CN108034078B

CN108034078B - Carbon fluoride material/zirconium phosphate binary composite material, preparation method and application thereof

Info

Publication number: CN108034078B
Application number: CN201711353727.8A
Authority: CN
Inventors: 孙大陟; 张至
Original assignee: Shenzhen Nanke 2d Composite Material Technology Co ltd
Current assignee: Shenzhen Nanke 2d Composite Material Technology Co ltd
Priority date: 2017-12-15
Filing date: 2017-12-15
Publication date: 2020-04-28
Anticipated expiration: 2037-12-15
Also published as: WO2019114414A1; CN108034078A

Abstract

The invention discloses a carbon fluoride material/zirconium phosphate binary composite material, a preparation method and application thereof, and belongs to the technical field of composite material preparation. The method of the invention comprises the following steps: adding the carbon fluoride material and zirconium phosphate into a solvent as a graft, and mixing to prepare the binary composite material. According to the invention, carbon fluoride materials such as graphite fluoride or carbon fluoride black and the like are compounded with lamellar nano zirconium phosphate through double-function or multifunctional molecules, so that the prepared binary composite material can be well dispersed in a high polymer material matrix, the mechanical properties such as tensile strength and the like of the high polymer material matrix can be improved, and the performances such as friction resistance, corrosion resistance and the like of a high polymer coating material are improved. The method is simple, easy to operate, low in cost and suitable for industrial production.

Description

Carbon fluoride material/zirconium phosphate binary composite material, preparation method and application thereof

Technical Field

The invention belongs to the technical field of composite material preparation, relates to a binary composite material, a preparation method and application thereof, and particularly relates to a carbon fluoride material/zirconium phosphate binary composite material, a preparation method and application thereof.

Background

Inorganic powder particles are widely used as filling materials in various products including rubber, plastics, coatings, paints, inks, lubricating greases, and the like, and include, but are not limited to, talc, kaolin, clay, calcium carbonate, carbon black, white carbon black, titanium dioxide, and the like. With the development of nano science and technology, inorganic powder filling materials are continuously developed towards the direction of refinement and nanocrystallization due to excellent physical and chemical properties such as high specific surface area and the like brought by nano materials. In the development of inorganic nano powder particle materials, on one hand, the traditional inorganic particle materials are continuously reduced and nanocrystallized due to the improvement of a synthesis preparation method; on the other hand, many novel high-performance nano materials are continuously discovered and applied to particle filling materials, such as carbon nanotubes, graphene, quantum dots, nano clay and the like.

The inorganic powder particles or the nano particles are used as filling materials, and the main function of the inorganic powder particles or the nano particles is to improve the service performance of a matrix, such as adding the inorganic powder particles or the nano particles into rubber and plastics to improve the mechanical strength and the barrier property of the rubber and plastics; the coating is added into paint coating and the like to improve the covering power, durability and the like of a matrix; the additive is added into lubricating grease to improve the lubricating and anti-wear properties of an oil phase.

Zirconium Phosphate (also known as Zirconium Hydrogen Phosphate, Zirconium hydroxide Phosphate) is a two-dimensional inorganic lamellar particulate material, typically synthesized by hydrothermal or reflux methods, with plate sizes ranging from nano-to micro-scale and thicknesses generally on the nano-scale, also known as Zirconium Phosphate nanoplates. Zirconium phosphate is a high-performance inorganic filling material, can be used as an additive of plastics, lubricating grease and the like, and improves the service performance of the zirconium phosphate.

Carbon fluoride materials are generally obtained by fluorinating carbon materials, including carbon black fluoride, graphite fluoride, carbon nanotube fluoride, carbon sphere fluoride, and the like. The materials are generally hydrophobic and oleophobic, are corrosion resistant, have excellent lubricating and dielectric properties and are high-performance multifunctional filling materials, but the application of the materials is severely limited due to high price and poor dispersibility.

Disclosure of Invention

In view of the above problems in the prior art, the present invention aims to provide a binary composite material, a preparation method and applications thereof, and in particular, to a carbon fluoride material/zirconium phosphate binary composite material, a preparation method and applications thereof in preparing a binary composite material reinforced epoxy resin and a binary composite material coating. The binary composite material can be well dispersed in a high polymer material matrix, can improve the mechanical properties such as tensile strength of the high polymer material matrix, and can improve the performances such as friction resistance, corrosion resistance and the like of a high polymer coating material.

The carbon fluoride material/zirconium phosphate binary composite material of the invention refers to: the carbon fluoride material and zirconium phosphate are compounded to form the binary composite material.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a binary composite material, which is a binary composite material formed by compounding a carbon fluoride material and zirconium phosphate.

Preferably, the complexing of the carbon fluoride material and zirconium phosphate is achieved by a graft linkage, which is preferably a covalent linkage.

Preferably, the graft is an organic substance having at least 2 amino groups at the terminal, an organic substance having at least 2 hydroxyl groups at the terminal, or an organic substance having at least 1 amino group and 1 hydroxyl group at the terminal, or a combination of at least two thereof.

The "terminal" of the present invention includes both the terminal of the main chain and the terminal of the branched chain.

Preferably, the fluorocarbon fluoride is bonded to the amino group and/or the hydroxyl group of the graft through a fluorine atom, and the zirconium phosphate is bonded to the amino group and/or the hydroxyl group of the graft through a hydroxyl group.

The "zirconium phosphate" is zirconium phosphate having hydroxyl group, and the preparation method thereof is not limited in the present invention, and it can be a common method disclosed in the prior art, and can be prepared by referring to the prior art by those skilled in the art. More preferably, the zirconium phosphate is prepared by a reflux method or a hydrothermal method.

As a preferable preparation scheme of the zirconium phosphate, the zirconium phosphate is prepared by a reflux method, and the method specifically comprises the following steps: 15.0g of zirconyl chloride (ZrOCl)_2.8·H₂O) and 150.0mL of phosphoric acid (H) having a concentration of 3.0mol/L₃PO₄) Mixing and pouring into a glass flask, uniformly stirring by magnetic force, placing into an oil bath pot, heating to 100 ℃, and refluxing for 24 hours. After the reaction was completed, the reaction product was washed three times with water, and the product was collected by centrifugation, and then, the resulting sample was dried at 65 ℃ for 24 hours. And then grinding the dried product into fine powder to obtain zirconium phosphate powder.

As a preferred preparation scheme of zirconium phosphate, a hydrothermal method is adoptedThe preparation of zirconium phosphate specifically comprises the following steps: in a hydrothermal reaction kettle (Teflon core) having a volume of about 150ml, 10.0g of ZrOCl was charged_2.8·H₂O was mixed with 100ml of 9.0mol/L phosphoric acid and poured thereinto. And (3) sealing the reaction kettle, placing the reaction kettle in an oven at 200 ℃ for reaction for 2h, taking out the reaction kettle after naturally cooling to room temperature, washing the reaction product with water for three times, collecting the product through centrifugation, and then drying the obtained sample at 65 ℃ for 24 h. And then grinding the dried product into fine powder to obtain zirconium phosphate powder.

As a preferable technical scheme of the binary composite material, the grafting material is a liquid grafting material. The graft preferably comprises any one or a combination of at least two of polymers of diamine, polyamine, diol, polyalcohol, hydramine, ether amine, polyether amine or alcohol, and further preferably comprises any one or a combination of at least two of polyether amine D230, polyether amine D2000, polyether amine T403, ethylene diamine, propylene diamine, phenylene diamine, ethanolamine, ethylene glycol or polyethylene glycol.

More preferably, the graft is any one of or a combination of at least two of polyether amine, diamine or alcohol amine.

As a preferred embodiment of the binary composite material of the present invention, the carbon fluoride material includes any one or a combination of at least two of graphite fluoride, graphene fluoride, carbon fluoride black, coke fluoride, carbon fluoride nanotube or fullerene fluoride, but is not limited to the above-mentioned carbon fluoride materials, and other carbon fluoride materials commonly used in the art to achieve the same technical effect may also be used in the present invention.

The carbon fluoride material of the present invention may be a commercially available carbon fluoride material or a carbon fluoride material directly prepared (see the methods disclosed in the prior art for preparation methods), and those skilled in the art can select the carbon fluoride material as needed.

Preferably, the zirconium phosphate has a size of 10nm to 100 μm, such as 10nm, 30nm, 65nm, 100nm, 150nm, 200nm, 400nm, 600nm, 800nm, 1 μm, 3 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or 100 μm, and the like.

Preferably, the zirconium phosphate is any one of α -zirconium phosphate, theta-zirconium phosphate or gamma-zirconium phosphate or a combination of at least two of them.

In a second aspect, the present invention provides a method for preparing the binary composite material according to the first aspect, the method comprising:

adding the carbon fluoride material and zirconium phosphate into a solvent as a graft, and mixing to prepare the binary composite material.

In the method, the grafting material is used as a functional molecule and a solvent, so that the composition of the carbon fluoride material and the zirconium phosphate is realized. In the binary composite material, the carbon fluoride material is connected with the amino group of the graft through a fluorine atom, and the zirconium phosphate is connected with the amino group and/or the hydroxyl group of the graft through a hydroxyl group.

The graft of the present invention is a functional molecule, which may be a bifunctional molecule or a multifunctional molecule, and at least one of ① the end of the graft contains at least 2 amino groups, ② the end of the graft contains at least 2 hydroxyl groups, and ③ the end of the graft contains at least 1 amino group and 1 hydroxyl group.

As the preferred technical scheme of the method for preparing the binary composite material, the mixing is uniformly stirring.

The ratio of the total mass of the graphite fluoride and the zirconium phosphate to the volume of the graft solvent is (1-4): 10, for example, 1:10, 1.5:10, 2:10, 2.5:10, 3:10, 3.2:10, 3.5:10 or 4:10, and preferably (1.5-3): 10.

Preferably, the mass ratio of the graphite fluoride to the zirconium phosphate is 1:0.001 to 1:1000, for example, 1:0.001, 1:0.005, 1:0.01, 1:0.05, 1:0.1, 1:0.5, 1:1, 1:5, 1:10, 1:50, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, etc., preferably 1 (0.5 to 2).

Preferably, the method further comprises the step of washing and drying after the mixing. The purpose of the washing is to remove excess grafts, thereby obtaining a purified binary composite.

As a further preferable technical scheme of the method for preparing the binary composite material, the method comprises the following steps: adding a carbon fluoride material and zirconium phosphate into a solvent as a graft, mixing, washing to remove the graft, and drying to prepare the purified binary composite material.

In a third aspect, the invention provides a binary composite material reinforced polymer material, and raw materials for preparing the binary composite material reinforced polymer material comprise the binary composite material of the first aspect.

Preferably, the polymer material comprises any one or a combination of at least two of epoxy resin, polyether, polyamide or polyester, preferably epoxy resin.

In a fourth aspect, the present invention provides a method for preparing the binary composite material reinforced polymer material according to the third aspect, the method comprising: mixing the binary composite material, the curing agent and the high polymer material, and stirring uniformly to obtain the binary composite material reinforced high polymer material.

Preferably, in the process of preparing the binary composite material reinforced polymer material, the curing agent is polyether amine.

Preferably, in the process of preparing the binary composite material reinforced polymer material, the ratio of the mass of the binary composite material to the total mass of the curing agent and the polymer material is 0.01: 128-128: 128, such as 0.01:128, 0.1:128, 1:128, 5:128, 10:128, 20:128, 30:128, 40:128, 50:128, 60:128, 70:128, 80:128, 90:128, 100:128 or 128:128, and the like, and preferably 6.7: 1.28.

Preferably, in the process of preparing the binary composite material reinforced polymer material, the curing is performed in a mold, and the curing conditions are preferably as follows: curing at 80 ℃ for 2h, and then at 120 ℃ for 2 h.

Preferably, the mold is a stainless steel mold pre-coated with a release agent.

In a fifth aspect, the invention provides a binary composite material reinforced polymer material coating, and the raw materials for preparing the coating binary composite material reinforced polymer material coating comprise the binary composite material of the first aspect.

In a sixth aspect, the present invention provides a method for preparing a binary composite reinforced polymer material coating according to the fifth aspect, the method comprising: dissolving the binary composite material in the first aspect in an organic solvent, adding a curing agent and a high polymer material, stirring uniformly, coating the mixture on the surface of a substrate, and curing to obtain the binary composite material coating.

Preferably, in the process of preparing the binary composite material reinforced polymer material coating, the curing agent is polyether amine.

Preferably, in the process of preparing the binary composite material reinforced high polymer material coating, the ratio of the mass of the binary composite material to the total mass of the curing agent and the high polymer material is 0.6: 1.28.

Preferably, the ratio of the total mass of the binary composite, curing agent and polymeric material to the volume of the organic solvent is 0.001g/50ml to 50g/50ml, such as 0.001g/50ml, 0.01g/50ml, 0.1g/50ml, 1g/50ml, 5g/50ml, 10g/50ml, 15g/50ml, 20g/50ml, 25g/50ml, 30g/50ml, 35g/50ml, 40g/50ml, 45g/50ml or 50g/50ml, etc., preferably 1.88g/50 ml.

The coating method in the present invention is not limited, and may be, for example, spray coating or spin coating.

Preferably, the substrate is glass.

Preferably, the organic solvent is volatilized prior to the curing.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention prepares a novel binary composite material, in particular to a carbon fluoride/zirconium phosphate binary composite material by compounding carbon fluoride materials such as graphite fluoride or carbon fluoride black with lamellar nano zirconium phosphate through double-function or multifunctional molecules. The binary composite material can be well dispersed in a high polymer material matrix, can improve the mechanical properties such as tensile strength of the high polymer material matrix and the like, and can improve the performances such as friction resistance, corrosion resistance and the like of a high polymer coating material.

(2) The preparation method is simple, easy to operate, low in cost and suitable for industrial production.

Drawings

FIG. 1 is an XRD spectrum of zirconium phosphate prepared by the reflux method of example 1.

Fig. 2 is an SEM image of zirconium phosphate prepared by the reflow method of example 1.

FIG. 3 is an XRD spectrum of zirconium phosphate prepared by a hydrothermal method of example 2.

FIG. 4 is a TEM image of a hydrothermally prepared zirconium phosphate of example 2.

Fig. 5 is an SEM image of graphite fluoride of example 1.

FIG. 6 is an SEM image of a graphite fluoride/zirconium phosphate binary composite prepared by polyetheramine D230 of example 1.

Fig. 7 is an SEM image of the graphite fluoride/zirconium phosphate binary composite prepared by polyetheramine T403 of example 2.

FIG. 8 is an SEM image of fluorinated carbon black of example 3.

FIG. 9 is an SEM image of a fluorinated carbon black/zirconium phosphate binary composite prepared by ethanolamine from example 3.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.

Example 1

This example provides a graphite fluoride/zirconium phosphate binary composite material

(1) Preparing zirconium phosphate nanosheets by adopting a reflux method:

15.0g of zirconyl chloride (ZrOCl)_2.8·H₂O) and 150.0mL of phosphoric acid (H) having a concentration of 3.0mol/L₃PO₄) Mixing and pouring into a glass flask, uniformly stirring by magnetic force, placing into an oil bath pot, heating to 100 ℃, and refluxing for 24 hours. After the reaction was completed, the reaction product was washed three times with water, and the product was collected by centrifugation, and then, the resulting sample was dried at 65 ℃ for 24 hours. Grinding the dried product into fine powder, and obtaining zirconium phosphate powderXRD (x-ray diffraction) and SEM (scanning electron microscope) detection were not performed. The XRD spectrogram and SEM image of the zirconium phosphate sample obtained by the reflux method are respectively shown in figures 1 and 2, and the figure shows that the prepared zirconium phosphate has a lamellar crystal structure and the diameter is less than 100 nm.

(2) Preparation of binary composite (graphite fluoride/zirconium phosphate binary composite):

adding 1g of graphite fluoride and 1g of zirconium phosphate by a reflux method into 10ml of polyetheramine D230, and uniformly stirring to obtain the graphite fluoride zirconium phosphate binary composite material. And (3) centrifugally cleaning the mixture of the graphite fluoride, the zirconium phosphate and the polyether amine D230 by using ethanol for 3 times to remove the redundant polyether amine D230, and drying to obtain the purified graphite fluoride zirconium phosphate binary composite material.

In this embodiment, the polyetheramine D230 is a bifunctional molecule with amino groups at two ends, and the graphite fluoride and the zirconium phosphate can be respectively connected through the amino groups at the two ends to prepare the graphite fluoride/zirconium phosphate binary composite material.

In this example, SEM images of graphite fluoride and the graphite fluoride/zirconium phosphate binary composite prepared by polyetheramine D230 are shown in fig. 5 and fig. 6, respectively, from which it can be seen that the graphite fluoride particle size is less than 10 microns, and is approximately between 3-8 microns; the graphite fluoride and the zirconium phosphate are grafted well through the polyether amine D230 to form the stable binary composite material.

Example 2

(1) Preparing zirconium phosphate nanosheets by a hydrothermal method:

in a hydrothermal reaction kettle (Teflon core) having a volume of about 150ml, 10.0g of ZrOCl was charged_2.8·H₂O was mixed with 100ml of 9.0mol/L phosphoric acid and poured thereinto. And (3) sealing the reaction kettle, placing the reaction kettle in an oven at 200 ℃ for reaction for 2h, taking out the reaction kettle after naturally cooling to room temperature, washing the reaction product with water for three times, collecting the product through centrifugation, and then drying the obtained sample at 65 ℃ for 24 h. Then, the dried product was ground into a fine powder, and the obtained zirconium phosphate powder was subjected to XRD and TEM (Transmission Electron emission)Microscope) for detection. The XRD spectrogram and TEM image of the zirconium phosphate sample obtained by the hydrothermal method are respectively shown in fig. 3 and fig. 4, and it can be seen from the images that the zirconium phosphate prepared by the method has a lamellar structure, and the particle size is mostly larger than 1 micron.

adding 1g of graphite fluoride and 0.5g of zirconium phosphate by a reflux method into 10ml of polyetheramine T403, and uniformly stirring to obtain the graphite fluoride zirconium phosphate binary composite material. And (3) centrifugally cleaning the mixture of the graphite fluoride, the zirconium phosphate and the polyetheramine T403 for 3 times by using ethanol to remove the redundant polyetheramine T403, and drying to obtain the purified graphite fluoride zirconium phosphate binary composite material.

In this embodiment, the polyetheramine T403 is a trifunctional molecule with three terminal groups as amino groups, and the graphite fluoride and the zirconium phosphate can be respectively connected through the amino groups of the three terminal groups to prepare a graphite fluoride/zirconium phosphate binary composite material.

In this example, an SEM image of the graphite fluoride/zirconium phosphate binary composite material prepared by the polyetheramine D403 is shown in fig. 7, and it can be seen from the figure that the graphite fluoride and the zirconium phosphate are well grafted by the polyetheramine D403, so that a stable binary composite material is formed.

Example 3

This example provides a fluorinated carbon black/zirconium phosphate binary composite

(1) The zirconium phosphate was prepared in the same manner as in example 2;

(2) preparation of binary composite (fluorinated carbon black/zirconium phosphate binary composite):

adding 1g of carbon fluoride black and 2g of zirconium phosphate by a hydrothermal method into 10ml of ethanolamine, and uniformly stirring to obtain the carbon fluoride black zirconium phosphate binary composite material. And (3) centrifugally cleaning the mixture of the fluorinated carbon black, the zirconium phosphate and the ethanolamine by using ethanol for 3 times to remove the redundant ethanolamine, and drying to obtain the purified fluorinated carbon black/zirconium phosphate binary composite material.

In this embodiment, the ethanolamine is a bifunctional molecule having an amino group at one end and a hydroxyl group at the other end, and can be respectively connected with the fluorinated carbon black and the zirconium phosphate through the amino group and the hydroxyl group at the two ends to prepare the fluorinated carbon black zirconium phosphate binary composite material.

In this example, SEM images of fluorinated carbon black and a fluorinated carbon black zirconium phosphate binary composite prepared with ethanolamine are shown in fig. 8 and 9, respectively, from which it can be seen that the size of fluorinated carbon black is between about 10-20 microns; and the two components of the fluorinated carbon black and the zirconium phosphate are well grafted through ethanolamine to form a stable binary composite material.

Example 4

The procedure and conditions were the same as in example 1 except that the polyetheramine was replaced with propylenediamine.

Example 5

The procedure and conditions were the same as in example 2 except that the polyetheramine T403 was replaced with polyethylene glycol.

Example 6

The procedure and conditions were the same as in example 3, except that the polyetheramine T403 was replaced with phenylenediamine.

The methods of embodiments 1-6 of the present invention can successfully prepare a binary composite material in which the carbon fluoride material and the zirconium phosphate are well compounded.

Example 7

This example provides a graphite fluoride/zirconium phosphate binary composite reinforced epoxy resin material, wherein the concentration of the binary composite in the epoxy resin is-5%.

The preparation method comprises the following steps:

6.7g of the graphite fluoride/zirconium phosphate binary composite material prepared in the example 1 and 32g of the polyetheramine D230 are uniformly stirred and then added into 96g of the epoxy resin E44, the three materials are fully and uniformly stirred and then poured into a stainless steel mold coated with a release agent in advance, and then the stainless steel mold is placed into an oven for curing. The curing conditions were 80 ℃ for two hours and then 120 ℃ for two hours. And naturally cooling to room temperature after solidification, and taking out the sample from the mold for mechanical property tensile test testing. Tensile test specimens were prepared according to the ASTM D638 standard, and fracture toughness test specimens were prepared according to the ASTM D5045 standard.

Comparative example 1

In this comparative example, the comparative sample was a neat epoxy resin (without any filler).

Comparative example 2

In this comparative example, the graphite fluoride/zirconium phosphate binary composite material of example 7 was replaced with an equal mass of graphite fluoride, i.e., the comparative sample of this comparative example was an epoxy resin with 5% graphite fluoride added.

Comparative example 3

In this comparative example, the graphite fluoride/zirconium phosphate binary composite in example 7 was replaced with an equal mass of zirconium phosphate, i.e., the comparative sample of this comparative example was an epoxy resin with 5% zirconium phosphate added.

The comparative samples of comparative examples 1-3 were prepared in the same manner as the binary composite-reinforced epoxy resin material described in example 7. The results of the mechanical property tests of the samples of example 7 and comparative examples 1 to 3 are shown in Table 1.

TABLE 1 mechanical Property test comparison results

As can be seen from Table 1, the mechanical properties of the epoxy resin material can be significantly improved by filling the epoxy resin with the binary composite material provided by the invention.

Example 8

The embodiment provides a graphite fluoride/zirconium phosphate binary composite material reinforced epoxy resin material coating, wherein the concentration of the binary composite material in epoxy resin is-30%.

The preparation method comprises the following steps:

0.6g of the graphite fluoride/zirconium phosphate binary composite material prepared in example 1 was dissolved in 50ml of acetone solution, and 0.32g of polyetheramine and 0.96g of epoxy resin E44 were added in this order. And (3) fully and uniformly stirring the solution, spraying the solution on the surface of glass, and putting the glass into an oven for curing after the solvent is volatilized. The curing conditions were 80 ℃ for two hours and then 120 ℃ for two hours. After curing, the sample is naturally cooled to room temperature, and the sample is subjected to a surface friction test.

Comparative example 4

In this comparative example, the comparative sample was a coating of neat epoxy (without any filler).

Comparative example 5

In this comparative example, the graphite fluoride/zirconium phosphate binary composite in example 8 was replaced with an equal mass of graphite fluoride, i.e., the comparative sample of this comparative example was an epoxy coating with 30% graphite fluoride added.

Comparative example 6

In this comparative example, the graphite fluoride/zirconium phosphate binary composite in example 8 was replaced with an equal mass of zirconium phosphate, i.e., the comparative sample of this comparative example was an epoxy coating with 30% zirconium phosphate added.

The comparative samples of comparative examples 4-6 were prepared using the same process as the coating of the binary composite reinforced epoxy material described in example 8. The coating surface friction coefficients of the samples of example 8 and comparative examples 4 to 6 were measured according to the national standard GB/T10006, and the surface contact angles were measured by a contact angle tester. The results of the surface tests of the samples of example 8 and comparative examples 4 to 6 are shown in Table 2.

Table 2 surface property test comparison results

As can be seen from Table 2, the surface properties of the epoxy resin coating can be significantly improved by using the binary composite material provided by the invention to prepare the epoxy resin coating.

The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. A binary composite material is characterized in that the binary composite material is formed by compounding a carbon fluoride material and zirconium phosphate;

the compounding of the carbon fluoride material and the zirconium phosphate is realized through graft connection, and the connection is covalent connection; the zirconium phosphate is zirconium phosphate with hydroxyl;

the graft is an organic matter of which the end contains at least 2 amino groups, an organic matter of which the end contains at least 2 hydroxyl groups, or an organic matter of which the end contains at least 1 amino group and 1 hydroxyl group, or a combination of at least two of the amino groups and the hydroxyl groups.

2. The binary composite material as claimed in claim 1, wherein said fluorinated carbon material is linked to the amino group and/or hydroxyl group of the graft through a fluorine atom, and said zirconium phosphate is linked to the amino group and/or hydroxyl group of the graft through a hydroxyl group.

3. The binary composite material as claimed in claim 1, wherein said graft is a liquid graft.

4. The binary composite material as claimed in claim 3, wherein said graft comprises any one or a combination of at least two of polyamine, polyol, alcohol amine, ether amine, polyether amine or alcohol polymer.

5. The binary composite material as claimed in claim 4, wherein said graft comprises any one or a combination of at least two of polyetheramine D230, polyetheramine D2000, polyetheramine T403, ethylenediamine, propylenediamine, phenylenediamine, ethanolamine, ethylene glycol or polyethylene glycol.

6. The binary composite material as claimed in claim 4, wherein the graft is any one or a combination of at least two of polyether amine, diamine or alcohol amine.

7. The binary composite material as claimed in claim 1, wherein said fluorinated carbon material comprises any one of or a combination of at least two of graphite fluoride, graphene fluoride, carbon black fluoride, coke fluoride, carbon nanotube fluoride or fullerene fluoride.

8. The binary composite according to claim 1, characterized in that said zirconium phosphate has a size comprised between 10nm and 100 μm.

9. The binary composite material as claimed in claim 1, wherein said zirconium phosphate is any one of α -zirconium phosphate, theta-zirconium phosphate or gamma-zirconium phosphate or a combination of at least two thereof.

10. A method for preparing a binary composite according to any one of claims 1 to 9, characterised in that the method comprises:

11. The method of claim 10, wherein the mixing is stirring.

12. The method according to claim 10, wherein the ratio of the total mass of the graphite fluoride and the zirconium phosphate to the volume of the graft solvent is (1-4): 10.

13. The method according to claim 12, wherein the ratio of the total mass of the graphite fluoride and the zirconium phosphate to the volume of the graft solvent is (1.5-3): 10.

14. The method according to claim 10, wherein the mass ratio of the graphite fluoride to the zirconium phosphate is 1:0.001 to 1: 1000.

15. The method according to claim 14, wherein the mass ratio of the graphite fluoride to the zirconium phosphate is 1 (0.5-2).

16. The method of claim 10, further comprising the step of washing and drying after mixing.

17. The method of claim 10, wherein the method comprises: adding a carbon fluoride material and zirconium phosphate into a solvent as a graft, mixing, washing to remove the graft, and drying to prepare the purified binary composite material.

18. A binary composite material reinforced polymer material, characterized in that the raw materials for preparing the binary composite material reinforced polymer material comprise the binary composite material of any one of claims 1 to 9.

19. The binary composite reinforced polymer material of claim 18, wherein the polymer material comprises any one or a combination of at least two of epoxy resin, polyether polyamide or polyester.

20. The binary composite reinforced polymer material of claim 19, wherein the polymer material is an epoxy resin.

21. The method for preparing the binary composite material reinforced polymer material according to any one of claims 18 to 20, wherein the method comprises: mixing the binary composite material as claimed in any one of claims 1 to 9, the curing agent and the polymer material, stirring, and curing with the curing agent to obtain the binary composite material reinforced polymer material.

22. The method according to claim 21, wherein the curing agent is polyetheramine in the process of preparing the binary composite material reinforced polymer material.

23. The preparation method of claim 21, wherein in the process of preparing the binary composite material reinforced polymer material, the ratio of the mass of the binary composite material to the total mass of the curing agent and the polymer material is 0.01: 128-128: 128.

24. The preparation method according to claim 23, wherein in the process of preparing the binary composite reinforced polymer material, the ratio of the mass of the binary composite to the total mass of the curing agent and the polymer material is 6.7: 128.

25. The method according to claim 21, wherein the curing is performed in a mold during the process of preparing the binary composite reinforced polymer material.

26. The method according to claim 25, wherein in the process of preparing the binary composite material reinforced polymer material, the curing conditions are as follows: curing at 80 ℃ for 2h, and then at 120 ℃ for 2 h.

27. The method of claim 25, wherein the mold is a stainless steel mold pre-coated with a release agent.

28. A binary composite material reinforced high polymer material coating is characterized in that raw materials for preparing the binary composite material reinforced high polymer material coating comprise the binary composite material of any one of claims 1 to 9.

29. The coating of claim 28, wherein the polymer material comprises any one or a combination of at least two of epoxy, polyether, polyamide, or polyester.

30. The coating of claim 29, wherein the polymer material is an epoxy resin.

31. The method for preparing a coating of a binary composite reinforced polymeric material according to claims 28 to 30, wherein the method comprises: the binary composite material of any one of claims 1 to 9 is dissolved in an organic solvent, and then the curing agent and the high molecular material are added, stirred uniformly, coated on the surface of a substrate, and cured to obtain the binary composite material coating.

32. The method as claimed in claim 31, wherein the curing agent is polyether amine during the process of preparing the binary composite material reinforced polymer material coating.

33. The preparation method of claim 31, wherein in the process of preparing the binary composite material reinforced polymer material coating, the ratio of the mass of the binary composite material to the total mass of the curing agent and the polymer material is 0.6: 1.28.

34. The preparation method according to claim 31, wherein the ratio of the total mass of the binary composite material, the curing agent and the polymer material to the volume of the organic solvent is 0.001g/50ml to 50g/50 ml.

35. The method according to claim 34, wherein the ratio of the total mass of the binary composite material, the curing agent and the polymer material to the volume of the organic solvent is 1.88g/50 ml.

36. The method according to claim 31, wherein the coating is performed by any one of spray coating and spin coating.

37. The method of claim 31, wherein the substrate is glass.

38. The method of claim 31, wherein the curing is preceded by volatilizing the organic solvent.