CN115197625B - Self-adhesion super-slip coating rich in coil-like liquid brush and preparation method and application thereof - Google Patents

Self-adhesion super-slip coating rich in coil-like liquid brush and preparation method and application thereof Download PDF

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Publication number
CN115197625B
CN115197625B CN202210862292.4A CN202210862292A CN115197625B CN 115197625 B CN115197625 B CN 115197625B CN 202210862292 A CN202210862292 A CN 202210862292A CN 115197625 B CN115197625 B CN 115197625B
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liquid
coating
coil
monomer
self
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CN115197625A (en
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孙健翔
付少海
于梦楠
张继超
刘俊青
徐立成
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Shandong Hengtai Textile Co ltd
Jiangnan University
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Shandong Hengtai Textile Co ltd
Jiangnan 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • B05D1/005—Spin coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/10—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an adhesive surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C09D5/08—Anti-corrosive paints
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0036—Polyester fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—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
    • D06N3/128—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 silicon polymers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/146—Soilproof, soil repellent

Abstract

The invention discloses a self-adhesion super-slip coating rich in coil-like liquid brushes and a preparation method and application thereof, and belongs to the technical field of nano anti-fouling coatings. The preparation method of the self-adhesive super-smooth coating rich in the coil-shaped liquid-like brush comprises the steps of preparing liquid-like polymer nano emulsion by adopting an ultrasonic and compatibilizer auxiliary method; then, diluting the liquid-like polymer nano emulsion, and coating the diluted liquid-like polymer nano emulsion on the surface of a substrate; and then adopting a unidirectional electrostatic field auxiliary and gradient heating mode to realize the microscopic gradient structures of the coil-shaped liquid-like brush and the coating adhesion layer-harmonizing layer-antifouling layer on the surface of the coating on the substrate, and improving the fastness of the liquid-like brush and simultaneously endowing the coating substrate with adhesion and suitability. The coating prepared by the invention has stable antifouling property, firm substrate adhesion and excellent transparency, can meet the antifouling requirement of common substrates, and has wide application value.

Description

Self-adhesion super-slip coating rich in coil-like liquid brush and preparation method and application thereof
Technical Field
The invention relates to a self-adhesion super-slip coating rich in coil-like liquid brushes, and a preparation method and application thereof, and belongs to the technical field of nano anti-fouling coatings.
Background
The antifouling properties are generally achieved by surfaces with extreme wettability. The self-cleaning properties of superhydrophobic surfaces are only directed at aqueous contaminants, and contaminants with low surface energy can penetrate into the superhydrophobic surfaces. Although the super-oleophobic surface has self-cleaning performance on both water-based and oil-based pollutants, the super-oleophobic surface has extremely strict requirements on the morphology of the micro-nano composite structure, the preparation cost is high, and the micro-nano structure is easily damaged so as to lose the original performance. In 2011, researchers have proposed, in the light of nepenthes structures, ultra-slippery self-cleaning surfaces (SLIPS) prepared by pouring lubricating fluids with very low surface energies into coarse porous micro-nano structures. Water or low surface energy liquid can slide freely off the very low tilt SLIPS surface without leaving any residue. Under the pushing of the work, the lubrication liquid is poured into the porous micro-nano structure to form a new thought and a new trend for constructing the antifouling surface. However, such surfaces are prepared on substrate materials having porous micro-nanostructures, thereby limiting the versatility of the method for application on different substrate materials. And the volatility and fluidity of the lubricating fluid itself can cause it to be consumed continuously during use, so that the corresponding surface loses its antifouling properties. Therefore, developing ultra-slippery solid surfaces or materials that are not dependent on micro-nanostructures and liquid lubricants is an effective way to solve the above-described problems.
A low surface energy monolayer liquid (such as polydimethylsiloxane, perfluoroalkyl, or perfluoropolyether) is grafted onto the substrate and the monolayer polymer grafted onto the solid surface imparts a "liquid-like" nature to the surface. The grafted monolayer polymer brush has an excellent self-cleaning effect, which is advantageous in improving the stability of the lubricating layer while avoiding the use of a roughened structure. However, the method requires activation pretreatment of the substrate, has complex preparation process and has poor universality because different chemical reactions are designed according to different active groups. In addition, single layer molecular brushes are easily damaged by wear in use, have very limited life and lack durability.
In order to solve the durability problem of the monolayer liquid super-slip coating, the low molecular weight Polydimethylsiloxane (PDMS), the perfluorinated hydrocarbon group or the perfluorinated polyether with active groups are grafted into a polymer cross-linked network by reaction to prepare the stable and durable super-slip self-cleaning coating. However, single-ended grafting into the polymer coating reduces the flowability of the lubricating fluid, resulting in a fluid sliding angle (about 30 °) that is much higher than that of a fluid-infused surface (about 5 °), significantly reducing the antifouling properties to fluids, particularly highly adherent fluids. In addition, the single-end grafted lubricating liquid brush and the polymer chain segment have relatively few grafting sites, and the friction resistance stability still needs to be improved. Therefore, the construction of the ultra-smooth liquid anti-fouling coating with low sliding angle, high liquid brushing fastness, high adhesion and substrate universality has more application prospect.
Disclosure of Invention
In order to solve at least one of the problems, the invention firstly adopts an ultrasonic and compatibilizer-assisted method to prepare liquid-like polymer nanoemulsion; diluting the liquid-like polymer nano emulsion to a certain concentration, and assembling the nano emulsion on the surface of a plane, textile or curved substrate in a spin coating, dip coating or spray coating mode; then, an electrostatic field assisted mode is adopted to induce the polydimethylsiloxane molecular brush copolymerized into the polymer chain segment to migrate orderly to the surface of the coating and form a coil-shaped liquid-like brush, and a double-end grafting mode effectively improves the fastness of the liquid-like brush and the antifouling property of the coating; and meanwhile, micro-phase separation of the coating is initiated by utilizing a gradient heating mode, so that a micro-gradient structure of a coating adhesion layer-a blending layer-an anti-fouling layer is realized, and the coating substrate is endowed with adhesion and suitability and meanwhile keeps transparency. The liquid-like ultra-smooth coating prepared by the invention has stable antifouling property, firm substrate adhesion and excellent transparency, can meet the antifouling requirement of common substrates, and has good stability and simple and convenient application process.
The first object of the present invention is to provide a method for preparing a self-adhesive super-slip coating rich in coil-like liquid brushes, comprising the steps of:
(1) Preparing liquid-like polymer nano emulsion:
uniformly mixing a soft monomer, a hard monomer, an amphiphilic water-soluble monomer, a divinyl end-capped lubricating functional monomer, a fluorine-containing compatibilizer and an initiator, and then pouring the mixture into water to obtain a reaction system, so as to prepare a pre-emulsion; ultrasonic crushing and polymerization reaction to obtain liquid-like polymer nano emulsion;
(2) Preparation of self-adhesive super-slip coating rich in coil-like liquid brush:
diluting the liquid-like polymer nano emulsion prepared in the step (1), and coating the diluted liquid-like polymer nano emulsion on the surface of a substrate; then placing the substrate in a unidirectional electrostatic field, and adopting a gradient heating film forming mode to prepare the self-adhesion super-slip coating rich in the coil-like liquid brush.
In one embodiment of the present invention, the hard monomer in step (1) comprises one or more of methyl acrylate, vinyl acetate, styrene, acrylonitrile, methyl methacrylate, glycidyl methacrylate.
In one embodiment of the present invention, the soft monomer in step (1) comprises one or more of ethyl acrylate, butyl acrylate, isooctyl acrylate, and lauryl acrylate.
In one embodiment of the present invention, the amphiphilic water-soluble monomer of step (1) comprises one or more of acrylic acid, itaconic acid, maleic acid, acrylamide.
In one embodiment of the present invention, the fluorine-containing compatibilizer of step (1) includes one or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate.
In one embodiment of the present invention, the divinyl-terminated lubricating functional monomer of step (1) comprises one or more of a divinyl-terminated polydimethylsiloxane, a divinyl-terminated perfluoropolyether.
In one embodiment of the invention, the initiator of step (1) comprises one or more of azobisisobutyronitrile, dibenzoyl peroxide, cumene hydroperoxide.
In one embodiment of the present invention, the soft monomer in the step (1) has a mass concentration of 2 to 7% relative to the reaction system, the hard monomer has a mass concentration of 0.5 to 5% relative to the reaction system, the fluoromonomer has a mass concentration of 1 to 10% relative to the reaction system, the amphiphilic water-soluble monomer has a mass concentration of 2 to 5% relative to the reaction system, the vinyl-terminated lubricating fluid has a mass concentration of 5 to 30% relative to the reaction system, and the initiator has a mass concentration of 0.1 to 0.5% relative to the reaction system.
In one embodiment of the present invention, the working power of the cell pulverizer used in the pulverizing in the step (1) is 200-800W, and the working time is 5-20min with 2s for one cycle.
In one embodiment of the invention, the polymerization reaction of step (1) is carried out in an ultrasonic generator; the ultrasonic vibration conditions of the ultrasonic generator are as follows: the frequency is 30-50kHz, the time is 5-10s, the frequency is 70-90kHz, the time is 5-10s, the frequency is 100-120kHz, the time is 10-20s is a cycle period, and the reaction is carried out for 2-8h at the temperature of 60-100 ℃.
In one embodiment of the present invention, the ultrasonic vibration of the ultrasonic generator is performed under the protection of nitrogen.
In one embodiment of the invention, the coating in step (2) comprises any one of spin coating, dip coating or spray coating.
In one embodiment of the invention, the substrate in step (2) comprises any one or more of metal, glass, wood, textile, PET tubing, PP tubing; preferably, the metal comprises one or more of copper sheet, iron sheet and stainless steel sheet; the wood comprises one or two of wood chips and bamboo chips; the textile comprises one or more of cotton fabric, polyester fabric, non-woven fabric and electrostatic spinning nano-fiber.
In one embodiment of the present invention, the liquid-like polymer nanoemulsion of step (1) has a particle size of 50-500nm and a solid content of 5-30%.
In one embodiment of the present invention, the mass fraction of the diluted liquid-like polymer nanoemulsion in the step (2) is 1-10%.
In one embodiment of the present invention, the unidirectional electrostatic field in step (2) is a positive charge field having a strength of 5 to 25kV/cm.
In one embodiment of the present invention, the gradient heating film forming mode in the step (2) is as follows: heating at 30-60 deg.c for 2-6 hr, 80-100 deg.c for 10-30min and 120-150 deg.c for 2-10min.
In one embodiment of the present invention, the spin coating method includes: placing the substrate on a spin coater, dripping the liquid-like polymer nanoemulsion on the surface of the substrate, rotating at 1000-3000rpm for 30-60s, and rotating at 4000-6000rpm for 20-40s, wherein the dripping amount is 0.1-0.3mL/cm 2 The spin coating times are 1-5 times; the dip-coating mode comprises the following steps: soaking the base material in the liquid-like polymer nano emulsion for 3-10min; the dip-coating times are 1-5 times; the spraying mode comprises the following steps: the distance between the spray gun and the base material is set to be 15-30cm, and the spraying amount is 0.2-0.4mL/cm 2 The spraying times are 1-5 times.
It is a second object of the present invention to provide a self-adhering super-slip coating rich in coil-like liquid brushes prepared by the above method.
The third object of the invention is to provide an application of the self-adhesive super-slip coating rich in the coil-like liquid brush in the aspects of substrate protection, self-cleaning and pollution prevention, low-resistance liquid transportation, corrosion resistance, fog resistance and ice coating prevention.
The invention has the beneficial effects that:
(1) The invention firstly forms a compact coil-shaped liquid-like brush on the surface of the coating by the method of assisting the migration of the electronegative polydimethylsiloxane chain segment by the unidirectional high-voltage electrostatic field, effectively improves the stability of the lubricating liquid by a double-end grafting mode, simultaneously maintains the low sliding angle (10 degrees) of the super-sliding coating, and solves the problem that the stability of the lubricating liquid and the sliding angle (30 degrees) of the liquid-like super-sliding coating cannot be optimized synchronously.
(2) According to the invention, the components with different surface energies in the polymer chain segments are induced to generate microphase separation in a gradient heating mode, so that a microscopic gradient structure of the polyacrylate adhesive layer-blending layer-polydimethylsiloxane liquid brush anti-fouling layer with high adhesion is formed, and the problem that the ultra-smooth coating with low surface energy is difficult to combine with a base material is solved.
(3) The invention adopts a film forming mode of electrostatic field auxiliary gradient heating to only cover the outline structure of the substrate, and maintains the original physical morphology (pore structure, coarse structure and the like) of the substrate while endowing the substrate with antifouling property, is suitable for substrates with different shapes and materials, and solves the problem of poor adaptability of the substrate with the ultra-smooth liquid coating.
Drawings
FIG. 1 is a schematic diagram of the electrostatic field assisted gradient heating and coating structure in example 1 of the present invention;
FIG. 2 is a graph showing the lyophobic properties of the ultra-smooth glass coated with the coating of example 1 and the adhesion properties of the coating on the glass surface;
FIG. 3 is a graph depicting the breathability and soil resistance of the ultra-smooth textile prepared in example 2 of the present invention;
FIG. 4 is a graph depicting the liquid transport capacity of the ultra-smooth PET tube prepared in example 3 of the present invention;
FIG. 5 is a graph showing the water contact angle performance of a coating according to comparative example 1 in which an electrostatic field is applied;
FIG. 6 is a graph showing the stability of the coatings prepared in comparative example 2 and example 1 according to the present invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
The testing method comprises the following steps:
coating transparency: sample transparency was tested using an ultraviolet spectrophotometer.
Adhesive strength: and testing by using a universal testing machine. The sample width was 1cm, the thickness was 0.1cm, the peeling distance was 1cm, and the chuck moving speed was 200mm/min.
Contact angle: the measuring instrument of the static contact angle of the coating is JC2000DM contact angle measuring instrument (Shanghai morning digital technology Co., ltd.). The test liquid is organic liquid with different surface tension such as water or glycol. The test liquid volume was 10 microliters, the time to read the contact angle was kept consistent after the drop was dropped onto the coating, 5 points were selected for each sample for contact angle measurement, the average was taken and the standard deviation was calculated.
Sliding angle: the measuring instrument of the sliding angle of the coating was JC2000DM contact angle measuring instrument (Shanghai morning digital technology Co., ltd.). The test liquid is organic liquid with different surface tension such as water or glycol. The volume of the test liquid is 10 microliters, after the liquid drops are dropped on the coating, the dip angle of the sample is changed by rotating the rotating table together, and the sliding angle of the liquid drops is the sliding angle of the liquid drops. 5 points were selected for sliding angle measurement for each sample, averaged and standard deviation calculated.
Abrasion resistance stability: the coating was subjected to 500 rubbing cycles using an anti-rub tester and tested for water slip angle after rubbing.
Example 1
A method for preparing glass with an ultra-smooth and anti-fouling surface, comprising the following steps:
(1) 2.5g of butyl acrylate, 1g of hydroxyethyl methacrylate, 2g of acrylamide, 2.5g of hexafluorobutyl methacrylate, 0.1g of azobisisobutyronitrile, 9g of a divinyl-terminated polydimethylsiloxane were taken in a 50mL beaker; after the monomers are uniformly mixed, dropwise adding 40mL of deionized water into the mixture, and stirring in an ice-water bath at a rotating speed of 200r/min for 20min to pre-emulsify; after the completion of the pre-emulsification, the power of the cell pulverizer was adjusted to 600W, and the mixture was pulverized in an ice water bath for 10 minutes to disperse the monomers into fine droplets having a particle size of about 100 nm. Putting the dispersed emulsion into a 100mL three-neck flask, putting the flask into an ultrasonic generator, and continuously reacting for 4 hours at 70 ℃ under the protection of nitrogen to obtain liquid-like polymer nano emulsion;
(2) The liquid-like polymer nano emulsion with the mass concentration of 10 percent is mixed with 0.2mL/cm 2 The glass sheet was then spun at 2000rpm for 40s and at 5000rpm for 30s, the spin-on times being 3 times. Then placing the glass sheet in an electrostatic field with the intensity of 15kV/cm, wherein the upper polar plate is positively charged; heating for 3h at 40 ℃, 20min at 90 ℃ and 5min at 140 ℃ to obtain the glass with the coil-like liquid brush super-smooth antifouling surface.
The performance test is carried out on the obtained glass sheet with the ultra-smooth antifouling surface of the coil-shaped liquid brush, and the test results of the preparation process and principle, the transparency, the substrate adhesion and the lyophobic performance are shown in fig. 1 and fig. 2.
As can be seen from fig. 1: the electrostatic field can effectively pull the electronegative polydimethylsiloxane chain segments to migrate to the surface of the coating to form a compact coil-like liquid brush, and the gradient heating mode is beneficial to the formation of the special structure of the coating microphase separation adhesion layer-harmonization layer-antifouling layer.
As can be seen from fig. 2 a: the liquid with the surface tension of 72.8mN/m (water) to 29.3mN/m (blend oil) on the surface of the ultra-smooth glass has excellent liquid repellency, and the sliding angle of the test liquid on the surface of the ultra-smooth glass is lower than 10 degrees, which indicates that the coil-shaped liquid-like brush effectively endows the glass surface with excellent liquid repellency; as can be seen from FIG. 2b, the adhesion of the coating to the glass substrate is as high as 12.08MPa, which fully satisfies the requirements of industrial and daily life for the adhesion fastness of the antifouling coating.
Example 2
A preparation method of a polyester fabric with an ultra-smooth antifouling surface comprises the following steps:
(1) 2.5g of butyl acrylate, 1g of hydroxyethyl methacrylate, 2g of acrylamide, 2.5g of hexafluorobutyl methacrylate, 0.1g of azobisisobutyronitrile, 9g of a divinyl-terminated polydimethylsiloxane were taken in a 50mL beaker. After the monomers were mixed uniformly, the mixture was added dropwise to 40mL of deionized water and stirred in an ice-water bath at a speed of 200r/min for 20min for pre-emulsification. After the completion of the pre-emulsification, the power of the cell pulverizer was adjusted to 600W, and the mixture was pulverized in an ice water bath for 10 minutes to disperse the monomers into fine droplets having a particle size of about 100 nm. And (3) putting the dispersed emulsion into a 100mL three-neck flask, putting the flask into an ultrasonic generator, and continuously reacting for 4 hours at 70 ℃ under the protection of nitrogen to obtain the liquid-like polymer nano emulsion.
(2) Soaking the cleaned polyester fabric in the nano emulsion with the mass concentration of 5% for 5min; the dip-coating times are 1-5 times; and then placing the polyester fabric into an electrostatic field with the intensity of 15kV/cm, wherein the upper polar plate is positively charged. Heating for 3h at 40 ℃, 20min at 90 ℃ and 5min at 140 ℃ to obtain the polyester fabric with the ultra-smooth antifouling surface.
The breathability of the original polyester and the coated polyester textile after dip-coating times of 1-5 times, and the antifouling performance of the ultra-smooth antifouling textile with the coil-like liquid brush at the coating times of 3 times were respectively tested, as shown in fig. 3.
As can be seen from fig. 3a, the air permeability of the textile after 3 applications is not significantly changed compared to the original polyester. Indicating that the coating can maintain the original breathability of the textile by a suitable coating process. In addition, the ultra-smooth textile prepared as shown in fig. 3b shows low adhesion to coffee, even honey and tomato paste with very high viscosity, and has excellent antifouling performance, which indicates that the coating can adapt to practical application and can prevent pollution by protecting the substrate from a wide range of pollution.
Example 3
A preparation method of a PET pipeline with an ultra-smooth anti-fouling surface comprises the following steps:
(1) 2.5g of butyl acrylate, 1g of hydroxyethyl methacrylate, 2g of acrylamide, 2.5g of hexafluorobutyl methacrylate, 0.1g of azobisisobutyronitrile, 9g of a divinyl-terminated polydimethylsiloxane were taken in a 50mL beaker. After the monomers were mixed uniformly, the mixture was added dropwise to 40mL of deionized water and stirred in an ice-water bath at a speed of 200r/min for 20min for pre-emulsification. After the completion of the pre-emulsification, the power of the cell pulverizer was adjusted to 600W, and the mixture was pulverized in an ice water bath for 10 minutes to disperse the monomers into fine droplets having a particle size of about 100 nm. And (3) putting the dispersed emulsion into a 100mL three-neck flask, putting the flask into an ultrasonic generator, and continuously reacting for 4 hours at 70 ℃ under the protection of nitrogen to obtain the liquid-like polymer nano emulsion.
(2) Spraying 10% nano emulsion to the surface of PET pipeline with a spray gun at a distance of 15-30cm and a spraying amount of 0.3mL/cm 2 The spraying times are 3 times. The PET tube was then placed in an electrostatic field of 15kV/cm strength with positive charge on the upper plate. Heating for 3h at 40 ℃, 20min at 90 ℃ and 5min at 140 ℃ to obtain the PET pipeline with the ultra-smooth antifouling surface.
The sliding behavior of oil droplets on the surface of the original PET tubing and the coated PET tubing is compared as shown in fig. 4.
As can be seen from fig. 4a and 4b, compared with the original PET pipe, the adhesion of the PET pipe with the super-slip coating to the liquid is obviously reduced, and the oil drops can rapidly slip down on the surface of the PET pipe, thereby proving the application prospect of the coating in the field of low-resistance liquid transmission.
Example 4
The static field strength in example 1 was adjusted as shown in table 1, and other parameters were kept consistent to obtain glass with an ultra-smooth antifouling surface.
The glass of example 4 with an ultra-smooth, anti-fouling surface was subjected to performance testing with the following table 1:
table 1 test results of example 4
Electrostatic field intensity (kV/m) Water contact angle (°) Sliding angle (°) Glycol contact angle (°) Glycol sliding angle (°)
5 100.6 30.6 75.8 88.4
10 101.8 21 77.1 42
15 Example 1 102.2 5.1 78.0 6.6
20 102.6 3.4 75.3 4.2
25 98.6 3.3 72.6 4.5
As can be seen from table 1: when the electrostatic field intensity is lower, the coil-shaped liquid brush content of the coating surface is low, the sliding angle of water and glycol on the glass surface is large, the liquid repellency of the coating is poor, and the sliding angle of water and glycol on the coating surface is obviously reduced to about 6 degrees along with the increase of the electrostatic field intensity from 5kV/m to 15 kV/m; the field intensity is continuously increased without obviously reducing the sliding angle of the coating liquid, but the liquid contact angle is reduced by changing the liquid-like brush into a suspension oil film due to excessively rapid mass migration of the polydimethylsiloxane. The above results demonstrate that good lyophobicity can already be provided when the electrostatic field strength is 15 kV/m.
Example 5
The manner of adjusting the gradient temperature rise in example 1 is shown in table 2, and other parameters are kept consistent, to obtain glass having an ultra-smooth antifouling surface.
The glass of example 5 with an ultra-smooth, anti-fouling surface was subjected to performance testing with the following table 2:
table 2 test results of example 5
Figure SMS_1
As can be seen from table 2: when no intermediate temperature (90 ℃) is used for heating, the mechanical property of the coating is reduced due to temperature shock, and the breaking strength is obviously lower than that of other samples. When the coating is not heated at a low temperature (40 ℃) and is suddenly placed at a high temperature, the molecular movement rate is accelerated, a micro layered structure is difficult to form through microphase separation, the adhesion layer and the anti-fouling layer are mutually entangled, and the adhesion of the substrate of the coating is obviously reduced. When the polydimethylsiloxane is not heated at a high temperature (140 ℃), the polydimethylsiloxane is difficult to smoothly migrate to the surface, the obtained coating has poor lyophobic performance, and the water sliding angle is far higher than that of other coatings. Therefore, the coating is prepared by adopting a low-temperature-medium-high-temperature three-stage gradient heating mode.
Comparative example 1
Referring to the method of example 1, the upper electrode plate is changed to be negatively charged, and the specific steps are as follows:
(1) 2.5g of butyl acrylate, 1g of hydroxyethyl methacrylate, 2.5g of hexafluorobutyl methacrylate, 0.1g of azobisisobutyronitrile, 9g of a divinyl-terminated polydimethylsiloxane were taken in a 50mL beaker. After the monomers were mixed uniformly, the mixture was added dropwise to 40mL of deionized water and stirred in an ice-water bath at a speed of 200r/min for 20min for pre-emulsification. After the completion of the pre-emulsification, the power of the cell pulverizer was adjusted to 600W, and the mixture was pulverized in an ice water bath for 10 minutes to disperse the monomers into fine droplets having a particle size of about 100 nm. And (3) putting the dispersed emulsion into a 100mL three-neck flask, putting the flask into an ultrasonic generator, and continuously reacting for 4 hours at 70 ℃ under the protection of nitrogen to obtain the liquid-like polymer nano emulsion.
(2) The nano emulsion with the mass concentration of 10 percent is added at the concentration of 0.2mL/cm 2 The glass sheet was then spun at 2000rpm for 40s and at 5000rpm for 30s, the spin-coating times being 3. The glass sheet was then placed in an electrostatic field of 15kV/cm strength with the upper plate negatively charged. Heating for 3h at 40 ℃, 20min at 90 ℃ and 5min at 140 ℃ to obtain the glass with the ultra-smooth antifouling surface.
The contact angle and sliding angle of water and ethylene glycol at the surfaces of the coatings prepared in example 1 and comparative example 1 under different electrostatic fields were respectively tested, and the results are shown in fig. 5; the surface sliding angle of the coating (comparative example 1) obtained by water and glycol in the electric field with negative electricity on the upper polar plate is as high as 50 degrees, which is obviously higher than that of example 1, and the lyophobic performance is poor; it is shown that the auxiliary effect of the electrostatic field is critical to the lyophobic properties of the coating.
Comparative example 2
The only difference from the coil-like liquid brush polymer coating prepared in example 1 is that the single-ended graft liquid brush polymer coating of lubricating fluid was formed by replacing the divinyl-terminated polydimethylsiloxane with the monovinyl-terminated polydimethylsiloxane during the preparation of the liquid polymer nanoemulsion.
The abrasion fastness of the coating prepared in example 1 and the coating prepared in this comparative example was determined by the following steps:
the water sliding angle of the coating is tested after the coating is subjected to repeated cyclic friction by using an antifriction tester, and the result is shown in a figure 6;
the single end graft type liquid brush polymer coating of lubricating liquid prepared in comparative example 2 had a tendency to start a significant increase in water slip angle after 150 times of friction, whereas the coil type liquid brush polymer coating prepared in example 1 had no significant change in water slip angle after 500 times of friction. The coil structure of double-end grafting can effectively improve the stability of the liquid-like brush.
Comparative example 3
The difference from the coil-like liquid brush polymer coating prepared in example 1 is that the hard monomer is replaced with glycidyl methacrylate and the soft monomer is replaced with lauryl acrylate in the preparation process of the liquid polymer nanoemulsion. The coating prepared in example 1 was compared with the glass coated with the coating prepared in this comparative example for transparency, substrate adhesion and lyophobic properties, and the results are shown in table 3.
Table 3 comparison of properties of comparative example 3 and example 1
Sample of Water contact angle (°) Sliding angle (°) Substrate adhesion (MPa) Transmittance (%)
Example 1 102.2 5.1 12.1 81.5
Comparative example 3 103.8 5.3 15.6 80.2
As can be seen from Table 3, the properties of the coating layer were not significantly changed after the soft and hard monomers were replaced, indicating that the coating layer was not particularly limited in the selection of the components of the monomers at the proper soft and hard monomer ratios.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (5)

1. A method for preparing a self-adhesive super-slip coating rich in a coil-like liquid brush, which is characterized by comprising the following steps:
(1) Preparing liquid-like polymer nano emulsion:
uniformly mixing a soft monomer, a hard monomer, an amphiphilic water-soluble monomer, a divinyl end-capped lubricating functional monomer, a fluorine-containing compatibilizer and an initiator, pouring the mixture into water to obtain a reaction system, preparing a pre-emulsion, performing ultrasonic grinding, and performing polymerization reaction to obtain a liquid-like polymer nano emulsion; the divinyl-terminated lubricating functional monomer is divinyl-terminated polydimethylsiloxane; the fluorine-containing compatibilizer comprises one or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate; the amphiphilic water-soluble monomer comprises one or more of acrylic acid, itaconic acid, maleic acid and acrylamide;
(2) Preparation of self-adhesive super-slip coating rich in coil-like liquid brush:
diluting the liquid-like polymer nano emulsion prepared in the step (1), and coating the diluted liquid-like polymer nano emulsion on the surface of a substrate; then placing the substrate in a unidirectional electrostatic field, and preparing the self-adhesive super-slip coating rich in the coil-like liquid brush by adopting a gradient heating film forming mode; the gradient heating film forming mode is as follows: heating at 30-60 deg.c for 2-6 hr, 80-100 deg.c for 10-30min and 120-150 deg.c for 2-10min; the unidirectional electrostatic field is a positive charge field, and the intensity is 5-25 kV/cm;
the hard monomer in the step (1) comprises one or more of methyl acrylate, vinyl acetate, styrene, acrylonitrile, methyl methacrylate and glycidyl methacrylate; the soft monomer comprises one or more of ethyl acrylate, butyl acrylate, isooctyl acrylate and lauryl acrylate.
2. The method according to claim 1, wherein the soft monomer in the step (1) is 2 to 7% by mass relative to the reaction system, the hard monomer is 0.5 to 5% by mass relative to the reaction system, the fluorine-containing monomer is 1 to 10% by mass relative to the reaction system, the amphiphilic water-soluble monomer is 2 to 5% by mass relative to the reaction system, the divinyl-terminated lubricating function monomer is 5 to 30% by mass relative to the reaction system, and the initiator is 0.1 to 0.5% by mass relative to the reaction system.
3. The method of claim 1, wherein the mass fraction of the liquid-like polymer nanoemulsion after dilution in step (2) is 1-10%.
4. A self-adhering super-slip coating rich in coil-like liquid brushes prepared by the method of any one of claims 1 to 3.
5. Use of the coil-like liquid brush rich self-adhering super-slip coating of claim 4 for substrate protection, low resistance liquid transport.
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