Magnesium oxide surface mechanical force synergistic chemical organic composite modified material and preparation method thereof

Abstract

According to the magnesium oxide surface mechanical force synergistic chemical organic composite modified material and the preparation method thereof, the magnesium oxide and absolute ethyl alcohol mixed solution adopted in the preparation method reduces pollution to the environment, and meanwhile the production cost is reduced; according to the present invention, the existing method of single mechanical force modification or single modifier addition in magnesium oxide powder modification is abandoned, the two methods are combined to carry out composite modification, and the composite modification method combines the advantages of the two methods, such that the magnesium oxide particle surface has strong surface activity and high surface energy through the extrusion impact effect of the mechanical force; under the action of the organic modifier, the magnesium oxide particles are endowed with oleophylic and hydrophobic properties, the compatibility of the powder and an organic matrix is improved, and the comprehensive performance of the prepared magnesium oxide powder is better.

Description

Technical Field

[0001] The present invention relates to the technical field of powder surface modification, and particularly to a surface mechanical force synergistic chemical organic composite modified material of magnesium oxide and a preparation method thereof. Background Art

[0002] As a new type of multifunctional inorganic material, nano-magnesium oxide has broad application prospects in many fields. Due to its special structure, it has electrical, magnetic, thermal and optical properties different from those of the bulk. For example, it can be used in the production of magnesite products, and can also be used as an antacid and adsorbent in the fields of food additives and biopharmaceuticals. It can also be used in rubber manufacturing to play a role in vulcanization cross-linking and resin chelation. Because of its broad application prospects, it has attracted more and more attention. However, in itself, it has fine particles, high surface energy, high surface activity, and there are strong electrostatic forces, van der Waals forces, capillary forces, mechanical hinge forces and other interaction forces between particles, resulting in uneven particle size distribution, poor fluidity and easy agglomeration. The Chinese patent with publication number CN107162025A adds a surfactant during the preparation process to prevent particles from further growing and agglomerating during the precipitation process of the prepared product, only solving the problem of magnesium oxide agglomeration. The Chinese patent with publication number CN108341607B uses a method of coating and modifying magnesium oxide with silica to regulate the surface properties of magnesium oxide, adjusting the coating degree of magnesium oxide to change the curing time and reduce the hydration temperature during the curing of bone repair materials, improving the performance of bone repair materials based on magnesium oxide, slowing down the setting speed of magnesium phosphate during application, and overcoming the disadvantages of increasing the particle size of magnesium oxide after high-temperature sintering and extending the sintering time. However, nano-magnesium oxide particles have a large polarity, are not easily dispersed in non-polar media, and have poor interfacial compatibility with organic matrices, which greatly limits the application range of nano-magnesium oxide. Therefore, certain measures must be taken, especially powder surface modification treatment, to reduce the agglomeration between particles, make it in a good and fully dispersed state in both polar and non-polar media, and be fully mixed with the matrix, which is of great significance for improving the comprehensive physical and chemical properties of magnesium oxide powder, broadening the application range of magnesium oxide powder in industrial production, and deepening the use depth of magnesium oxide powder in high-end fields.

[0003] Therefore, aiming at the deficiencies of the prior art, it is very necessary to provide a surface mechanical force synergistic chemical organic composite modified material of magnesium oxide and a preparation method thereof to solve the deficiencies of the prior art. Summary of the Invention

[0004] The object of the present invention is to avoid the deficiencies of the prior art and provide a surface mechanical force synergistic chemical organic composite modified material of magnesium oxide and its preparation method. The magnesium oxide anhydrous ethanol mixed solution used in the preparation method of the present application reduces environmental pollution and production costs. It abandons the current methods of single mechanical force modification or single addition of modifiers in the modification of magnesium oxide powder, but combines the two methods for composite modification. The composite modification method combines the advantages of the two methods. That is, with the extrusion and impact of mechanical force, the surface of magnesium oxide particles has strong surface activity and high surface energy; under the action of organic modifiers, the magnesium oxide particles are given lipophilic and hydrophobic properties, and the compatibility between the powder and the organic matrix is improved, and the comprehensive performance of the prepared magnesium oxide powder is better.

[0005] The above object of the present invention is achieved by the following technical means.

[0006] Provide a surface mechanical force synergistic chemical organic composite modified material of magnesium oxide and its preparation method, including the following steps:

[0007] S1: Prepare a solution: Prepare a magnesium oxide anhydrous ethanol mixed solution;

[0008] S2: Remove impurities: Place the prepared magnesium oxide anhydrous ethanol mixed solution in an ultrasonic cleaner for impurity removal treatment;

[0009] S3: Filtration by suction: Put the magnesium oxide anhydrous ethanol mixed solution after impurity removal into a suction filter for vacuum filtration;

[0010] S4: First drying: Put the magnesium oxide anhydrous ethanol mixed solution after vacuum filtration into an oven for the first drying treatment to obtain magnesium oxide powder;

[0011] S5: Mixing: Add the magnesium oxide powder to a ball mill for ball milling treatment, and at the same time add a modifier. After adding the modifier to the magnesium oxide powder and ball milling in the ball mill, a suspension is obtained;

[0012] S6: Second drying: Put the suspension into an oven for secondary drying;

[0013] S7: Obtain a test sample.

[0014] Specifically, in step S2, the magnesium oxide anhydrous ethanol mixed solution is placed in an ultrasonic cleaner for dispersion and aging for 0 - 4h.

[0015] Specifically, the oven is dried for the first time at 100°C to dry the magnesium oxide anhydrous ethanol mixed solution for 16 - 30h to obtain magnesium oxide powder.

[0016] Specifically, the mass ratio of the modifier is 5-20% of the magnesium oxide powder. The modifiers include sodium laurate, sodium stearate, titanate coupling agent TCA-KTTT, KH550, lauric acid, palmitic acid, and 1H,1H,2H,2H-perfluorooctyltrichlorosilane.

[0017] Preferably, the ball milling medium inside the ball mill is zirconia beads.

[0018] Further, the zirconia beads are ball-milled by the multi-stage grading method with a mass ratio of 4:3:3. Among them, 50-600 g of zirconia ball milling beads with a diameter of 1 mm, 50-600 g of zirconia ball milling beads with a diameter of 3 mm, and 50-600 g of zirconia ball milling beads with a diameter of 5 mm are used, and ball milling is carried out at a speed of 100-500 r / min for 1-10 h.

[0019] Specifically, the suspension is placed in a drying oven for secondary drying at 100-200 °C for 15-30 h to obtain the test sample.

[0020] The anhydrous ethanol mixed solution of magnesium oxide used in the preparation method of this application reduces environmental pollution and production costs. It abandons the current methods of single mechanical force modification or single addition of modifiers in the modification of magnesium oxide powder, but combines the two methods for composite modification. The composite modification method combines the advantages of the two methods. That is, due to the extrusion and impact of mechanical force, the surface of magnesium oxide particles has strong surface activity and high surface energy; under the action of organic modifiers, the magnesium oxide particles are given lipophilic and hydrophobic properties, and the compatibility between the powder and the organic matrix is improved, and the comprehensive performance of the prepared magnesium oxide powder is better. Description of the Drawings

[0021] The present invention is further described with the accompanying drawings, but the content in the drawings does not constitute any limitation to the present invention.

[0022] Figure 1 It is a flowchart of a method for preparing a magnesium oxide surface mechanical force synergistic chemical organic composite modification material and its preparation method according to the present invention.

[0023] Figure 2 It is an appearance diagram of a paraffin oil suspension of the powder modified with 10% sodium stearate prepared in Example 5 of a method for preparing a magnesium oxide surface mechanical force synergistic chemical organic composite modification material and its preparation method according to the present invention.

[0024] Figure 3 It is a microscopic morphology diagram of the powder modified with 10% sodium stearate prepared in Example 5 of a method for preparing a magnesium oxide surface mechanical force synergistic chemical organic composite modification material and its preparation method according to the present invention. Detailed Embodiments

[0025] The present invention is further described in conjunction with the following embodiments.

[0026] Example 1:

[0027] As Figures 1-3 shown, a surface mechanical force synergistic chemical organic composite modified magnesium oxide material and its preparation method include the following steps:

[0028] S1: Prepare a solution: Prepare a mixed solution of magnesium oxide and absolute ethanol;

[0029] S2: Remove impurities: Place the prepared mixed solution of magnesium oxide and absolute ethanol in an ultrasonic cleaner for impurity removal treatment;

[0030] S3: Filtration by suction: Put the mixed solution of magnesium oxide and absolute ethanol after impurity removal into a suction filter for vacuum suction filtration;

[0031] S4: First drying: Put the mixed solution of magnesium oxide and absolute ethanol after vacuum filtration into an oven for the first drying treatment to obtain magnesium oxide powder;

[0032] S5: Mixing: Add the magnesium oxide powder into a ball mill for ball milling treatment, and at the same time add a modifier. After adding the modifier to the magnesium oxide powder and undergoing ball milling treatment in the ball mill, a suspension is obtained;

[0033] S6: Second drying: Put the suspension into an oven for the second drying;

[0034] S7: Obtain the sample for testing.

[0035] In step S2, the mixed solution of magnesium oxide and absolute ethanol is placed in an ultrasonic cleaner for dispersion and aging for 0 - 4h.

[0036] The first drying in the drying oven is to dry the mixed solution of magnesium oxide and absolute ethanol at 100°C for 16 - 30h to obtain magnesium oxide powder.

[0037] The mass ratio of the modifier is 5 - 20% of the magnesium oxide powder. The modifier includes sodium laurate, sodium stearate, titanate coupling agent TCA - KTTT, KH550, lauric acid, palmitic acid, and 1H,1H,2H,2H - perfluorooctyltrichlorosilane.

[0038] The internal ball - milling medium of the ball mill is zirconia beads.

[0039] The zirconia beads are configured by the multi - grade ball - matching method with a mass ratio of 4:3:3. Among them, 50 - 600g of zirconia ball - milling beads with a diameter of 1mm, 50 - 600g of zirconia ball - milling beads with a diameter of 3mm, and 50 - 600g of zirconia ball - milling beads with a diameter of 5mm, and ball - milling is carried out at a speed of 100 - 500r / min for 1 - 10h.

[0040] The suspension is placed in a drying oven for secondary drying at 100 - 200 °C for 15 - 30 h to obtain the sample for testing.

[0041] Impurity removal: The prepared mixed solution of magnesium oxide and absolute ethanol is placed in an ultrasonic cleaner for dispersion and aging for 1 h.

[0042] Filtration under suction + drying: The obtained solution is put into a suction filter for vacuum filtration. The precipitate obtained after filtration is placed in an oven for the first drying at 100 °C for 20 h to obtain the treated magnesium oxide powder.

[0043] Mixing: 180 g of the treated magnesium oxide is ball-milled. Subsequently, sodium stearate accounting for 5% of the mass of magnesium oxide is added. Zirconia beads are used as the grinding medium, and 180 g of distilled water is added for assisting grinding. 450 g of zirconia grinding beads are added. The multi-stage ball matching method with a mass ratio of 4:3:3 is used for ball matching, where 180 g of zirconia grinding beads with a diameter of 1 mm, 135 g of zirconia grinding beads with a diameter of 3 mm, and 135 g of zirconia grinding beads with a diameter of 5 mm. High-energy ball milling is carried out at a speed of 100 r / min for 3 h; the ball-milled suspension is placed in an oven for the second drying at 100 °C for 20 h to obtain the sample for testing.

[0044] The oleophilic degree of the magnesium oxide obtained in this example is 26.4%, the activation index is 95.1%, and the viscosity of the liquid paraffin suspension is 7560 mPa·s.

[0045] Example 2:

[0046] Impurity removal: The prepared mixed solution of magnesium oxide and absolute ethanol is placed in an ultrasonic cleaner for dispersion and aging for 2 h.

[0047] Filtration under suction + drying: The obtained solution is put into a suction filter for vacuum filtration. The precipitate obtained after filtration is placed in an oven for the first drying at 100 °C for 16 h to obtain the treated magnesium oxide powder.

[0048] Mixing: 180 g of the treated magnesium oxide is ball-milled. Subsequently, sodium laurate accounting for 9.5% of the mass of magnesium oxide is added. Zirconia beads are used as the grinding medium, and 180 g of distilled water is added for assisting grinding. 450 g of zirconia grinding beads are added. The multi-stage ball matching method with a mass ratio of 4:3:3 is used for ball matching, where 180 g of zirconia grinding beads with a diameter of 1 mm, 135 g of zirconia grinding beads with a diameter of 3 mm, and 135 g of zirconia grinding beads with a diameter of 5 mm. High-energy ball milling is carried out at a speed of 200 r / min for 2 h; the ball-milled suspension is placed in an oven for the second drying at 100 °C for 16 h to obtain the sample for testing.

[0049] The oleophilic degree of the magnesium oxide obtained in this example is 17.6%, the activation index is 92.3%, and the viscosity of the liquid paraffin suspension is 6530 mPa·s.

[0050] Example 3:

[0051] Impurity removal: The prepared mixed solution of magnesium oxide and absolute ethanol was placed in an ultrasonic cleaner for dispersion and aging for 2 h;

[0052] Filtration + drying: The obtained solution was put into a suction filter for vacuum filtration, and the precipitate obtained after filtration was put into an oven for the first drying at 100 °C for 25 h to obtain the treated magnesium oxide powder.

[0053] Mixing: 500 g of the treated magnesium oxide powder was ball-milled, and then 7% of the titanate coupling agent TCA-KTTT based on the mass of magnesium oxide was added. Zirconia beads were used as the grinding medium, and 500 g of distilled water was added to assist grinding. 1250 g of zirconia milling beads were added, and the multi-stage ball matching method with a mass ratio of 4:3:3 was used for ball matching, where 500 g of zirconia milling beads with a diameter of 1 mm, 375 g of zirconia milling beads with a diameter of 3 mm, and 375 g of zirconia milling beads with a diameter of 5 mm. High-energy ball milling was carried out at a speed of 200 r / min for 3 h; the ball-milled suspension was put into an oven for the second drying at 200 °C for 25 h to obtain the test sample.

[0054] The oleophilicity degree of the magnesium oxide obtained in this example is 33.6%, the activation index is 94.7%, and the viscosity of the liquid paraffin suspension is 6240 mPa·s.

[0055] Example 4:

[0056] Impurity removal: The prepared mixed solution of magnesium oxide and absolute ethanol was placed in an ultrasonic cleaner for dispersion and aging for 2 h;

[0057] Filtration + drying: The obtained solution was put into a suction filter for vacuum filtration, and the precipitate obtained after filtration was put into an oven for the first drying at 100 °C for 24 h to obtain the treated magnesium oxide powder.

[0058] Mixing: 160 g of the treated magnesium oxide powder was ball-milled, and then 16.5% of palmitic acid based on the mass of magnesium oxide was added. Zirconia beads were used as the grinding medium, and 160 g of distilled water was added to assist grinding. 400 g of zirconia milling beads were added, and the multi-stage ball matching method with a mass ratio of 4:3:3 was used for ball matching, where 160 g of zirconia milling beads with a diameter of 1 mm, 120 g of zirconia milling beads with a diameter of 3 mm, and 120 g of zirconia milling beads with a diameter of 5 mm. High-energy ball milling was carried out at a speed of 300 r / min for 4 h; the ball-milled suspension was put into an oven for the second drying at 100 °C for 24 h to obtain the test sample.

[0059] The oleophilicity degree of the magnesium oxide obtained in this example is 46.6%, the activation index is 95.2%, and the viscosity of the liquid paraffin suspension is 5530 mPa·s.

[0060] Example 5:

[0061] Impurity removal: The prepared mixed solution of magnesium oxide and absolute ethanol was placed in an ultrasonic cleaner for dispersion and aging for 1 h;

[0062] Filtration + drying: The obtained solution was put into a suction filter for vacuum filtration. The precipitate obtained after filtration was put into an oven for the first drying at 100 °C for 24 h to obtain the treated magnesium oxide powder.

[0063] Mixing: 300 g of the treated magnesium oxide powder was ball-milled. Subsequently, sodium stearate accounting for 10% of the mass of magnesium oxide was added. Zirconia beads were used as the grinding medium, and 300 g of distilled water was added to assist grinding. 750 g of zirconia milling beads were added. The multi-stage ball matching method with a mass ratio of 4:3:3 was used for ball matching, including 300 g of zirconia milling beads with a diameter of 1 mm, 225 g of zirconia milling beads with a diameter of 3 mm, and 225 g of zirconia milling beads with a diameter of 5 mm. High-energy ball milling was carried out at a speed of 300 r / min for 5 h; the ball-milled suspension was put into an oven for the second drying at 100 °C for 24 h to obtain the test sample.

[0064] The lipophilization degree of the magnesium oxide obtained in this example was 36.1%, the activation index was 96.4%, and the viscosity of the liquid paraffin suspension was 3270 mPa·s.

[0065] Example 6:

[0066] Impurity removal: The prepared mixed solution of magnesium oxide and absolute ethanol was placed in an ultrasonic cleaner for dispersion and aging for 3 h;

[0067] Filtration + drying: The obtained solution was put into a suction filter for vacuum filtration. The precipitate obtained after filtration was put into an oven for the first drying at 100 °C for 18 h to obtain the treated magnesium oxide powder.

[0068] Mixing: 800 g of the treated magnesium oxide powder was ball-milled. Subsequently, 1H,1H,2H,2H-perfluorooctyltrichlorosilane accounting for 10% of the mass of magnesium oxide was added. Zirconia beads were used as the grinding medium, and 1000 g of distilled water was added to assist grinding. 1250 g of zirconia milling beads were added. The multi-stage ball matching method with a mass ratio of 4:3:3 was used for ball matching, including 500 g of zirconia milling beads with a diameter of 1 mm, 375 g of zirconia milling beads with a diameter of 3 mm, and 375 g of zirconia milling beads with a diameter of 5 mm. High-energy ball milling was carried out at a speed of 300 r / min for 5 h; the ball-milled suspension was put into an oven for the second drying at 200 °C for 18 h to obtain the test sample.

[0069] The oleophilic degree of the magnesium oxide obtained in this example is 44.1%, the activation index is 92.4%, and the viscosity of the liquid paraffin suspension is 6570 mPa·s.

[0070] The magnesium oxide absolute ethanol mixed solution used in the preparation method of this application reduces environmental pollution and production costs. It abandons the current methods of single mechanical force modification or single addition of modifiers in the modification of magnesium oxide powder, but combines the two methods for composite modification. The composite modification method combines the advantages of the two methods. That is, due to the extrusion and impact of mechanical force, the surface of magnesium oxide particles has strong surface activity and high surface energy; under the action of organic modifiers, the magnesium oxide particles are given oleophilic and hydrophobic properties, and the compatibility between the powder and the organic matrix is improved. The comprehensive performance of the prepared magnesium oxide powder is better.

[0071] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A magnesium oxide surface mechanical force synergistic chemical organic composite modified material and a preparation method thereof, characterized in that: The following steps are involved: S1: preparing solution: preparing a magnesium oxide anhydrous ethanol mixed solution; S2: impurity removal: placing the prepared magnesium oxide anhydrous ethanol mixed solution in an ultrasonic cleaning machine for impurity removal; S3: Filtration: Put the magnesium oxide anhydrous ethanol mixed solution after impurities removal into a suction filter for vacuum filtration; S4: First drying: placing the vacuum-filtered magnesium oxide anhydrous ethanol mixed solution into an oven for first drying to obtain magnesium oxide powder; S5: Mixing: adding magnesium oxide powder into a ball mill for ball milling, and adding a modifier at the same time. After adding the modifier, the magnesium oxide powder is ball milled in the ball mill to obtain a suspension; S6: Second drying: placing the suspension in an oven for a second drying; S7: Obtain a test sample.

2. A magnesium oxide surface mechanical force synergistic chemical organic composite modified material and a preparation method thereof according to claim 1, characterized in that: The magnesium oxide anhydrous ethanol mixed solution in step S2 is placed in the ultrasonic cleaning machine for dispersion and aging for 0-4 hours.

3. A magnesium oxide surface mechanical force synergistic chemical organic composite modified material and a preparation method thereof according to claim 2, characterized in that: The drying oven first dries the magnesium oxide anhydrous ethanol mixed solution at 100° C. for 16 to 30 hours to obtain the magnesium oxide powder.

4. The magnesium oxide surface mechanical force synergistic chemical organic composite modified material and preparation method thereof according to claim 3, characterized in that: The mass proportion of the modifier is 5-20% of the magnesium oxide powder, and the modifier includes sodium laurate, sodium stearate, titanate coupling agent TCA-KTTT, KH550, lauric acid, palmitic acid, and 1H,1H,2H,2H-perfluorooctyltrichlorosilane.

5. The magnesium oxide surface mechanical force synergistic chemical organic composite modified material and its preparation method according to claim 4, characterized in that: The ball milling medium inside the ball mill is zirconia beads.

6. The magnesium oxide surface mechanical force synergistic chemical organic composite modified material and its preparation method according to claim 5, characterized in that: The zirconia beads are prepared by a multi-stage ball milling method with a mass ratio of 4:3:3, including 50-600g of 1mm diameter zirconia ball milling beads, 50-600g of 3mm diameter zirconia ball milling beads, and 50-600g of 5mm diameter zirconia ball milling beads, and are ball milled at a speed of 100-500r / min for 1-10h.

7. The magnesium oxide surface mechanical force synergistic chemical organic composite modified material and its preparation method according to claim 6, characterized in that: The suspension is placed in the drying oven for a second drying at 100-200° C. for 15-30 hours to obtain a test sample.

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