG / Fe3O4 magnetic fluid, polyurethane, polyethylene glycol, dispersant, and crosslinking agent at 81-90℃. Apply an external magnetic field of 6.5-8.5mT and stir ultrasonically for 1-2 hours to obtain a mixture. S2. The mixture is fed into a kneading granulator and granulated at 81-90°C. After granulation, it is washed with deionized water and then placed in a dryer and dried continuously at 100°C for 8 hours to obtain a porous material. S3. Weigh the following raw materials B according to the following mass percentages: 50-84 parts polymer emulsion, 0.1-0.5 parts stabilizer, 10-30 parts modified nano-grade natural mineral, 5-10 parts inorganic filler, and 0.9-5 parts additives. First, add the modified nano-grade natural mineral to the polymer emulsion and disperse it ultrasonically to obtain a mixed emulsion. Then, add the stabilizer, inorganic filler, and additives to the mixed emulsion and stir evenly to obtain the functional coating. S4. Physically coat the porous material with functional coating and dry it to obtain a composite material with functional coating on the outer surface. S5. The composite material is placed in a magnetizer for magnetization to obtain a biomagnetic composite material.

2. The preparation process of a biomagnetic composite material according to claim 1, characterized in that, The permanent magnet spheres are neodymium iron boron magnets, and the particle size of the permanent magnet spheres is 1-6 mm, while the particle size of the nano PEG / Fe3O4 magnetic fluid is 500-800 nm.

3. The preparation process of a biomagnetic composite material according to claim 1, characterized in that, The polyurethane is obtained by copolymerization modification of polyurethane with an organosilicon emulsion, and the organosilicon emulsion includes an emulsifier and phenyltrichlorosilane in a mass ratio of (2-2.5):

1.

4. The preparation process of a biomagnetic composite material according to claim 1, characterized in that, The dispersant is any one of polyether polysiloxane copolymer, polyacrylate, and polyoxyethylene alkylphenol.

5. The preparation process of a biomagnetic composite material according to claim 1, characterized in that, The crosslinking agent is any one of alkyl isocyanate, phthalic anhydride, and polyisocyanate.

6. The preparation process of a biomagnetic composite material according to claim 1, characterized in that, The polymer emulsion is formed by dissolving polyurethane or polyamide in water, and the stabilizer is polyvinyl alcohol or polyethylene glycol.

7. The preparation process of a biomagnetic composite material according to claim 1, characterized in that, The modified nano-sized natural mineral is a natural mineral nanoparticle modified by a titanate coupling agent. The natural mineral nanoparticle is any one or a mixture of more than one of maifanite, tourmaline and taiji stone.

8. The preparation process of a biomagnetic composite material according to claim 1, characterized in that, The additives include a leveling agent and a curing agent in a mass ratio of 1:(1-4).

9. An application of a biomagnetic composite material, comprising the preparation process of the biomagnetic composite material as described in any one of claims 1 to 8, characterized in that, Biomagnetic composite materials are embedded in the surface of the massage device.

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