Fireproof glass fiber composite material and preparation method thereof

Abstract

The invention discloses a fireproof glass fiber composite material and a preparation method thereof.Modified filler and caprolactam are mixed, under the action of deionized water, polycaprolactam chain segments are formed on the surface of the modified filler, and the fireproof glass fiber composite material is prepared. An organophosphorus structure in the material is heated and decomposed to generate strong dehydrating agents such as polymetaphosphoric acid, dehydration and carbonization of the surface of a high polymer material are promoted, a compact carbon layer is formed, meanwhile, organic silicon chain segments and nitrogen are doped, organic silicon can form a silicon dioxide inorganic layer at a high temperature, and the thermal stability of the carbon layer is enhanced; nH, N and other inert gases can be generated through doping of the nitrogen element, the concentration of oxygen and combustible gas is diluted, flame propagation is inhibited, the glass fiber serves as a physical framework, a carbon layer structure can be prepared, carbon layer breakage is delayed, then the stability of the carbon layer is guaranteed, molten drops are reduced, and the fireproof effect of the composite material is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of fireproof glass fiber composite material preparation, and in particular to a fireproof glass fiber composite material and a preparation method thereof. Background Art

[0002] As the world's largest engineering plastic, nylon possesses excellent oil resistance, chemical resistance, heat resistance, wear resistance, and mechanical properties. Glass fiber reinforcement and modification can significantly improve the strength, rigidity, heat resistance, and other properties of nylon materials, and has been widely used in the automotive, electrical, and industrial fields. With the vigorous development of the modified plastics industry in recent years, higher-performance nylon modified materials have been continuously produced to meet the market demand for "plastics replacing steel." Although traditional nylon materials have good mechanical properties, they are prone to burning when exposed to high temperatures or flames, posing a safety hazard. To improve this situation, researchers began exploring ways to improve the fire resistance of nylon materials by adding flame retardants, resulting in flame-retardant nylon materials. However, although flame-retardant nylon materials have shown some improvement in their flame retardancy, the improvement is limited and cannot meet the needs of use. Summary of the Invention

[0003] The purpose of the present invention is to provide a fireproof glass fiber composite material and a preparation method thereof, which solves the problem that the current nylon composite material has poor flame retardant effect.

[0004] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing a fireproof glass fiber composite material comprises the following steps: Step A1: calcining glass fiber in a muffle furnace at 500-550°C for 1.5 hours, cooling, mixing with concentrated sulfuric acid and hydrogen peroxide, and soaking at 20-25°C for 1-1.5 hours. Filtering and removing the filtrate to obtain pretreated glass cellulose, dispersing the pretreated glass fiber in ethanol, stirring at a speed of 200-300 r / min and a temperature of 60-70°C, adding KH570 and deionized water, and reacting for 3-5 hours to obtain modified glass fiber; Step A2: Disperse the modified glass fiber in DMF, introduce nitrogen protection, stir and add chloroplatinic acid and a modification additive at a speed of 200-300 r / min and a temperature of 70-80°C, and react for 4-6 hours to obtain a modified filler. The modified filler, caprolactam, deionized water and DMF are mixed evenly, and reacted for 2-3 hours at a speed of 150-200 r / min, a temperature of 220-230°C and a pressure of 1.8-2.0 MPa. After the pressure is released to normal pressure, the temperature is raised to 250-260°C, and the reaction is continued for 1-1.5 hours to obtain a fire-resistant glass fiber composite material.

[0005] Furthermore, the amount ratio of the glass fiber, concentrated sulfuric acid and hydrogen peroxide described in step A1 is 2g:7mL:3mL, the mass fraction of concentrated sulfuric acid is 98%, and the amount ratio of the pretreated glass fiber, ethanol, KH570 and deionized water is 2g:20mL:1mL:2mL.

[0006] Furthermore, the mass ratio of the modified glass fiber and the modified additive in step A2 is 1:10, and the amount ratio of the modified filler, caprolactam and deionized water is 8g:100g:3mL.

[0007] Furthermore, the modified additive is prepared by the following steps: Step B1: 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide, epichlorohydrin, boron trifluoride etherate, and tetrahydrofuran are uniformly mixed and reacted at a speed of 150-200 r / min and a temperature of 65-70° C. for 2-3 hours. Sodium carbonate is then added to a pH of 8. The temperature is raised to 75-80° C., and tetrabutylammonium bromide is added. The reaction is continued for 3-5 hours to obtain a modifier. Step B2: Tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(aminopropyl)tetramethyldisiloxane, and dimethyl sulfoxide are mixed, nitrogen is introduced, and the mixture is reacted at a speed of 60-80 r / min and a temperature of 100-105°C for 8-10 hours to obtain a diamine-terminated polysiloxane. The diamine-terminated polysiloxane, a modifier, and DMF are uniformly mixed, nitrogen is introduced, aluminum chloride is added, and the mixture is stirred at a speed of 150-200 r / min and a temperature of 50-60°C, and the mixture is reacted for 2-3 hours to obtain a pretreated polysiloxane. Step B3: p-nitrobromobenzene, triethyl phosphite and DMF are mixed uniformly, stirred and potassium iodide is added at a speed of 120-150 r / min and a temperature of 120-140° C., and the reaction is carried out for 6-8 hours to obtain intermediate 1. Intermediate 1, hydrochloric acid, ethanol and deionized water are mixed uniformly, and the reaction is carried out at a speed of 200-300 r / min and a temperature of 60-65° C. for 4-6 hours to obtain intermediate 2. Intermediate 2, phosphorus pentachloride and dichloromethane are mixed uniformly, and the reaction is carried out at a speed of 150-200 r / min and a temperature of 40-50° C. for 4-6 hours to obtain an additive; Step B4: The additive, pretreated polysiloxane, sodium trifluoromethanesulfonate and DMF are mixed, and the reaction is carried out for 3-5 hours at a speed of 200-300 r / min and a temperature of 80-85°C to obtain a modified polysiloxane. The modified polysiloxane, palladium carbon catalyst, triethylamine and DMF are mixed evenly, hydrogen is introduced to maintain a pressure of 0.5-1 MPa, and the reaction is carried out for 3-5 hours at a speed of 120-150 r / min and a temperature of 40-50°C to obtain a modified additive.

[0008] Furthermore, the amount ratio of 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide, epichlorohydrin and boron trifluoride etherate described in step B1 is 36mmol:18mmol:1g, and the amount of tetrabutylammonium bromide is 3% of the mass of epichlorohydrin.

[0009] Furthermore, the molar ratio of tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, and 1,3-bis(aminopropyl)tetramethyldisiloxane described in step B2 is 2:1.5:1, and the molar ratio of diamine-terminated polysiloxane, modifier, and aluminum chloride is 1:4:3.8.

[0010] Furthermore, the molar ratio of p-nitrobromobenzene, triethyl phosphite and potassium iodide in step B3 is 1:1.2:0.5, the usage ratio of intermediate 1, hydrochloric acid, ethanol and deionized water is 1 mmol:2 mmol:2 mL:2 mL, and the molar ratio of intermediate 2 and phosphorus pentachloride is 1:2.5.

[0011] Furthermore, the molar ratio of the additive in step B4 to the pretreated polysiloxane is 1:2, the amount of sodium trifluoromethanesulfonate is 2.5% of the mass of the pretreated polysiloxane, and the amount ratio of modified polysiloxane, palladium carbon catalyst, triethylamine and DMF is 10 mmol:200 mg:1 mg:80 mL.

[0012] The beneficial effects of the present invention are as follows: a fireproof glass fiber composite material disclosed by the present invention uses glass fiber as raw material, which is first calcined and then treated with concentrated sulfuric acid and hydrogen peroxide to graft hydroxyl groups on the surface to obtain pretreated glass fiber, and the pretreated glass fiber is treated with KH570 to graft double bonds on the surface to obtain modified glass fiber, and the modified glass fiber is reacted with a modified additive to react the double bonds on the surface of the modified glass fiber with the Si-H bonds on the modified additive to obtain a modified filler, and the modified filler is mixed with caprolactam, and under the action of deionized water, polycaprolactam segments are formed on the surface of the modified filler to obtain a fireproof glass fiber composite material.

[0013] The modified additive is prepared by reacting 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide and epichlorohydrin in the presence of boron trifluoride ether, so that the hydroxyl group on 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide reacts with the epoxy group on epichlorohydrin, and then in a weakly alkaline environment and the presence of tetrabutylammonium bromide, a ring closure occurs to form a new epoxy group to prepare a modifier, tetramethylcyclotetrasiloxane is ring-opened and polymerized, and then end-capped with 1,3-bis(aminopropyl)tetramethyldisiloxane to prepare a diamine-terminated polysiloxane, and the diamine-terminated polysiloxane and the modifier are reacted in the presence of aluminum chloride. The following reaction is used to react the amino group on the diamine-terminated polysiloxane with the epoxy group on the modifier to obtain a pretreated polysiloxane; p-nitrobromobenzene is reacted with triethyl phosphite to form a p-nitrophenyl phosphate structure to obtain an intermediate 1; the intermediate 1 is hydrolyzed to form a phosphoric acid structure to obtain an intermediate 2; the intermediate 2 is reacted with phosphorus pentachloride to convert the phosphoric acid into phosphorus oxychloride to obtain an additive; the additive is reacted with the pretreated polysiloxane to react the chlorine atom site on the additive with the hydroxyl group on the pretreated polysiloxane to obtain a modified polysiloxane; the modified polysiloxane is treated with a palladium-carbon catalyst in the presence of hydrogen to convert the nitro group into an amino group to obtain a modified additive.

[0014] When the composite material burns, the organic phosphorus structure in the material decomposes under heat to generate strong dehydrating agents such as polymetaphosphoric acid, which promotes dehydration and carbonization of the surface of the polymer material to form a dense carbon layer. At the same time, the doping of organic silicon segments and nitrogen elements allows the organic silicon to form an inorganic silicon dioxide layer at high temperatures, enhancing the thermal stability of the carbon layer. The doping of nitrogen elements can produce inert gases such as NH3 and N2, diluting the concentration of oxygen and combustible gases and inhibiting the spread of flames. Glass fiber acts as a physical skeleton to form a carbon layer structure, delaying the rupture of the carbon layer, thereby ensuring the stability of the carbon layer, reducing the appearance of molten droplets, and increasing the fireproof effect of the composite material. DETAILED DESCRIPTION

[0015] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0016] Example 1, a method for preparing a fireproof glass fiber composite material, specifically comprising the following steps: Step A1: calcining glass fiber in a muffle furnace at 500°C for 1.5 hours, cooling, mixing with concentrated sulfuric acid and hydrogen peroxide, and soaking at 20°C for 1 hour. The filtrate was filtered to remove pretreated glass cellulose. The pretreated glass fiber was dispersed in ethanol, stirred at 200 r / min and 60°C, and KH570 and deionized water were added. The mixture was reacted for 3 hours to produce modified glass fiber. Step A2: Disperse the modified glass fiber in DMF, introduce nitrogen protection, stir and add chloroplatinic acid and modification additives at a speed of 200 r / min and a temperature of 70°C, and react for 4 hours to obtain a modified filler. Mix the modified filler, caprolactam, deionized water and DMF evenly, react for 2 hours at a speed of 150 r / min, a temperature of 220°C and a pressure of 1.8 MPa, then release the pressure to normal pressure, raise the temperature to 250°C, and continue the reaction for 1 hour to obtain a fire-resistant glass fiber composite material.

[0017] The amount ratio of the glass fiber, concentrated sulfuric acid and hydrogen peroxide described in step A1 is 2g:7mL:3mL, the mass fraction of concentrated sulfuric acid is 98%, and the amount ratio of the pretreated glass fiber, ethanol, KH570 and deionized water is 2g:20mL:1mL:2mL.

[0018] The mass ratio of the modified glass fiber and the modified additive described in step A2 is 1:10, and the amount ratio of the modified filler, caprolactam and deionized water is 8g:100g:3mL.

[0019] The modified additive is prepared by the following steps: Step B1: 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide, epichlorohydrin, boron trifluoride etherate, and tetrahydrofuran were uniformly mixed and reacted at a speed of 150 r / min and a temperature of 65° C. for 2 h. Then, sodium carbonate was added to a pH of 8. The temperature was raised to 75° C., and tetrabutylammonium bromide was added. The reaction was continued for 3 h to prepare a modifier. Step B2: Tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(aminopropyl)tetramethyldisiloxane, and dimethyl sulfoxide were mixed, nitrogen was introduced, and the reaction was carried out at a speed of 60 r / min and a temperature of 100°C for 8 hours to obtain a diamine-terminated polysiloxane. The diamine-terminated polysiloxane, the modifier, and DMF were mixed uniformly, nitrogen was introduced, and aluminum chloride was added at a speed of 150 r / min and a temperature of 50°C. The mixture was stirred and reacted for 2 hours to obtain a pretreated polysiloxane. Step B3: p-Nitrobromobenzene, triethyl phosphite and DMF were mixed uniformly, stirred and potassium iodide was added at a speed of 120 r / min and a temperature of 120°C, and the reaction was carried out for 6 hours to obtain intermediate 1. Intermediate 1, hydrochloric acid, ethanol and deionized water were mixed uniformly, and the reaction was carried out at a speed of 200 r / min and a temperature of 60°C for 4 hours to obtain intermediate 2. Intermediate 2, phosphorus pentachloride and dichloromethane were mixed uniformly, and the reaction was carried out at a speed of 150 r / min and a temperature of 40°C for 4 hours to obtain an additive; Step B4: The additive, pretreated polysiloxane, sodium trifluoromethanesulfonate and DMF were mixed, and the reaction was carried out at a speed of 200 r / min and a temperature of 80°C for 3 hours to obtain a modified polysiloxane. The modified polysiloxane, palladium carbon catalyst, triethylamine and DMF were mixed evenly, and hydrogen was introduced to maintain the pressure at 0.5 MPa. The reaction was carried out at a speed of 120 r / min and a temperature of 40°C for 3 hours to obtain a modified additive.

[0020] The amount ratio of 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide, epichlorohydrin and boron trifluoride etherate described in step B1 is 36mmol:18mmol:1g, and the amount of tetrabutylammonium bromide is 3% of the mass of epichlorohydrin.

[0021] The molar ratio of tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, and 1,3-bis(aminopropyl)tetramethyldisiloxane described in step B2 is 2:1.5:1, and the molar ratio of diamine-terminated polysiloxane, modifier, and aluminum chloride is 1:4:3.8.

[0022] The molar ratio of p-nitrobromobenzene, triethyl phosphite and potassium iodide in step B3 is 1:1.2:0.5, the amount ratio of intermediate 1, hydrochloric acid, ethanol and deionized water is 1mmol:2mmol:2mL:2mL, and the molar ratio of intermediate 2 and phosphorus pentachloride is 1:2.5.

[0023] The molar ratio of the additive in step B4 to the pretreated polysiloxane is 1:2, the amount of sodium trifluoromethanesulfonate is 2.5% of the mass of the pretreated polysiloxane, and the amount ratio of modified polysiloxane, palladium carbon catalyst, triethylamine and DMF is 10 mmol:200 mg:1 mg:80 mL.

[0024] Example 2, a method for preparing a fireproof glass fiber composite material, specifically comprising the following steps: Step A1: calcining glass fiber in a muffle furnace at 530°C for 1.5 hours, cooling the mixture, mixing it with concentrated sulfuric acid and hydrogen peroxide, and soaking it at 20°C for 1.5 hours. The filtrate was filtered to remove the pretreated glass cellulose. The pretreated glass fiber was dispersed in ethanol and stirred at 200 r / min and 65°C. KH570 and deionized water were added and reacted for 4 hours to produce modified glass fiber. Step A2: Disperse the modified glass fiber in DMF, introduce nitrogen protection, stir and add chloroplatinic acid and modification additives at a speed of 200 r / min and a temperature of 75°C, and react for 5 hours to obtain a modified filler. Mix the modified filler, caprolactam, deionized water and DMF evenly, react for 3 hours at a speed of 150 r / min, a temperature of 225°C and a pressure of 1.9 MPa, then release the pressure to normal pressure, raise the temperature to 255°C, and continue the reaction for 1.5 hours to obtain a fire-resistant glass fiber composite material.

[0025] The amount ratio of the glass fiber, concentrated sulfuric acid and hydrogen peroxide described in step A1 is 2g:7mL:3mL, the mass fraction of concentrated sulfuric acid is 98%, and the amount ratio of the pretreated glass fiber, ethanol, KH570 and deionized water is 2g:20mL:1mL:2mL.

[0026] The mass ratio of the modified glass fiber and the modified additive described in step A2 is 1:10, and the amount ratio of the modified filler, caprolactam and deionized water is 8g:100g:3mL.

[0027] The modified additive is prepared by the following steps: Step B1: 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide, epichlorohydrin, boron trifluoride etherate, and tetrahydrofuran were uniformly mixed and reacted at a speed of 150 r / min and a temperature of 70° C. for 2 h. Then, sodium carbonate was added to a pH of 8. The temperature was raised to 80° C., and tetrabutylammonium bromide was added to carry out reaction 4 to obtain a modifier. Step B2: Tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(aminopropyl)tetramethyldisiloxane, and dimethyl sulfoxide were mixed, nitrogen was introduced, and the mixture was reacted at a speed of 60 r / min and a temperature of 105° C. for 9 hours to obtain a diamine-terminated polysiloxane. The diamine-terminated polysiloxane, the modifier, and DMF were mixed uniformly, nitrogen was introduced, aluminum chloride was added, and the mixture was stirred at a speed of 200 r / min and a temperature of 55° C. for 3 hours to obtain a pretreated polysiloxane. Step B3: p-Nitrobromobenzene, triethyl phosphite and DMF were mixed uniformly, stirred and potassium iodide was added at a speed of 120 r / min and a temperature of 130°C, and the reaction was carried out for 7 hours to obtain intermediate 1. Intermediate 1, hydrochloric acid, ethanol and deionized water were mixed uniformly, and the reaction was carried out at a speed of 200 r / min and a temperature of 65°C for 5 hours to obtain intermediate 2. Intermediate 2, phosphorus pentachloride and dichloromethane were mixed uniformly, and the reaction was carried out at a speed of 150 r / min and a temperature of 45°C for 5 hours to obtain an additive; Step B4: The additive, pretreated polysiloxane, sodium trifluoromethanesulfonate and DMF were mixed, and the reaction was carried out at a speed of 300 r / min and a temperature of 80°C for 4 hours to obtain a modified polysiloxane. The modified polysiloxane, palladium carbon catalyst, triethylamine and DMF were mixed evenly, hydrogen was introduced to maintain the pressure at 1 MPa, and the reaction was carried out at a speed of 120 r / min and a temperature of 45°C for 4 hours to obtain a modified additive.

[0028] The amount ratio of 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide, epichlorohydrin and boron trifluoride etherate described in step B1 is 36mmol:18mmol:1g, and the amount of tetrabutylammonium bromide is 3% of the mass of epichlorohydrin.

[0029] The molar ratio of tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, and 1,3-bis(aminopropyl)tetramethyldisiloxane described in step B2 is 2:1.5:1, and the molar ratio of diamine-terminated polysiloxane, modifier, and aluminum chloride is 1:4:3.8.

[0030] The molar ratio of p-nitrobromobenzene, triethyl phosphite and potassium iodide in step B3 is 1:1.2:0.5, the amount ratio of intermediate 1, hydrochloric acid, ethanol and deionized water is 1mmol:2mmol:2mL:2mL, and the molar ratio of intermediate 2 and phosphorus pentachloride is 1:2.5.

[0031] The molar ratio of the additive in step B4 to the pretreated polysiloxane is 1:2, the amount of sodium trifluoromethanesulfonate is 2.5% of the mass of the pretreated polysiloxane, and the amount ratio of modified polysiloxane, palladium carbon catalyst, triethylamine and DMF is 10 mmol:200 mg:1 mg:80 mL.

[0032] Example 3, a method for preparing a fireproof glass fiber composite material, specifically comprising the following steps: Step A1: calcining glass fiber in a muffle furnace at 550°C for 1.5 hours, cooling the mixture, mixing it with concentrated sulfuric acid and hydrogen peroxide, and soaking it at 25°C for 1.5 hours. The filtrate was filtered to remove the pretreated glass cellulose. The pretreated glass fiber was dispersed in ethanol and stirred at 300 r / min and 70°C. KH570 and deionized water were added and reacted for 5 hours to produce modified glass fiber. Step A2: Disperse the modified glass fiber in DMF, introduce nitrogen protection, stir and add chloroplatinic acid and modification additives at a speed of 300 r / min and a temperature of 80°C, and react for 6 hours to obtain a modified filler. Mix the modified filler, caprolactam, deionized water and DMF evenly, react for 3 hours at a speed of 200 r / min, a temperature of 230°C and a pressure of 2.0 MPa, then release the pressure to normal pressure, raise the temperature to 260°C, and continue the reaction for 1.5 hours to obtain a fire-resistant glass fiber composite material.

[0033] The amount ratio of the glass fiber, concentrated sulfuric acid and hydrogen peroxide described in step A1 is 2g:7mL:3mL, the mass fraction of concentrated sulfuric acid is 98%, and the amount ratio of the pretreated glass fiber, ethanol, KH570 and deionized water is 2g:20mL:1mL:2mL.

[0034] The mass ratio of the modified glass fiber and the modified additive described in step A2 is 1:10, and the amount ratio of the modified filler, caprolactam and deionized water is 8g:100g:3mL.

[0035] The modified additive is prepared by the following steps: Step B1: 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide, epichlorohydrin, boron trifluoride etherate, and tetrahydrofuran were uniformly mixed and reacted at a speed of 200 r / min and a temperature of 70° C. for 3 h. Then, sodium carbonate was added to a pH of 8. The temperature was raised to 80° C., and tetrabutylammonium bromide was added. The reaction was continued for 5 h to prepare a modifier. Step B2: Tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(aminopropyl)tetramethyldisiloxane, and dimethyl sulfoxide were mixed, nitrogen was introduced, and the mixture was reacted at a speed of 80 r / min and a temperature of 105° C. for 10 hours to obtain a diamine-terminated polysiloxane. The diamine-terminated polysiloxane, the modifier, and DMF were mixed uniformly, nitrogen was introduced, aluminum chloride was added, and the mixture was stirred at a speed of 200 r / min and a temperature of 60° C. for 3 hours to obtain a pretreated polysiloxane. Step B3: p-Nitrobromobenzene, triethyl phosphite and DMF were mixed uniformly, stirred and potassium iodide was added at a speed of 150 r / min and a temperature of 140°C, and the reaction was carried out for 8 hours to obtain intermediate 1. Intermediate 1, hydrochloric acid, ethanol and deionized water were mixed uniformly, and the reaction was carried out at a speed of 300 r / min and a temperature of 65°C for 6 hours to obtain intermediate 2. Intermediate 2, phosphorus pentachloride and dichloromethane were mixed uniformly, and the reaction was carried out at a speed of 200 r / min and a temperature of 50°C for 6 hours to obtain an additive; Step B4: The additive, pretreated polysiloxane, sodium trifluoromethanesulfonate and DMF were mixed, and the reaction was carried out at a speed of 300 r / min and a temperature of 85°C for 5 hours to obtain a modified polysiloxane. The modified polysiloxane, palladium carbon catalyst, triethylamine and DMF were mixed evenly, hydrogen was introduced to maintain the pressure at 1 MPa, and the reaction was carried out at a speed of 150 r / min and a temperature of 50°C for 5 hours to obtain a modified additive.

[0036] The amount ratio of 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide, epichlorohydrin and boron trifluoride etherate described in step B1 is 36mmol:18mmol:1g, and the amount of tetrabutylammonium bromide is 3% of the mass of epichlorohydrin.

[0037] The molar ratio of tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, and 1,3-bis(aminopropyl)tetramethyldisiloxane described in step B2 is 2:1.5:1, and the molar ratio of diamine-terminated polysiloxane, modifier, and aluminum chloride is 1:4:3.8.

[0038] The molar ratio of p-nitrobromobenzene, triethyl phosphite and potassium iodide in step B3 is 1:1.2:0.5, the amount ratio of intermediate 1, hydrochloric acid, ethanol and deionized water is 1mmol:2mmol:2mL:2mL, and the molar ratio of intermediate 2 and phosphorus pentachloride is 1:2.5.

[0039] The molar ratio of the additive in step B4 to the pretreated polysiloxane is 1:2, the amount of sodium trifluoromethanesulfonate is 2.5% of the mass of the pretreated polysiloxane, and the amount ratio of modified polysiloxane, palladium carbon catalyst, triethylamine and DMF is 10 mmol:200 mg:1 mg:80 mL.

[0040] Comparative Example 1: Compared with Example 1, propylene oxide was used instead of the modifier, and the remaining steps were the same.

[0041] Comparative Example 2: Compared with Example 1, this comparative example uses phenylphosphonyl dichloride instead of the additive, and uses the reaction product of the additive and pretreated polysiloxane instead of the modified polysiloxane. The remaining steps are the same.

[0042] Comparative Example 3: Compared with Example 1, this comparative example uses glass fiber instead of modified fiber, and the glass fiber, modified additive and caprolactam reaction product instead of composite material, and the remaining steps are the same.

[0043] The composite materials prepared in Examples 1-3 and Comparative Examples 1-3 were made into 125 mm × 13 mm × 10 mm specimens according to the standard of GB / T2408-2008, and the vertical burning grade was tested. The composite materials prepared in Examples 1-3 and Comparative Examples 1-3 were made into 130 mm × 10 mm × 10 mm specimens according to the standard of GB / T2406.2-2009, and the limiting oxygen index was tested. The test results are shown in Table 1 below.

[0044] Table 1

[0045] It can be seen from the above table that this application has a very good flame retardant and fireproof effect.

[0046] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a fireproof glass fiber composite material, characterized in that: The specific steps include: Step A1: calcining glass fibers in a muffle furnace, cooling, and soaking them in a mixture of concentrated sulfuric acid and hydrogen peroxide. The filtrate is filtered to remove pretreated glass cellulose. The pretreated glass fibers are dispersed in ethanol, stirred, and KH570 and deionized water are added to react to produce modified glass fibers. Step A2: Dispersing the modified glass fiber in DMF, introducing nitrogen protection, stirring, and adding chloroplatinic acid and a modification additive to react to obtain a modified filler. After mixing the modified filler, caprolactam, deionized water, and DMF for reaction, the pressure is released to normal pressure, and the temperature is increased to continue the reaction to obtain a fire-resistant glass fiber composite material.

2. The method for preparing a fireproof glass fiber composite material according to claim 1, characterized in that: The amount ratio of the glass fiber, concentrated sulfuric acid and hydrogen peroxide described in step A1 is 2g:7mL:3mL, and the amount ratio of the pretreated glass fiber, ethanol, KH570 and deionized water is 2g:20mL:1mL:2mL.

3. The method for preparing a fireproof glass fiber composite material according to claim 1, characterized in that: The mass ratio of the modified glass fiber and the modified additive described in step A2 is 1:10, and the amount ratio of the modified filler, caprolactam and deionized water is 8g:100g:3mL.

4. The method for preparing a fireproof glass fiber composite material according to claim 1, characterized in that: The modified additive is prepared by the following steps: Step B1: 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide, epichlorohydrin, boron trifluoride etherate, and tetrahydrofuran are mixed for reaction, sodium carbonate is added until the pH is 8, the temperature is increased, tetrabutylammonium bromide is added, and the reaction is carried out to prepare a modifier; Step B2: Tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(aminopropyl)tetramethyldisiloxane, and dimethyl sulfoxide are mixed, nitrogen is introduced, and the mixture is reacted to obtain a diamine-terminated polysiloxane. The diamine-terminated polysiloxane, a modifier, and DMF are uniformly mixed, nitrogen is introduced, aluminum chloride is added, and the mixture is reacted to obtain a pretreated polysiloxane. Step B3: p-nitrobromobenzene, triethyl phosphite, and DMF are mixed and stirred, and potassium iodide is added to react to obtain intermediate 1, intermediate 1 is mixed with hydrochloric acid, ethanol, and deionized water to obtain intermediate 2, and intermediate 2, phosphorus pentachloride, and dichloromethane are mixed to obtain an additive; Step B4: The additive, pretreated polysiloxane, sodium trifluoromethanesulfonate and DMF are mixed and reacted to obtain modified polysiloxane. The modified polysiloxane, palladium carbon catalyst, triethylamine and DMF are mixed evenly and reacted under a hydrogen atmosphere to obtain a modified additive.

5. The method for preparing a fireproof glass fiber composite material according to claim 4, characterized in that: The amount ratio of 4-hydroxymethyl-2,6,7-trioxo-1-phosphabicyclo[2.2.2]octane 1-oxide, epichlorohydrin and boron trifluoride etherate described in step B1 is 36mmol:18mmol:1g.

6. The method for preparing a fireproof glass fiber composite material according to claim 4, characterized in that: The molar ratio of tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, and 1,3-bis(aminopropyl)tetramethyldisiloxane described in step B2 is 2:1.5:1, and the molar ratio of diamine-terminated polysiloxane, modifier, and aluminum chloride is 1:4:3.

8.

7. The method for preparing a fireproof glass fiber composite material according to claim 4, characterized in that: The molar ratio of p-nitrobromobenzene, triethyl phosphite and potassium iodide in step B3 is 1:1.2:0.5, the amount ratio of intermediate 1, hydrochloric acid, ethanol and deionized water is 1mmol:2mmol:2mL:2mL, and the molar ratio of intermediate 2 and phosphorus pentachloride is 1:2.

5.

8. The method for preparing a fireproof glass fiber composite material according to claim 4, characterized in that: The molar ratio of the additive in step B4 to the pretreated polysiloxane is 1:2, and the amount ratio of the modified polysiloxane, palladium carbon catalyst, triethylamine and DMF is 10 mmol:200 mg:1 mg:80 mL.

9. A fireproof glass fiber composite material, characterized by: Prepared according to any one of claims 1 to 8.

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