Flame-retardant phenolic resin composite material and preparation method thereof

Abstract

The invention relates to the technical field of composite materials, in particular to a flame-retardant phenolic resin composite material and a preparation method thereof. The flame-retardant phenolic resin composite material is prepared from the following raw materials in parts by weight: 00-120 parts of phenolic resin, 5-10 parts of a functional aid, 3-5 parts of a synergistic aid, 2-4 parts of an active agent, 1-3 parts of methyl phenyl silicone oil, 1-3 parts of a foaming agent and 2-5 parts of a curing agent, the preparation method comprises the following steps: adding phenolic resin, a functional aid, a synergistic aid, an active agent and methyl phenyl silicone oil into mixing equipment, mixing and stirring, adding a foaming agent and a curing agent into the mixture after the materials are uniformly mixed, and foaming and curing to obtain a finished product of the flame-retardant phenolic resin composite material. The flame-retardant phenolic resin composite material prepared by the invention not only has better mechanical properties, but also has excellent flame retardant property and antibacterial property, and the quality of the flame-retardant phenolic resin composite material is effectively ensured.

Description

Technical Field

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

[0002] Phenolic resin foam materials have occupied an important position in many fields due to their unique performance advantages. However, with the development of society and the continuous improvement of people's safety awareness, higher requirements are placed on the flame retardant properties of phenolic resin foam materials. In the event of a fire, although ordinary phenolic resin foam materials have a certain flame retardant ability, there is still a risk of combustion. Once burned, it will spread rapidly. At the same time, in the field of health and hygiene, the problems caused by the growth of microorganisms are becoming increasingly prominent. In public places, medical facilities, food processing workshops and other environments, bacteria, molds and other microorganisms are easily attached to the surface of the material, which will not only corrode the material and shorten its service life, but may also spread diseases and endanger human health.

[0003] Based on this, the present invention provides a flame retardant phenolic resin composite material and a preparation method thereof to solve the above-mentioned technical problems. Summary of the invention

[0004] The purpose of the present invention is to provide a flame retardant phenolic resin composite material and a preparation method thereof. The prepared flame retardant phenolic resin composite material not only has good mechanical properties, but also has excellent flame retardant and antibacterial properties, effectively ensuring its quality.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] The first aspect of the present invention provides a flame retardant phenolic resin composite material, which is composed of the following raw materials in parts by weight: 100 to 120 parts of phenolic resin, 5 to 10 parts of functional additives, 3 to 5 parts of synergistic additives, 2 to 4 parts of active agents, 1 to 3 parts of methylphenyl silicone oil, 1 to 3 parts of foaming agent and 2 to 5 parts of curing agent.

[0007] The present invention is further configured as follows: the preparation process of the functional additive is as follows:

[0008] The montmorillonite is placed in the first composite liquid at a dosage ratio of 0.05 to 0.1 g / mL, treated at 60 to 80° C. and 300 to 380 r / min for 5 to 6 hours, filtered, washed with deionized water for 2 to 4 times, and dried under vacuum at 60 to 70° C. to constant weight to obtain pretreated montmorillonite;

[0009] A zinc nitrate aqueous solution with a mass fraction of 8 to 10% and pretreated montmorillonite are stirred at 120 to 160 r / min for 20 to 30 minutes in a mass ratio of 0.1 to 0.4:1, and the pH value is adjusted to 8 to 10 with a sodium hydroxide solution. The mixture is allowed to stand for 2 to 4 hours, filtered, washed with deionized water for 2 to 4 times, and dried under vacuum at 60 to 70° C. to constant weight to obtain a first base material;

[0010] The first base material and the pretreated montmorillonite are placed in the second composite liquid at a mass ratio of 0.1 to 0.3:1, stirred at 120 to 160 r / min for 120 to 180 min, filtered, and then vacuum dried at 60 to 70° C. to constant weight to obtain the second base material;

[0011] The γ-aminopropyltriethoxysilane is placed in an ethanol aqueous solution with a volume fraction of 75-80% at a mass ratio of 0.05-0.1:1, and the pH value is adjusted to 4-5 with acetic acid to obtain a γ-aminopropyltriethoxysilane solution. The second base material and the γ-aminopropyltriethoxysilane solution are treated at a mass ratio of 0.08-0.12:1 at 50-60°C and 200-300r / min for 4-6h, filtered, washed with deionized water for 2-4 times, and dried under vacuum at 60-70°C to constant weight to obtain a functional additive.

[0012] The present invention is further configured as follows: the compound liquid is compounded by octadecyltrimethylammonium chloride and deionized water in a dosage ratio of 0.02 to 0.08 g / mL.

[0013] The present invention is further configured as follows: the second compound liquid is compounded by mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and acetone at a dosage ratio of 0.04 to 0.12 g / mL.

[0014] The present invention is further configured as follows: the preparation process of the synergistic aid is as follows:

[0015] The carbon nanotubes are placed in dimethyl sulfoxide at a dosage ratio of 0.01 to 0.06 g / mL and ultrasonically treated for 20 to 30 minutes, N,N'-carbonyldiimidazole in an amount of 160 to 200% of the mass of the carbon nanotubes is added thereto, and the mixture is treated at 25 to 30° C. and 400 to 450 r / min for 4 to 6 hours to obtain a first preformulation;

[0016] Treat polyethyleneimine and deionized water at a mass ratio of 0.06 to 0.1:1 at 80 to 120 r / min for 20 to 30 minutes to obtain a second preformulation;

[0017] The first preformulation is placed in the second preformulation at a mass ratio of 1:1.2-1.5, treated at 50-70°C and 300-500r / min for 20-22h, filtered, washed with deionized water for 2-4 times, and vacuum dried at 60-70°C to constant weight to obtain a synergistic additive.

[0018] The present invention is further configured as follows: the active agent is selected from any one of polyvinyl alcohol, fatty alcohol polyoxyethylene ether, and alkylphenol polyoxyethylene ether.

[0019] The present invention is further configured as follows: the foaming agent is selected from any one of n-pentane, n-hexane, and 4,4'-diphenylmethane diisocyanate.

[0020] The present invention is further configured as follows: the curing agent is prepared by mixing hydrochloric acid, ethylene glycol and water in a mass ratio of 8 to 10:1 to 2:1.

[0021] The second aspect of the present invention: also provides a method for preparing the flame retardant phenolic resin composite material, comprising the following steps:

[0022] Step 1: Accurately weigh phenolic resin, functional additives, synergistic additives, active agents, methylphenyl silicone oil, foaming agent and curing agent for later use;

[0023] Step 2: Phenolic resin, functional additives, synergistic additives, active agents and methylphenyl silicone oil are put into a mixing device for mixing and stirring. After the mixture is evenly mixed, a foaming agent and a curing agent are added thereto for foaming and curing to obtain a finished flame-retardant phenolic resin composite material.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] In the present invention, phenolic resin, functional additives, synergistic additives, active agents, methylphenyl silicone oil, foaming agents and curing agents are used as raw materials. Phenolic resin, functional additives, synergistic additives, active agents and methylphenyl silicone oil are put into a mixing device for mixing and stirring. After being evenly mixed, foaming agents and curing agents are added thereto for foaming and curing to obtain a finished flame-retardant phenolic resin composite material. The flame-retardant phenolic resin composite material prepared by the present invention not only has good mechanical properties, but also has excellent flame retardant properties and antibacterial properties, effectively ensuring its quality. The flame-retardant phenolic resin composite material and the preparation method thereof provided by the present invention have a broader market prospect and are more suitable for promotion. DETAILED DESCRIPTION

[0026] 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.

[0027] Example 1

[0028] The present embodiment provides a flame retardant phenolic resin composite material, which is composed of the following raw materials in parts by weight: 100 parts of phenolic resin, 5 parts of functional additives, 3 parts of synergistic additives, 2 parts of active agents, 1 part of methylphenyl silicone oil, 1 part of foaming agent and 2 parts of curing agent.

[0029] In this embodiment, it should be noted that the phenolic resin is S-157, which is purchased from Guangzhou Haoyun Chemical Co., Ltd.

[0030] The preparation process of the functional additive is as follows:

[0031] The montmorillonite was placed in the first composite solution at a dosage ratio of 0.05 g / mL, treated at 60° C. and 300 r / min for 5 h, filtered, washed twice with deionized water, and dried under vacuum at 60° C. to constant weight to obtain pretreated montmorillonite;

[0032] An aqueous solution of zinc nitrate with a mass fraction of 8% and pretreated montmorillonite were stirred at 120 r / min for 20 min in a mass ratio of 0.1:1, and the pH value was adjusted to 8 with a sodium hydroxide solution. The mixture was allowed to stand for 2 h, filtered, washed twice with deionized water, and dried under vacuum at 60° C. to constant weight to obtain a first base material.

[0033] The first base material and the pretreated montmorillonite were placed in the second composite liquid at a mass ratio of 0.1:1, stirred at 120 r / min for 120 min, filtered, and dried under vacuum at 60° C. to constant weight to obtain the second base material;

[0034] γ-aminopropyltriethoxysilane was placed in an ethanol aqueous solution with a volume fraction of 75% at a mass ratio of 0.05:1, and the pH value was adjusted to 4 with acetic acid to obtain a γ-aminopropyltriethoxysilane solution. The second base material and the γ-aminopropyltriethoxysilane solution were treated at a mass ratio of 0.08:1 at 50°C and 200r / min for 4h. After filtration, the mixture was washed twice with deionized water and dried under vacuum at 60°C to constant weight to obtain a functional additive.

[0035] Furthermore, the compound liquid is compounded by octadecyltrimethylammonium chloride and deionized water at a dosage ratio of 0.02 g / mL.

[0036] The second compound liquid is compounded by mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and acetone at a dosage ratio of 0.04 g / mL.

[0037] In this embodiment, it should be noted that montmorillonite was purchased from Zhejiang Fenghong New Materials Co., Ltd.

[0038] The preparation process of the synergistic agent is as follows:

[0039] The carbon nanotubes were placed in dimethyl sulfoxide at a dosage ratio of 0.01 g / mL and ultrasonically treated for 20 minutes, N,N'-carbonyldiimidazole (160% by weight of the carbon nanotubes) was added thereto, and the mixture was treated at 25° C. and 400 r / min for 4 hours to obtain a first preformulation;

[0040] Polyethyleneimine and deionized water were treated at a mass ratio of 0.06:1 at 80 r / min for 20 min to obtain a second preformulation;

[0041] The first preformulation was placed in the second preformulation at a mass ratio of 1:1.2, and treated at 50°C and 300 r / min for 20 hours. After filtration, the mixture was washed twice with deionized water and vacuum dried at 60°C to constant weight to obtain a synergistic additive.

[0042] In this embodiment, it should be noted that the carbon nanotubes were purchased from Shandong Tanfeng New Material Technology Co., Ltd.

[0043] Wherein, polyvinyl alcohol is selected as the active agent.

[0044] The blowing agent is n-pentane.

[0045] The curing agent is prepared by mixing hydrochloric acid, ethylene glycol and water in a mass ratio of 8:1:1.

[0046] In addition, this embodiment also provides a method for preparing the flame retardant phenolic resin composite material, comprising the following steps:

[0047] Step 1: Accurately weigh phenolic resin, functional additives, synergistic additives, active agents, methylphenyl silicone oil, foaming agent and curing agent for later use;

[0048] Step 2: Phenolic resin, functional additives, synergistic additives, active agents and methylphenyl silicone oil are put into a mixing device for mixing and stirring. After the mixture is evenly mixed, a foaming agent and a curing agent are added thereto for foaming and curing to obtain a finished flame-retardant phenolic resin composite material.

[0049] Example 2

[0050] The preparation method of the flame-retardant phenolic resin composite material provided in this embodiment is basically the same as that in Example 1, except that: the specific raw material composition and the specific preparation method of the flame-retardant phenolic resin composite material in this embodiment are different; the specific raw material composition and the specific preparation method of the flame-retardant phenolic resin composite material in this embodiment are as follows:

[0051] A flame retardant phenolic resin composite material is composed of the following raw materials in parts by weight: 110 parts of phenolic resin, 7 parts of functional additives, 4 parts of synergistic additives, 3 parts of active agents, 2 parts of methylphenyl silicone oil, 2 parts of foaming agents and 3 parts of curing agents.

[0052] In this embodiment, it should be noted that the phenolic resin is S-157, which is purchased from Guangzhou Haoyun Chemical Co., Ltd.

[0053] The preparation process of the functional additive is as follows:

[0054] The montmorillonite was placed in the first composite solution at a dosage ratio of 0.07 g / mL, treated at 70° C. and 340 r / min for 6 h, filtered, washed with deionized water for 3 times, and dried under vacuum at 65° C. to constant weight to obtain pretreated montmorillonite;

[0055] A 9% zinc nitrate aqueous solution and pretreated montmorillonite were stirred at 140 r / min for 25 min in a mass ratio of 0.2:1, and the pH value was adjusted to 9 with a sodium hydroxide solution. The mixture was allowed to stand for 3 h, filtered, washed with deionized water for 3 times, and dried under vacuum at 65° C. to constant weight to obtain a first base material.

[0056] The first base material and the pretreated montmorillonite were placed in the second composite liquid at a mass ratio of 0.2:1, stirred at 140 r / min for 150 min, filtered, and dried under vacuum at 65° C. to constant weight to obtain the second base material;

[0057] γ-aminopropyltriethoxysilane was placed in an ethanol aqueous solution with a volume fraction of 77% at a mass ratio of 0.07:1, and the pH value was adjusted to 5 with acetic acid to obtain a γ-aminopropyltriethoxysilane solution. The second base material and the γ-aminopropyltriethoxysilane solution were treated at a mass ratio of 0.1:1 at 55°C and 250r / min for 5h. After filtration, the mixture was washed with deionized water for 3 times, and vacuum dried at 65°C to constant weight to obtain a functional additive.

[0058] Furthermore, the compound liquid is compounded by octadecyltrimethylammonium chloride and deionized water at a dosage ratio of 0.05 g / mL.

[0059] The second compound liquid is compounded by mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and acetone at a dosage ratio of 0.08 g / mL.

[0060] In this embodiment, it should be noted that montmorillonite was purchased from Zhejiang Fenghong New Materials Co., Ltd.

[0061] The preparation process of the synergistic agent is as follows:

[0062] The carbon nanotubes were placed in dimethyl sulfoxide at a dosage ratio of 0.03 g / mL and ultrasonically treated for 25 minutes, N,N'-carbonyldiimidazole (180% of the mass of the carbon nanotubes) was added thereto, and the mixture was treated at 27° C. and 425 r / min for 5 hours to obtain a first preformulation;

[0063] Polyethyleneimine and deionized water were treated at a mass ratio of 0.08:1 at 100 r / min for 25 min to obtain a second preformulation;

[0064] The first preformulation was placed in the second preformulation at a mass ratio of 1:1.3, and treated at 60°C and 400 r / min for 21 hours. After filtration, the mixture was washed three times with deionized water and dried under vacuum at 65°C to constant weight to obtain a synergistic additive.

[0065] In this embodiment, it should be noted that the carbon nanotubes were purchased from Shandong Tanfeng New Material Technology Co., Ltd.

[0066] Among them, the active agent is fatty alcohol polyoxyethylene ether.

[0067] The foaming agent is n-hexane.

[0068] The curing agent is prepared by mixing hydrochloric acid, ethylene glycol and water in a mass ratio of 9:2:1.

[0069] In addition, this embodiment also provides a method for preparing the flame retardant phenolic resin composite material, comprising the following steps:

[0070] Step 1: Accurately weigh phenolic resin, functional additives, synergistic additives, active agents, methylphenyl silicone oil, foaming agent and curing agent for later use;

[0071] Step 2: Phenolic resin, functional additives, synergistic additives, active agents and methylphenyl silicone oil are put into a mixing device for mixing and stirring. After the mixture is evenly mixed, a foaming agent and a curing agent are added thereto for foaming and curing to obtain a finished flame-retardant phenolic resin composite material.

[0072] Example 3

[0073] The preparation method of the flame-retardant phenolic resin composite material provided in this embodiment is basically the same as that in Example 1, except that: the specific raw material composition and the specific preparation method of the flame-retardant phenolic resin composite material in this embodiment are different; the specific raw material composition and the specific preparation method of the flame-retardant phenolic resin composite material in this embodiment are as follows:

[0074] A flame retardant phenolic resin composite material is composed of the following raw materials in parts by weight: 120 parts of phenolic resin, 10 parts of functional additives, 5 parts of synergistic additives, 4 parts of active agents, 3 parts of methylphenyl silicone oils, 3 parts of foaming agents and 5 parts of curing agents.

[0075] In this embodiment, it should be noted that the phenolic resin is S-157, which is purchased from Guangzhou Haoyun Chemical Co., Ltd.

[0076] The preparation process of the functional additive is as follows:

[0077] The montmorillonite was placed in the first composite solution at a dosage ratio of 0.1 g / mL, treated at 80° C. and 380 r / min for 6 h, filtered, washed with deionized water for 4 times, and dried under vacuum at 70° C. to constant weight to obtain pretreated montmorillonite;

[0078] A 10% zinc nitrate aqueous solution and pretreated montmorillonite were stirred at 160 r / min for 30 min in a mass ratio of 0.4:1, and the pH value was adjusted to 10 with a sodium hydroxide solution. The mixture was allowed to stand for 4 h, filtered, washed with deionized water for 4 times, and dried under vacuum at 70° C. to constant weight to obtain a first base material.

[0079] The first base material and the pretreated montmorillonite were placed in the second composite liquid at a mass ratio of 0.3:1, stirred at 160 r / min for 180 min, filtered, and dried under vacuum at 70° C. to constant weight to obtain the second base material;

[0080] γ-aminopropyltriethoxysilane was placed in an ethanol aqueous solution with a volume fraction of 80% at a mass ratio of 0.1:1, and the pH value was adjusted to 5 with acetic acid to obtain a γ-aminopropyltriethoxysilane solution. The second base material and the γ-aminopropyltriethoxysilane solution were treated at a mass ratio of 0.12:1 at 60°C and 300r / min for 6h. After filtration, the mixture was washed with deionized water for 4 times and vacuum dried at 70°C to constant weight to obtain a functional additive.

[0081] Furthermore, the compound liquid is compounded by octadecyltrimethylammonium chloride and deionized water at a dosage ratio of 0.08 g / mL.

[0082] The second compound liquid is compounded by mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 0.12 g / mL of acetone.

[0083] In this embodiment, it should be noted that montmorillonite was purchased from Zhejiang Fenghong New Materials Co., Ltd.

[0084] The preparation process of the synergistic agent is as follows:

[0085] The carbon nanotubes were placed in dimethyl sulfoxide at a dosage ratio of 0.06 g / mL and ultrasonically treated for 30 minutes, and N,N'-carbonyldiimidazole (200% by weight of the carbon nanotubes) was added thereto, and the mixture was treated at 30° C. and 450 r / min for 6 hours to obtain a first preformulation;

[0086] Polyethyleneimine and deionized water were treated at a mass ratio of 0.1:1 at 120 r / min for 30 min to obtain a second preformulation;

[0087] The first preformulation was placed in the second preformulation at a mass ratio of 1:1.5, and treated at 70°C and 500 r / min for 22 hours. After filtration, the mixture was washed with deionized water for 4 times, and vacuum dried at 70°C to constant weight to obtain a synergistic additive.

[0088] In this embodiment, it should be noted that the carbon nanotubes were purchased from Shandong Tanfeng New Material Technology Co., Ltd.

[0089] Among them, the active agent is alkylphenol polyoxyethylene ether.

[0090] The foaming agent is 4,4'-diphenylmethane diisocyanate.

[0091] The curing agent is prepared by mixing hydrochloric acid, ethylene glycol and water in a mass ratio of 10:2:1.

[0092] In addition, this embodiment also provides a method for preparing the flame retardant phenolic resin composite material, comprising the following steps:

[0093] Step 1: Accurately weigh phenolic resin, functional additives, synergistic additives, active agents, methylphenyl silicone oil, foaming agent and curing agent for later use;

[0094] Step 2: Phenolic resin, functional additives, synergistic additives, active agents and methylphenyl silicone oil are put into a mixing device for mixing and stirring. After the mixture is evenly mixed, a foaming agent and a curing agent are added thereto for foaming and curing to obtain a finished flame-retardant phenolic resin composite material.

[0095] Comparative Example 1: The difference from Example 1 is that an equal amount of montmorillonite is used to replace the functional additive in this example.

[0096] Comparative Example 2: The difference from Example 1 is that in this example, an equal amount of carbon nanotubes is used to replace the synergistic aid.

[0097] Performance test: The flame retardant phenolic resin composite material samples provided in Examples 1 to 3 and Comparative Examples 1 to 2 are marked as Examples 1 to 3 and Comparative Examples 1 to 2, respectively; and the relevant properties of the flame retardant phenolic resin composite materials provided in Examples 1 to 3 and Comparative Examples 1 to 2 are tested as follows:

[0098] 1. Flame retardant test: The test method is GB / T8624-2012.

[0099] 2. Antibacterial test: The antibacterial rate was tested by immersion method, and the experimental strains were Escherichia coli and Staphylococcus aureus. The flame-retardant phenolic resin composite materials prepared in Examples 1 to 3 and Comparative Examples 1 to 2 were cut into 25 mm × 25 mm sample pieces, and the sample pieces were placed in 250 ml conical bottles containing 70 ml PBS and 5 ml bacterial suspension. The concentration of the bacterial suspension in PBS was 1 × 10 4 ~2×10 4 cfu / ml. After the sample strips were immersed in the conical flask for 1 hour, 0.5 ml of the sample solution was taken from the conical flask and diluted appropriately for agar plate culture for 24 hours, and then the viable bacteria were counted. The sample strips were not added as the negative control group.

[0100] Antibacterial rate (%) = (N 0 -N 1 ) / N 0 ×100%, where N 0 is the average colony count of the negative control group after 1 hour, N 1 It is the average colony count of the bacterial suspension in the conical flask after the sample strip has been immersed for 1 hour.

[0101] 3. Mechanical test: The test method is GB / T5486-2008.

[0102] The obtained test data are recorded in Table 1 and Table 3 below:

[0103] Table 1 Flame retardant properties test results of each group of flame retardant phenolic resin composite materials

[0104] Group Fire rating Example 1 Group A2 Example 2 Group A2 Example 3 Group A2 Comparison group 1 B1 Comparison of 2 groups B1

[0105] Table 2 Antibacterial performance test results of each group of flame retardant phenolic resin composite materials

[0106] Group Escherichia coli (%) Staphylococcus aureus (%) Example 1 Group 98.6 97.1 Example 2 Group 98.2 96.5 Example 3 Group 98.5 96.8 Comparison group 1 92.6 91.7 Comparison of 2 groups 88.8 88.2 Negative control group 0 0

[0107] Table 3 Mechanical properties test results of each group of flame retardant phenolic resin composites

[0108] Group Compressive strength(MPa) Example 1 Group 2.52 Example 2 Group 2.47 Example 3 Group 2.51 Comparison group 1 1.87 Comparison of 2 groups 1.56

[0109] By comparing and analyzing the relevant data in Table 1 and Table 3, it can be seen that the flame-retardant phenolic resin composite material prepared by the present invention not only has good mechanical properties, but also has excellent flame retardant properties and antibacterial properties, which effectively guarantees its quality. This shows that the flame-retardant phenolic resin composite material and the preparation method thereof provided by the present invention have a broader market prospect and are more suitable for promotion.

[0110] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0111] 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 phenolic resin composite material, characterized in that: The invention is composed of the following raw materials in parts by weight: 100-120 parts of phenolic resin, 5-10 parts of functional additives, 3-5 parts of synergistic additives, 2-4 parts of active agents, 1-3 parts of methylphenyl silicone oil, 1-3 parts of foaming agents and 2-5 parts of curing agents.

2. The flame retardant phenolic resin composite material according to claim 1, characterized in that: The preparation process of the functional additive is as follows: The montmorillonite is placed in the first composite liquid at a dosage ratio of 0.05 to 0.1 g / mL, treated at 60 to 80° C. and 300 to 380 r / min for 5 to 6 hours, filtered, washed with deionized water for 2 to 4 times, and dried under vacuum at 60 to 70° C. to constant weight to obtain pretreated montmorillonite; A zinc nitrate aqueous solution with a mass fraction of 8-10% and pretreated montmorillonite are stirred at 120-160 r / min for 20-30 min in a mass ratio of 0.1-0.4:1, and the pH value is adjusted to 8-10 with a sodium hydroxide solution. The mixture is allowed to stand for 2-4 h, filtered, washed with deionized water for 2-4 times, and dried under vacuum at 60-70° C. to constant weight to obtain a first base material; The first base material and the pretreated montmorillonite are placed in the second composite liquid at a mass ratio of 0.1 to 0.3:1, stirred at 120 to 160 r / min for 120 to 180 min, filtered, and then vacuum dried at 60 to 70° C. to constant weight to obtain the second base material; The γ-aminopropyltriethoxysilane is placed in an ethanol aqueous solution with a volume fraction of 75-80% at a mass ratio of 0.05-0.1:1, and the pH value is adjusted to 4-5 with acetic acid to obtain a γ-aminopropyltriethoxysilane solution. The second base material and the γ-aminopropyltriethoxysilane solution are treated at a mass ratio of 0.08-0.12:1 at 50-60°C and 200-300r / min for 4-6h, filtered, washed with deionized water for 2-4 times, and dried under vacuum at 60-70°C to constant weight to obtain a functional additive.

3. A flame retardant phenolic resin composite material according to claim 2, characterized in that: The compound liquid is prepared by compounding octadecyltrimethylammonium chloride and deionized water in a dosage ratio of 0.02 to 0.08 g / mL.

4. The flame retardant phenolic resin composite material according to claim 2, characterized in that: The second compound liquid is compounded by mixing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and acetone in a dosage ratio of 0.04 to 0.12 g / mL.

5. The flame retardant phenolic resin composite material according to claim 1, characterized in that: The preparation process of the synergistic aid is as follows: The carbon nanotubes are placed in dimethyl sulfoxide at a dosage ratio of 0.01 to 0.06 g / mL and ultrasonically treated for 20 to 30 minutes, N,N'-carbonyldiimidazole in an amount of 160 to 200% by weight of the carbon nanotubes is added thereto, and the mixture is treated at 25 to 30° C. and 400 to 450 r / min for 4 to 6 hours to obtain a first preformulation; Treat polyethyleneimine and deionized water at a mass ratio of 0.06 to 0.1:1 at 80 to 120 r / min for 20 to 30 minutes to obtain a second preformulation; The first preformulation is placed in the second preformulation at a mass ratio of 1:1.2-1.5, treated at 50-70°C and 300-500r / min for 20-22h, filtered, washed with deionized water for 2-4 times, and vacuum dried at 60-70°C to constant weight to obtain a synergistic additive.

6. The flame retardant phenolic resin composite material according to claim 1, characterized in that: The active agent is selected from any one of polyvinyl alcohol, fatty alcohol polyoxyethylene ether, and alkylphenol polyoxyethylene ether.

7. The flame retardant phenolic resin composite material according to claim 1, characterized in that: The foaming agent is selected from any one of n-pentane, n-hexane and 4,4'-diphenylmethane diisocyanate.

8. The flame retardant phenolic resin composite material according to claim 1, characterized in that: The curing agent is prepared by mixing hydrochloric acid, ethylene glycol and water in a mass ratio of 8 to 10:1 to 2:

1.

9. The method for preparing a flame-retardant phenolic resin composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step 1: Accurately weigh phenolic resin, functional additives, synergistic additives, active agents, methylphenyl silicone oil, foaming agent and curing agent for later use; Step 2: Phenolic resin, functional additives, synergistic additives, active agents and methylphenyl silicone oil are put into a mixing device for mixing and stirring. After the mixture is evenly mixed, a foaming agent and a curing agent are added thereto for foaming and curing to obtain a finished flame-retardant phenolic resin composite material.