CN112831240A - High-binding-force fluorine-silicon coating material and preparation method thereof - Google Patents

High-binding-force fluorine-silicon coating material and preparation method thereof Download PDF

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CN112831240A
CN112831240A CN202110173783.3A CN202110173783A CN112831240A CN 112831240 A CN112831240 A CN 112831240A CN 202110173783 A CN202110173783 A CN 202110173783A CN 112831240 A CN112831240 A CN 112831240A
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fluorine
silicon
coating material
fluorosilicone
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CN112831240B (en
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郝云霞
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Beijing Zhongsi High Tech Co.,Ltd.
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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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance

Abstract

The invention provides a high-bonding-force fluorine-silicon coating material and a preparation method thereof.

Description

High-binding-force fluorine-silicon coating material and preparation method thereof
Technical Field
The invention relates to a fluorine-silicon-containing coating composition, which belongs to a surface functional material in a new material industry contained in strategic emerging industry key products and service guide catalogues and belongs to the technical field of novel polymer antifouling materials.
Background
The fluorinated siloxane compound can form chemical crosslinks with the substrate surface to provide adhesion by hydrolytic condensation of siloxane groups, while fluorinated organic groups have a lower critical surface tension to provide stain resistance. However, the existing fluorine-silicon antifouling product has low polymer surface hardness, poor wear resistance and durability, or insufficient film forming, the adhesion between the product and a base material cannot meet the requirement, and a coating film can fall off after being slightly rubbed.
The invention patent with application number 201810793497.5 discloses a fluorine-containing super-hydrophilic self-cleaning coating, which can be added into a water-based coating to make the coating have high hydrophilic self-cleaning property and good adhesion with a substrate, but is only suitable for the water-based coating, and the mechanical properties of the water-based coating film, such as wear resistance and impact resistance, are poor, and only oil repellency and no water repellency exist, so that the application is limited.
The invention patent application No. 201910192216.5 discloses a surface antifouling treatment agent composition comprising fluorinated polyether siloxane, an amino group-containing fluorinated polyether compound and an inert fluorine oil, wherein the treatment agent forms a surface treatment layer having a static contact angle with water of 114 DEG and a friction durability of 18000 times, but the bonding force between the surface treatment layer and a substrate is general and the antifouling property is to be improved.
Disclosure of Invention
The invention provides a high-bonding-force fluorine-silicon coating material and a preparation method thereof.
A preparation method of a high-bonding-force fluorine-silicon coating material is characterized by comprising the following steps:
(1) self-assembling single-layer PS beads on the surface of the pretreated aluminum material;
(2) preparing a spherical storage space on the surface of the aluminum material by taking the PS pellets as a template;
(3) weighing the organic fluorosilicone resin prepolymer, the fluorosilicone surfactant and the fluorinated solvent according to the proportion, fully and uniformly stirring in a reaction kettle to obtain the fluorine-containing silicon coating, uniformly spraying the fluorine-containing silicon coating on the surface of the aluminum material treated in the step (2) by adopting a spraying device, standing for 24-48 hours at room temperature, and curing to form the fluorine-containing silicon coating.
Wherein the organic fluorine-silicon resin prepolymer accounts for 30-75 parts, and the structural formula is as follows:
Figure DEST_PATH_IMAGE001
wherein a, b and c are integers of 1-3, and are the same or different; m and n are integers of 1-4, and are the same or different; the number average molecular weight of the organic fluorine-silicon resin prepolymer is 8000-50000;
wherein the fluorine-silicon surfactant accounts for 15-35 parts;
wherein the fluorinated solvent is 20-50 parts.
Further, the preparation process of the self-assembled monolayer PS beads on the surface of the pretreated aluminum material is as follows: weighing 0.2g sodium dodecyl sulfate and 0.1g potassium persulfate, dissolving in 70ml methanol-water solution with methanol ratio of 10:3.5, maintaining nitrogen atmosphere, magnetically stirring for 30min, and heating to 75 deg.CoC, addAdding a polystyrene monomer which is extracted and washed for three times by 10wt.% of NaOH, reacting for 12h, taking out the obtained white emulsion, slowly adding the white emulsion into 6wt.% of sodium dodecyl sulfate deionized water solution by using a syringe, fishing out the polystyrene monolayer floating on the water surface by using the pretreated aluminum material, and naturally drying.
Further, the preparation process of preparing the spherical storage space on the surface of the aluminum material by using the PS pellets as the template is as follows: the reaction ion etching technology is adopted to reduce the nanometer size of the PS pellets: parameters of reactive ion etching: the radio frequency power is 30W, the pressure is 9.5Pa, the oxygen flow is 50SCCM, then the sample which is processed by the reactive ion etching technology is processed by electron beam evaporation metal layer, the parameters of the electron beam evaporation metal layer are as follows: vacuum degree 5 x 10-3The evaporation power is 17.5kW, the evaporation speed is 0.35nm/s, the time is 22.5min, the metal is nickel, and the thickness of the metal layer is larger than the diameter of the PS pellets.
Further, after the metal layer is subjected to electron beam evaporation treatment, polishing the metal layer to expose the PS beads: and the polishing is chemical mechanical polishing, the polishing removal amount is 250nm/min, the polishing time is to expose a small part of PS beads, then the sample is put into an organic solvent tetrahydrofuran solution, the sample is soaked for 20min under magnetic stirring to dissolve the PS beads, and the residual liquid is removed by washing and drying.
Further, the preparation process of the organic fluorosilicone resin prepolymer comprises the following steps: preparing a flask equipped with a stirrer, a thermometer, a condenser tube and a constant-pressure dropping funnel, heating in a water bath, adding a polymerization monomer, a solvent and an initiator into a reactor under the protection of inert gas, stirring a mixed system for 5-10min to completely dissolve the monomer and the initiator, and then heating to 60-70 ℃ for polymerization reaction for 5-10 h. And after the reaction is finished, cooling to room temperature, transferring the reaction mixed solution into a measuring flask, and evaporating to remove the solvent to obtain the organic fluorosilicone resin prepolymer.
Further, the polymerized monomers include: 15-45wt.% fluorinated alkyl acrylate, 25-55wt.% fluoroalkene ether, 20-50wt.% unsaturated siloxane compound, the initiator being AIBN or BPO; the solvent is one or more of toluene, ethyl acetate and methanol.
Further, the fluorinated alkyl acrylate is CH2=CHCOOCH2(CF(CF3)CF2O)mOCF3M is an integer of 1 to 4; the fluoroalkene ether is CH2=CHCH2CF2O(CF(CF3)CF2O)nCF3N is an integer of 1 to 4; the unsaturated siloxane compound is CH2=CHCH2CH2OSi(OCH3)3。
Further, the fluorosilicone surfactant is a perfluoroalkyl ether type silicon-containing surfactant, preferably selected from INTECHEM-18, and the fluorinated solvent is selected from hydrofluorocarbon and/or hydrofluoro hydrocarbon ether.
Further, the hydrofluorocarbons are selected from CF3CFHCFHCF2CF3、CF3CF2CH2CH2F、C5F11One or more of H; said hydrofluorohydrocarbon ether is selected from (CF)3)2CFOCH3、CH3O(CF2)4OCH3、C5F11OC2H5One or more of (a).
The preparation process of the present invention is explained as follows:
(1) pretreatment: rough polishing, degreasing, washing with water, heat treatment and electrolytic polishing;
the rough polishing is to polish the surface of the aluminum material by using 600-mesh and 800-mesh water-mill sandpaper in sequence;
the degreasing is cleaning and soaking by using an acetone solution;
the heat treatment is carried out under inert conditions at 450-oC, high-temperature treatment for 20-30 min;
the electrolytic polishing is 50g/L phosphoric acid, 20g/L sulfuric acid, 3g/L glycerol, voltage of 15V, time of 2-5min, and temperature of 45oC。
The main purpose of the pretreatment is to obtain a smooth and flat surface, obtain the flat surface primarily by rough polishing and grinding, then remove grease and pollution impurities in the rough polishing process, remove mechanical stress of the aluminum material by heat treatment at high temperature, make metal grains of aluminum larger, facilitate metal coating, and finally obtain the flat and smooth surface of the aluminum material by electrochemical polishing, wherein the surface is favorable for PS (polystyrene) globules to present single-layer distribution, and the single-layer distribution is crucial to the long-range order of a spherical storage space.
(2) Preparing PS beads: the preparation process of the PS bead tube comprises the following steps: weighing 0.1-0.3g of sodium dodecyl sulfate and 0.1g of potassium persulfate, dissolving in 70ml of a solution of methanol and water, wherein the ratio of methanol is 10: 2-10: 5, keeping the nitrogen atmosphere, magnetically stirring for 30min, raising the temperature to 75 DEGoAnd C, adding a polystyrene monomer which is extracted and washed by 10wt.% NaOH for three times, reacting for 12h, taking out the obtained white emulsion, slowly adding the white emulsion into 5-7wt.% sodium dodecyl sulfate deionized water solution through an injector, fishing out the polystyrene single layer floating on the water surface by using the pretreated aluminum material, naturally drying to obtain the aluminum material with 400-plus-500 nm single-layer polystyrene spheres adsorbed on the surface, controlling the diameter of the nanospheres by adjusting the relative proportion relation of a sodium dodecyl sulfate emulsifier, a potassium persulfate initiator, a monomer and a water phase oil phase, wherein the pore diameter of the nanospheres directly influences the size of the storage space.
(3) The nano size of the PS pellets is reduced by adopting a reactive ion etching technology; the radio frequency power is 20-40W, the pressure is 9-10Pa, the oxygen flow is 40-60 SCCM, the size of the polystyrene is reduced by 20-40%, the reactive ion etching technology is a common method for reducing the nano size of the PS pellets in the prior art, and the PS pellets are reduced to 300-400nm by the reactive ion etching technology.
(4) Evaporating the metal layer by using an electron beam, wherein the thickness of the metal layer is larger than that of the PS pellets in the step (3); electron beam evaporation metal parameters: degree of vacuum 4 x 10-3-6*10-3The evaporation power is 15-20kW, the evaporation speed is 0.3-0.4nm/s, the time is 15-30min, the metal is selected from one or more alloy metals of aluminum, copper, nickel and iron, the method for obtaining the metal coating can be electroplating, electroless chemical plating and physical sputtering, and the technology can be realized on PS pelletsThe method comprises the following steps of (1) inter-plating metal, but for the nano-pore channel, electroplating is not applicable due to uneven distribution of electric lines and high requirement for deep hole plating of electroplating solution configuration, the binding force of a plating layer of chemical plating is effective, due to the arc structure of the PS pellets, physical sputtering is obviously blocked, electron beam evaporation can effectively solve the problems, the invention preferably adopts an electron beam evaporation metal layer, and the thickness of the metal layer is more than the diameter of the PS pellets, namely the metal layer completely covers the PS pellets.
(5) Polishing to expose PS beads, wherein the polishing is chemical mechanical polishing, the polishing removal amount is 200-300nm/min, the polishing time is to expose a small part of PS beads, a chemical polishing solution is adopted to realize nano-scale polishing treatment, the opening size of the top of the metal spherical storage space can be effectively controlled through the polishing treatment, and the opening size is preferably 1/5-1/4 of the diameter of the metal spherical storage space.
(6) Removing PS beads, washing with water, and vacuum drying: putting a sample into an organic solvent tetrahydrofuran solution, magnetically stirring and soaking for 15-20min to dissolve PS beads, washing and drying to remove redundant residual liquid, polishing to obtain an opening at the upper part of the metal spherical storage space, allowing the organic solvent tetrahydrofuran solution to enter the spherical storage space through the opening to dissolve the PS beads in the spherical storage space, and finally obtaining a hollow spherical storage space with a controllable opening size.
(7) With respect to the coating composition: polymerized monomer fluorinated alkyl acrylate CH of organic fluorine-silicon prepolymer2=CHCOOCH2(CF(CF3)CF2O)mOCF3Fluoroolefin ether CH2=CHCH2CF2O(CF(CF3)CF2O)nCF3The long-chain fluoroalkyl structure is provided, and the chain length, content, stacking state and main chain composition of the side chain fluoroalkyl in the fluorine-containing group play a decisive role in the oil-proof and water-proof performance.
The organic fluorine has strong electron-withdrawing property, and the electrostatic influence is weakened, so that the coating is not easy to accumulate dirt, the dirt accumulation is slowed down, or accumulated floating dirt is easy to clean by natural wind and rain. The structure enables the coating to have extremely low surface free energy, endows the base material with good water repellency and oil repellency, and excellent performances such as weather resistance, ageing resistance, solvent resistance and chemical corrosion resistance, along with the increase of the content of the fluorine monomer, the longer the fluoroalkyl chain is, the tail ends of the fluoroalkyl chains can be directionally and regularly arranged on the surface of the base material due to intermolecular action (Van der Waals force and hydrophobic effect), the better the waterproof, oil-proof and anti-pollution performances of the fluorosilicone resin prepolymer are, but when the content of the fluorine monomer reaches a threshold value, the content of the fluorine monomer is increased, the improvement degree of the waterproof, oil-proof and anti-pollution performances of the coating is lower, and the overlong fluoroalkyl chain can cause a steric hindrance effect between the fluorosilicone resin prepolymers, is not beneficial to the directional arrangement (tail end orientation) of the fluoroalkyl chain, and the waterproof, oil-proof and anti-pollution performances of. Through research, when m and n are determined to be between 1 and 4, preferably, the content of the fluorine-containing monomer accounts for 60wt.% to 80 wt.% of the weight of the organic fluorine-silicon prepolymer, more preferably 75 wt.%, and the number average molecular weight of the organic fluorine-silicon resin prepolymer is between 8000 and 50000, the organic fluorine-silicon prepolymer can achieve the best water repellency, oil repellency and anti-fouling performance.
The fluorine-containing acrylate has excellent performance, but the price is high, and the application range of the copolymer is influenced by using a large amount of the fluorine-containing acrylate. Relatively low-priced organosilicon, unsaturated siloxane monomer CH2=CHCH2CH2OSi(OCH3)3The organic silicon monomer has lower surface energy, the provided organic silicon monomer has outstanding water repellent effect, the introduction of the organic silicon monomer can also reduce the dosage of the fluorine-containing monomer, the unsaturated siloxane monomer can also be used as a self-crosslinking agent and is introduced into a fluorine-containing acrylate main chain structure in a copolymerization way, when the obtained fluorine-containing silicon copolymer coating composition acts on the surface of a substrate, the fluorine-containing silicon copolymer coating composition is connected with the substrate through a silicon-oxygen covalent bond, the outermost layer is a fluorine-containing group, a new surface layer of fluorine atoms or atomic groups is formed on the surface of the substrate, and oil and water can not wet the new surface layer by virtue of the chemical force of the fluorine atoms or atomic groups of the new surface layer.
The fluorosilicone surfactant adopted by the invention is a perfluoroalkyl ether silicon-containing surfactant which has excellent interface wetting, spreading and dispersing properties, preferably INTECHEM-18 with ultra-low surface tension and can be decomposed into coupling groups and hydrophobic and oleophobic groups of fluorine chains, and the surfactant and the organic fluorosilicone prepolymer have synergistic effect, so that the adhesive effect between the resin prepolymer and the surface of the base material can be improved, the waterproof and oil-proof effects of the coating can be further improved, and a good effect can be achieved at low consumption.
Compared with other organic solvents, the hydrofluorocarbon/hydrofluorocarbon ether has lower surface tension and viscosity, has weaker requirements on the properties of the base material, can obtain a continuous, uniform and pore-free coating even if the surface shape of the base material is complex, does not degrade resin and has poorer water solubility compared with the common ketone and ester solvents, and can prevent the coating composition from generating gel due to the hydrolysis of silane monomer units in the copolymer, so the obtained coating composition has higher storage stability. Hydrofluorocarbons, preferably CF3CFHCFHCF2CF3、CF3CF2CH2CH2F、C5F11One or more of H, hydrofluoro hydrocarbon ether is preferably (CF)3)2CFOCH3、CH3O(CF2)4OCH3、C5F11OC2H5One or more of (a).
Compared with the prior art, the invention has the following advantages:
(1) by a template method, a uniform nano-pore array is obtained on the surface of the metal aluminum material, the array is simple and controllable, the technology for preparing the PS pellets in the prior art is mature, the required PS pellets with any size can be obtained by a person skilled in the art, and the size of the pellets directly corresponds to the pore structure, namely the pore size can be controlled by the method.
(2) Through the metal spherical storage space can be effectively attached with the fluorine-silicon coating, and the binding force of the base material and the coating is obviously improved.
(3) The fluorinated siloxane antifouling coating has excellent water repellency, oil repellency, antifouling property and wear resistance.
Detailed Description
The treatment processes of the aluminum materials to be coated of examples 1 to 3 of the present invention were as follows:
(1) pretreatment: rough polishing, degreasing, washing, heat treatment and electrolytic polishing:
and the rough polishing is to polish the surface of the aluminum material by using 600-mesh and 800-mesh water-mill sandpaper in sequence.
The degreasing is cleaning and soaking by using an acetone solution.
The heat treatment is carried out under inert conditions at 475oAnd C, high-temperature treatment for 25 min.
The electrolytic polishing is 50g/L phosphoric acid, 20g/L sulfuric acid, 3g/L glycerol, voltage of 15V, time of 3.5min, and temperature of 45oC。
(2) Weighing 0.2g of sodium dodecyl sulfate and 0.1g of potassium persulfate to dissolve in 70ml of a solution of methanol and water, wherein the ratio of the methanol is 10:3.5, keeping the nitrogen atmosphere, magnetically stirring for 30min, raising the temperature to 75 DEG, and self-assembling a single-layer PS pellet on the surface of the pretreated aluminum materialoAnd C, adding a polystyrene monomer which is extracted and washed three times by 10wt.% NaOH, reacting for 12 hours, and taking out the obtained white emulsion.
Slowly adding the white emulsion into 6wt.% lauryl sodium sulfate deionized water solution through a syringe, fishing out the polystyrene monolayer floating on the water surface by using the pretreated aluminum material, and naturally drying.
(3) The reaction ion etching technology is adopted to reduce the nanometer size of the PS pellets: parameters of reactive ion etching: the radio frequency power is 30W, the pressure is 9.5Pa, and the oxygen flow is 50 SCCM.
(4) Evaporating a metal layer by using an electron beam, wherein the thickness of the metal layer is greater than that of the PS pellets in the step (3), and the metal parameters of the electron beam evaporation are as follows: vacuum degree 5 x 10-3The evaporation power is 17.5kW, the evaporation speed is 0.35nm/s, the time is 22.5min, and the metal is nickel.
(5) Polishing to expose PS beads: the polishing is chemical mechanical polishing, the polishing removal amount is 250nm/min, and the polishing time is to expose a small part of PS beads.
(6) Removing the PS beads, washing with water, and vacuum drying: and putting the sample into an organic solvent tetrahydrofuran solution, magnetically stirring and soaking for 15-20min to dissolve the PS globule, and washing and drying to remove the redundant residual liquid.
Example 1
The surface of the base material is sprayed with the coating, and the mixture ratio of the coating is as follows: the composite material comprises the following raw materials in parts by weight: 35 parts of organic fluorine-silicon resin prepolymer, INTECHEM-1815 parts, CF3CFHCFHCF2CF3 And 25 parts. The organic fluorine-silicon prepolymer has the following structural formula:
Figure 165203DEST_PATH_IMAGE002
wherein a, b and c are all 1, m is 1, n is 2, and the number average molecular weight is 10000.
Example 2
The surface of the base material is sprayed with the coating, and the mixture ratio of the coating is as follows: the composite material comprises the following raw materials in parts by weight: 50 parts of organic fluorine silicone resin prepolymer, INTECHEM-1820 parts, CF3CFHCFHCF2CF3 30 parts of. The organic fluorine-silicon prepolymer has the following structural formula:
Figure 20027DEST_PATH_IMAGE002
wherein a is 1, b is 2, c is 1, m is 4, n is 3, and the number average molecular weight is 20000.
Example 3
The surface of the base material is sprayed with the coating, and the mixture ratio of the coating is as follows: the composite material comprises the following raw materials in parts by weight: 65 parts of organic fluorine-silicon resin prepolymer, 1830 parts of INTECHEM-1830 parts of CF3CFHCFHCF2CF3 50 parts of the raw materials. The organic fluorine-silicon prepolymer has the following structural formula:
Figure 330922DEST_PATH_IMAGE002
wherein a is 3, b is 1, c is 2, m is 2, n is 1, and the number average molecular weight is 35000.
After the spray coating of examples 1-3, the coating was allowed to stand at room temperature for 36 hours and cured to form a fluorine-containing silicon coating.
Comparative example 1
The aluminum material is treated as follows:
(1) pretreatment: rough polishing, degreasing, washing, heat treatment and electrolytic polishing:
and the rough polishing is to polish the surface of the aluminum material by using 600-mesh and 800-mesh water-mill sandpaper in sequence.
The degreasing is cleaning and soaking by using an acetone solution.
The heat treatment is carried out under inert conditions at 475oAnd C, high-temperature treatment for 25 min.
The electrolytic polishing is 50g/L phosphoric acid, 20g/L sulfuric acid, 3g/L glycerol, voltage of 15V, time of 3.5min, and temperature of 45oC。
(2) The surface of the base material is sprayed with the coating, and the mixture ratio of the coating is as follows: the composite material comprises the following raw materials in parts by weight: 35 parts of organic fluorine-silicon resin prepolymer, INTECHEM-1815 parts, CF3CFHCFHCF2CF3 And 25 parts. The organic fluorine-silicon prepolymer has the following structural formula:
Figure 883389DEST_PATH_IMAGE002
wherein a, b and c are all 1, m is 1, n is 2, and the number average molecular weight is 10000.
After spraying, standing for 36 hours at room temperature, and curing to form the fluorine-containing silicon coating.
And (3) testing the binding force: and (3) carrying out coating bonding force test on the prepared TNT coating on the titanium surface by using a scratch instrument, wherein the scratch length is 5mm at a loading rate of 50N/m and a loading load of 50N. The scratch bonding force experiment uses a conical diamond indenter which scratches on the surface of the coating at a set rate under an increasing load, and when the coating begins to break, an acoustic emission signal is suddenly enhanced, and the loaded load is called a critical load, so as to determine the bonding force of the coating.
Through tests, the bonding strength of the high-bonding-force fluorosilicone coating aluminum alloy is 20-23N, the bonding strength obtained by the comparison document 1 is 4.9N, the contribution of the metal spherical storage space to the bonding force is further proved,
furthermore, the hydrophobic contact angle ranges 137-140 for the coating materials of inventive examples 1-3 and comparative example 1oHas extremely high water repellency.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the substantially same technical problems and achieve the substantially same technical effects are within the scope of the present invention.

Claims (9)

1. A preparation method of a high-bonding-force fluorine-silicon coating material is characterized by comprising the following steps:
(1) self-assembling single-layer PS beads on the surface of the pretreated aluminum material;
(2) preparing a metal spherical storage space on the surface of the aluminum material by taking the PS pellets as a template;
(3) weighing the organic fluorine-silicon resin prepolymer, the fluorine-silicon surfactant and the fluorinated solvent according to the proportion, fully and uniformly stirring in a reaction kettle to obtain the fluorine-silicon-containing coating, uniformly spraying the fluorine-silicon-containing coating on the surface of the aluminum material treated in the step (2) by adopting a spraying device, standing for 24-48 hours at room temperature, curing to form the fluorine-silicon-containing coating,
wherein the organic fluorine-silicon resin prepolymer accounts for 30-75 parts, and the structural formula is as follows:
Figure 91466DEST_PATH_IMAGE001
wherein a, b and c are integers of 1-3, and are the same or different; m and n are integers of 1-4, and are the same or different; the number average molecular weight of the organic fluorine-silicon resin prepolymer is 8000-50000;
wherein the fluorine-silicon surfactant accounts for 15-35 parts;
wherein the fluorinated solvent is 20-50 parts.
2. The preparation method of the high-bonding-force fluorosilicone coating material as claimed in claim 1, wherein the preparation process of the single-layer PS beads self-assembled on the surface of the pretreated aluminum material is as follows: weighing 0.2g sodium dodecyl sulfate and 0.1g potassium persulfate, dissolving in 70ml methanol-water solution with methanol ratio of 10:3.5, maintaining nitrogen atmosphere, magnetically stirring for 30min, and heating to 75 deg.CoAnd C, adding a polystyrene monomer which is extracted and washed three times by 10wt.% NaOH, reacting for 12h, taking out the obtained white emulsion, slowly adding the white emulsion into 6wt.% sodium dodecyl sulfate deionized water solution through a syringe, taking out the polystyrene single layer floating on the water surface by using the pretreated aluminum material, and naturally drying.
3. The method for preparing a fluorosilicone coating material with high binding force according to claim 1, wherein the preparation process for preparing the spherical storage space on the surface of the aluminum material by using the PS beads as the template is as follows: the reaction ion etching technology is adopted to reduce the nanometer size of the PS pellets: parameters of reactive ion etching: the radio frequency power is 30W, the pressure is 9.5Pa, the oxygen flow is 50SCCM, then the sample which is processed by the reactive ion etching technology is processed by electron beam evaporation metal layer, the parameters of the electron beam evaporation metal layer are as follows: vacuum degree 5 x 10-3The evaporation power is 17.5kW, the evaporation speed is 0.35nm/s, the time is 22.5min, the metal is nickel, and the thickness of the metal layer is larger than the diameter of the PS pellets.
4. The method for preparing a fluorosilicone coating material with high bonding force according to claim 3, wherein after the metal layer is subjected to electron beam evaporation treatment, the metal layer is polished to expose PS beads: and the polishing is chemical mechanical polishing, the polishing removal amount is 250nm/min, the polishing time is to expose a small part of PS beads, then the sample is put into an organic solvent tetrahydrofuran solution, the sample is soaked for 20min under magnetic stirring to dissolve the PS beads, and the residual liquid is removed by washing and drying.
5. The method for preparing a fluorosilicone coating material with high bonding force according to claim 1, wherein the preparation process of the organic fluorosilicone prepolymer comprises the following steps: preparing a flask equipped with a stirrer, a thermometer, a condenser tube and a constant-pressure dropping funnel, heating in a water bath, adding a polymerization monomer, a solvent and an initiator into the reactor under the protection of inert gas, stirring the mixed system for 5-10min to completely dissolve the monomer and the initiator, heating to 60-70 ℃, carrying out polymerization for 5-10h, cooling to room temperature after the reaction is finished, transferring the reaction mixed solution into a measuring flask, and evaporating to remove the solvent to obtain the organic fluorosilicone prepolymer.
6. The method for preparing a high-bonding fluorosilicone coating material according to claim 4, wherein the polymerization monomer comprises: 15-45wt.% fluorinated alkyl acrylate, 25-55wt.% fluoroalkene ether, 20-50wt.% unsaturated siloxane compound, the initiator being AIBN or BPO; the solvent is one or more of toluene, ethyl acetate and methanol.
7. The method for preparing a fluorosilicone coating material with high binding force as claimed in claim 6, wherein said fluorinated alkyl acrylate is CH2=CHCOOCH2(CF(CF3)CF2O)mOCF3M is an integer of 1 to 4; the fluoroalkene ether is CH2=CHCH2CF2O(CF(CF3)CF2O)nCF3N is an integer of 1 to 4; the unsaturated siloxane compound is CH2=CHCH2CH2OSi(OCH3)3。
8. The method for preparing a high-bonding-force fluorosilicone coating material according to claim 1, wherein said fluorosilicone surfactant is a perfluoroalkyl ether type silicon-containing surfactant, preferably selected from INTECHEM-18, said fluorinated solvent is selected from hydrofluorocarbons and/or hydrofluorocarbon ether, said hydrofluorocarbons are selected from CF3CFHCFHCF2CF3、CF3CF2CH2CH2F、C5F11One or more of H; said hydrofluorohydrocarbon ether is selected from (CF)3)2CFOCH3、CH3O(CF2)4OCH3、C5F11OC2H5One or more of (a).
9. A fluorine-silicon coating material obtained by the preparation method of the high-binding-force fluorine-silicon coating material in the claims 1-8, which is characterized in that the binding force strength of the coating material is 20-23N, and the hydrophobic contact angle of the coating material is 137-o。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115304964A (en) * 2022-10-08 2022-11-08 杜娜丽 Application of water-based paint composition
CN115322626A (en) * 2022-10-08 2022-11-11 杜娜丽 Preparation method of water-based paint composition
CN115466546A (en) * 2022-10-08 2022-12-13 杜娜丽 Water-based paint

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030104316A1 (en) * 2001-11-30 2003-06-05 Wang Hongying Polystyrene as a resist for making patterned media
CN1474837A (en) * 2000-11-16 2004-02-11 3M创新有限公司 Water-repellent, or-repellent and soil resistant coating composition
CN1588236A (en) * 2004-10-13 2005-03-02 清华大学 Method for preparing nano dot array of controllable unit size using nano ball template
CN1687488A (en) * 2005-03-18 2005-10-26 中国兵器工业第五九研究所 Technique for treating synergism coat of aluminium alloy material and fluorine polymer
CN102173376A (en) * 2011-02-25 2011-09-07 复旦大学 Preparation method for small silicon-based nano hollow array with orderly heights
CN109504994A (en) * 2018-12-13 2019-03-22 上海科技大学 A kind of preparation method of Novel anode alumina formwork and nano-array

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1474837A (en) * 2000-11-16 2004-02-11 3M创新有限公司 Water-repellent, or-repellent and soil resistant coating composition
US20030104316A1 (en) * 2001-11-30 2003-06-05 Wang Hongying Polystyrene as a resist for making patterned media
CN1588236A (en) * 2004-10-13 2005-03-02 清华大学 Method for preparing nano dot array of controllable unit size using nano ball template
CN1687488A (en) * 2005-03-18 2005-10-26 中国兵器工业第五九研究所 Technique for treating synergism coat of aluminium alloy material and fluorine polymer
CN102173376A (en) * 2011-02-25 2011-09-07 复旦大学 Preparation method for small silicon-based nano hollow array with orderly heights
CN109504994A (en) * 2018-12-13 2019-03-22 上海科技大学 A kind of preparation method of Novel anode alumina formwork and nano-array

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
于娜等: "尺寸可控的单分散聚苯乙烯微球的制备", 《青岛科技大学学报(自然科学版)》 *
罗源军等: "氟硅表面活性剂的制备方法与应用探讨", 《化工生产与技术》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115304964A (en) * 2022-10-08 2022-11-08 杜娜丽 Application of water-based paint composition
CN115322626A (en) * 2022-10-08 2022-11-11 杜娜丽 Preparation method of water-based paint composition
CN115466546A (en) * 2022-10-08 2022-12-13 杜娜丽 Water-based paint
CN115466546B (en) * 2022-10-08 2023-08-15 江苏皓月涂料有限公司 Water-based paint
CN115304964B (en) * 2022-10-08 2023-08-18 东莞市威一霸涂料有限公司 Application of water-based coating composition
CN115322626B (en) * 2022-10-08 2023-08-18 中远关西涂料（上海）有限公司 Preparation method of water-based paint composition

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