Flame-retardant fireproof phenolic resin laminated board and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and discloses a flame-retardant fireproof phenolic resin laminated board and a preparation method thereof.The preparation method comprises the steps that phenolic resin and absolute ethyl alcohol are mixed, then a paper-based material is subjected to infiltration treatment with the prepared mixed solution and dried, and prepreg is obtained; carrying out stacking hot press molding treatment on the prepreg to obtain a phenolic resin laminated board; and spraying and drying the flame-retardant liquid on the surface of the phenolic resin laminated board to obtain the flame-retardant fireproof phenolic resin laminated board. The phenolic resin laminated board disclosed by the invention has relatively good flame-retardant and fireproof effects.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a flame retardant and fireproof phenolic resin laminate and a preparation method thereof. Background Art

[0002] Phenolic resin laminates are made of aldehyde resin as adhesive and fillers such as kraft paper, cotton cloth, asbestos cloth, glass cloth and insulating paper as base materials. They are cured after heating, pressurizing and laminating. They have good tolerance and are not easily corroded. They are widely used in electrical appliances, construction, automobiles and other fields. However, their fireproof and flame retardant effects are poor, which greatly limits their application.

[0003] For example, patent CN109651758A discloses a modified phenolic resin and a preparation method thereof, and a modified phenolic resin sheet. This invention can significantly improve the heat resistance, corrosion resistance and mechanical properties of the phenolic resin while maintaining a large anti-friction coefficient; however, the flame retardant and fireproof properties are not improved. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a flame retardant and fireproof phenolic resin laminate and a preparation method thereof. The prepared laminate product has good flame retardant and fireproof effects.

[0005] To achieve the above object, the present invention provides the following technical solution: a flame retardant and fireproof phenolic resin laminate, comprising the following weight components: 40-60 parts by weight of phenolic resin laminate, 1-1.6 parts by weight of flame retardant liquid; The flame retardant liquid is obtained by mixing a boron-modified phosphorus-containing silane and an intermediate containing a halogenamine.

[0006] Furthermore, the preparation method of the flame retardant liquid is: (1) Add DOPO to tetrahydrofuran solvent, and after it is completely dissolved, add azobisisobutyronitrile initiator and dimethoxymethylvinylsiloxane, and then heat to 60-70°C, react under nitrogen protection for 20-24 hours, and then distill under reduced pressure and dry to obtain phosphorus-modified silane; (2) Add phosphorus-modified silane and hexaboron phosphazene to tetrahydrofuran solvent, add 1.5-2 mL of hydrochloric acid with a pH of 1, react at 70-75° C. for 10-12 hours, and then distill under reduced pressure and wash with acetone to obtain boron-modified phosphorus-containing silane; In the above reaction process, the phosphorus-hydrogen bond in DOPO and the alkenyl group in dimethoxymethylvinylsiloxane undergo a lengthening reaction, and then undergo a dehydration condensation reaction with the boric acid in hexaboron phosphazene to obtain a boron-modified phosphorus-containing silane.

[0007] (3) Adding graphene oxide modified boric acid and tetramethylpiperidinol to N,N-dimethylformamide solvent, stirring and dispersing, and continuing to add anhydrous magnesium sulfate, reacting at 50-75° C. for 4-7 hours, washing and drying after completion, to obtain modified tetramethylpiperidinol; (4) Add modified tetramethylpiperidine to acetone, stir evenly, then add 4-6% sodium hypochlorite aqueous solution, stir at room temperature for 5-8 hours, filter, wash and dry to obtain a halogenamine-containing intermediate; In the above reaction process, the boric acid group in the graphene oxide-modified boric acid and the hydroxyl group in the tetramethylpiperidinol undergo an esterification reaction, introducing the secondary amine in the tetramethylpiperidinol, and then the halogen atom is introduced under the action of the sodium hypochlorite aqueous solution, thereby obtaining a halogenamine-containing intermediate; (5) Add 0.42-0.75 g of boron-modified phosphorus-containing silane, 0.6-0.8 g of the halogenated amine intermediate, and 40-52 mL of N,N-dimethylformamide solvent into a stirrer and stir to obtain a flame retardant liquid.

[0008] Furthermore, the usage ratio of DOPO, tetrahydrofuran, azobisisobutyronitrile initiator and dimethoxymethylvinylsiloxane in (1) is 6.45-6.48 g: 45-50 mL: 0.001-0.002 mol: 3.95-3.97 g.

[0009] Furthermore, the usage ratio of phosphorus-modified silane, hexaboron phosphazene and tetrahydrofuran in (2) is 0.015-0.03 mol: 0.01-0.02 mol: 40-50 mL.

[0010] Furthermore, the dosage ratio of N,N-dimethylformamide, graphene oxide modified boric acid, tetramethylpiperidinol, and anhydrous magnesium sulfate in (3) is 35-50 mL: 1.3-1.5 g: 2.4-2.8 g: 0.021-0.03 g.

[0011] Furthermore, the amount of modified tetramethylpiperidine used in (4) is 1.26-1.34 g.

[0012] Furthermore, the stirring time in (5) is 2-4 min.

[0013] Furthermore, the preparation method of the flame retardant and fireproof phenolic resin laminate is as follows: prepare a phenolic resin / anhydrous ethanol mixed solution with a mass fraction of 5wt%, then use the mixed solution to impregnate a paper-based material, dry it at 110-130°C for 20-40min to obtain a prepreg; then stack and hot-press the prepreg to obtain a phenolic resin laminate; then spray and dry the surface of the phenolic resin laminate with a flame retardant liquid to obtain a flame retardant and fireproof phenolic resin laminate.

[0014] The invention comprises the following steps: mixing phenolic resin with a mass fraction of 5wt% with anhydrous ethanol, then impregnating a paper-based material with the prepared mixed solution, and drying the mixture to obtain a prepreg; then stacking and hot pressing the prepreg to obtain a phenolic resin laminate; and then spraying a flame retardant liquid on the surface of the phenolic resin laminate and drying the laminate to obtain a flame retardant and fireproof phenolic resin laminate.

[0015] The phosphorus, silicon, nitrogen, boron and chlorine groups contained in the intermediates of boron-modified phosphorus-containing silane and halogenamine together with the graphene oxide structure constitute a fire retardant system. Graphene oxide itself has a large flame retardant effect; phosphorus can generate polyphosphoric acid and metaphosphoric acid with strong dehydration when burning. Since polyphosphoric acid and metaphosphoric acid are not easy to volatilize, they can form a dense protective layer on the surface of the laminate, thus playing a flame retardant effect. When silicon is heated, it can produce a glass-like substance on the surface of the material to isolate material transportation and energy transfer. When nitrogen is heated, it can produce non-flammable gas, which can not only dilute the concentration of flammable gas, but also take away some heat, further limiting the combustion of the material. Boron melts at high temperature to form a glass covering layer, which covers the surface of the burning material, plays a role in isolating oxygen and heat, and achieves a flame retardant effect. The chlorine atoms in it will produce hydrogen chloride gas during the thermal decomposition process. The gas can dilute the combustible gas, inhibit the combustion reaction, and capture free radicals to prevent the spread of flames, thereby improving the flame retardant properties of the material. The phenolic resin laminate of the invention has good flame retardancy and fireproofing properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a flame retardant oxygen index test chart of flame retardant and fireproof phenolic resin laminate. DETAILED DESCRIPTION

[0017] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] The preparation of hexaboron phosphazene involved in the specific implementation of the present application is based on the reference "Preparation and Application of Flame Retardant for Cotton Containing Boron / Phosphorus / Nitrogen Flame Retardant Elements": 3.48g of hexachlorophosphazene (HCCP) was dissolved in 50mL of acetone, and 3.72g of boric acid was dissolved in 50mL of aqueous solution and transferred to a dropping funnel. The molar ratio of HCCP to boric acid was 1:6. The HCCP acetone solution was poured into a three-necked flask. The three-necked flask was equipped with a nitrogen vent, a spherical condenser, a magnetic stirrer, a dropping funnel, and an oil bath with a thermometer. After nitrogen was introduced, the boric acid aqueous solution was slowly added dropwise under stirring (about 1h). After the addition was completed, the reaction was carried out at 60°C for 3h. The reacted solution was transferred to a rotary evaporator for rotary evaporation (85°C, 10min) to obtain hexaboron phosphazene.

[0019] The preparation method of graphene oxide modified boric acid is as follows: ultrasonically dispersing graphene oxide in dichlorothionyl, wherein the mass ratio of graphene oxide to dichlorothionyl is 100:24000, after being evenly dispersed, reacting at 70°C for 18 hours, after the reaction, filtering, washing with tetrahydrofuran, and vacuum drying at 60°C for 12 hours to obtain graphene chloride; ultrasonically dispersing graphene chloride in N,N-dimethylformamide, adding 4-aminophenylboric acid in a nitrogen atmosphere, wherein the mass ratio of graphene chloride, N,N-dimethylformamide and 4-aminophenylboric acid is 35:2200:100, mixing evenly, reacting at 45°C for 8 hours, after the reaction, filtering, washing with ethyl acetate, and drying at 60°C for 12 hours to obtain graphene oxide modified boric acid.

[0020] Preparation of phenolic resin laminate: bake kraft paper at 110°C for 1h, dry it for later use, and store it in a sealed bag in a dry environment; prepare a phenolic resin / anhydrous ethanol mixed solution with an anhydrous ethanol mass fraction of 5wt%; evenly apply a layer of the above phenolic resin mixed solution on both sides of the dried kraft paper, let it stand until the phenolic resin completely soaks the kraft paper; bake the soaked kraft paper at 110°C for a certain time of 30min, take it out after drying, and cool it at room temperature; cut off the edges of the dried and cooled prepregs, and cut them into the same size; turn on the flat vulcanizer, set the temperature to 120°C, and adjust the pressure to 2MPa; stack the cut 6 prepregs Place it on an iron plate, and press three iron plates on the prepreg. The prepreg and the iron plate are separated by ten pieces of paper, and the prepreg and the paper are separated by a PET polyester film to prevent adhesion; the first curing hot pressing process: after the flat plate vulcanizer is heated to 120°C, the material is placed between the middle and lower plates of the flat plate vulcanizer, and the motor is turned on. After the iron plate contacts the middle plate of the flat plate vulcanizer and before it contacts the upper plate, the motor is turned off. The gravity of the iron plate and the middle plate of the flat plate vulcanizer is used as the first curing pressure, and the heat is kept for 20 minutes; the second curing hot pressing process: after the first stage of the heat preservation process is completed, the flat plate vulcanizer motor is turned on, the temperature is adjusted to 160°C, and the heat is kept for 15 minutes. After the end, the formed laminate is taken out to obtain a phenolic resin laminate.

[0021] Example 1 A flame retardant and fireproof phenolic resin laminate comprises the following weight components: 40 parts by weight of phenolic resin laminate and 1 part by weight of flame retardant liquid.

[0022] The preparation method of the flame retardant liquid is: (1) Add 6.45 g of DOPO into 45 mL of tetrahydrofuran solvent, and after it is completely dissolved, add 0.001 mol of azobisisobutyronitrile initiator and 3.95 g of dimethoxymethylvinylsiloxane, then heat to 60 °C and react for 20 h under nitrogen protection. After the reaction, perform vacuum distillation and dry to obtain phosphorus-modified silane; (2) Add 0.015 mol of phosphorus-modified silane and 0.01 mol of hexaboron phosphazene into 40 mL of tetrahydrofuran solvent, add 1.5 mL of hydrochloric acid with a pH of 1, react at 70 °C for 10 h, and then perform vacuum distillation after reaction, wash with acetone to obtain boron-modified phosphorus-containing silane; (3) Add 1.3 g of graphene oxide modified boric acid and 2.4 g of tetramethylpiperidinol to 35 mL of N,N-dimethylformamide solvent, stir and disperse, continue to add 0.021 g of anhydrous magnesium sulfate, react at 50 ° C for 4 h, wash and dry after completion, and obtain modified tetramethylpiperidinol; (4) Add 1.26 g of modified tetramethylpiperidine to acetone, stir evenly, then add 3 mL of a 4% sodium hypochlorite aqueous solution, stir at room temperature for 5 h, filter, wash and dry to obtain a halogenamine-containing intermediate; (5) Add 0.42 g of boron-modified phosphorus-containing silane, 0.6 g of the halogenated amine intermediate, and 40 mL of N,N-dimethylformamide solvent into a stirrer and stir for 2 min to obtain a flame retardant liquid.

[0023] The preparation method of the flame retardant and fireproof phenolic resin laminate is as follows: A phenolic resin / anhydrous ethanol mixed solution with a mass fraction of 5wt% is prepared, and then a paper-based material is impregnated with the mixed solution, and dried at 110°C for 20 minutes to obtain a prepreg; the prepreg is then stacked and hot-pressed to obtain a phenolic resin laminate; and a flame retardant liquid is sprayed on the surface of the phenolic resin laminate and then dried to obtain a flame-retardant and fireproof phenolic resin laminate.

[0024] Example 2 A flame retardant and fireproof phenolic resin laminate comprises the following weight components: 60 parts by weight of phenolic resin laminate and 1.6 parts by weight of flame retardant liquid.

[0025] The preparation method of the flame retardant liquid is: (1) Add 6.48 g of DOPO into 50 mL of tetrahydrofuran solvent, and after it is completely dissolved, add 0.002 mol of azobisisobutyronitrile initiator and 3.97 g of dimethoxymethylvinylsiloxane, then heat to 70 ° C, react under nitrogen protection for 24 h, and then distill under reduced pressure and dry to obtain phosphorus-modified silane; (2) Add 0.03 mol of phosphorus-modified silane and 0.02 mol of hexaboron phosphazene into 50 mL of tetrahydrofuran solvent, add 2 mL of hydrochloric acid with a pH of 1, react at 75 °C for 12 h, and then perform vacuum distillation after reaction, wash with acetone, and obtain boron-modified phosphorus-containing silane; (3) Add 1.5 g of graphene oxide modified boric acid and 2.8 g of tetramethylpiperidinol to 50 mL of N,N-dimethylformamide solvent, stir and disperse, continue to add 0.03 g of anhydrous magnesium sulfate, react at 75 ° C for 7 h, wash and dry after completion, and obtain modified tetramethylpiperidinol; (4) Add 1.34 g of modified tetramethylpiperidine to acetone, stir evenly, then add 4 mL of a 6% sodium hypochlorite aqueous solution, stir at room temperature for 8 h, filter, wash and dry to obtain a halogenamine-containing intermediate; (5) Add 0.75 g of boron-modified phosphorus-containing silane, 0.8 g of the halogenated amine intermediate, and 52 mL of N,N-dimethylformamide solvent into a stirrer and stir for 4 min to obtain a flame retardant liquid.

[0026] The preparation method of the flame retardant and fireproof phenolic resin laminate is as follows: A phenolic resin / anhydrous ethanol mixed solution with a mass fraction of 5wt% is prepared, and then a paper-based material is impregnated with the mixed solution, and dried at 130°C for 40 minutes to obtain a prepreg; the prepreg is then stacked and hot-pressed to obtain a phenolic resin laminate; and a flame retardant liquid is sprayed on the surface of the phenolic resin laminate and then dried to obtain a flame-retardant and fireproof phenolic resin laminate.

[0027] Example 3 A flame retardant and fireproof phenolic resin laminate comprises the following components by weight: 50 parts by weight of the phenolic resin laminate and 1.3 parts by weight of a flame retardant liquid.

[0028] The preparation method of the flame retardant liquid is: (1) Add 6.46 g of DOPO into 48 mL of tetrahydrofuran solvent, and after it is completely dissolved, add 0.001 mol of azobisisobutyronitrile initiator and 3.96 g of dimethoxymethylvinylsiloxane, then heat to 65 °C and react for 22 h under nitrogen protection. After the reaction, distill under reduced pressure and dry to obtain phosphorus-modified silane; (2) Add 0.02 mol of phosphorus-modified silane and 0.02 mol of hexaboron phosphazene into 45 mL of tetrahydrofuran solvent, add 1.8 mL of hydrochloric acid with a pH of 1, react at 72 °C for 11 h, and then distill under reduced pressure and wash with acetone to obtain boron-modified phosphorus-containing silane; (3) Add 1.4 g of graphene oxide modified boric acid and 2.6 g of tetramethylpiperidinol to 40 mL of N,N-dimethylformamide solvent, stir and disperse, continue to add 0.025 g of anhydrous magnesium sulfate, react at 65 ° C for 5 h, wash and dry after completion, and obtain modified tetramethylpiperidinol; (4) Add 1.32 g of modified tetramethylpiperidine to acetone, stir evenly, then add 3.5 mL of 5% sodium hypochlorite aqueous solution, stir at room temperature for 6 h, filter, wash and dry to obtain a halogenamine-containing intermediate; (5) Add 0.65 g of boron-modified phosphorus-containing silane, 0.7 g of the halogenated amine intermediate, and 45 mL of N,N-dimethylformamide solvent into a stirrer and stir for 3 min to obtain a flame retardant liquid.

[0029] The preparation method of the flame retardant and fireproof phenolic resin laminate is as follows: A phenolic resin / anhydrous ethanol mixed solution with a mass fraction of 5wt% is prepared, and then a paper-based material is impregnated with the mixed solution, and dried at 120°C for 30 minutes to obtain a prepreg; the prepreg is then stacked and hot-pressed to obtain a phenolic resin laminate; and a flame retardant liquid is sprayed on the surface of the phenolic resin laminate and then dried to obtain a flame-retardant and fireproof phenolic resin laminate.

[0030] Example 4 A flame retardant and fireproof phenolic resin laminate comprises the following weight components: 40 parts by weight of phenolic resin laminate and 1 part by weight of flame retardant liquid.

[0031] The preparation method of the flame retardant liquid is: (1) Add 6.45 g of DOPO into 45 mL of tetrahydrofuran solvent, and after it is completely dissolved, add 0.001 mol of azobisisobutyronitrile initiator and 3.95 g of dimethoxymethylvinylsiloxane, then heat to 60 °C and react for 20 h under nitrogen protection. After the reaction, perform vacuum distillation and dry to obtain phosphorus-modified silane; (2) Add 0.015 mol of phosphorus-modified silane and 0.01 mol of hexaboron phosphazene into 40 mL of tetrahydrofuran solvent, add 1.5 mL of hydrochloric acid with a pH of 1, react at 70 °C for 10 h, distill under reduced pressure after reaction, and wash with acetone to obtain boron-modified phosphorus-containing silane; (3) Add 1.5 g of graphene oxide modified boric acid and 2.8 g of tetramethylpiperidinol to 50 mL of N,N-dimethylformamide solvent, stir and disperse, continue to add 0.03 g of anhydrous magnesium sulfate, react at 75 ° C for 7 h, wash and dry after completion, and obtain modified tetramethylpiperidinol; (4) Add 1.34 g of modified tetramethylpiperidine to acetone, stir evenly, then add 3 mL of a 6% sodium hypochlorite aqueous solution, stir at room temperature for 8 h, filter, wash and dry to obtain a halogenamine-containing intermediate; (5) Add 0.65 g of boron-modified phosphorus-containing silane, 0.7 g of the halogenated amine intermediate, and 45 mL of N,N-dimethylformamide solvent into a stirrer and stir for 3 min to obtain a flame retardant liquid.

[0032] The preparation method of the flame retardant and fireproof phenolic resin laminate is as follows: A phenolic resin / anhydrous ethanol mixed solution with a mass fraction of 5wt% is prepared, and then a paper-based material is impregnated with the mixed solution, and dried at 120°C for 30 minutes to obtain a prepreg; the prepreg is then stacked and hot-pressed to obtain a phenolic resin laminate; and a flame retardant liquid is sprayed on the surface of the phenolic resin laminate and then dried to obtain a flame-retardant and fireproof phenolic resin laminate.

[0033] Example 5 A flame retardant and fireproof phenolic resin laminate comprises the following weight components: 60 parts by weight of phenolic resin laminate and 1.6 parts by weight of flame retardant liquid.

[0034] The preparation method of the flame retardant liquid is: (1) Add 6.48 g of DOPO into 50 mL of tetrahydrofuran solvent, and after it is completely dissolved, add 0.002 mol of azobisisobutyronitrile initiator and 3.97 g of dimethoxymethylvinylsiloxane, then heat to 70 ° C, react under nitrogen protection for 24 h, and then distill under reduced pressure and dry to obtain phosphorus-modified silane; (2) Add 0.03 mol of phosphorus-modified silane and 0.02 mol of hexaboron phosphazene into 50 mL of tetrahydrofuran solvent, add 2 mL of hydrochloric acid with a pH of 1, react at 75 °C for 12 h, and then perform vacuum distillation after reaction, wash with acetone, and obtain boron-modified phosphorus-containing silane; (3) Add 1.4 g of graphene oxide modified boric acid and 2.6 g of tetramethylpiperidinol to 40 mL of N,N-dimethylformamide solvent, stir and disperse, continue to add 0.025 g of anhydrous magnesium sulfate, react at 65 ° C for 5 h, wash and dry after completion, and obtain modified tetramethylpiperidinol; (4) Add 1.32 g of modified tetramethylpiperidine to acetone, stir evenly, then add 4 mL of a 5% sodium hypochlorite aqueous solution, stir at room temperature for 6 h, filter, wash and dry to obtain a halogenamine-containing intermediate; (5) Add 0.42 g of boron-modified phosphorus-containing silane, 0.6 g of the halogenated amine intermediate, and 40 mL of N,N-dimethylformamide solvent into a stirrer and stir for 2 min to obtain a flame retardant liquid.

[0035] The preparation method of the flame retardant and fireproof phenolic resin laminate is as follows: A phenolic resin / anhydrous ethanol mixed solution with a mass fraction of 5wt% is prepared, and then a paper-based material is impregnated with the mixed solution, and dried at 110°C for 20 minutes to obtain a prepreg; the prepreg is then stacked and hot-pressed to obtain a phenolic resin laminate; and a flame retardant liquid is sprayed on the surface of the phenolic resin laminate and then dried to obtain a flame-retardant and fireproof phenolic resin laminate.

[0036] Comparative Example 1 Compared with Example 5, the difference between Comparative Example 1 and Example 5 is that hexachlorophosphazene is used instead of boron-modified phosphorus-containing silane.

[0037] Comparative Example 2 Compared with Example 5, the difference in Comparative Example 1 is that graphene oxide-modified boric acid is used instead of the halogenamine-containing intermediate.

[0038] Comparative Example 3 Compared with Example 5, the difference between this comparative example 1 and Example 5 is that hexachlorophosphazene is used instead of boron-modified phosphorus-containing silane, and graphene oxide-modified boric acid is used instead of the intermediate containing halogenamine.

[0039] Use an oxygen index tester to test the oxygen index of the material. The specific test results are as follows Figure 1 shown.

[0040] Depend on Figure 1 It can be seen that Examples 1-5 of the present invention have better flame retardant effects than Comparative Examples 1-3.

[0041] According to ISO5660 standard, a 100mm× 100mm× 4mm sample was prepared and the fire performance index was calculated in units of 10. - 2 s / (kW / m 2 ), the test results are shown in the following table.

[0042] Table 1: Fire resistance tests.

[0043]

[0044] It can be seen from Table 1 that Examples 1-5 of the present invention have better fireproofing effects than Comparative Examples 1-3.

[0045] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A flame retardant and fireproof phenolic resin laminate, characterized in that: The invention comprises the following components by weight: 40-60 parts by weight of phenolic resin laminate, 1-1.6 parts by weight of flame retardant liquid; The flame retardant liquid is obtained by mixing a boron-modified phosphorus-containing silane and an intermediate containing a halogenamine.

2. The flame retardant and fireproof phenolic resin laminate according to claim 1, characterized in that: The preparation method of the flame retardant liquid is: (1) Add DOPO to tetrahydrofuran solvent, and after it is completely dissolved, add azobisisobutyronitrile initiator and dimethoxymethylvinylsiloxane, and then heat to 60-70°C, react under nitrogen protection for 20-24 hours, and then distill under reduced pressure and dry to obtain phosphorus-modified silane; (2) Add phosphorus-modified silane and hexaboron phosphazene to tetrahydrofuran solvent, add 1.5-2 mL of hydrochloric acid with a pH of 1, react at 70-75° C. for 10-12 hours, and then distill under reduced pressure and wash with acetone to obtain boron-modified phosphorus-containing silane; (3) Adding graphene oxide modified boric acid and tetramethylpiperidinol to N,N-dimethylformamide solvent, stirring and dispersing, and continuing to add anhydrous magnesium sulfate, reacting at 50-75° C. for 4-7 hours, washing and drying after completion, to obtain modified tetramethylpiperidinol; (4) Add modified tetramethylpiperidine to acetone, stir evenly, then add 4-6% sodium hypochlorite aqueous solution, stir at room temperature for 5-8 hours, filter, wash and dry to obtain a halogenamine-containing intermediate; (5) Add 0.42-0.75 g of boron-modified phosphorus-containing silane, 0.6-0.8 g of the halogenated amine intermediate, and 40-52 mL of N,N-dimethylformamide solvent into a stirrer and stir to obtain a flame retardant liquid.

3. The flame retardant and fireproof phenolic resin laminate according to claim 2, characterized in that: The usage ratio of DOPO, tetrahydrofuran, azobisisobutyronitrile initiator and dimethoxymethylvinylsiloxane in (1) is 6.45-6.48 g: 45-50 mL: 0.001-0.002 mol: 3.95-3.97 g.

4. The flame retardant and fireproof phenolic resin laminate according to claim 2, characterized in that: The amount ratio of phosphorus-modified silane, hexaboron phosphazene and tetrahydrofuran in (2) is 0.015-0.03 mol: 0.01-0.02 mol: 40-50 mL.

5. The flame retardant and fireproof phenolic resin laminate according to claim 2, characterized in that: The dosage ratio of N,N-dimethylformamide, graphene oxide modified boric acid, tetramethylpiperidinol, and anhydrous magnesium sulfate in (3) is 35-50 mL: 1.3-1.5 g: 2.4-2.8 g: 0.021-0.03 g.

6. The flame retardant and fireproof phenolic resin laminate according to claim 2, characterized in that: The amount of modified tetramethylpiperidine used in (4) is 1.26-1.34 g.

7. The flame retardant and fireproof phenolic resin laminate according to claim 2, characterized in that: The stirring time in (5) is 2-4 minutes.

8. A method for preparing a flame retardant and fireproof phenolic resin laminate according to any one of claims 1 to 7, characterized in that: The preparation method of the flame-retardant and fireproof phenolic resin laminate is as follows: prepare a phenolic resin / anhydrous ethanol mixed solution with a mass fraction of 5wt%, then use the mixed solution to impregnate a paper-based material, dry it at 110-130°C for 20-40min to obtain a prepreg; then stack and hot-press the prepreg to obtain a phenolic resin laminate; then spray and dry the surface of the phenolic resin laminate with a flame retardant liquid to obtain a flame-retardant and fireproof phenolic resin laminate.

Images