CN108641356B - Cyclotriphosphazene polymer modified graphene/graphene-like WS2Bismaleimide composite material and preparation method thereof - Google Patents
Cyclotriphosphazene polymer modified graphene/graphene-like WS2Bismaleimide composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a cyclotriphosphazene polymer modified graphene/graphene-like WS2Firstly, the WS is ball milled by low energy and is treated by ultrasonic method2Exfoliation of graphene-like WS2Then adding the obtained product and graphene oxide into a high-temperature high-pressure reaction kettle together, adding a proper amount of hydrazine hydrate, and carrying out a one-pot hydrothermal method to prepare graphene/graphene-like WS2. Then, the precursor, hexachlorocyclotriphosphazene and branched polyethyleneimine are used as raw materials, triethylamine is used as an acid-binding agent, and an in-situ template method is utilized to prepare cyclotriphosphazene polymer modified graphene/graphene-like WS2. Finally, the composite material is prepared by mixing the diphenyl methane bismaleimide and the diallyl bisphenol A according to a certain proportion. The prepared composite material has good interface bonding strength, excellent mechanical property and tribological property.
Description
Technical Field
The invention belongs to the technical field of advanced composite material science, and relates to cyclotriphosphazene polymer modified graphene/graphene-like WS2A bismaleimide composite material and a preparation method thereof.
Background
Graphene is a novel two-dimensional layered material, and has excellent tensile strength, high flexibility, good thermal conductivity, good mechanical properties, and good electron transport properties, and thus has become a hot spot in recent years. The graphene is used as a solid lubricant, so that the friction performance of the composite material can be greatly improved. For example, Wang Han et al [ composition. part a. appl.s 67(2014)268-273] add multi-layer graphene as a filler to polyvinyl chloride to prepare composites, and the presence of multi-layer graphene was found to significantly reduce the coefficient of friction and wear rate of the composites. For another example, a solvent-free graphene nanoribbon colloid is prepared by using a hyperbranched silane coupling agent KH-560 and polyether amine, and then is added into epoxy resin to prepare a composite material. Thus, graphene or modified graphene may be used in a solid lubricant to improve the tribological properties of a polymer matrix.
However, graphene cannot be stably dispersed in a solvent due to very strong van der waals force existing between sheets, and is poor in compatibility with other materials, so that the application of graphene is severely limited. With the rise of graphene, transition metal sulfides have also begun to attract a great deal of attention because they can be exfoliated into a layered structure similar to graphene. Tungsten disulfide is a typical representative thereof, and is a compound having a hexagonal structure similar to a two-dimensional layered compound. WS2The sandwich structure is formed by a W atomic layer and two S atomic layers, each layer is formed by connecting S-W-S covalent bonds, weak van der Waals force exists between the layers, and the interlayer spacing is 0.62 nm. WS2The bonding effect between layers is relatively strong, but the bonding effect between layers is relatively weak, and the special structure makes the lubricating oil composition have wide application in lubrication. For example, Xu Shusheng et al [ Materials ]&Design,2016,93:494-502]Sb2O3And WS2The W-S-type composite coating is co-introduced to a Cu-based composite coating to prepare a wear-resistant multilayer film with excellent low friction coefficient, and the result shows that WS2-Sb2O3The wear life of the/Cu multilayer film can be as long as 1.1 multiplied by 106And (4) period. Furthermore, we have found that graphene-like WS2And graphene, and exfoliated WS2The number of layers is greatly reduced, and the graphene composite material has the appearance and the layered structure similar to those of graphene, so that the friction coefficient of the graphene composite material is lower. Thus, the present invention patent first prepares the stoneGraphene/graphene-like WS2The composite particles enable the material to have excellent friction reduction and good wear resistance. In addition, considering that the prepared nanoparticles are added to a bismaleimide resin matrix to prepare a composite material, interfacial bondability between the nanoparticles and the resin matrix is a great problem.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a cyclotriphosphazene polymer modified graphene/graphene-like WS2The bismaleimide composite material and the preparation method solve the problems that the graphene composite material is not uniformly dispersed in a polymer and has poor compatibility with bismaleimide resin.
Technical scheme
Cyclotriphosphazene polymer modified graphene/graphene-like WS2The bismaleimide composite material is characterized by comprising 0.1-20 parts of cyclotriphosphazene polymer modified graphene/graphene-like WS2The nano composite particles comprise 100 parts of diphenylmethane bismaleimide and 10-100 parts of diallyl bisphenol A.
The cyclotriphosphazene polymer modified graphene/graphene-like WS2The nano composite particles are prepared by adopting an in-situ template method to prepare cyclotriphosphazene modified graphene/graphene-like WS2Nanocomposite particles wherein: graphene and graphene-like WS2The mass ratio of the component (A) to (B) is 1 to (0.1 to 10), and the grafting ratio of the cyclotriphosphazene polymer is 0.1 to 50 percent; the cyclotriphosphazene polymer is formed by condensation polymerization of hexachlorocyclotriphosphazene and branched polyethyleneimine.
Preparation of cyclotriphosphazene polymer modified graphene/graphene-like WS of claim 1 or 22The method for preparing the bismaleimide composite material is characterized by comprising the following steps:
step 1: let WS be2Mechanically and chemically treating the NaCl dry mixture and NaCl dry mixture in a ball mill agate grinding bowl in a ratio of 1:10 for 2 hours to obtain a nano-structured product, washing the nano-structured product with water, drying the nano-structured product at 100 ℃, and then drying the nano-structured productPreparation of graphene-like WS by ultrasonic treatment for 30min2；
Step 2: mixing graphene oxide and graphene WS2Mixing and adding the materials into 100-500 mL of ethanol according to a mass ratio of 1 (0.1-10), performing ultrasonic treatment for 30min at 180W, transferring the mixture into a high-temperature high-pressure hydrothermal reaction kettle, adding 1-5 mL of hydrazine hydrate, and performing sealed reaction at 220 ℃ for 24 hours; after the obtained product is cooled to room temperature, carrying out suction filtration, washing the obtained product for a plurality of times by using deionized water and ethanol, and carrying out vacuum drying at 60 ℃ overnight to obtain the graphene/graphene-like WS2Nano composite particle rGO/GL-WS2；
And step 3: mixing rGO/GL-WS2Mixing hexachlorocyclotriphosphazene and branched polyethyleneimine according to the proportion of (0.5-3) to (1-4), adding 100-500 mL of tetrahydrofuran and 1-8 mL of triethylamine, and reacting at 25-60 ℃ for 4-10 h; then carrying out suction filtration, washing for several times by tetrahydrofuran, and carrying out vacuum drying overnight at 60 ℃ to obtain the cyclotriphosphazene polymer modified rGO/GL-WS2Is PHbP/rGO/GL-WS2；
And 4, step 4: 0.1-20 parts of PHbP/rGO/GL-WS2After 100 parts of diphenylmethane bismaleimide and 10-100 parts of diallyl bisphenol A are ultrasonically dispersed for 10-80 min under the power of 120-300W, the materials are heated and melted at the temperature of 130-150 ℃, prepolymerized for 15-80 min, poured into a preheated mold, put into a vacuum box at the temperature of 130-150 ℃, vacuumized to remove bubbles, put into an air-blast drying box for staged temperature rise curing, wherein the curing process is 150 ℃/2h +180 ℃/2h +220 ℃/4h +250 ℃/4h, then naturally cooled, and demolded to obtain PHbP/rGO/GL-WS2A bismaleimide composite material.
The preparation method comprises the steps of preparing a part of PHbP/rGO/GL-WS2The proportion of the bismaleimide composite material.
The ratio of the reaction mixture to the ball weight during grinding in the step 1 is 1: 7.
Advantageous effects
The invention provides a cyclotriphosphazene polymer modified graphene/graphene-like WS2Composite bismaleimide material, preparation method thereof and WS prepared by polyphosphazene modification2The/graphene composite particles can improve the dispersibility of the graphene and improve the dispersibility of the grapheneThe interfacial bond strength of graphene and resin.
Polyphosphazenes are linear or cyclic inorganic-organic polymers with N, P atom alternate single and double bonds arranged on a main chain and organic groups as side groups, and have excellent performance and wide application. In recent years, researchers have utilized polyphosphazenes to perform surface functionalization on traditional fillers, and thus modified resins to improve the interfacial bonding of composite materials. For example, Zhang Xiaoqing RSC Advances,2014,4(24): 12198-. Therefore, the composite material prepared by the method has excellent mechanical properties and excellent friction properties, and can be used as a sealing material of aerospace engines and the like. The dispersibility of the graphene can be improved, the interface bonding strength of the graphene and the resin can be improved, and in addition, the prepared material has the characteristics of antifriction, wear resistance, high temperature resistance, super wear resistance, self lubrication and the like.
Compared with the prior art, the invention has the following advantages:
the invention firstly prepares rGO/GL-WS2Class of graphene WS2And the graphene can generate a synergistic effect, and the doping of the graphene can inhibit the similar graphene WS2Stacking of layers to layers, and graphene-like WS2The existence of the graphene can prevent the agglomeration of the graphene and improve the dispersibility of the nano particles in the organic solvent; then modifying rGO/GL-WS with cyclotriphosphazene2And the graphene-based two-dimensional nano composite material is added into bismaleimide resin as a solid lubricating additive to prepare the composite material, so that a large number of active amino groups are carried on the surface of the nanoparticles, the Michael addition reaction can be carried out on the nanoparticles and the bismaleimide resin matrix, the interface bonding property of the nanoparticles and the resin matrix is improved, and the graphene-based two-dimensional nano composite material with ultra-wear resistance, low friction, high bonding strength and excellent processing technology can be obtained.
Drawings
FIG. 1: cyclotriphosphazene polymer modified graphene/graphene-like WS2(PHbP/rGO/GL-WS2) Schematic diagram of the reaction process
FIG. 2: diphenylmethane bismaleimide structure
FIG. 3: diallyl bisphenol A structural formula
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
due to poor dispersion of graphene in solvents, consider and resemble graphene WS2Composite preparation of graphene/graphene-like WS2The nanometer composite particles can generate synergistic effect between the two, thereby not only enhancing the antifriction and wear resistance, but also improving the dispersibility of the nanometer composite particles in organic solvents. However, the method also has the problem of poor compatibility with a resin matrix, so that the cyclotriphosphazene polymer is used for modifying and modifying the cyclotriphosphazene polymer to prepare the cyclotriphosphazene modified rGO/GL-WS2Therefore, the surface of the nano particle has a large number of active amino groups, and the nano particle can be subjected to Michael addition reaction with the bismaleimide resin matrix, so that the interfacial associativity of the nano particle and the resin matrix can be improved. Firstly, preparing the graphene-like WS by a low-energy ball milling and ultrasonic method2Then adding the obtained product, graphene oxide and hydrazine hydrate into a high-temperature high-pressure reaction kettle, and preparing graphene/graphene-like WS by using a one-pot hydrothermal method2A nanocomposite particle. Then, the nano particles, hexachlorocyclotriphosphazene and branched polyethyleneimine are used as raw materials, triethylamine is used as an acid-binding agent, and an in-situ template method is utilized to prepare polyphosphazene modified graphene/graphene-like WS2. The nano particles are used as a solid lubricating additive, and are mixed with diphenylmethane bismaleimide and diallyl bisphenol A in a certain proportion, and the mixture is solidified and formed by a casting method to prepare the composite material.
The technical scheme adopted by the invention is as follows:
0.1-20 parts of cyclotriphosphazene polymer modified graphene/graphene-like WS2100 parts of diphenylmethane bismaleimide and 10-100 parts of diallyl bisphenol A by castingAnd (4) obtaining.
The preparation method comprises the following steps:
firstly, preparing graphite-like WS by low-energy ball milling and ultrasonic method2(GL-WS2) (ii) a Graphene Oxide (GO) was prepared by a modified Hummer's method.
Step two, the GO and the graphene-like WS prepared in the step one are treated2Dissolving in deionized water, ultrasonic dispersing, and stirring for 30 min. Then transferring the mixture into a high-temperature high-pressure reaction kettle, adding a proper amount of hydrazine hydrate, and reacting for 24 hours at high temperature and high pressure. Finally, cooling the obtained product to room temperature, performing suction filtration, washing the product for a plurality of times by using deionized water, and drying the product to obtain the graphene/graphene-like WS2Nano composite particles (rGO/GL-WS)2)。
Thirdly, the graphene/graphene-like WS is treated2Dissolving the nano composite particles in tetrahydrofuran, performing ultrasonic dispersion for half an hour, adding Hexachlorocyclotriphosphazene (HCCP) and branched polyethyleneimine (bPEI) into the reaction solution under stirring, adding a proper amount of triethylamine serving as an acid-binding agent, and performing heating reaction for 5 hours to obtain cyclotriphosphazene polymer modified graphene/graphene-like WS2(PHbP/rGO/GL-WS2). The reaction process is shown in figure 1.
Fourthly, PHbP/rGO/GL-WS in a certain proportion2Mixing the diphenylmethane bismaleimide and the diallyl bisphenol A, heating for prepolymerization, vacuumizing to remove bubbles, pouring into a preheated mold, and curing in an oven.
The specific method comprises the following steps:
step 1: let WS be2Mechanically and chemically treating with NaCl dry mixture at a ratio of 1:10 in agate grinding bowl of a ball mill for 2h (reaction mixture: ball weight ratio of 1:7), thoroughly washing the obtained nano-structured product with water (to remove salt), drying at 100 ℃, and performing ultrasonic treatment for 30min to prepare graphene-like WS2。
Step 2: mixing graphene oxide and graphene WS2Mixing and adding the materials into 100-500 mL of ethanol according to a mass ratio of 1 (0.5-3), performing ultrasonic treatment for 30min under 180W, transferring the mixture into a high-temperature high-pressure hydrothermal reaction kettle, adding 1-5 mL of hydrazine hydrate, and sealing and reacting at 220 DEG CAnd the time is 24 hours. Then, after the product is cooled to room temperature, carrying out suction filtration, washing the product for a plurality of times by using deionized water and ethanol, and carrying out vacuum drying on the product at 60 ℃ overnight to obtain the graphene/graphene-like WS2Nano composite particles (rGO/GL-WS)2)。
And step 3: the prepared rGO/GL-WS2The hexachlorocyclotriphosphazene and the branched polyethyleneimine are added into a three-neck flask according to the proportion of (0.5-3) to (1-4), then 100-500 mL of tetrahydrofuran and 1-8 mL of triethylamine are added, and the reaction is carried out for 4-10 h at 25-60 ℃. Then carrying out suction filtration, washing for several times by tetrahydrofuran, and carrying out vacuum drying overnight at 60 ℃ to obtain the cyclotriphosphazene polymer modified rGO/GL-WS2(PHbP/rGO/GL-WS2)。
And 4, step 4: 0.1-20 parts of PHbP/rGO/GL-WS2After 100 parts of diphenylmethane bismaleimide and 10-100 parts of diallyl bisphenol A are ultrasonically dispersed for 10-80 min under the power of 120-300W, the materials are heated and melted at the temperature of 130-150 ℃, prepolymerized for 15-80 min, poured into a preheated mold, put into a vacuum box at the temperature of 130-150 ℃, vacuumized to remove bubbles, put into an air-blast drying box for staged temperature rise curing, wherein the curing process is 150 ℃/2h +180 ℃/2h +220 ℃/4h +250 ℃/4h, then naturally cooled, and demolded to obtain PHbP/rGO/GL-WS2A bismaleimide composite material.
Example 1 was carried out:
step 1: let WS be2Mechanically and chemically treating the dried mixture with NaCl in a ratio of 1:10 in an agate grinding bowl of a ball mill for 2 hours (the weight ratio of a reaction mixture to the ball is 1:7), thoroughly washing the obtained product with water, drying at 100 ℃, and performing ultrasonic treatment for 30min to prepare the graphene-like WS2。
Step 2: mixing graphene oxide and graphene WS2Mixing and adding the materials into 100mL of ethanol according to the mass ratio of 1:0.5, performing ultrasonic treatment for 30min at 180W, transferring the mixture into a high-temperature high-pressure hydrothermal reaction kettle, adding 5mL of hydrazine hydrate, and performing sealed reaction for 24h at 220 ℃. Then, after the product is cooled to room temperature, carrying out suction filtration, washing the product for a plurality of times by using deionized water and ethanol, and carrying out vacuum drying on the product at 60 ℃ overnight to obtain the graphene/graphene-like WS2Nano composite particles (rGO/GL-WS)2)。
And step 3: the prepared rGO/GL-WS2The hexachlorocyclotriphosphazene and the branched polyethyleneimine are added into a three-neck flask according to the ratio of 1:0.5:1, 100mL of tetrahydrofuran and 1mL of triethylamine are added, and the mixture reacts for 4 hours at 25 ℃. Then carrying out suction filtration, washing for several times by tetrahydrofuran, and carrying out vacuum drying overnight at 60 ℃ to obtain the cyclotriphosphazene polymer modified rGO/GL-WS2(PHbP/rGO/GL-WS2)。
And 4, step 4: 0.1 part of PHbP/rGO/GL-WS2After 100 parts of diphenylmethane bismaleimide and 10 parts of diallyl bisphenol A are subjected to ultrasonic dispersion for 10min under the power of 120W, the materials are heated and melted at the temperature of 130 ℃, prepolymerized for 15 min, poured into a preheated mold, placed into a vacuum box at the temperature of 130 ℃, vacuumized to remove bubbles, placed into a blast drying box for staged temperature rise solidification, the solidification process is 150 ℃/2h +180 ℃/2h +220 ℃/4h +250 ℃/4h, then natural cooling is carried out, and demolding is carried out to obtain PHbP/rGO/GL-WS2A bismaleimide composite material.
Example 2 was carried out:
step 1: let WS be2Mechanically and chemically treating the dried mixture with NaCl in a ratio of 1:10 in an agate grinding bowl of a ball mill for 2 hours (the weight ratio of a reaction mixture to the ball is 1:7), thoroughly washing the obtained product with water, drying at 100 ℃, and performing ultrasonic treatment for 30min to prepare the graphene-like WS2。
Step 2: mixing graphene oxide and graphene WS2Mixing and adding the materials into 200mL of ethanol according to the mass ratio of 1:1, performing ultrasonic treatment for 30min at 180W, transferring the mixture into a high-temperature high-pressure hydrothermal reaction kettle, adding 3mL of hydrazine hydrate, and performing sealed reaction for 24h at 220 ℃. Then, after the product is cooled to room temperature, carrying out suction filtration, washing the product for a plurality of times by using deionized water and ethanol, and carrying out vacuum drying on the product at 60 ℃ overnight to obtain the graphene/graphene-like WS2Nano composite particles (rGO/GL-WS)2)。
And step 3: the prepared rGO/GL-WS2The hexachlorocyclotriphosphazene and the branched polyethyleneimine are added into a three-neck flask according to the ratio of 1:1:1.5, 200mL of tetrahydrofuran and 3mL of triethylamine are added, and the mixture reacts for 6 hours at 40 ℃. Then suction filtering, washing several times with tetrahydrofuran, vacuum drying at 60 deg.COvernight to obtain the cyclotriphosphazene polymer modified rGO/GL-WS2(PHbP/rGO/GL-WS2)。
And 4, step 4: 2 parts of PHbP/rGO/GL-WS2After 100 parts of diphenylmethane bismaleimide and 50 parts of diallyl bisphenol A are subjected to ultrasonic dispersion for 30min under the power of 180W, the materials are heated and melted at the temperature of 135 ℃, prepolymerized for 30min, poured into a preheated mold, placed into a vacuum box at the temperature of 135 ℃, vacuumized to remove bubbles, placed into a blast drying box for staged temperature rise solidification, the solidification process is 150 ℃/2h +180 ℃/2h +220 ℃/4h +250 ℃/4h, then natural cooling is carried out, and demolding is carried out to obtain PHbP/rGO/GL-WS2A bismaleimide composite material.
Example 3 of implementation:
step 1: let WS be2Mechanically and chemically treating the dried mixture with NaCl in a ratio of 1:10 in an agate grinding bowl of a ball mill for 2 hours (the weight ratio of a reaction mixture to the ball is 1:7), thoroughly washing the obtained product with water, drying at 100 ℃, and performing ultrasonic treatment for 30min to prepare the graphene-like WS2。
Step 2: mixing graphene oxide and graphene WS2Mixing and adding the materials into 300mL of ethanol according to the mass ratio of 1:2, performing ultrasonic treatment for 30min at 180W, transferring the mixture into a high-temperature high-pressure hydrothermal reaction kettle, adding 2mL of hydrazine hydrate, and performing sealed reaction for 24h at 220 ℃. Then, after the product is cooled to room temperature, carrying out suction filtration, washing the product for a plurality of times by using deionized water and ethanol, and carrying out vacuum drying on the product at 60 ℃ overnight to obtain the graphene/graphene-like WS2Nano composite particles (rGO/GL-WS)2)。
And step 3: the prepared rGO/GL-WS2The hexachlorocyclotriphosphazene and the branched polyethyleneimine are added into a three-neck flask according to the ratio of 1:2:3, and then 300mL of tetrahydrofuran and 5mL of triethylamine are added to react for 8h at 50 ℃. Then carrying out suction filtration, washing for several times by tetrahydrofuran, and carrying out vacuum drying overnight at 60 ℃ to obtain the cyclotriphosphazene polymer modified rGO/GL-WS2(PHbP/rGO/GL-WS2)。
And 4, step 4: 8 parts of PHbP/rGO/GL-WS2100 parts of bismaleimide of diphenylmethane type and 80 parts of diallyl bisphenol A were ultrasonically dispersed at a power of 240W for 60min, and thenHeating and melting at 140 ℃, pre-polymerizing for 60min, pouring into a preheated mold, putting into a vacuum box at 140 ℃, vacuumizing to remove bubbles, putting into a forced air drying box for staged heating and solidification, wherein the solidification process is 150 ℃/2h +180 ℃/2h +220 ℃/4h +250 ℃/4h, then naturally cooling, and demolding to obtain PHbP/rGO/GL-WS2A bismaleimide composite material.
Example 4 was carried out:
step 1: and performing mechanochemical treatment on the WS2 and NaCl dry mixture in a ball mill agate grinding bowl for 2h (the ratio of the reaction mixture to the ball weight is 1:7) according to a ratio of 1:10 to obtain a nano-structured product, thoroughly washing the nano-structured product with water, drying the nano-structured product at 100 ℃, and performing ultrasonic treatment for 30min to prepare the graphene-like WS 2.
Step 2: mixing graphene oxide and graphene WS2Mixing and adding the materials into 500mL of ethanol according to the mass ratio of 1:3, performing ultrasonic treatment for 30min at 180W, transferring the mixture into a high-temperature high-pressure hydrothermal reaction kettle, adding 1mL of hydrazine hydrate, and performing sealed reaction for 24h at 220 ℃. Then, after the product is cooled to room temperature, carrying out suction filtration, washing the product for a plurality of times by using deionized water and ethanol, and carrying out vacuum drying on the product at 60 ℃ overnight to obtain the graphene/graphene-like WS2Nano composite particles (rGO/GL-WS)2)。
And step 3: the prepared rGO/GL-WS2The hexachlorocyclotriphosphazene and the branched polyethyleneimine are added into a three-neck flask according to the ratio of 1:3:4, and then 500mL of tetrahydrofuran and 8mL of triethylamine are added to react for 10h at 60 ℃. Then carrying out suction filtration, washing for several times by tetrahydrofuran, and carrying out vacuum drying overnight at 60 ℃ to obtain the cyclotriphosphazene polymer modified rGO/GL-WS2(PHbP/rGO/GL-WS2)。
And 4, step 4: 10 portions of PHbP/rGO/GL-WS2After 100 parts of diphenylmethane bismaleimide and 100 parts of diallyl bisphenol A are ultrasonically dispersed for 80min under the power of 300W, the mixture is heated and melted at the temperature of 150 ℃, prepolymerized for 80min, poured into a preheated mold, placed into a vacuum box at the temperature of 150 ℃, vacuumized to remove bubbles, placed into an air-blowing drying box for staged heating and solidification, the solidification process is 150 ℃/2h +180 ℃/2h +220 ℃/4h +250 ℃/4h, then natural cooling is carried out, and demolding is carried out to obtain PHbP/rGO/GL-WS2A bismaleimide composite material.
Claims (3)
1. Cyclotriphosphazene polymer modified graphene/graphene-like WS2The bismaleimide composite material is characterized by comprising 0.1-20 parts of cyclotriphosphazene polymer modified graphene/graphene-like WS2Nano composite particles, 100 parts of diphenylmethane bismaleimide and 10-100 parts of diallyl bisphenol A;
the cyclotriphosphazene polymer modified graphene/graphene-like WS2The nano composite particles are prepared by adopting an in-situ template method to prepare cyclotriphosphazene modified graphene/graphene-like WS2Nanocomposite particles wherein: graphene and graphene-like WS2The mass ratio of the component (A) to (B) is 1 to (0.1 to 10), and the grafting ratio of the cyclotriphosphazene polymer is 0.1 to 50 percent; the cyclotriphosphazene polymer is formed by condensation polymerization of hexachlorocyclotriphosphazene and branched polyethyleneimine.
2. Preparation of cyclotriphosphazene polymer modified graphene/graphene-like WS of claim 12The method for preparing the bismaleimide composite material is characterized by comprising the following steps:
step 1: let WS be2Mechanically and chemically treating the NaCl dry mixture and NaCl dry mixture in a ball mill agate grinding bowl according to the ratio of 1:10 for 2 hours to obtain a product with a nano structure, washing the product with water to dry at 100 ℃, and then ultrasonically treating for 30min to prepare the graphene-like WS2；
Step 2: mixing graphene oxide and graphene WS2Mixing and adding the materials into 100-500 mL of ethanol according to a mass ratio of 1 (0.1-10), performing ultrasonic treatment for 30min at 180W, transferring the mixture into a high-temperature high-pressure hydrothermal reaction kettle, adding 1-5 mL of hydrazine hydrate, and performing sealed reaction at 220 ℃ for 24 hours; after the obtained product is cooled to room temperature, carrying out suction filtration, washing the obtained product for a plurality of times by using deionized water and ethanol, and carrying out vacuum drying at 60 ℃ overnight to obtain the graphene/graphene-like WS2Nano composite particle rGO/GL-WS2；
And step 3: mixing rGO/GL-WS2Mixing hexachlorocyclotriphosphazene and branched polyethyleneimine according to the ratio of (0.5-3) to (1-4) of 1, and adding 100-50Reacting 0mL of tetrahydrofuran and 1-8 mL of triethylamine at 25-60 ℃ for 4-10 h; then carrying out suction filtration, washing for several times by tetrahydrofuran, and carrying out vacuum drying overnight at 60 ℃ to obtain the cyclotriphosphazene polymer modified rGO/GL-WS2Is PHbP/rGO/GL-WS2；
And 4, step 4: 0.1-20 parts of PHbP/rGO/GL-WS2After 100 parts of diphenylmethane bismaleimide and 10-100 parts of diallyl bisphenol A are ultrasonically dispersed for 10-80 min under the power of 120-300W, the materials are heated and melted at the temperature of 130-150 ℃, prepolymerized for 15-80 min, poured into a preheated mold, put into a vacuum box at the temperature of 130-150 ℃, vacuumized to remove bubbles, put into an air-blast drying box for staged temperature rise curing, wherein the curing process is 150 ℃/2h +180 ℃/2h +220 ℃/4h +250 ℃/4h, then naturally cooled, and demolded to obtain PHbP/rGO/GL-WS2A bismaleimide composite;
the preparation method comprises the steps of preparing a part of PHbP/rGO/GL-WS2The proportion of the bismaleimide composite material.
3. The method of claim 2, further comprising: the ratio of the reaction mixture to the ball weight during grinding in the step 1 is 1: 7.
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