Method for chemically modifying inorganic filler with graphene oxide, product and application

Abstract

The invention discloses a method for chemically modifying inorganic filler with graphene oxide and a product. The method comprises the following steps: performing surface hydroxylation treatment and silane coupling agent treatment on the inorganic filler; maintaining the pH of a graphene oxide solution at 5.8-6.0 with an MES buffer solution; sequentially adding EDC and NHS, and performing ultrasonic treatment for 1-3 hours; adding the treated inorganic filler, and performing an amidation reaction at room temperature; and after the reaction, filtering, washing and drying to obtain the graphene oxide modified inorganic filler. The invention also discloses a method for preparing an inorganic filler / epoxy resin composite by use of the product. The process flow of the method disclosed by the invention is simple and environmentally friendly; the GO is connected to the surface of the inorganic filler by a chemical modification process, and the firm covalent bond combination between the GO and inorganic particles is generated, so that the interface adhesiveness and mechanical strength between the inorganic filler and the polymer are enhanced, and a new idea is provided to the modification of an inorganic filler surface and the preparation of a high-performance composite.

Description

technical field

[0001] The invention relates to a method for treating the surface of an inorganic filler, in particular to a method for chemically modifying glass fibers and hollow glass microspheres by using graphene oxide, and the product obtained by the method and prepared by using the modified inorganic filler The invention relates to a polymer-based composite material method with excellent interfacial properties, belonging to the technical field of new materials. Background technique

[0002] Polymer composites filled with inorganic fillers are an important class of composite materials, which are widely used in aerospace, automobile industry and sports. There are many factors affecting the properties of inorganic filler-filled polymer composites, among which the interface bonding effect is one of the most important factors. The interface is the link between the reinforced phase and the matrix phase, and also a bridge for the transmission of stress and other information...

Examples

Embodiment 1

[0059] 1. Surface hydroxylation modification: Make a mixed solution of 98wt% concentrated sulfuric acid and 30wt% hydrogen peroxide at a volume ratio of 7:3, add glass fiber with a solution mass of 10wt% to it, and soak at 90°C for 30 minutes. Wash the glass fiber three times with deionized water, and dry it in an oven at 100°C until constant weight.

[0060] 2. Coupling agent modification: Prepare a solution with water and absolute ethanol at a mass ratio of 45:5, and adjust the pH of the solution to 6.0 with glacial acetic acid. Add the coupling agent dropwise to the solution while stirring until the concentration of the coupling agent in the solution is 0.5wt%, and continue stirring for 1.5h to make it hydrolyze. Adjust the hydrolyzed coupling agent solution to pH = 6.0, add 10wt% glass fiber to it, stir at 60°C for 40min, filter with suction, rinse with deionized water for 3 times, and dry in an oven at 100°C until constant weight.

[0061] 3. Preparation of GO aqueous s...

Embodiment 2

[0065] 1. The preparation of GO solution, the surface hydroxylation of glass fiber and the modification method of coupling agent are the same as in Example 1.

[0066] 2. Chemical modification of glass fiber surface by GO: Add GO solution to MES buffer solution with a concentration of 1mol / L, adjust the pH of the mixture to 5.8-6.0, and adjust the concentration of GO in the mixture to 2.0mg / ml ; According to the content of -COOH in the measured GO, and according to -COOH:EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride):NHS (N-hydroxysuccinyl imine) at a molar ratio of 1:15:20, EDC and NHS were added to the solution in sequence, and the mixed solution was sonicated for 2 h.

[0067] Add glass fiber treated with silane coupling agent with 10% solution mass, and stir magnetically for 36 h at room temperature to carry out amidation reaction. After the reaction, let it stand still, filter, wash the glass fiber three times with deionized water, and finally dry it i...

Embodiment 3

[0069] 1. The surface hydroxylation of glass fibers and the modification method of coupling agent are the same as in Example 1.

[0070] 2. Preparation of GO aqueous solution: Add 1.5g of sodium nitrate, 3g of graphite powder and 138g of concentrated sulfuric acid (98%) into the there-necked flask under ice bath conditions, stir for 30 min, then slowly add 9g of potassium permanganate into the there-necked flask , stirred for 30 min. Heated to 35 °C and stirred thoroughly for 24 h to obtain a brown suspension. Slowly add 150ml of deionized water to the suspension, stir, raise the temperature, continue the reaction at 98°C for 10min, and cool to room temperature. Pour the reaction solution into 500ml deionized water while stirring, add 15ml H 2 o 2 (30%) solution, let stand for 24h. The precipitate in the lower layer was taken out, and centrifuged and washed three times with deionized water at 8000 r / min, each time for 8 min. The product was dialyzed against deionized wate...

technical field

[0001] The invention relates to a method for treating the surface of an inorganic filler, in particular to a method for chemically modifying glass fibers and hollow glass microspheres by using graphene oxide, and the product obtained by the method and prepared by using the modified inorganic filler The invention relates to a polymer-based composite material method with excellent interfacial properties, belonging to the technical field of new materials. Background technique

[0002] Polymer composites filled with inorganic fillers are an important class of composite materials, which are widely used in aerospace, automobile industry and sports. There are many factors affecting the properties of inorganic filler-filled polymer composites, among which the interface bonding effect is one of the most important factors. The interface is the link between the reinforced phase and the matrix phase, and also a bridge for the transmission of stress and other information...

Examples

Embodiment 1

[0059] 1. Surface hydroxylation modification: Make a mixed solution of 98wt% concentrated sulfuric acid and 30wt% hydrogen peroxide at a volume ratio of 7:3, add glass fiber with a solution mass of 10wt% to it, and soak at 90°C for 30 minutes. Wash the glass fiber three times with deionized water, and dry it in an oven at 100°C until constant weight.

[0060] 2. Coupling agent modification: Prepare a solution with water and absolute ethanol at a mass ratio of 45:5, and adjust the pH of the solution to 6.0 with glacial acetic acid. Add the coupling agent dropwise to the solution while stirring until the concentration of the coupling agent in the solution is 0.5wt%, and continue stirring for 1.5h to make it hydrolyze. Adjust the hydrolyzed coupling agent solution to pH = 6.0, add 10wt% glass fiber to it, stir at 60°C for 40min, filter with suction, rinse with deionized water for 3 times, and dry in an oven at 100°C until constant weight.

[0061] 3. Preparation of GO aqueous s...

Embodiment 2

[0065] 1. The preparation of GO solution, the surface hydroxylation of glass fiber and the modification method of coupling agent are the same as in Example 1.

[0066] 2. Chemical modification of glass fiber surface by GO: Add GO solution to MES buffer solution with a concentration of 1mol / L, adjust the pH of the mixture to 5.8-6.0, and adjust the concentration of GO in the mixture to 2.0mg / ml ; According to the content of -COOH in the measured GO, and according to -COOH:EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride):NHS (N-hydroxysuccinyl imine) at a molar ratio of 1:15:20, EDC and NHS were added to the solution in sequence, and the mixed solution was sonicated for 2 h.

[0067] Add glass fiber treated with silane coupling agent with 10% solution mass, and stir magnetically for 36 h at room temperature to carry out amidation reaction. After the reaction, let it stand still, filter, wash the glass fiber three times with deionized water, and finally dry it i...

Embodiment 3

[0069] 1. The surface hydroxylation of glass fibers and the modification method of coupling agent are the same as in Example 1.

[0070] 2. Preparation of GO aqueous solution: Add 1.5g of sodium nitrate, 3g of graphite powder and 138g of concentrated sulfuric acid (98%) into the there-necked flask under ice bath conditions, stir for 30 min, then slowly add 9g of potassium permanganate into the there-necked flask , stirred for 30 min. Heated to 35 °C and stirred thoroughly for 24 h to obtain a brown suspension. Slowly add 150ml of deionized water to the suspension, stir, raise the temperature, continue the reaction at 98°C for 10min, and cool to room temperature. Pour the reaction solution into 500ml deionized water while stirring, add 15ml H 2 o 2 (30%) solution, let stand for 24h. The precipitate in the lower layer was taken out, and centrifuged and washed three times with deionized water at 8000 r / min, each time for 8 min. The product was dialyzed against deionized wate...

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