A phenol-formaldehyde resin foam material and a method for producing the same

Abstract

The present application provides a kind of phenolic resin foamed material and its preparation method, the phenolic resin foamed material includes the following weight parts components: 60-80 parts phenolic resin, 6-8 parts curing agent, 5-7 parts crosslinking toughening agent, 3-5 parts polyisocyanate, 4-8 parts inorganic filler, 2-5 parts foaming agent and 1 part bubble uniformizing agent, wherein crosslinking toughening agent is the soy-based compound with a large number of cardanol branches, the large number of hydroxyl groups on the multi-branch structure in crosslinking toughening agent can react with isocyanate so that crosslinking toughening agent participates in the curing process of phenolic resin, crosslinking chain extension reaction occurs, a complex interpenetrating network structure is formed, the toughness of the phenolic resin foamed material is effectively improved, and due to the introduction of flexible segment in rigid phenolic resin molecule, the toughness of phenolic resin is effectively improved, and the flame retardant performance is effectively reduced due to the addition of toughening agent.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of phenolic resin, in particular to a kind of phenolic resin foamed material and preparation method thereof. BACKGROUND

[0002] Phenolic resin is a commonly used resin variety, because its foamed body has the characteristics of light weight, low toxicity, flame retardant, low smoke, heat insulation and high and low temperature resistance, it is more and more widely used in chemical industry, transportation, energy, aerospace and other fields, but the traditional phenolic foam prepared by phenol and formaldehyde usually has the problems of high content of rigid molecular structure of aromatic ring, high brittleness, easy pulverization and easy smoldering, in order to improve these problems, usually add toughening agent in phenolic resin foaming base material, to enhance the toughness of phenolic foam;

[0003] The commonly used toughening modification method of phenolic resin foamed material is external toughening and internal toughening, external toughening is a physical blending method, after synthesizing ordinary phenolic resin, external toughening agent is added in the system, to achieve the effect of toughening of phenolic resin foamed material by blending, common external toughening agent includes rubber elastomer, polyethylene glycol, ethylene glycol and inorganic filler, internal toughening is through chemical reaction of phenolic resin and toughening agent, phenolic hydroxyl and hydroxymethyl and flexible chain graft copolymerization, to obtain internally toughened phenolic resin, then dehydrate and foam, to achieve the effect of toughening, common internal toughening agent includes polyurethane prepolymer containing reaction group and phenol containing flexible chain, but no matter which toughening method, usually because of the addition of toughening agent, the mechanical properties and flame retardant properties of phenolic resin foamed material are reduced. SUMMARY

[0004] In order to solve the above problems, the purpose of the present application is to provide a kind of phenolic resin foamed material and preparation method thereof.

[0005] The purpose of the present application can be realized by the following technical scheme: a kind of phenolic resin foamed material includes the following components by weight: 60-80 parts of phenolic resin, 6-8 parts of curing agent, 5-7 parts of crosslinking toughening agent, 3-5 parts of polyisocyanate, 4-8 parts of inorganic filler, 2-5 parts of foaming agent and 1 part of bubble uniformizer;

[0006] The phenolic resin foamed material is prepared by the following steps:

[0007] The thermosetting phenolic resin, inorganic filler, foaming agent and bubble uniformizer are added into a high-speed mixer and stirred and mixed to obtain a mixture, then the crosslinking toughening agent, polyisocyanate and curing agent are added into the mixture and stirred uniformly, then transferred into a mold for molding to obtain the phenolic resin foamed material;

[0008] The crosslinking toughening agent is prepared by the following steps:

[0009] A1: add cardanol and formic acid into a container, stir and reduce the system to 0°C, slowly add hydrogen peroxide solution, react for 24 h at a stirring rate of 100-150 rpm and a temperature of 0°C, extract with ethyl acetate, wash the organic phase with deionized water until neutral, dry with anhydrous sodium sulfate, and spin to obtain intermediate 1; the mass concentration of the hydrogen peroxide solution is 30%, and the dosages of cardanol, hydrogen peroxide solution and formic acid are 50-60 g: 30-35 mL: 5-6 g;

[0010] During the reaction, the double bond in the cardanol is epoxidized by the hydrogen peroxide to form an epoxy group, and the intermediate 1 is as shown in the figure;

[0011]

[0012] A2: add DOPO and 4-aminobenzophenone into a container, stir and mix, react for 3-4 h at a stirring rate of 100-200 rpm and a temperature of 190°C, cool to 100°C, then add toluene, filter, wash three times with toluene, and dry at 80°C under vacuum for 12 h to obtain intermediate 2; the dosages of DOPO, 4-aminobenzophenone and toluene are 1 mol: 0.4-0.5 mol: 10 mL;

[0013] During the reaction, the DOPO group is introduced by the reaction of DOPO with the carbonyl group in the 4-aminobenzophenone, and the intermediate 2 is as shown in the figure;

[0014]

[0015] A3: add intermediate 1 into N,N-dimethylacetamide, stir and mix, add intermediate 2, react for 4-6 h at a stirring rate of 100-200 rpm and a temperature of 50°C, and spin to obtain intermediate 3; the dosages of intermediate 1, intermediate 2 and N,N-dimethylacetamide are 20 g: 10-20 g: 100-150 mL;

[0016] During the reaction, the amino group in the intermediate 2 undergoes ring-opening reaction with the epoxy group in the intermediate, and the intermediate 3 is as shown in the figure;

[0017]

[0018] A4: Intermediate 3 and anhydrous zinc chloride are added into a container, stirred and warmed to 90℃, then slowly drop epoxy chloropropane, stirred and add sodium hydroxide solution, react for 3-4h under the condition of stirring rate of 200-300rpm and 95-100℃, filter, wash with deionized water for three times, vacuum dry at 80℃ for 12h to obtain intermediate 4, the mass concentration of sodium hydroxide solution is 1g / mL, the dosage ratio of intermediate 4, epoxy chloropropane, anhydrous zinc chloride and sodium hydroxide solution is 0.5mol: 0.8-1mol: 0.1-0.2g: 30mL;

[0019] During the reaction, the phenolic hydroxyl group in intermediate 3 reacts with epoxy chloropropane to introduce an epoxy group, and intermediate 4 is as shown in the figure;

[0020]

[0021] A5: Intermediate 4 and 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane are added into N,N-dimethylacetamide, stirred and mixed, and sodium hydroxide solution is added to react for 12-14h under the condition of stirring rate of 100-200rpm and 80℃, then rotary evaporation is performed to obtain intermediate 5, the mass concentration of sodium hydroxide solution is 10%, and the dosage ratio of intermediate 4, 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, sodium hydroxide solution and N,N-dimethylacetamide is 50g: 10-20g: 10-15mL: 200-300mL;

[0022] During the reaction, the epoxy group in intermediate 4 reacts with the amino group in 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and intermediate 5 is as shown in the figure;

[0023]

[0024] A6: Under the condition of nitrogen protection, intermediate 5, triphenylphosphine and epoxidized soybean oil are added into a container to react for 48-72h under the condition of stirring rate of 50-100rpm and 120℃ to obtain a crosslinking toughening agent, and the dosage ratio of intermediate 5, epoxidized soybean oil and triphenylphosphine is 60g: 40-50g: 2-3g;

[0025] During the reaction, the hydroxyl group in intermediate 5 reacts with the epoxy group in epoxidized soybean oil to obtain a crosslinking toughening agent, and the crosslinking toughening agent is as shown in the figure;

[0026]

[0027] Further, the phenolic resin is a thermosetting phenolic resin;

[0028] Further, the curing agent is at least one of benzene sulfonic acid, p-toluene sulfonic acid and acetic acid;

[0029] Further, the inorganic filler is at least one of calcium carbonate, barium carbonate and magnesium carbonate;

[0030] Further, the foaming agent is n-pentane;

[0031] Further, the cell stabilizer is at least one of Tween-60 and Tween-80;

[0032] The application has the following beneficial effects: the phenolic resin foaming material is prepared, the crosslinking toughening agent is obtained by modifying the toughening agent, and the crosslinking toughening agent is added into the base material, so that the toughness of the phenolic resin foaming material is effectively improved, and the problem of the decline of the flame retardant performance caused by the addition of the toughening agent is solved; the crosslinking toughening agent is obtained by the reaction of the hydroxyl group in the intermediate 5 and the epoxy group in the epoxy soybean oil, and is a soybean-based compound with a large number of cardanol branches, and a large number of hydroxyl groups on the multi-branch structure of the crosslinking toughening agent can react with isocyanate to make the crosslinking toughening agent participate in the curing process of the phenolic resin, crosslinking chain extension reaction occurs, a complex interpenetrating network structure is formed, the toughness of the phenolic resin foaming material is effectively improved, and due to the introduction of the flexible segment into the rigid phenolic resin molecule, the toughness of the phenolic resin is effectively improved, and the apparent molar mass of the phenolic resin is increased, the cell of the phenolic resin foaming material is more compact, and the mechanical properties are improved, and the siloxane is introduced by the reaction of the intermediate 4 and 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, the introduction of the siloxane group makes it participate in the curing process of the phenolic resin, the toughness of the phenolic resin is improved, and the siloxane group also has a certain flame retardant effect, the epoxy group is introduced by the reaction of the intermediate 3 and the epichlorohydrin, the intermediate 3 is obtained, the intermediate 1 reacts with the intermediate 2 to obtain the intermediate 3, the nitrogen-phosphorus flame retardant system is introduced, the nitrogen-phosphorus flame retardant and the siloxane form a composite flame retardant system, the composite flame retardant system forms a dense flame-retardant carbon layer when burning, and the decline of the flame retardant performance caused by the addition of the crosslinking toughening agent is effectively improved. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application. Embodiment 1

[0034] The crosslinking toughening agent is prepared by the following steps:

[0035] A1: cashew phenol and formic acid are added into a container, stirred and the system is reduced to 0°C, hydrogen peroxide solution is slowly added dropwise, the reaction is carried out at a stirring rate of 100 rpm and a temperature of 0°C for 24 h, ethyl acetate is used for extraction, the organic phase is washed with deionized water until neutral, dried with anhydrous sodium sulfate, and rotary evaporated to obtain intermediate 1, the mass concentration of hydrogen peroxide solution is 30%, the amount ratio of cashew phenol, hydrogen peroxide solution and formic acid is 50 g: 30 mL: 5 g;

[0036] A2: DOPO and 4-aminobenzophenone are added into a container, stirred and mixed, the reaction is carried out at a stirring rate of 100 rpm and a temperature of 190°C for 3 h, cooled to 100°C, then toluene is added, filtered, washed with toluene for three times, and dried at 80°C under vacuum for 12 h to obtain intermediate 2, the amount ratio of DOPO, 4-aminobenzophenone and toluene is 1 mol: 0.4 mol: 10 mL;

[0037] A3: intermediate 1 is added into N,N-dimethylacetamide, stirred and mixed, then intermediate 2 is added, the reaction is carried out at a stirring rate of 100 rpm and a temperature of 50°C for 4 h, and rotary evaporated to obtain intermediate 3, the amount ratio of intermediate 1, intermediate 2 and N,N-dimethylacetamide is 20 g: 10 g: 100 mL;

[0038] A4: intermediate 3 and anhydrous zinc chloride are added into a container, stirred and heated to 90°C, then epichlorohydrin is slowly added dropwise, stirred and sodium hydroxide solution is added, the reaction is carried out at a stirring rate of 200 rpm and a temperature of 95°C for 3 h, filtered, washed with deionized water for three times, and dried at 80°C under vacuum for 12 h to obtain intermediate 4, the mass concentration of sodium hydroxide solution is 1 g / mL, the amount ratio of intermediate 4, epichlorohydrin, anhydrous zinc chloride and sodium hydroxide solution is 0.5 mol: 0.8 mol: 0.1 g: 30 mL;

[0039] A5: intermediate 4 and 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane are added into N,N-dimethylacetamide, stirred and mixed, then sodium hydroxide solution is added, the reaction is carried out at a stirring rate of 100 rpm and a temperature of 80°C for 12 h, and rotary evaporated to obtain intermediate 5, the mass concentration of sodium hydroxide solution is 10%, the amount ratio of intermediate 4, 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, sodium hydroxide solution and N,N-dimethylacetamide is 50 g: 10 g: 10 mL: 200 mL;

[0040] A6: under the condition of nitrogen protection, intermediate 5, triphenylphosphine and epoxidized soybean oil are added into a container, the reaction is carried out at a stirring rate of 50 rpm and a temperature of 120°C for 48 h to obtain a crosslinking toughening agent, the amount ratio of intermediate 5, epoxidized soybean oil and triphenylphosphine is 60 g: 40 g: 2 g; Example 2

[0041] The cross-linking toughening agent is made by the following steps:

[0042] A1: cashew phenol and formic acid are added to a container, stirred and the system is reduced to 0°C, a hydrogen peroxide solution is slowly added dropwise, the reaction is carried out at a stirring rate of 150 rpm and a temperature of 0°C for 24 h, ethyl acetate is extracted, the organic phase is washed with deionized water until neutral, dried with anhydrous sodium sulfate, and rotary evaporated to obtain intermediate 1, the mass concentration of the hydrogen peroxide solution is 30%, the amount ratio of cashew phenol, hydrogen peroxide solution and formic acid is 50 g:30 mL:5 g;

[0043] A2: DOPO and 4-aminobenzophenone are added to a container, stirred and mixed, the reaction is carried out at a stirring rate of 200 rpm and a temperature of 190°C for 4 h, cooled to 100°C, then toluene is added, filtered, washed with toluene three times, and dried at 80°C under vacuum for 12 h to obtain intermediate 2, the amount ratio of DOPO, 4-aminobenzophenone and toluene is 1 mol:0.4 mol:10 mL;

[0044] A3: intermediate 1 is added to N,N-dimethylacetamide, stirred and mixed, then intermediate 2 is added, the reaction is carried out at a stirring rate of 200 rpm and a temperature of 50°C for 6 h, and rotary evaporated to obtain intermediate 3, the amount ratio of intermediate 1, intermediate 2 and N,N-dimethylacetamide is 20 g:10 g:100 mL;

[0045] A4: intermediate 3 and anhydrous zinc chloride are added to a container, stirred and heated to 90°C, then epichlorohydrin is slowly added dropwise, stirred and sodium hydroxide solution is added, the reaction is carried out at a stirring rate of 300 rpm and a temperature of 100°C for 4 h, filtered, washed with deionized water three times, and dried at 80°C under vacuum for 12 h to obtain intermediate 4, the mass concentration of the sodium hydroxide solution is 1 g / mL, the amount ratio of intermediate 4, epichlorohydrin, anhydrous zinc chloride and sodium hydroxide solution is 0.5 mol:0.8 mol:0.1 g:30 mL;

[0046] A5: intermediate 4 and 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane are added to N,N-dimethylacetamide, stirred and mixed, then sodium hydroxide solution is added, the reaction is carried out at a stirring rate of 200 rpm and a temperature of 80°C for 14 h, and rotary evaporated to obtain intermediate 5, the mass concentration of the sodium hydroxide solution is 10%, the amount ratio of intermediate 4, 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, sodium hydroxide solution and N,N-dimethylacetamide is 50 g:10 g:10 mL:200 mL;

[0047] A6: under the condition of nitrogen protection, intermediate 5, triphenylphosphine and epoxidized soybean oil were added into a container, and reacted for 72 h under the condition of stirring rate of 100 rpm and 120℃ to obtain the crosslinking toughening agent, the amount ratio of intermediate 5, epoxidized soybean oil and triphenylphosphine was 60 g:40 g:2 g; Example 3

[0048] The crosslinking toughening agent was prepared by the following steps:

[0049] A1: cashew phenol and formic acid were added into a container, stirred and the system was reduced to 0℃, hydrogen peroxide solution was slowly added dropwise, and reacted for 24 h under the condition of stirring rate of 150 rpm and 0℃, extracted with ethyl acetate, washed with deionized water until the organic phase was neutral, dried with anhydrous sodium sulfate, and rotary evaporated to obtain intermediate 1, the mass concentration of hydrogen peroxide solution was 30%, the amount ratio of cashew phenol, hydrogen peroxide solution and formic acid was 60 g:35 mL:6 g;

[0050] A2: DOPO and 4-aminobenzophenone were added into a container, stirred and mixed, and reacted for 4 h under the condition of stirring rate of 200 rpm and 190℃, cooled to 100℃, then toluene was added, filtered, washed with toluene for three times, and dried at 80℃ under vacuum for 12 h to obtain intermediate 2, the amount ratio of DOPO, 4-aminobenzophenone and toluene was 1 mol:0.5 mol:10 mL;

[0051] A3: intermediate 1 was added into N,N-dimethylacetamide, stirred and mixed, and intermediate 2 was added, and reacted for 6 h under the condition of stirring rate of 200 rpm and 50℃, and rotary evaporated to obtain intermediate 3, the amount ratio of intermediate 1, intermediate 2 and N,N-dimethylacetamide was 20 g:20 g:150 mL;

[0052] A4: intermediate 3 and anhydrous zinc chloride were added into a container, stirred and heated to 90℃, then epichlorohydrin was slowly added dropwise, stirred and sodium hydroxide solution was added, and reacted for 4 h under the condition of stirring rate of 300 rpm and 100℃, filtered, washed with deionized water for three times, and dried at 80℃ under vacuum for 12 h to obtain intermediate 4, the mass concentration of sodium hydroxide solution was 1 g / mL, the amount ratio of intermediate 4, epichlorohydrin, anhydrous zinc chloride and sodium hydroxide solution was 0.5 mol:1 mol:0.2 g:30 mL;

[0053] A5: Intermediate 4 and 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane were added into N,N-dimethylacetamide, mixed under stirring, sodium hydroxide solution was added, and the mixture was reacted at 80℃ for 14h under stirring at a stirring rate of 200rpm, and intermediate 5 was obtained by rotary evaporation. The amount ratio of intermediate 4, 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, sodium hydroxide solution and N,N-dimethylacetamide was 50g:20g:15mL:300mL, and the mass concentration of sodium hydroxide solution was 10%;

[0054] A6: Intermediate 5, triphenylphosphine and epoxidized soybean oil were added into a container under the protection of nitrogen, and the mixture was reacted at 120℃ for 72h under stirring at a stirring rate of 100rpm to obtain a cross-linking toughening agent. The amount ratio of intermediate 5, epoxidized soybean oil and triphenylphosphine was 60g:50g:3g; Example 4

[0055] A phenolic resin foam material comprises the following components by weight: 60 parts of a commercially available thermosetting phenolic resin, 6 parts of a commercially available benzene sulfonic acid curing agent, 5 parts of a cross-linking toughening agent, 3 parts of a commercially available MDI polyisocyanate, 4 parts of a commercially available barium carbonate inorganic filler, 2 parts of a commercially available n-pentane foaming agent and 1 part of a commercially available Tween-60 foam stabilizer;

[0056] The phenolic resin foam material is prepared by the following steps:

[0057] The thermosetting phenolic resin, the commercially available barium carbonate inorganic filler, the commercially available n-pentane foaming agent and the commercially available Tween-60 foam stabilizer were added into a high-speed mixer and mixed under stirring to obtain a mixture. The cross-linking toughening agent, the commercially available MDI polyisocyanate and the commercially available benzene sulfonic acid curing agent were added into the mixture and stirred uniformly. The mixture was transferred into a mold and molded to obtain the phenolic resin foam material. Example 5

[0058] A phenolic resin foam material comprises the following components by weight: 80 parts of a commercially available thermosetting phenolic resin, 6 parts of a commercially available p-toluene sulfonic acid curing agent, 7 parts of a cross-linking toughening agent, 3 parts of a commercially available MDI polyisocyanate, 4 parts of a commercially available calcium carbonate inorganic filler, 2 parts of a commercially available n-pentane foaming agent and 1 part of a commercially available Tween-60 foam stabilizer;

[0059] The phenolic resin foam material is prepared by the following steps:

[0060] The thermosetting phenolic resin, the commercially available calcium carbonate inorganic filler, the commercially available n-pentane foaming agent and the commercially available Tween-60 foam stabilizer were added into a high-speed mixer and mixed under stirring to obtain a mixture. The cross-linking toughening agent, the commercially available MDI polyisocyanate and the curing agent were added into the mixture and stirred uniformly. The mixture was transferred into a mold and molded to obtain the phenolic resin foam material. Example 6

[0061] A phenolic resin foaming material comprises the following components by weight: 80 parts of a commercially available thermosetting phenolic resin, 8 parts of a curing agent, 7 parts of a cross-linking toughening agent, 5 parts of a commercially available MDI polyisocyanate, 8 parts of a commercially available magnesium carbonate inorganic filler, 5 parts of a commercially available n-pentane foaming agent, and 1 part of a commercially available Tween-80 foam stabilizer;

[0062] The phenolic resin foaming material is prepared by the following steps:

[0063] The thermosetting phenolic resin, the commercially available magnesium carbonate inorganic filler, the commercially available n-pentane foaming agent, and the commercially available Tween-80 foam stabilizer are added into a high-speed mixer and stirred and mixed to obtain a mixture. The cross-linking toughening agent, the commercially available MDI polyisocyanate, and the curing agent are added into the mixture and stirred uniformly. Then, the mixture is transferred into a mold for molding to obtain the phenolic resin foaming material.

[0064] Comparative Example 1

[0065] In the comparative example 1, the cross-linking toughening agent in the example 6 is replaced by a mixture of a commercially available FR-MPP nitrogen-phosphorus flame retardant and a commercially available PEG-100 toughening agent, wherein the weight ratio of the nitrogen-phosphorus flame retardant to the toughening agent in the mixture is 1:1. Other steps are the same as those in the example 6. The phenolic resin foaming material is prepared.

[0066] Comparative Example 2

[0067] In the comparative example 2, the cross-linking toughening agent in the example 6 is replaced by a mixture of a commercially available FR-MPP nitrogen-phosphorus flame retardant and a commercially available RM4-7081 silicone flame retardant, wherein the weight ratio of the nitrogen-phosphorus flame retardant to the silicone flame retardant in the mixture is 1:1. Other steps are the same as those in the example 6. The phenolic resin foaming material is prepared.

[0068] Comparative Example 3

[0069] In the comparative example 3, the cross-linking toughening agent in the example 6 is replaced by a mixture of a commercially available epoxy soybean oil and a commercially available cardanol, wherein the weight ratio of the epoxy soybean oil to the cardanol in the mixture is 1:1. Other steps are the same as those in the example 6. The phenolic resin foaming material is prepared.

[0070] The phenolic resin foaming materials prepared in the example 4, the example 5, the example 6, the comparative example 1, the comparative example 2, and the comparative example 3 are taken. The compression strength is determined according to GB / T 8813-2020. The bending strength is measured according to GB / T 8812.1-2007. The crushing performance is measured according to GB / T 12812-2006. The standard samples with a size of 120 mm x 10 mm x 10 mm are prepared. The limiting oxygen index test is performed according to ASTM D3801 and GB / T 2406.1-2008. The specific test results are as follows:

[0071]

[0072] From the test results of the table, comparing Example 4, Example 5 and Example 6 with Comparative Example 1, Comparative Example 2 and Comparative Example 3, it is found that the compressive strength, bending strength, crushing performance and limiting oxygen index of Example 4, Example 5 and Example 6 are obviously superior to Comparative Example 1, which indicates that the addition of the cross-linking toughening agent effectively improves the toughness of the phenolic resin foaming material, and at the same time reduces the decrease of the flame retardant performance caused by the addition of the cross-linking agent.

[0073] The above is only an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as the concept of the present application is not deviated or the scope defined by the present claims is not exceeded, which shall belong to the protection scope of the present application.

Claims

1. A phenolic resin foam material, characterized in that: It contains the following components by weight: 60-80 parts phenolic resin, 6-8 parts curing agent, 5-7 parts crosslinking toughening agent, 3-5 parts polyisocyanate, 4-8 parts inorganic filler, 2-5 parts foaming agent and 1 part foam leveling agent; The phenolic resin foam material is prepared through the following steps: Thermosetting phenolic resin, inorganic filler, foaming agent and foam leveling agent are added to a high-speed mixer and mixed to obtain a mixture. Then, crosslinking toughening agent, polyisocyanate and curing agent are added to the mixture and stirred evenly. The mixture is then transferred into a mold and molded to obtain phenolic resin foam material. The crosslinking toughening agent is prepared by the following steps: A1: Add cashew phenol and formic acid to a container, stir and lower the system to 0℃, slowly add hydrogen peroxide solution, react for 24h at a stirring rate of 100-150rpm and a temperature of 0℃, extract with ethyl acetate, wash the organic phase with deionized water until neutral, dry with anhydrous sodium sulfate, and rotary evaporate to obtain intermediate 1. A2: Add DOPO and 4-aminobenzophenone to a container, stir and mix, react for 3-4 hours at a stirring rate of 100-200 rpm and 190°C, cool to 100°C, add toluene, filter, wash three times with toluene, and dry under vacuum at 80°C for 12 hours to obtain intermediate 2. A3: Add intermediate 1 to N,N-dimethylacetamide, stir and mix, add intermediate 2, react at a stirring rate of 100-200 rpm and 50℃ for 4-6 h, and then evaporate by rotary evaporation to obtain intermediate 3. A4: Add intermediate 3 and anhydrous zinc chloride to a container, stir and heat to 90°C, then slowly add epichlorohydrin, stir and add sodium hydroxide solution, react at a stirring rate of 200-300 rpm and 95-100°C for 3-4 hours, filter, wash three times with deionized water, and vacuum dry at 80°C for 12 hours to obtain intermediate 4. A5: Intermediate 4 and 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane were added to N,N-dimethylacetamide, stirred and mixed, sodium hydroxide solution was added, and the mixture was reacted at a stirring rate of 100-200 rpm and 80 °C for 12-14 h. The mixture was then rotary evaporated to obtain intermediate 5. A6: Under nitrogen protection, intermediate 5, triphenylphosphine and epoxidized soybean oil are added to a container and reacted at a stirring rate of 50-100 rpm and 120°C for 48-72 h to obtain a crosslinking toughening agent.

2. The phenolic resin foaming material according to claim 1, characterized in that: In step A1: the mass concentration of hydrogen peroxide solution is 30%, and the ratio of cashew phenol, hydrogen peroxide solution and formic acid is 50-60g: 30-35mL: 5-6g; In step A2: the ratio of DOPO, 4-aminobenzophenone, and toluene is 1 mol: 0.4-0.5 mol: 10 mL; In step A3: the ratio of intermediate 1, intermediate 2 and N,N-dimethylacetamide is 20g: 10-20g: 100-150mL; In step A4: the mass concentration of sodium hydroxide solution is 1 g / mL, and the volume ratio of intermediate 4, epichlorohydrin, anhydrous zinc chloride and sodium hydroxide solution is 0.5 mol: 0.8-1 mol: 0.1-0.2 g: 30 mL; In step A5: the sodium hydroxide solution has a mass concentration of 10%, and the ratio of intermediate 4,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, sodium hydroxide solution and N,N-dimethylacetamide is 50g:10-20g:10-15mL:200-300mL. In step A6: the ratio of intermediate 5, epoxidized soybean oil and triphenylphosphine is 60g: 40-50g: 2-3g.

3. The phenolic resin foaming material according to claim 1, characterized in that: The phenolic resin is a thermosetting phenolic resin.

4. The phenolic resin foaming material according to claim 1, characterized in that: The curing agent is at least one of benzenesulfonic acid, p-toluenesulfonic acid, and acetic acid.

5. The phenolic resin foaming material according to claim 1, characterized in that: The inorganic filler is at least one of calcium carbonate, barium carbonate, and magnesium carbonate.

6. The phenolic resin foaming material according to claim 1, characterized in that: The foaming agent is n-pentane.

7. The phenolic resin foaming material according to claim 1, characterized in that: The foaming agent is at least one of Tween-60 and Tween-80.

8. The method for preparing a phenolic resin foam material according to claim 1, characterized in that: The process includes the following steps: adding thermosetting phenolic resin, inorganic filler, foaming agent and foam leveling agent into a high-speed mixer and mixing to obtain a mixture; then adding crosslinking toughening agent, polyisocyanate and curing agent to the mixture and mixing evenly; then transferring the mixture into a mold for compression molding to obtain phenolic resin foam material.

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