CN113637399A - Functional coating, and preparation method and application thereof - Google Patents

Functional coating, and preparation method and application thereof Download PDF

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Publication number
CN113637399A
CN113637399A CN202110915846.8A CN202110915846A CN113637399A CN 113637399 A CN113637399 A CN 113637399A CN 202110915846 A CN202110915846 A CN 202110915846A CN 113637399 A CN113637399 A CN 113637399A
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polymer
functional coating
coating
filler
micron
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CN113637399B (en
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邓华
***
傅强
赵国杰
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Sichuan University
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • C—CHEMISTRY; METALLURGY
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/06—Polystyrene
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/49—Oxides or hydroxides of elements of Groups 8, 9, 10 or 18 of the Periodic System; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
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    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
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    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
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    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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    • D06N3/125—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyamides
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Abstract

The invention discloses a functional coating, and a preparation method and application thereof. The functional coating comprises a core-shell structure; the core of the core-shell structure is a micron-sized polymer, and the shell of the core-shell structure is a functionalized filler; the thickness of the shell is 50-200 nm. The polymer material surface and the functional coating have strong interface action, the mechanical and chemical stability of the coating is strong, the adverse effect on functionality caused by adding the polymer in the coating raw material can be greatly reduced, and the filler content in the functional coating can reach 90 wt% at most.

Description

Functional coating, and preparation method and application thereof
Technical Field
The invention relates to a functional coating, and a preparation method and application thereof.
Background
Functional materials can be prepared by applying functionalized fillers or polymer composites containing functionalized nanofillers to the surface of substrates such as fibers, fabrics, films, nonwovens, and foams to form functional coatings. Functional coatings can be used to alter the surface properties of the substrate, such as adhesion, wettability, corrosion or abrasion resistance, and the like. In other cases, such as in semiconductor device manufacturing (where the substrate is a wafer), the coating may add new properties (e.g., magnetic responsiveness or electrical conductivity) and may also constitute an essential part of the finished product, showing broad application prospects in flexible strain sensors, supercapacitors, electromagnetic shielding, and thermal conduction.
When a functional coating is prepared, if only the functionalized nano filler is coated on the surface of a substrate, the problems of poor interfacial action, poor coating adhesion, poor mechanical stability, poor weather resistance and the like between a polymer substrate and the functionalized filler are often faced, an aging phenomenon inevitably occurs under the action of sunlight ultraviolet rays, and the coating is more difficult to endure due to the thinness of the coating. The traditional improvement method is to prepare a functional coating after compounding a polymer and a functionalized filler and then coat the functional coating on the surface of a polymer matrix, but the method can only improve the interfacial action between the coating and the polymer matrix and the mechanical and chemical stability of the coating to a certain extent, and the polymer in the coating wraps the functionalized filler, thereby inevitably causing the functional reduction. In addition, because of the rigidity of the inorganic filler, the stability of the coating is reduced along with the increase of the content of the filler, so that the coating prepared by the method is difficult to combine high stability and high content of the inorganic filler. Therefore, maintaining the stability of the coating at high levels of inorganic filler remains an insurmountable hurdle in the art.
Disclosure of Invention
The invention provides a functional coating, a preparation method and application thereof, and aims to overcome the defects that when a functional coating is prepared on the surface of a polymer material in the prior art, a functional filler is wrapped by a raw polymer in the coating, so that the functionality of the coating is weakened, the mechanical and chemical stability is insufficient, and the stability of the coating and the high-content inorganic filler cannot be combined. The polymer material surface and the functional coating have strong interface action, the mechanical and chemical stability of the coating is strong, the adverse effect on functionality caused by adding the polymer in the coating raw material can be greatly reduced, and the filler content in the functional coating can reach 90 wt% at most.
The invention solves the technical problems through the following technical scheme.
The invention provides a functional coating, which comprises a core-shell structure;
the core of the core-shell structure is a micron-sized polymer, and the shell of the core-shell structure is a functionalized filler; the thickness of the shell is 50-200 nm.
In the present invention, the core-shell structure may be spherical, fibrous or dendritic. When the core-shell structure is dendritic, the length-diameter ratio is preferably 40-50.
In the invention, the specific surface area of the core-shell structure is 2500-20000 m2A/g, for example, of 2500 to 4000m2/g。
In the present invention, the polymer may be a polymer conventionally used in the art for surface modification of a matrix polymer, and the polymer may be one or more of polyurethanes, polyolefins, polystyrene, epoxy resins, polyacrylonitrile, polycaprolactam, polyvinylidene fluoride, aramid fibers, polyvinyl alcohol, polycarbonate, nanocellulose, cellulose acetate, and polymethyl methacrylate, such as polyurethane, polystyrene, aramid, or epoxy resin.
In the present invention, the particle size of the polymer is preferably 5 to 500 μm, for example, 100 to 200 μm.
In the present invention, the functionalized filler may be a functionalized filler conventional in the art, and is generally an inorganic filler, preferably one or more of an electrically conductive filler, a thermally conductive filler, a magnetic filler and a dielectric filler, more preferably a carbon filler, a metal oxide filler or a transition metal carbon/nitride filler, such as carbon nanotube, graphene, MXene (Ti) carbon3SiC2) Silicon dioxide, ferroferric oxide, manganese dioxide, nickel, barium titanate, boron nitride or carbon black.
In the present invention, the thickness of the housing is preferably 100 to 200 nm.
In the present invention, the functional coating is generally present in the form of a suspension, and the suspension further contains a solvent. Preferably, the solvent is a mixed solvent of a good solvent and a poor solvent of the polymer, and the core-shell structure is dispersed in the mixed solvent.
Wherein, the good solvent generally means that the polymer is easily soluble or soluble in the good solvent; the poor solvent generally means that the polymer is slightly soluble or poorly soluble in the poor solvent.
Preferably, the good solvent is one or more of N, N' -dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and acetone.
Preferably, the poor solvent is one or more of methanol, ethanol, isopropanol, tert-butanol and ethylene glycol.
Preferably, the volume ratio of the good solvent to the poor solvent is 1:1 to 1:10, for example, 1: 4.
In the present invention, preferably, the concentration of the polymer in the functional coating is 0.05-4 g/L, such as 0.2g/L or 1 g/L.
In the present invention, the mass percentage of the functionalized filler in the "polymer and the functionalized filler" is preferably 5 to 90%, more preferably 60 to 80%, for example 10%, 20%, 30%, 40%, 50% or 70%.
The invention provides a preparation method of the functional coating, which comprises the following steps:
and mixing the micelle solution containing the micron-sized polymer with the functionalized filler.
In the present invention, preferably, the micellar solution containing the micron-sized polymer can be prepared by turbulent shear and a solvent-poor solvent induced phase separation method. The turbulent shear generally refers to the shear stress generated when a fluid is in turbulent motion. The solvent-poor solvent induced phase separation generally refers to a method of dissolving a substance in a good solvent according to the solubility principle, and then adding a poor solvent to separate out the substance in the form of crystallization or coating on the surface of other substances; wherein the good solvent and the poor solvent are both for the substance to be dissolved.
The micellar solution containing the micron-sized polymer is preferably prepared by any one of the following methods:
mode I: dripping the solution containing the polymer into a poor solvent of the polymer, and mixing;
mode II: and (3) dripping a poor solvent of the polymer into the solution containing the polymer, and mixing.
In the mode I, the dropping speed of the polymer solution is preferably 3 to 10mL/min, for example, 5 mL/min.
In the mode I, in the dropping process, the stirring speed of the poor solvent is preferably 13000-20000 rpm.
In the mode II, the dropping speed of the poor solvent is preferably 3 to 10mL/min, for example, 5 mL/min.
In the mode II, the stirring speed of the solution containing the polymer during the dropping is preferably 13000 to 20000 rpm.
In the mode I or the mode II, when the stirring rotating speed is 13000-16000 rpm, the core-shell structure is spherical and/or fibrous; when the stirring speed is 16000-20000 rpm, the core-shell structure is dendritic.
In the mode I or II, the solvent used in the polymer solution is a good solvent for the polymer, which is conventional in the art, and the kind and the amount of the good solvent are preferably as described above.
In the embodiment I or II, the kind and amount of the poor solvent are preferably as described above.
In the invention, preferably, the functionalized filler is filler after ultrasonic treatment. More preferably, the functionalized filler is a filler that has not been surface modified with a modifier.
In the present invention, the stirring speed of the mixing is preferably 300 to 600rpm, for example, 400 rpm.
In the present invention, the mixing time is preferably 10 to 60 min.
The invention also provides a functional coating which is prepared by the preparation method of the functional coating.
The invention also provides the application of the functional coating as a coating material in the surface modification of the polymer.
The invention also provides a preparation method of the functional coating, which comprises the following steps:
applying a functional coating as described above to the surface of a substrate, wherein the functional coating is applied per square meter of substrateThe dosage of the functional coating on the surface is 15-20 g/m2。
In the present invention, the thickness of the functional coating layer on the surface of the substrate is preferably 1 μm or more, for example, 1 to 2 μm.
In the present invention, preferably, the coating is generally spin coating, drop coating, dip coating, spray coating, 3D print coating, or roll coating.
Preferably, the number of coating times is 3 to 18.
In the present invention, preferably, the substrate is a fiber, a film, a non-woven fabric, a foam or a sponge, and the functional coating has wide applicability.
The invention also provides a functional coating which is prepared by the preparation method of the functional coating.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) when the functional coating is applied to the surface of a matrix polymer to form a functional coating, the interface action between the polymer surface and the functional coating is strong, the mechanical and chemical stability of the coating is strong, the environmental stability is high, the multifunctional coating has multiple functions, the reduction of the functionality caused by the polymer wrapping the functional filler is avoided, and the performance of the functional coating is improved.
(2) The content of the filler in the functional coating can reach 90 wt% at most, and a stable and compact filler network can be formed.
(3) In addition, the preparation method of the functional coating and the functional coating has simple process, and the shape and the structure of the polymer micelle can be accurately adjusted by adjusting the concentration of the polymer solution and the stirring revolution.
(4) In a preferred embodiment of the present invention, when the content of the carbon nanotubes is 60 wt%, the conductivity of the modified sponge material is increased by 35 times, the electromagnetic shielding performance is increased by 105%, the electromagnetic shielding performance is still maintained by nearly 96% after water washing or acid-base treatment, and good environmental stability is exhibited.
Drawings
Fig. 1 is a polarization microscope image of the micron-sized polymer micelle of example 1.
Fig. 2 is a scanning electron microscope image of the micron-sized functionalized polymer micelle of example 1, wherein 1 is the micron-sized functionalized polymer micelle, and 2 is the carbon nanotube.
FIG. 3 is a scanning electron microscope image of the foam substrate and the functional coating of example 1, wherein 1 is the micron-sized functionalized polymer micelle, and 2 is the foam substrate.
Fig. 4 is a graph of the electrical conductivity of the functional coatings of examples 1, 5, 11 and 16.
Fig. 5 is a graph of the electromagnetic shielding effectiveness of the functional coatings of examples 1, 5, 11 and 16.
FIG. 6 is a graph of electromagnetic shielding effectiveness of the coating of comparative example 1, the functional coatings of comparative examples 2-5, and example 1.
Fig. 7 is a graph showing the electromagnetic shielding effectiveness of the functional coatings of comparative examples 2 to 5 and example 1 after acid or alkali treatment.
Fig. 8 is a graph of electromagnetic shielding effectiveness after the coating of comparative example 1, the functional coatings of comparative examples 2 to 5, and example 1 were stripped 10 times.
Fig. 9 is a scanning electron microscope image of the functional coating of example 2, wherein 1 is a textile substrate, and 2 is a micron-sized functionalized polymer micelle.
FIG. 10 is a scanning electron micrograph of the functional coating of example 4.
FIG. 11 is a graph of transmission, reflection and absorption coefficients for the functional coating of example 4.
FIG. 12 is a graph showing the effect of the number of coatings on the electromagnetic shielding effectiveness of the polymer matrix in example 5.
FIG. 13 is a graph showing the effect of the amount of carbon nanotubes used on the conductivity of the polymer matrix in example 6.
FIG. 14 is a polarization microscope photograph of the micron-sized polymer micelles produced at a low shear rate in example 17.
Fig. 15 is a graph of electromagnetic shielding effectiveness of the functional coating of example 17.
Fig. 16 is a graph of electromagnetic shielding effectiveness of the functional coating of example 18.
FIG. 17 is a graph of the lengths of the micron-sized polymer micelles of examples 1, 17, and 18.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples, the changes in the parameters are shown in table 1 below.
TABLE 1 variation of parameters of examples 1 to 18
Figure BDA0003205563040000071
Example 1
(1) Dissolving 0.05g of polyurethane in 50mL of N, N' -dimethylformamide to obtain a polyurethane solution, dropwise adding the polyurethane solution into 200mL of isopropanol with the stirring revolution number of 20000rpm at the speed of 5mL/min, and performing turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized polyurethane micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized polyurethane micelle suspension and 0.075g of the carbon nano tube filler subjected to ultrasonic treatment at the stirring speed of 400rpm for 10min to obtain the micron-sized functional polyurethane micelle suspension (functional coating) with high filler content.
(3) Dripping the micron-sized functional polyurethane micelle suspension with high filler content on the surface of a foam matrix for 6-8 times to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the matrix is 15g/m2。
FIG. 1 is a polarization microscope image of the micron-sized polymer micelle (product of step 1) of example 1, and it can be seen from FIG. 1 that the polymer micelle has a multiple branched structure similar to a "tree branch", and the micron-sized polymer micelle has a high aspect ratio (40-50) and a large specific surface area. This is because the droplets of the polymer are randomly stretched by the shearing action of the turbulent stress, and the dendritic polymer micelles are precipitated in equilibrium, while the solvent outflow and the poor solvent inflow occur in the poor solvent having a certain viscosity.
Fig. 2 is a scanning electron microscope image of the micron-sized functionalized polymer micelle (the product of step 2) in example 1, and it can be seen from fig. 2 that the carbon nanotube, as an "outer shell", is wrapped on the surface of the "inner core" of the micron-sized functionalized polymer micelle to form a "core-shell structure" with a high aspect ratio, wherein the thickness of the "outer shell" is about 100-200 nm. The residual solution in the polymer micelle enables the polymer micelle to be in a slightly swelling state for a long time, and the functionalized filler is more easily embedded into the surface layer of the polymer micelle to form a continuous and compact filler network.
FIG. 3 is a scanning electron microscope image of the foam substrate and the functional coating (product of step 3) of example 1, and it can be seen from FIG. 3 that the functional coating forms a dense continuous network on the surface of the porous foam substrate, and the thickness of the functional coating is about 1-2 μm. The result shows that the prepared micron-sized functionalized polymer micelle has good adhesion, so that the interfacial interaction between the filler and the matrix is increased, and the mechanical and chemical stability of the functional coating is improved.
As can be seen from FIG. 4, the foam matrix material modified by the micron-sized functionalized polymer micelle has very high conductivity (the conductivity of the products of examples 1, 5, 11 and 16 is 2.01S/cm, 1.87S/cm, 2.23S/cm and 1.79S/cm, respectively). The polymer micelle is used as an intermediate layer to connect the outer-layer functionalized filler and the inner matrix, so that the interfacial interaction between the filler and the matrix is improved, and the surface of the filler is not wrapped, so that the functionality of the filler is not reduced.
As can be seen from fig. 5, the foam base material modified by the micron-sized functionalized polymer micelle has high electromagnetic shielding effectiveness (the electromagnetic shielding effects of the products of examples 1, 5, 11, and 16 are 40.1dB, 39.2dB, 37.6dB, and 38.6dB, respectively). In FIG. 5, the testing frequency of the electromagnetic shielding effect is 8.2 to 12.4 GHz.
Comparative example 1
(1) 0.05g of polyurethane was dissolved in 50mL of N, N' -dimethylformamide to obtain a polyurethane solution, and the polyurethane solution was added dropwise at a rate of 5mL/min to 200mL of isopropanol with stirring revolution of 20000rpm, followed by turbulent shear and solvent-poor solvent induced phase separation to form a micron-sized polymer micelle solution (paint).
(2) Dripping the pure polyurethane micelle suspension on the surface of a foam matrix for 6-8 times to form a coating, wherein the dosage of the coating per square meter of the surface of the matrix is 10g/m2。
Comparative example 2
0.075g of the carbon nanotube filler after ultrasonic treatment and 0.675g of Sodium Dodecyl Benzene Sulfonate (SDBS) solution are blended, the stirring speed is 400rpm, and the stirring time is 10min, so that the modified carbon nanotube suspension (functional coating) with high filler content is obtained.
Dropping the modified carbon nanotube suspension with high filler content on the surface of the foam matrix for 6-8 times to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the matrix is 15g/m2。
Comparative example 3
In comparison with comparative example 2, Sodium Dodecylbenzenesulfonate (SDBS) was replaced with a silane coupling agent KH550 solution, and the remaining operations and conditions were the same as in comparative example 2.
Comparative example 4
In comparison with comparative example 2, Sodium Dodecylbenzenesulfonate (SDBS) was replaced with a cetylammonium bromide (CTBA) solution, and the remaining operations and conditions were the same as in comparative example 2.
Comparative example 5
In comparison with comparative example 2, Sodium Dodecylbenzenesulfonate (SDBS) was replaced with Polydopamine (PDA) solution, and the remaining operations and conditions were the same as in comparative example 2.
As can be seen from fig. 6, compared with the foam base material treated by other surfactants, the foam base material of example 1 has greatly improved electrical conductivity, and has higher electromagnetic shielding effectiveness.
As can be seen from fig. 7, the foam base material of example 1 has better chemical stability than the foam base material treated with other surfactants, and the electromagnetic shielding effectiveness is still maintained above 97% after the foam base material is subjected to acid or alkali treatment (wherein the acid or alkali treatment is to immerse the product of example or comparative example in an acid solution or an alkali solution for 1 hour, the acid solution is hydrochloric acid solution with pH 1, and the alkali solution is sodium hydroxide solution with pH 13). The test frequency of the electromagnetic shielding effect corresponding to fig. 7 is 8.2 to 12.4 GHz. The results are shown in table 2 below.
TABLE 2 comparison of electromagnetic shielding effectiveness after acid treatment and alkali treatment of example 1 and comparative examples 2 to 5
Example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Original 40.1 16.7 16.9 26.8 16.2
Acid treatment 39.6 1.8 1.6 2.5 1.7
Alkali treatment 39.8 1.7 1.8 2.6 1.6
As can be seen from fig. 8, compared to the foam base material treated with other surfactants, the foam base material of example 1 has better mechanical stability, and when the tape is repeatedly peeled off for 10 times, the electromagnetic shielding effectiveness is still as high as 36.1 dB. The test frequency of the electromagnetic shielding effect corresponding to fig. 8 is 8.2 to 12.4 GHz.
Example 2
(1) Dissolving 0.05g of polystyrene in 50mL of tetrahydrofuran to obtain a polystyrene solution, dropwise adding the polystyrene solution into 200mL of isopropanol with the stirring revolution number of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized polystyrene micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized polystyrene micelle suspension and 0.075g of the metal nickel filler after ultrasonic treatment at the stirring speed of 400rpm for 10min to obtain the micron-sized functionalized polystyrene micelle suspension (functional coating) with high filler content.
(3) Dripping the micron-sized functionalized polystyrene micelle suspension with high filler content on the surface of the fabric substrate for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the substrate surface is 15g/m2。
From the scanning electron micrograph of the functional coating of fig. 9, the functional coating forms a dense continuous network on the surface of the fabric substrate. Wherein the functionalized filler is arranged on the outermost layer, and the polymer is distributed between the functionalized filler and the matrix material. The prepared micron-sized functionalized polystyrene micelle has good adhesion, so that the interfacial interaction between the metal filler and the fabric is increased, and the mechanical and chemical stability of the functional coating is improved.
Example 3
(1) Dissolving 0.05g of aramid fiber in 50mL of dimethyl sulfoxide to obtain an aramid fiber solution, dropwise adding the aramid fiber solution into 200mL of isopropanol with the stirring revolution of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized aramid fiber micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized aramid fiber micelle suspension and 0.075g of ultrasonically treated MXene filler at the stirring speed of 400rpm for 10min to obtain the micron-sized functionalized aramid fiber micelle suspension (functional coating) with high filler content.
(3) Dripping micron-sized functionalized aramid fiber micelle suspension with high filler content on the surface of a film matrix for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the matrix is 15g/m2。
MXene filler is arranged on the outermost layer, and polymer is distributed between the functionalized filler and the matrix material, so that a stable and compact functional coating with strong interface action, strong adhesion, high filler content is formed on the surface of the matrix. The method not only enhances the interfacial interaction between the filler and the matrix and improves the mechanical and chemical stability of the coating, but also is convenient for large-scale industrialized preparation of the coating material with high filler content.
Example 4
(1) Dissolving 0.05g of epoxy resin in 50mL of acetone to obtain an epoxy resin solution, dropwise adding the epoxy resin solution into 200mL of isopropanol with the stirring revolution of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized epoxy resin micelle suspension.
(2) Mixing the micron-sized epoxy micelle suspension with0.075g of sonicated Fe3O4And (3) carrying out solution blending on the filler, wherein the stirring speed is 400rpm, and the stirring time is 10min, so as to obtain the micron-sized functionalized epoxy resin micelle suspension (functional coating) with high filler content.
(3) Dripping micron-sized functionalized epoxy resin micelle suspension with high filler content on the surface of a fiber matrix for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the matrix is 15g/m2。
From FIG. 10, the metal oxide (Fe)3O4) A continuous and compact coating is formed on the surface of the fiber, the thickness of the coating is about 1 mu m, the magnetic permeability of the material is remarkably improved, and the absorption capacity of the material to electromagnetic waves is enhanced. As shown in fig. 11, the absorption ratio is about 0.9.
Example 5
(1) Dissolving 0.05g of aramid fiber in 50mL of dimethyl sulfoxide to obtain an aramid fiber solution, dropwise adding the aramid fiber solution into 200mL of isopropanol with the stirring revolution of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized aramid fiber micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized aramid fiber micelle suspension and 0.075g of metal nickel filler subjected to ultrasonic treatment at the stirring speed of 400rpm for 10min to obtain the micron-sized functionalized aramid fiber micelle suspension (functional coating) with high filler content.
(3) The micron-sized functionalized aramid fiber micelle suspension with high filler content is coated on the surface of a foam matrix for 3-18 times in a spinning mode to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the matrix is 15g/m2。
As can be seen from fig. 12, the electromagnetic shielding effectiveness of the foam is greatly improved as the number of coating times is increased, and the electromagnetic shielding effectiveness of the entire foam exceeds 100dB when the number of coating times is 5. And the coating times are continuously increased, so that the electromagnetic shielding efficiency of the foam is improved slightly and is close to the limit of materials. Specific data are shown in table 3.
TABLE 3 Effect of the number of coatings on the electromagnetic shielding effectiveness of the Polymer matrix in example 5
Figure BDA0003205563040000121
Figure BDA0003205563040000131
Example 6
(1) Dissolving 0.05g of epoxy resin in 50mL of acetone to obtain an epoxy resin solution, dropwise adding the epoxy resin solution into 200mL of isopropanol with the stirring revolution of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized epoxy resin micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized epoxy resin micelle suspension and 0.075g of the carbon nano tube filler after ultrasonic treatment at the stirring speed of 400rpm for 10min to obtain the micron-sized functionalized epoxy resin micelle suspension (functional coating) with high filler content.
(3) The micron-sized functionalized epoxy resin micelle suspension with high filler content is coated on the surface of a fabric substrate for 3-18 times in a spinning mode to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the substrate is 15g/m2。
As shown in fig. 13, as the mass percentage of the carbon nanotubes in the total mass of the polymer and the carbon nanotubes increases, the conductivity of the fabric is significantly increased, when the content of the carbon nanotubes reaches 60 wt%, the conductivity of the fabric reaches a maximum of about 10S/cm, and when the content of the carbon nanotubes is continuously increased, the interfacial action between the carbon nanotubes and the fabric substrate is decreased, and the conductivity is decreased instead. Specific data are shown in table 4.
Table 4 effect of amount of carbon nanotubes used on conductivity of polymer matrix in example 6
Figure BDA0003205563040000141
Example 7
(1) Dissolving 0.05g of polyurethane in 50mL of N, N' -dimethylformamide to obtain a polyurethane solution, dropwise adding the polyurethane solution into 200mL of isopropanol with the stirring revolution number of 20000rpm at the speed of 5mL/min, and performing turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized polyurethane micelle suspension.
(2) Mixing the micron-sized polyurethane micelle suspension with 0.075g of Fe subjected to ultrasonic treatment3O4And (3) carrying out solution blending on the filler, wherein the stirring speed is 400rpm, and the stirring time is 10min, so as to obtain the micron-sized functional polyurethane micelle suspension (functional coating) with high filler content.
(3) The micron-sized functional polyurethane micelle suspension with high filler content is coated on the surface of a film matrix for 3-18 times in a spinning mode to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the matrix is 15g/m2。
Example 8
(1) Dissolving 0.05g of polystyrene in 50mL of tetrahydrofuran to obtain a polystyrene solution, dropwise adding the polystyrene solution into 200mL of isopropanol with the stirring revolution number of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized polystyrene micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized polystyrene micelle suspension and 0.075g of ultrasonically treated MXene filler at the stirring speed of 400rpm for 10min to obtain the micron-sized functionalized polystyrene micelle suspension (functional coating) with high filler content.
(3) The micron-sized functionalized polystyrene micelle suspension with high filler content is coated on the surface of a fiber matrix for 3-18 times in a spinning mode to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the matrix is 15g/m2。
Example 9
(1) Dissolving 0.05g of epoxy resin in 50mL of acetone to obtain an epoxy resin solution, dropwise adding the epoxy resin solution into 200mL of isopropanol with the stirring revolution of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized epoxy resin micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized epoxy resin micelle suspension and 0.075g of ultrasonically treated MXene filler at the stirring speed of 400rpm for 10min to obtain the micron-sized functionalized epoxy resin micelle suspension (functional coating) with high filler content.
(3) Soaking the foam matrix in micron-sized functionalized epoxy resin micelle suspension with high filler content for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the matrix surface is 15g/m2。
Example 10
(1) Dissolving 0.05g of aramid fiber in 50mL of dimethyl sulfoxide to obtain an aramid fiber solution, dropwise adding the aramid fiber solution into 200mL of isopropanol with the stirring revolution of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized aramid fiber micelle suspension.
(2) Mixing the micron aramid fiber micelle suspension with 0.075g of ultrasonically treated Fe3O4And (3) carrying out solution blending on the filler, wherein the stirring speed is 400rpm, and the stirring time is 10min, so as to obtain the micron-sized functionalized aramid fiber micelle suspension (functional coating) with high filler content.
(3) Soaking a fabric substrate in micron-sized functionalized aramid fiber micelle suspension with high filler content for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the substrate surface is 15g/m2。
Example 11
(1) Dissolving 0.05g of polystyrene in 50mL of tetrahydrofuran to obtain a polystyrene solution, dropwise adding the polystyrene solution into 200mL of isopropanol with the stirring revolution number of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized polystyrene micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized polystyrene fiber micelle suspension and 0.075g of the carbon nano tube filler after ultrasonic treatment at the stirring speed of 400rpm for 10min to obtain the micron-sized functionalized polystyrene suspension (functional coating) with high filler content.
(3) Soaking the film substrate in micron-sized functional polystyrene micelle suspension with high filler content for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the substrate surface is 15g/m2。
Example 12
(1) Dissolving 0.05g of polyurethane in 50mL of N, N' -dimethylformamide to obtain a polyurethane solution, dropwise adding the polyurethane solution into 200mL of isopropanol with the stirring revolution number of 20000rpm at the speed of 5mL/min, and performing turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized polyurethane micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized polyurethane fiber micelle suspension and 0.075g of the metal nickel filler after ultrasonic treatment at the stirring speed of 400rpm for 10min to obtain the micron-sized functional polyurethane suspension (functional coating) with high filler content.
(3) Soaking a fiber matrix in micron-sized functional polyurethane micelle suspension with high filler content for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the matrix surface is 15g/m2。
Example 13
(1) Dissolving 0.05g of polystyrene in 50mL of tetrahydrofuran to obtain a polystyrene solution, dropwise adding the polystyrene solution into 200mL of isopropanol with the stirring revolution number of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized polystyrene micelle suspension.
(2) Mixing the micron-sized polystyrene micelle suspension with 0.075g of ultrasonically treated Fe3O4And (3) carrying out solution blending on the filler, wherein the stirring speed is 400rpm, and the stirring time is 10min, so as to obtain the micron-sized functionalized polystyrene micelle suspension (functional coating) with high filler content.
(3) Spraying the micron-sized functionalized polystyrene micelle suspension with high filler content on the surface of a foam matrix for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the matrix is 15g/m2。
Example 14
(1) Dissolving 0.05g of polyurethane in 50mL of N, N' -dimethylformamide to obtain a polyurethane solution, dropwise adding the polyurethane solution into 200mL of isopropanol with the stirring revolution number of 20000rpm at the speed of 5mL/min, and performing turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized polyurethane micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized polyurethane micelle suspension and 0.075g of ultrasonically treated MXene filler at the stirring speed of 400rpm for 10min to obtain the micron-sized functional polyurethane micelle suspension (functional coating) with high filler content.
(3) Spraying the micron-sized functional polyurethane micelle suspension with high filler content on the surface of a fabric substrate for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the substrate is 15g/m2。
Example 15
(1) Dissolving 0.05g of epoxy resin in 50mL of acetone to obtain an epoxy resin solution, dropwise adding the epoxy resin solution into 200mL of isopropanol with the stirring revolution of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized epoxy resin micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized epoxy resin micelle suspension and 0.075g of metal nickel filler subjected to ultrasonic treatment at the stirring speed of 400rpm for 10min to obtain the micron-sized functionalized epoxy resin micelle suspension (functional coating) with high filler content.
(3) Spraying the micron-sized functionalized epoxy resin micelle suspension with high filler content on the surface of a film matrix for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the matrix is 15g/m2。
Example 16
(1) Dissolving 0.05g of aramid fiber in 50mL of dimethyl sulfoxide to obtain an aramid fiber solution, dropwise adding the aramid fiber solution into 200mL of isopropanol with the stirring revolution of 20000rpm at the speed of 5mL/min, and carrying out turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized aramid fiber micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized aramid fiber micelle suspension and 0.075g of ultrasonically treated carbon nano tube filler at the stirring speed of 400rpm for 10min to obtain the micron-sized functionalized aramid fiber micelle suspension (functional coating) with high filler content.
(3) Spraying the micron-sized functionalized aramid fiber micelle suspension with high filler content on the surface of a fiber substrate for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the substrate is 15g/m2。
Example 17
(1) 0.05g of polyurethane is dissolved in 50mL of N, N' -dimethylformamide to obtain a polyurethane solution, the polyurethane solution is dripped into 200mL of isopropanol with the stirring revolution of 13000rpm at the speed of 5mL/min, and a micron-sized polyurethane micelle suspension is formed by turbulent shear and solvent-poor solvent induced phase separation.
(2) And (3) carrying out solution blending on the micron-sized polyurethane micelle suspension and 0.075g of the carbon nano tube filler subjected to ultrasonic treatment at the stirring speed of 400rpm for 10min to obtain the micron-sized functional polyurethane micelle suspension (functional coating) with high filler content.
(3) Spraying the micron-sized functional polyurethane micelle suspension with high filler content on the surface of a fiber matrix for 3-18 times to form a functional coating, wherein the dosage of the functional coating per square meter of the surface of the matrix is 15g/m2。
As can be seen from fig. 14, when the number of revolutions is lower, the polymer solution is subjected to less shear under the poor solvent, the size of the formed polymer fiber is larger, and the morphology is more spherical and fibrous.
As can be seen from fig. 15 and 17, when the number of revolutions is low, the polymer solution is less sheared under the poor solvent, the size of the formed polymer fiber is larger, the covering effect of the filler is reduced, and the electromagnetic shielding effectiveness is somewhat reduced (-32.6 dB). Specific data are shown in table 5 below.
TABLE 5 Length and electromagnetic shielding effectiveness of examples 1, 17, 18
Examples Length (mm) Electromagnetic shielding effectiveness (dB)
1 200 40.1
17 350 36.2
18 300 38.7
Example 18
(1) Dissolving 0.25g of polyurethane in 50mL of N, N' -dimethylformamide to obtain a polyurethane solution, dropwise adding the polyurethane solution into 200mL of isopropanol with the stirring revolution number of 20000rpm at the speed of 5mL/min, and performing turbulent shear and solvent-poor solvent induced phase separation to form the micron-sized polyurethane micelle suspension.
(2) And (3) carrying out solution blending on the micron-sized polyurethane micelle suspension and 0.375g of the carbon nano tube filler after ultrasonic treatment at the stirring speed of 400rpm for 10min to obtain the micron-sized functional polyurethane micelle suspension (functional coating) with high filler content.
(3) Spraying the micron-sized functionalized polyurethane micelle suspension with high filler content on the surface of the fiber matrix for 3-18 times to form a functional coating, wherein the function of each square meter of the surface of the matrixThe amount of the coating is 15g/m2。
As can be seen from fig. 16 and 17, when the concentration of the polymer solution is increased, the polymer solution is subjected to less shear under the poor solvent, the size of the formed polymer fiber is larger, the covering effect of the filler is reduced, and the electromagnetic shielding effectiveness is reduced to a certain extent (36.5 dB).
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.

Claims (10)

1. A functional coating is characterized in that the functional coating comprises a core-shell structure;
the core of the core-shell structure is a micron-sized polymer, and the shell of the core-shell structure is a functionalized filler; the thickness of the shell is 50-200 nm.
2. The functional coating of claim 1, wherein the core-shell structure is spherical, fibrous, or dendritic; when the core-shell structure is dendritic, the length-diameter ratio of the core-shell structure is preferably 40-50;
and/or the specific surface area of the core-shell structure is 2500-20000 m2A/g, for example, of 2500 to 4000m2/g；
And/or the polymer is one or more of polyurethanes, polyolefins, polystyrene, epoxy resins, polyacrylonitrile, polycaprolactam, polyvinylidene fluoride, aramid fibers, polyvinyl alcohol, polycarbonate, nanocellulose, acetate fibers and polymethyl methacrylate, such as polyurethane, polystyrene, aramid or epoxy resin;
and/or the particle size of the polymer is 5-500 μm, such as 100-200 μm;
and/or the functionalized filler is one or more of an electrically conductive filler, a thermally conductive filler, a magnetic filler and a dielectric filler, preferably a carbon filler, a metal oxide filler or a transition metal carbon/nitride filler, such as carbon nanotubes, graphene, MXene, silica, ferroferric oxide, manganese dioxide, nickel, barium titanate, boron nitride or carbon black;
and/or the thickness of the shell is 100-200 nm.
3. The functional coating of claim 1, further comprising a solvent; preferably, the solvent is a mixed solvent of a good solvent and a poor solvent of the polymer; the good solvent is preferably one or more of N, N' -dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and acetone; the poor solvent is preferably one or more of methanol, ethanol, isopropanol, tert-butanol and ethylene glycol; the volume ratio of the good solvent to the poor solvent is preferably 1:1 to 1:10, for example, 1: 4;
and/or, in the functional coating, the concentration of the polymer is 0.05-100 g/L, preferably 0.05-4 g/L, such as 0.2g/L or 1 g/L;
and/or the functionalized filler accounts for 5-90% of the polymer and the functionalized filler, preferably 60-80%, for example 10%, 20%, 30%, 40%, 50% or 70%.
4. A method for preparing the functional paint according to any one of claims 1 to 3, characterized by comprising the steps of:
and mixing the micelle solution containing the micron-sized polymer with the functionalized filler.
5. The method of preparing a functional paint according to claim 4, wherein the micellar solution containing the micron-sized polymer is prepared by a turbulent shear and a solvent-poor solvent induced phase separation method;
the micellar solution containing the micron-sized polymer is preferably prepared by any one of the following methods:
mode I: dripping the solution containing the polymer into a poor solvent of the polymer, and mixing;
mode II: and (3) dripping a poor solvent of the polymer into the solution containing the polymer, and mixing.
6. The method for preparing the functional coating according to claim 5, wherein in the mode I, the dropping speed of the solution of the polymer is 3 to 10mL/min, such as 5 mL/min;
and/or in the mode I, in the dripping process, the stirring speed of the poor solvent is 13000-20000 rpm;
and/or, in the mode II, the dropping speed of the poor solvent is 3-10 mL/min, for example, 5 mL/min;
and/or in the mode II, in the dripping process, the stirring speed of the solution containing the polymer is 13000-20000 rpm;
and/or in the mode I or the mode II, when the stirring rotating speed is 13000-16000 rpm, the core-shell structure is spherical and/or fibrous; when the stirring speed is 16000-20000 rpm, the core-shell structure is dendritic;
and/or the functionalized filler is filler after ultrasonic treatment; preferably, the functionalized filler is a filler which is not subjected to surface modification by a modifier;
and/or the mixing stirring speed is 300-600 rpm, such as 400 rpm;
and/or the mixing stirring time is 10-60 min.
7. A functional coating, which is prepared by the preparation method of the functional coating as claimed in any one of claims 4 to 6.
8. Use of a functional coating as claimed in any one of claims 1 to 3 or 7 as a coating material for the surface modification of polymers.
9. A method for preparing a functional coating is characterized by comprising the following steps:
applying a functional coating as claimed in any one of claims 1 to 3 or 7 to the surface of a substrate, wherein the amount of the functional coating per square meter of the surface of the substrate is 15 to 20g/m2；
Preferably, the thickness of the functional coating on the surface of the substrate is more than 1 μm, for example, 1 to 2 μm;
preferably, the coating is spin coating, drop coating, dip coating, spray coating, 3D printing coating or roller coating; the number of the coating is preferably 3 to 18;
preferably, the substrate is a fiber, film, nonwoven, fabric, foam or sponge.
10. A functional coating produced by the method for producing a functional coating according to claim 9.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114085532A (en) * 2021-12-13 2022-02-25 苏州洁利昌科技有限公司 High-strength heat-conducting silica gel material and preparation method thereof
CN114150496A (en) * 2021-11-15 2022-03-08 吉林大学 Flexible nanofiber membrane with electromagnetic shielding and piezoresistive sensing performances and preparation method thereof
CN114437603A (en) * 2022-03-10 2022-05-06 山东鑫纳超疏新材料有限公司 Preparation method of durable super-hydrophobic micro-droplet self-cleaning coating based on conductive nanoparticles
CN114958094A (en) * 2022-06-09 2022-08-30 四川大学 Water-based MXene nano cellulose-based functional ink and preparation method and application method thereof
CN115651521A (en) * 2022-11-03 2023-01-31 合肥工业大学 Preparation method of silver-loaded carbon nanotube/MXene/biodegradable polyurethane electromagnetic shielding water-based paint
CN116607736A (en) * 2023-05-17 2023-08-18 华通建设发展集团有限公司 Bracket type overhanging scaffold and construction method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106205774A (en) * 2016-07-19 2016-12-07 哈尔滨工业大学深圳研究生院 A kind of electrocondution slurry and transparent conducting coating
CN110684512A (en) * 2019-10-18 2020-01-14 吉林大学 High-thermal-conductivity spherical sulfonated polyether ether ketone/graphite core-shell structure filler and preparation method thereof
CN111267434A (en) * 2020-03-06 2020-06-12 深圳先进技术研究院 Heat-conducting electromagnetic shielding material with oriented structure and preparation method thereof
CN112521702A (en) * 2020-06-22 2021-03-19 四川大学 Polymer composition, flexible self-supporting film, and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106205774A (en) * 2016-07-19 2016-12-07 哈尔滨工业大学深圳研究生院 A kind of electrocondution slurry and transparent conducting coating
CN110684512A (en) * 2019-10-18 2020-01-14 吉林大学 High-thermal-conductivity spherical sulfonated polyether ether ketone/graphite core-shell structure filler and preparation method thereof
CN111267434A (en) * 2020-03-06 2020-06-12 深圳先进技术研究院 Heat-conducting electromagnetic shielding material with oriented structure and preparation method thereof
CN112521702A (en) * 2020-06-22 2021-03-19 四川大学 Polymer composition, flexible self-supporting film, and preparation method and application thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114150496A (en) * 2021-11-15 2022-03-08 吉林大学 Flexible nanofiber membrane with electromagnetic shielding and piezoresistive sensing performances and preparation method thereof
CN114150496B (en) * 2021-11-15 2023-07-28 吉林大学 Flexible nanofiber membrane with electromagnetic shielding and piezoresistive sensing performances and preparation method thereof
CN114085532A (en) * 2021-12-13 2022-02-25 苏州洁利昌科技有限公司 High-strength heat-conducting silica gel material and preparation method thereof
CN114437603A (en) * 2022-03-10 2022-05-06 山东鑫纳超疏新材料有限公司 Preparation method of durable super-hydrophobic micro-droplet self-cleaning coating based on conductive nanoparticles
CN114958094A (en) * 2022-06-09 2022-08-30 四川大学 Water-based MXene nano cellulose-based functional ink and preparation method and application method thereof
CN114958094B (en) * 2022-06-09 2023-03-10 四川大学 Water-system MXene nanocellulose-based functional ink and preparation method and application method thereof
CN115651521A (en) * 2022-11-03 2023-01-31 合肥工业大学 Preparation method of silver-loaded carbon nanotube/MXene/biodegradable polyurethane electromagnetic shielding water-based paint
CN115651521B (en) * 2022-11-03 2023-11-03 合肥工业大学 Preparation method of silver-loaded carbon nanotube/MXene/biodegradable polyurethane electromagnetic shielding water-based paint
CN116607736A (en) * 2023-05-17 2023-08-18 华通建设发展集团有限公司 Bracket type overhanging scaffold and construction method
CN116607736B (en) * 2023-05-17 2024-04-19 华通建设发展集团有限公司 Bracket type overhanging scaffold and construction method

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