Polymer composite nano coating material and preparation method thereof

Abstract

The invention discloses a polymer composite nano coating material which comprises the following components in parts by mass: 100 parts of fluorine-containing block A1, 42.86-100 parts of non-fluorine-containing block A2, 2.01-16.67 parts of high-conductivity filler B and 16.10-144.47 parts of fluorine modified high-dielectric filler C which are compounded by an in-situ miniemulsion polymerization method. A double-filler fluorine-containing polymer-based nano composite coating material three-phase system is prepared, and a high-dielectric and low-resistance nano composite material can be obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to a polymer composite nanocoating, in particular to a polymer composite nanocoating material and a preparation method thereof. BACKGROUND

[0002] At present, materials with the functions of "three-repellent and one-antistatic" (the "three-repellent" refers to water-repellent, oil-repellent and blood-repellent, and the "one-antistatic" refers to antistatic) can be used in the design of medical protective clothing. The main preparation method is to use the "three-repellent" components and the "one-antistatic" components in combination. However, the materials only with the functions of "three-repellent and one-antistatic" cannot be applied to scenarios requiring high dielectricity, such as thin film capacitors and flexible devices such as triboelectricity.

[0003] Patent No. CN118880610A discloses a preparation method and application of a polypropylene medical protective clothing "three-repellent and one-antistatic" finishing agent. The finishing agent prepared by mixing a high-permeability antistatic agent and a waterproof agent through padding and drying steps can be applied to polypropylene medical protective clothing, so that the polypropylene medical protective clothing has good "three-repellent and one-antistatic" functions. However, in the invention, the waterproof agent and the high-permeability antistatic agent are both high-molecular components, and the flexibility of the high-molecular chain limits the rapid response of the dipole under different frequency electric fields. It needs an external electric field to overcome the energy barrier of the molecular chain segment, so the response speed is slow, and therefore the overall dielectric property of the material is poor. SUMMARY

[0004] To solve the above problems, the present application provides a polymer composite nanocoating material and a preparation method thereof.

[0005] The present application provides the following technical scheme: a polymer composite nanocoating material, comprising 100 parts by mass of a fluorine-containing block A1, 42.86-100 parts by mass of a non-fluorine-containing block A2 and 2.01-16.67 parts by mass of a high-conductive filler B, which are compounded by an in-situ miniemulsion polymerization method, so that the fluorine-containing block A1 is connected with the non-fluorine-containing block A2 and coats the high-conductive filler B; and 16.10-144.47 parts by mass of a fluorine-modified high-dielectric filler C, which has a fluorine-fluorine interaction with the fluorine block A1. The fluorine-containing block A1 is a perfluorohexyl ethyl acrylate-octadecyl acrylate random copolymer; The non-fluorine-containing block A2 is a non-fluorine-containing acrylate monomer; The high-conductive filler B is one of a carboxylated multi-walled carbon nanotube modified by γ-methacryloxypropyl trimethoxysilane or a carboxylated single-walled carbon nanotube modified by γ-methacryloxypropyl trimethoxysilane; The fluorine-modified high-dielectric filler C is an inorganic nanoparticle modified by tridecafluorooctyl triethoxysilane.

[0006] The fluorine-containing block A1 mainly uses a side-chain fluorine-containing acrylate, supplemented by a functional acrylate monomer (non-fluorine-containing block A2), to prepare a block copolymer by an iodine transfer miniemulsion polymerization method. The prepared block copolymer has a microphase separation property, and the "molecular fence" property of the first segment fluorinated acrylate-octadecyl acrylate can make the polymer have a certain crystallinity, so that a good surface "three-repelling" anti-fouling function can be obtained at a reduced cost. The functional design not only improves the adhesion of the material to the substrate, but also improves the film forming temperature of the material and enhances the flexibility of the material.

[0007] The carbon nanotube conductive filler has a high aspect ratio, and can obviously improve the conductivity of the composite material.

[0008] The fluorine-modified high-dielectric filler can further solve the dispersion difficulty and poor interface compatibility between the high-dielectric filler and the polymer matrix by utilizing the interaction between fluorine and fluorine, so that the high-dielectric filler can be effectively formed during the processing.

[0009] Further, the mass ratio of perfluorohexyl ethyl acrylate to octadecyl acrylate in the fluorine-containing block A1 is 1:1.

[0010] Further, the non-fluorine-containing block A2 is a monomer homopolymerization or random copolymerization of one of butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofurfuryl acrylate and isobornyl acrylate.

[0011] Further, the inorganic nano-particle is one of calcium copper titanate, barium titanate, strontium titanate, barium strontium titanate and titanium dioxide.

[0012] A preparation method of the above-mentioned polymer composite nano-coating material, comprising the following steps: (1) using an in-situ miniemulsion polymerization method to composite the fluorine-containing block A1, the non-fluorine-containing block A2 and the high-conductive filler B; (2) using tridecafluorooctyltriethoxysilane to perform surface fluorination modification on one of calcium copper titanate, barium titanate, strontium titanate, barium strontium titanate and titanium dioxide, to obtain a fluorine-modified high-dielectric filler C; (3) mixing the fluorine-modified high-dielectric filler C with the fluorine-containing polymer A and the composite emulsion of the high-conductive filler B.

[0013] Further, in step (1), the step of compounding the fluorine-containing block A1, the non-fluorine-containing block A2 and the high-conductive filler B by in-situ miniemulsion polymerization is as follows: 3 parts by mass of cetyltrimethylammonium bromide is dissolved in 100 parts by mass of deionized water to obtain an aqueous phase; 0.2 parts by mass of perfluoroiodohexane, 6 parts by mass of n-hexadecane, 50 parts by mass of perfluorohexyl ethyl acrylate and 50 parts by mass of octadecyl acrylate are mixed, and 2.01-16.67 parts by mass of the high-conductive filler B is added to obtain an oil phase; the above aqueous phase and oil phase are stirred and mixed and ultrasonically dispersed to obtain a miniemulsion; the obtained miniemulsion is stirred and deoxygenated by argon, heated to 55 ℃, and 0.27 parts by mass of a solution of azobisdimethylamid hydrochloride mixed with 100 parts by mass of water is added to start polymerization, and after 6-8 h of reaction, the temperature is cooled to room temperature, 42.86-100 parts by mass of the non-fluorine-containing block A2 is added, deoxygenated by argon, and stirred until fully swollen, and then heated to 55 ℃ and a solution of azobisdimethylamid hydrochloride mixed with 100 parts by mass of water is added to polymerize for 3 h; after the reaction is completed, the obtained composite emulsion is cooled to room temperature.

[0014] Further, the preparation method of the high-conductive filler B is as follows: The carboxylated single-walled or multi-walled carbon nanotube is added to a mixed solution of ethanol and water in a volume ratio of 3:1, and ultrasonically dispersed, and 3% by volume of γ-methacryloyloxypropyltrimethoxysilane based on the mixed solution of ethanol and water is added; stirring is maintained, and the reaction is fully carried out at 60 ℃ for 1 h; after the reaction is completed, the reaction liquid is cooled to room temperature and centrifuged at 8000 rpm for 10 min, the supernatant is poured out, the bottom solid product is collected and vacuum dried at 50-60 ℃ for 6 h to obtain the high-conductive filler B.

[0015] Further, the preparation method of the fluorine-modified high-dielectric filler C is as follows: the inorganic nano-particle is naturally deliquesced at 50%-70% RH for 12 h to have hydroxyl groups on the surface; the inorganic nano-particle with hydroxyl groups on the surface is added to a mixed solution of ethanol and water in a volume ratio of 3:1, and ultrasonically dispersed, and 3% by volume of tridecafluorooctyltriethoxysilane based on the mixed solution of ethanol and water is added and ultrasonically dispersed again; stirring is maintained, and the reaction is carried out at 60 ℃ for 1 h; after the reaction is completed, the reaction liquid is cooled to room temperature and centrifuged at 8000 rpm for 10 min, the supernatant is poured out, the bottom solid product is collected and vacuum dried at 50-60 ℃ for 6 h to obtain the fluorine-modified high-dielectric filler C.

[0016] The beneficial effects of the present application are as follows: The three-phase system of the dual filler fluoropolymer-based nanocomposite coating material is prepared, and the nanocomposite material with high dielectric and low resistance can be obtained. The fluorine-modified high-dielectric filler C will settle in the plane during the film forming process, forming a layered structure. The layered structure design of the high-dielectric filler layer C and the fluorine-containing block A1, the non-fluorine-containing block A2 and the high-conductive filler B not only can retain the excellent surface "three-repelling" performance of the material, but also can improve the dielectric performance and reduce the resistance of the material. The fluorine-modified high-dielectric filler C can utilize the fluorine-fluorine interaction to regulate the chemical properties and physical forces of the filler and the polymer interface, so as to ensure that the high-dielectric filler C and the fluoropolymer have good interfacial compatibility, and will not agglomerate in the polymer matrix. The high-conductive filler B is compounded with the fluorine-containing block A1 and the non-fluorine-containing block A2 in an in-situ polymerization manner, the fluorine-containing block A1 and the non-fluorine-containing block A2 can well coat the high-conductive filler B, so as to ensure that the material has high dielectric and low resistance, and reduce the influence of the high-conductive filler B with polarity on the surface "three-repelling" performance of the material. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 The morphology and element analysis of the fluorine-modified high-dielectric filler C prepared in Example 1 of the present application, wherein (a) is the morphology of the fluorine-modified copper calcium titanate under the scanning electron microscope SU-8010 of Hitachi Company in Japan, (b) is the total diagram of the distribution of all elements of the fluorine-modified copper calcium titanate under the energy dispersive spectrometer (EDS) of Oxford X-max20; Figure 2 The distribution diagram of the fluorine-modified high-dielectric filler C prepared in Example 1 of the present application, wherein (a) is the distribution of carbon element (C), (b) is the distribution of oxygen element (O), (c) is the distribution of copper element (Cu), (d) is the distribution of titanium element (Ti), (e) is the distribution of fluorine element (F), (f) is the distribution of calcium element (Ca), and (g) is the distribution of silicon element (Si), which proves the successful preparation of the fluorine-modified copper calcium titanate. DETAILED DESCRIPTION

[0018] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined purposes, the specific embodiments, structures, features and effects according to the present application will be described in detail below in combination with the drawings and preferred embodiments.

[0019] In the present application, the high-conductive filler B is modified by γ-methacryloxypropyltrimethoxysilane, and the surface thereof has a polymerizable C=C structure, which provides a polymerization growth site for the fluorine-containing block A1. After the A1 and the A2 form the fluorine-containing block copolymer, the molecular size thereof is far larger than that of the high-conductive filler B, and the polymerization environment is emulsion. Under the thermodynamic driving, the fluorine-containing block A1 and the non-fluorine-containing block A2 self-assemble, so as to coat the high-conductive filler B.

[0020] The prepared process adopts a direct pouring film forming method. Due to the fact that the fluorine modified inorganic particle size is greater than the polymer emulsion latex particle size (inorganic particle size ~ 500 nm is greater than polymer latex particle size ~ 280 nm) and the physical property of the inorganic particle density is relatively large, in the film forming process, the fluorine modified inorganic particle is pressed and gravity settled to the bottom of the film, forming a high dielectric filler C and a double layer structure of a fluorine modified inorganic particle and a fluorine modified inorganic particle.

[0021] The polymer composite nanocoating material is prepared by the following method, comprising the following steps: (1) The fluorine modified inorganic particle is prepared by the following method, comprising the following steps:

[0022] The preparation method of the high conductive filler B is as follows: The carboxylated single-walled or multi-walled carbon nanotube is added into a mixed solution of ethanol and water, the volume ratio of ethanol and water is 3:1, and ultrasonic dispersion is performed, 3% of the volume fraction of the mixed solution of ethanol and water is added into γ-methacryloyloxypropyl trimethoxysilane; stirring is maintained, and the reaction is performed at 60 ℃ for 1 h; after the reaction is completed, the reaction liquid is cooled to room temperature and centrifuged at 8000 rpm for 10 min, the supernatant is poured out, the bottom solid product is collected and vacuum dried at 50-60 ℃ for 6 h, and the high conductive filler B is obtained.

[0023] (2) The surface of one of copper calcium titanate, barium titanate, strontium titanate, barium strontium titanate and titanium dioxide is modified by fluorination using tridecafluoro octyl triethoxysilane to obtain the fluorine modified high dielectric filler C; The preparation method of the fluorine-modified high-dielectric filler C is as follows: the inorganic nanoparticles are placed in an environment with a humidity of 50%-70% RH for natural deliquescence for 12 h, so that the surface of the inorganic nanoparticles is provided with hydroxyl groups; the inorganic nanoparticles with the surface provided with the hydroxyl groups are added into a mixed solution of ethanol and water, the volume ratio of the ethanol to the water is 3:1, and ultrasonic dispersion is performed, 3% of the volume fraction of the mixed solution of the ethanol and the water is added with tridecafluorooctyltriethoxysilane and ultrasonic dispersion is performed again; stirring is maintained, and reaction is performed at 60 ℃ for 1 h; after the reaction is completed, the reaction solution is cooled to room temperature and centrifuged at 8000 rpm for 10 min, the supernatant is poured out, the bottom solid product is collected and vacuum dried at 50-60 ℃ for 6 h, and the fluorine-modified high-dielectric filler C is obtained.

[0024] (3) The fluorine-modified high-dielectric filler C is mixed with the fluorine-containing block A1, the non-fluorine-containing block A2 and the high-conductive filler B.

[0025] In the fluorine-containing block A1, the mass ratio of the perfluorohexyl ethyl acrylate to the stearyl acrylate is 1:1.

[0026] In example 1, the non-fluorine-containing block A2 is butyl acrylate; the high-conductive filler B is carboxylated multi-walled carbon nanotube modified by γ-methacryloyloxypropyl trimethoxysilane, and the inorganic nanoparticles are calcium copper titanate, In example 2, the non-fluorine-containing block A2 is isooctyl acrylate; the high-conductive filler B is carboxylated multi-walled carbon nanotube modified by γ-methacryloyloxypropyl trimethoxysilane, and the inorganic nanoparticles are barium titanate, In example 3, the non-fluorine-containing block A2 is hydroxyethyl acrylate; the high-conductive filler B is carboxylated single-walled carbon nanotube modified by γ-methacryloyloxypropyl trimethoxysilane, and the inorganic nanoparticles are strontium titanate, In example 4, the non-fluorine-containing block A2 is ethoxyethoxyethyl acrylate; the high-conductive filler B is carboxylated single-walled carbon nanotube modified by γ-methacryloyloxypropyl trimethoxysilane, and the inorganic nanoparticles are strontium barium titanate, In example 5, the non-fluorine-containing block A2 is tetrahydrofurfuryl acrylate; the high-conductive filler B is carboxylated single-walled carbon nanotube modified by γ-methacryloyloxypropyl trimethoxysilane, and the inorganic nanoparticles are titanium dioxide, The examples of the present application are further described in the following multiple examples.

[0027] Example 1 A polymer composite nanocoating material, comprising 100 parts by mass of a fluorine-containing block A1, 100 parts by mass of a non-fluorine-containing block A2 and 16.67 parts by mass of a high-conductive filler B, which are compounded by an in-situ miniemulsion polymerization method, so that the fluorine-containing block A1 is connected with the non-fluorine-containing block A2 and coats the high-conductive filler B; and 144.47 parts by mass of a fluorine-modified high-dielectric filler C, which has a fluorine-fluorine interaction with the fluorine block A1. Wherein, Figure 1 With Figure 2 The modified morphology and element distribution map of the fluorine-modified high-dielectric filler C (i.e. fluorine-modified calcium copper titanate) in the present embodiment are shown. Figure 1 (a) is the morphology photo of the fluorine-modified calcium copper titanate under the scanning electron microscope of Japan Hitachi SU-8010, and (b) is the total element distribution map of the fluorine-modified calcium copper titanate under the Oxford X-max20 energy spectrometer (EDS). Figure 2 is the distribution map of specific elements of the fluorine-modified calcium copper titanate. (a) is the carbon element (C) distribution, (b) is the oxygen element (O) distribution, (c) is the copper element (Cu) distribution, (d) is the titanium element (Ti) distribution, (e) is the fluorine element (F) distribution, (f) is the calcium element (Ca) distribution, and (g) is the silicon element (Si) distribution, which proves the successful preparation of the fluorine-modified calcium copper titanate.

[0028] The ratio of the fluorine-containing block A1 to the non-fluorine-containing block A2 is appropriate, and the addition amount of the high-conductive filler B and the fluorine-modified high-dielectric filler C is relatively large. The high-conductive filler B forms a conductive network, and the fluorine-modified high-dielectric filler C also forms a continuous phase, which is beneficial to form a double-layer structure, and the dielectric performance of the whole material is relatively high.

[0029] Example 2 A polymer composite nanocoating material, comprising 100 parts by mass of a fluorine-containing block A1, 80 parts by mass of a non-fluorine-containing block A2 and 13 parts by mass of a high-conductive filler B, which are compounded by an in-situ miniemulsion polymerization method, so that the fluorine-containing block A1 is connected with the non-fluorine-containing block A2 and coats the high-conductive filler B; and 112.38 parts by mass of a fluorine-modified high-dielectric filler C, which has a fluorine-fluorine interaction with the fluorine block A1.

[0030] Compared with Example 1, the ratio of the non-fluorine-containing block A2, the high-conductive filler B and the fluorine-modified high-dielectric filler C is appropriately reduced at the same time, which can match the distribution state of the high-conductive filler B, the high-dielectric filler C, the fluorine-containing block A1 and the non-fluorine-containing block A2, so as to maintain good dielectric performance. At the same time, the content of the fluorine-containing block A1 is increased, and the three-repellence of the material of Example 1 is improved.

[0031] Example 3 A polymer composite nanocoating material, comprising 100 parts by mass of a fluorine-containing block A1, 66.67 parts by mass of a non-fluorine-containing block A2 and 9.34 parts by mass of a high-conductive filler B, which are compounded by an in-situ miniemulsion polymerization method, so that the fluorine-containing block A1 is connected with the non-fluorine-containing block A2 and coats the high-conductive filler B; and 80.285 parts by mass of a fluorine-modified high-dielectric filler C, which has a fluorine-fluorine interaction with the fluorine block A1.

[0032] Compared with Example 1, the proportions of the non-fluorine-containing block A2, the high-conductive filler B and the fluorine-modified high-dielectric filler C are appropriately reduced at the same time, which can match the distribution state of the high-conductive filler B, the high-dielectric filler C, the fluorine-containing block A1 and the non-fluorine-containing block A2, so as to maintain good dielectric properties. At the same time, the content of the fluorine-containing block A1 is further increased, and the tri-rejection property of the material is further improved compared with Example 2.

[0033] Example 4 A polymer composite nanocoating material, comprising 100 parts by mass of a fluorine-containing block A1, 57.14 parts by mass of a non-fluorine-containing block A2 and 5.675 parts by mass of a high-conductive filler B, which are compounded by an in-situ miniemulsion polymerization method, so that the fluorine-containing block A1 is connected with the non-fluorine-containing block A2 and coats the high-conductive filler B; and 48.19 parts by mass of a fluorine-modified high-dielectric filler C, which has a fluorine-fluorine interaction with the fluorine block A1.

[0034] Compared with Example 1, the proportions of the non-fluorine-containing block A2, the high-conductive filler B and the fluorine-modified high-dielectric filler C are appropriately reduced at the same time, which can match the distribution state of the high-conductive filler B, the high-dielectric filler C, the fluorine-containing block A1 and the non-fluorine-containing block A2, so as to maintain good dielectric properties. At the same time, the content of the fluorine-containing block A1 is further increased, and the tri-rejection property of the material is further improved compared with Example 3.

[0035] Example 5 A polymer composite nanocoating material, comprising 100 parts by mass of a fluorine-containing block A1, 42.86 parts by mass of a non-fluorine-containing block A2 and 2.01 parts by mass of a high-conductive filler B, which are compounded by an in-situ miniemulsion polymerization method, so that the fluorine-containing block A1 is connected with the non-fluorine-containing block A2 and coats the high-conductive filler B; and 16.10 parts by mass of a fluorine-modified high-dielectric filler C, which has a fluorine-fluorine interaction with the fluorine block A1.

[0036] Compared with Example 1, the ratio of non-fluorine-containing block A2, high-conductive filler B and fluorine-modified high-dielectric filler C is appropriately reduced at the same time, which can match the distribution state of high-conductive filler B, fluorine-modified high-dielectric filler C and fluorine-containing block A1 and non-fluorine-containing block A2, so as to maintain good dielectric performance. At the same time, the content of fluorine-containing block A1 is further increased, and the tri-rejection of the material is improved compared with Example 4.

[0037] Comparative Example 1 The difference between the present comparative example and Example 1 is that the amount of fluorine-containing block A1 is 120 parts by mass, specifically, 120 parts by mass of fluorine-containing block A1, 100 parts by mass of non-fluorine-containing block A2 and 16.67 parts by mass of high-conductive filler B, and 144.47 parts by mass of fluorine-modified high-dielectric filler C are compounded by in-situ miniemulsion polymerization method.

[0038] Compared with Example 1, the content of fluorine-containing block A1 is further increased, which improves the tri-rejection of the material. However, too much fluorine-containing block A1 greatly limits the activity of the polymer chain segment in the material, and the dipole orientation polarization is limited, which in turn inhibits the dielectric performance.

[0039] Comparative Example 2 The difference between the present comparative example and Example 1 is that the amount of fluorine-containing block A1 is 80 parts by mass, specifically, 80 parts by mass of fluorine-containing block A1, 100 parts by mass of non-fluorine-containing block A2 and 16.67 parts by mass of high-conductive filler B, and 144.47 parts by mass of fluorine-modified high-dielectric filler C are compounded by in-situ miniemulsion polymerization method.

[0040] Compared with Example 1, the content of fluorine-containing block A1 is less than that of non-fluorine-containing block A2, and the enrichment of fluorine to the surface of the material during the film forming process is severely inhibited, which greatly affects the tri-rejection of the material.

[0041] Comparative Example 3 The difference between the present comparative example and Example 1 is that the amount of non-fluorine-containing block A2 is 120 parts by mass, specifically, 100 parts by mass of fluorine-containing block A1, 120 parts by mass of non-fluorine-containing block A2 and 16.67 parts by mass of high-conductive filler B, and 144.47 parts by mass of fluorine-modified high-dielectric filler C are compounded by in-situ miniemulsion polymerization method.

[0042] Compared with Example 1, the content of non-fluorine-containing block A2 is increased, which inhibits the microphase separation with fluorine-containing block A1, and the tendency of fluorine-containing block A1 to enrich to the surface of the material during the film forming process is weakened, so the tri-rejection of the material is lower than that of Example 1, but compared with Comparative Example 2, the absolute content of fluorine-containing block A1 is higher, so the tri-rejection is higher than that of Comparative Example 2.

[0043] Comparative Example 4 The difference between the present comparative example and Example 1 is that the amount of non-fluorine-containing block A2 is 40 parts by mass. Specifically, it includes 100 parts by mass of fluorine-containing block Al, 40 parts by mass of non-fluorine-containing block A2, and 16.67 parts by mass of high-conductivity filler B, which are compounded by in-situ miniemulsion polymerization method, and 144.47 parts by mass of fluorine-modified high-dielectric filler C.

[0044] Compared with Example 1, the content of non-fluorine-containing block A2 is greatly reduced. Although the tri-rejection property of the material increases, the reduction of the content of soft segment A2 will cause the deterioration of filler dispersion, and the high-conductivity filler and the fluorine-modified high-dielectric filler C will tend to self-enrich, thereby failing to form a continuous phase, resulting in a decrease in dielectric property.

[0045] Comparative Example 5 The difference between the present comparative example and Example 1 is that the amount of high-conductivity filler B is 20 parts by mass. Specifically, it includes 100 parts by mass of fluorine-containing block Al, 100 parts by mass of non-fluorine-containing block A2, and 20 parts by mass of high-conductivity filler B, which are compounded by in-situ miniemulsion polymerization method, and 144.47 parts by mass of fluorine-modified high-dielectric filler C.

[0046] Compared with Example 1, the content of high-conductivity filler B is greatly increased. In the process of coating the high-conductivity filler B with the fluorine-containing block Al and the non-fluorine-containing block A2, it is inevitable that there will be a state of incomplete coating, forming a local continuous phase of the high-conductivity filler B itself. Moreover, since the polarity of the high-conductivity filler B is greater than that of the fluorine-containing block Al, the non-fluorine-containing block A2, and the fluorine-modified high-dielectric filler C, the polarity of the material is greatly enhanced, which will significantly damage the tri-rejection property of the material.

[0047] Comparative Example 6 The difference between the present comparative example and Example 1 is that the amount of high-conductivity filler B is 1 part by mass. Specifically, it includes 100 parts by mass of fluorine-containing block Al, 100 parts by mass of non-fluorine-containing block A2, and 1 part by mass of high-conductivity filler B, which are compounded by in-situ miniemulsion polymerization method, and 144.47 parts by mass of fluorine-modified high-dielectric filler C.

[0048] Compared with Example 1, the content of high-conductivity filler B is greatly reduced. The fluorine-containing block Al and the non-fluorine-containing block A2 almost completely coat the high-conductivity filler B. The polarity of the material is greatly reduced. Moreover, the amount of high-conductivity filler B added in the material forming process is far from the percolation threshold reached by the system, which means that the high-conductivity filler B cannot play a role in improving the dielectric property. Therefore, the dielectric property decreases significantly.

[0049] Comparative Example 7 The difference between the present comparative example and Example 1 is that the amount of fluorine-modified high-dielectric filler C is 150 parts by mass, specifically, 100 parts by mass of fluorine-containing block A1, 100 parts by mass of non-fluorine-containing block A2 and 16.67 parts by mass of high-conductive filler B are compounded by in-situ miniemulsion polymerization method, and 150 parts by mass of fluorine-modified high-dielectric filler C.

[0050] Compared with Example 1, the content of fluorine-modified high-dielectric filler C is higher, and too high filler concentration will cause a large amount of fluorine-modified high-dielectric filler C to agglomerate itself, and many fluorine-modified high-dielectric filler C will be enriched in the polymer layer, so there are more filler-polymer interface defects in the material, which not only affects the dielectric performance, but also damages the three-rejection performance of the material.

[0051] Comparative Example 8 The difference between the present comparative example and Example 1 is that the amount of fluorine-modified high-dielectric filler C is 15 parts by mass, specifically, 100 parts by mass of fluorine-containing block A1, 100 parts by mass of non-fluorine-containing block A2 and 16.67 parts by mass of high-conductive filler B are compounded by in-situ miniemulsion polymerization method, and 15 parts by mass of fluorine-modified high-dielectric filler C.

[0052] Compared with Example 1, the content of fluorine-modified high-dielectric filler C is very low, and too low fluorine-modified high-dielectric filler C not only cannot fully play the fluorine-fluorine interaction between it and the fluorine-containing block A1 to induce interface polarization, but also cannot completely form a double-layer structure, so the dielectric performance is low.

[0053] Comparative Example 9 The difference between the present comparative example and Example 1 is that the mixing method of fluorine-containing block A1, non-fluorine-containing block A2, high-conductive filler B and fluorine-modified high-dielectric filler C is different, specifically, 16.67 parts of high-conductive filler B and 144.47 parts of fluorine-modified high-dielectric filler C are added into 100 parts by mass of fluorine-containing block A1 and 100 parts by mass of non-fluorine-containing block A2 at the same time in the in-situ miniemulsion polymerization method.

[0054] Compared with Example 1, the compounding method of high-conductive filler B and fluorine-modified high-dielectric filler C with fluorine-containing block A1 and non-fluorine-containing block A2 is different, because the high-polarity high-conductive filler B is not coated by fluorine-containing block A1 and non-fluorine-containing block A2, it is exposed more outside the polymer, the dispersion of high-conductive filler B and fluorine-modified high-dielectric filler C is poor due to steric hindrance, so the damage to the three-rejection performance of the material is obvious.

[0055] The test method of dielectric constant, dielectric loss and resistivity is as follows: the material directly poured into a film is clamped between two copper sheets of Concept 40 broadband dielectric impedance spectrometer of Germany Novocontrol Technologies Company, the thickness of the film is input on the computer software corresponding to the instrument, and the instrument is started to measure the dielectric constant, dielectric loss and resistivity at 1 Hz and 100 Hz.

[0056] The test method of "three-repelling" performance is as follows: the material directly poured into a film is placed under OCA 20 video optical contact angle measuring instrument of Germany Dataphysics Company, the software corresponding to the instrument is controlled to keep the amount of water or n-hexadecane liquid dropped on the surface of the material as 5 μL each time, and the surface contact angle data is measured by the software.

[0057] Table 1: Dielectric constant, dielectric loss and resistivity of products of examples and comparative examples at electric field frequencies of 1 Hz and 100 Hz Table 2: Static surface water contact angle and n-hexadecane contact angle of products of examples and comparative examples It can be seen from Tables 1 and 2 that the product prepared by the scheme of the present application has good performance in "three-repelling and one-resistance" and dielectric performance.

[0058] The above is only the preferred embodiment of the present application, and does not limit the present application in any form. Although the present application has been disclosed as above with the preferred embodiment, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content to make equivalent embodiments with equivalent changes, without departing from the technical solution of the present application. Any modification, equivalent change and modification of the above embodiments made according to the technical essence of the present application, without departing from the technical solution of the present application, still belongs to the scope of the technical solution of the present application.

Claims

1. A polymer composite nanocoating material, characterized in that, It includes 100 parts by weight of fluorinated block A1, 42.86~100 parts by weight of non-fluorinated block A2 and 2.01~16.67 parts by weight of highly conductive filler B, which are compounded by in-situ microemulsion polymerization, so that the fluorinated block A1 and the non-fluorinated block A2 are connected and coated with highly conductive filler B; And, 16.10-144.47 parts by weight of fluorine-modified high-dielectric filler C, wherein the fluorine-modified high-dielectric filler C has a fluorine-fluorine interaction with the fluorine block A1; The fluorinated block A1 is a random copolymer of perfluorohexyl ethyl acrylate and octadecyl acrylate; The non-fluorinated block A2 is a homopolymer of fluorinated acrylate monomers; The highly conductive filler B is one of γ-methacryloxypropyltrimethoxysilane-modified carboxylated multi-walled carbon nanotubes or γ-methacryloxypropyltrimethoxysilane-modified carboxylated single-walled carbon nanotubes. The fluorine-modified high-dielectric filler C is an inorganic nanoparticle modified with tridecafluorooctyltriethoxysilane.

2. The polymer composite nanocoating material according to claim 1, characterized in that, The mass ratio of perfluorohexyl ethyl acrylate to octadecyl acrylate in the fluorinated block A1 is 1:

1.

3. The polymer composite nanocoating material according to claim 1, characterized in that, The fluorine-free acrylate monomers are butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, ethoxyethoxyethyl acrylate, or tetrahydrofuran acrylate.

4. The polymer composite nanocoating material according to claim 1, characterized in that, The inorganic nanoparticles are one of the following: calcium copper titanate, barium titanate, strontium titanate, barium strontium titanate, and titanium dioxide.

5. A method for preparing the polymer composite nanocoating material according to claim 1, characterized in that, Includes the following steps: (1) A composite emulsion was obtained by combining fluorinated block A1, non-fluorinated block A2 and highly conductive filler B using an in-situ fine emulsion polymerization method; (2) The surface of one of calcium copper titanate, barium titanate, strontium titanate, barium strontium titanate, and titanium dioxide was modified by fluorination using tridecafluorooctyltriethoxysilane to obtain fluorinated high dielectric filler C; (3) Mix the fluorine-modified high dielectric filler C with the composite emulsion so that the fluorine-modified high dielectric filler C and the fluorine-containing block A1 in the composite emulsion produce a fluorine-fluorine reaction.

6. The method according to claim 5, characterized in that, In step (1), the in-situ fine emulsion polymerization method is used to composite the fluorinated block A1, the non-fluorinated block A2, and the highly conductive filler B as follows: Dissolve 3 parts by mass of hexadecyltrimethylammonium bromide in 100 parts by mass of deionized water to obtain an aqueous phase; mix 0.2 parts by mass of perfluoroiodohexane, 6 parts by mass of n-hexadecane, 50 parts by mass of perfluorohexylethyl acrylate, and 50 parts by mass of octadecyl acrylate, and add 2.01~16.67 parts by mass of the highly conductive filler B to obtain an oil phase; stir and mix the above aqueous and oil phases and ultrasonically disperse them to obtain a fine emulsion; stir the obtained fine emulsion and purge oxygen with argon, heat to 55 ℃, add a solution of 0.27 parts by mass of azobisisobutylamidine hydrochloride mixed with 100 parts by mass of water to start polymerization, and react for 6~8 days. After cooling to room temperature for h, 42.86~100 parts by weight of fluorine-free acrylate monomers were added, argon was passed through to remove oxygen, and the mixture was stirred until fully swollen. The temperature was raised to 55 °C again and a solution of azobisisobutylamidine hydrochloride and 100 parts by weight of water was added for polymerization for 3 h. After the reaction was completed, the resulting composite emulsion was cooled to room temperature.

7. The method according to claim 5, characterized in that, The preparation method of highly conductive filler B is as follows: Carboxylated single-walled or multi-walled carbon nanotubes were added to a mixed solution of ethanol and water at a volume ratio of 3:1 and ultrasonically dispersed. γ-methacryloyloxypropyltrimethoxysilane was added at a volume fraction of 3% of the ethanol-water mixture. The mixture was stirred and reacted at 60 °C for 1 h. After the reaction, the reaction solution was cooled to room temperature and centrifuged at 8000 rpm for 10 min. The supernatant was discarded, and the bottom solid product was collected and vacuum dried at 50–60 °C for 6 h to obtain highly conductive filler B.

8. The method according to claim 5, characterized in that, The preparation method of fluorine-modified high-dielectric filler C is as follows: Inorganic nanoparticles are placed in an environment with a humidity of 50%-70%RH and allowed to naturally deliquesce for 12 h to generate hydroxyl groups on their surface; the inorganic nanoparticles with hydroxyl groups are added to a mixed solution of ethanol and water with a volume ratio of ethanol to water of 3:1 and ultrasonically dispersed; 3% (v / v) of tridecafluorooctyltriethoxysilane is added to the mixed solution of ethanol and water and ultrasonically dispersed again; stirring is maintained and the reaction is carried out at 60℃ for 1 h; after the reaction is completed, the reaction solution is cooled to room temperature and centrifuged at 8000 rpm for 10 min, the supernatant is poured off, the bottom solid product is collected and vacuum dried at 50~60℃ for 6 h to obtain fluorine-modified high-dielectric filler C.

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