CN113372016B - Wear-resistant and renewable polymer brush initiator coating and preparation method and application thereof - Google Patents
Wear-resistant and renewable polymer brush initiator coating and preparation method and application thereof Download PDFInfo
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- CN113372016B CN113372016B CN202110703004.6A CN202110703004A CN113372016B CN 113372016 B CN113372016 B CN 113372016B CN 202110703004 A CN202110703004 A CN 202110703004A CN 113372016 B CN113372016 B CN 113372016B
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- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
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- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
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- 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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
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- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
Abstract
The invention provides a wear-resistant and renewable polymer brush initiator coating as well as a preparation method and application thereof, belonging to the technical field of material surface modification. The preparation method of the wear-resistant renewable polymer brush initiator coating comprises the following steps: mixing ethyl orthosilicate, alcohol, water, inorganic acid and an ATRP initiator, hydrolyzing, coating the obtained hydrolysate on the surface of a matrix, and forming a wear-resistant and renewable polymer brush initiator coating on the surface of the matrix. The initiator coating prepared by the invention has good wear resistance, has excellent water lubricating property and high bearing capacity after grafting the polymer brush, can form the polymer brush on the surface of any material by an ATRP method, and can initiate polymerization of the graft polymer brush again after the surface is worn.
Description
Technical Field
The invention relates to the technical field of material surface modification, in particular to a wear-resistant and renewable polymer brush initiator coating and a preparation method and application thereof.
Background
Polymer brushes are ultra-thin polymer coatings formed by anchoring one end of a high molecular weight polymer to a solid surface. The preparation method of the polymer brush can be divided into two methods of grafting from the surface (grafting from) and grafting to the surface (grafting to). Among them, the "gradient from" method of Atom Transfer Radical Polymerization (ATRP) is the most common method for researchers to prepare polymer brushes because of its high selectivity of monomers and strong structure designability. The method is characterized in that halogen-containing initiation groups are introduced to the surface of a material, and then polymerization can be initiated on the surface of the material under the action of a catalyst to prepare the polymer brush. However, the preparation of polymer brushes by this method faces a number of obstacles in large scale applications. For example, high monomer and catalyst concentrations require anaerobic conditions, low monomer utilization, cumbersome further processing of the reaction solution, etc., which limits its applications.
At present, many improvements are made to the traditional ATRP, such as adding excessive reducing agent into the reaction solution or regenerating the activator in situ by external energy such as light or electricity, etc., so as to graft the polymer brush in the air, and solve the problems of deoxidation and reuse of the monomer solution during the reaction. In addition, a small amount of monomer solution is used in a limited range or reaction solution is coated on the initiator substrate, so that the problem of monomer waste is solved, and the preparation cost is greatly reduced. However, in the prior art, the monomolecular initiator layer is prepared by gas-phase assembly or liquid-phase assembly, and the method has the problems of complicated preparation steps, strong selectivity to a substrate, poor wear resistance of the monomolecular initiator layer and the polymer brush, no possibility of initiating grafting of the polymer brush for multiple times and the like.
Disclosure of Invention
The initiator coating prepared by the invention has good wear resistance, has excellent water lubricating property and high bearing capacity after being grafted with a polymer brush, can form the polymer brush on the surface of any material by an ATRP (atom transfer radical polymerization) method, and can initiate polymerization of the grafted polymer brush again after the surface is abraded.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a wear-resistant and renewable polymer brush initiator coating, which comprises the following steps:
mixing ethyl orthosilicate, alcohol, water, inorganic acid and an ATRP initiator, hydrolyzing, coating the obtained hydrolysate on the surface of a matrix, and forming a wear-resistant and renewable polymer brush initiator coating on the surface of the matrix.
Preferably, the ATRP initiator comprises 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon) propyl ester.
Preferably, the volume ratio of the alcohol to the tetraethyl orthosilicate to the water to the inorganic acid is 12: (2-8): 1: (0.2 to 1); the alcohol is a monohydric alcohol; the inorganic acid comprises concentrated nitric acid or concentrated hydrochloric acid.
Preferably, the mass ratio of the tetraethoxysilane to the ATRP initiator is (3-100): 1.
Preferably, the coating mode is dip coating; the dip-coating pulling speed is 10-200 mm/min.
The invention provides a wear-resistant renewable polymer brush initiator coating prepared by the preparation method in the scheme.
The invention provides application of the wear-resistant renewable polymer brush initiator coating in the scheme in preparation of a polymer brush.
Preferably, the method of application comprises the steps of: immersing a substrate containing an abrasion-resistant and renewable polymer brush initiator coating into a reaction solution containing an alkenyl monomer, L-ascorbic acid, a catalyst and 2, 2-bipyridyl to carry out ATRP reaction, and forming a polymer brush on the surface of the substrate; the catalyst is CuCl2Or CuBr2。
Preferably, the ATRP reaction temperature is room temperature, and the time is 1-6 h.
Preferably, the alkenyl monomer is 3-sulfopropyl methacrylate potassium, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, dimethylaminoethyl methacrylate or trimethylammonium methacrylate; the mass ratio of the alkenyl monomer to the catalyst is (5-200): 1; the mass ratio of the L-ascorbic acid to the catalyst is (1-30): 1; the mass ratio of the 2, 2-bipyridyl to the catalyst is 2: 1; the solvent of the reaction solution is a mixed solution of water and methanol, and the volume ratio of the water to the methanol in the mixed solution is 1: 1; the concentration of the alkenyl monomer in the reaction solution is 0.01-0.1 g/mL.
The invention provides a preparation method of a wear-resistant and renewable polymer brush initiator coating, which comprises the following steps: mixing ethyl orthosilicate, alcohol, water, inorganic acid and an ATRP initiator, hydrolyzing, coating the obtained hydrolysate on the surface of a matrix, and forming a wear-resistant and renewable polymer brush initiator coating on the surface of the matrix.
The tetraethoxysilane is hydrolyzed under the condition of alcohol/water, and then is subjected to dehydration condensation to form an organic-inorganic hybrid coating (namely a polymer brush initiator coating) containing initiator molecules, and because the initiator coating formed by the invention is organic-inorganic hybrid, has high strength and certain thickness, the wear resistance of the initiator coating is better than that of the initiator coating assembled by the traditional single molecule; meanwhile, more initiator molecules can be modified on the solid surface by a certain thickness, and even if the surface initiator molecules are worn away after being worn, the initiator in the initiator coating can still be exposed for re-initiation, so that the solid surface initiator has the characteristics of re-initiation and high strength; according to the invention, by utilizing the characteristic of high bonding strength between the silica sol obtained by hydrolyzing tetraethoxysilane and a substrate, a silica sol layer can be formed on the surface of most of substrates, and in addition, an ATRP initiator can be embedded into the silica sol layer to form a coating structure of the silica sol-initiator (namely the polymer brush initiator coating of the invention), so that a polymer brush is formed on the surface of most of materials, and the polymer brush is simple and convenient and has strong universality.
Drawings
FIG. 1 is a static contact angle diagram, which is a graph of the glass sheet of example 1, the glass sheet of example 1 containing an initiator coating, and the glass sheet of application example 1 after being brushed with a graft-modified polymer, in order from left to right;
FIG. 2 is a graph comparing the abrasion resistance of the surface of a conventional machined polymer brush of comparative example 1 with the surface of a grafted polymer brush of application example 1 coated with an initiator coating of the present invention;
FIG. 3 is a graph of the effect of multiple initiation of a modified polymer brush coated with an initiator coating of the present invention in application example 1 on achieving an ultra-low coefficient of friction compared to a conventional initiator coating of comparative example 1;
FIG. 4 is a physical representation of water droplets dropped on the surface of a polymer brush and on the surface of a bare material after the polymer brush was prepared on the surface of a different solid material according to example 1 and application example 1, wherein the right side shows the water droplets spread on the surface of the polymer brush; the left side is the bare material surface where the water droplets do not spread.
Detailed Description
The invention provides a preparation method of a wear-resistant and renewable polymer brush initiator coating, which comprises the following steps:
mixing ethyl orthosilicate, alcohol, water, inorganic acid and an ATRP initiator, hydrolyzing, coating the obtained hydrolysate on the surface of a matrix, and forming a wear-resistant and renewable polymer brush initiator coating on the surface of the matrix.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The invention mixes ethyl orthosilicate, alcohol, water, inorganic acid and ATRP initiator to hydrolyze.
In the present invention, the alcohol is preferably a monohydric alcohol, more preferably ethanol; the inorganic acid preferably comprises concentrated nitric acid or concentrated hydrochloric acid, more preferably concentrated nitric acid. In the invention, the concentrated nitric acid and the concentrated hydrochloric acid are both commercial products well known in the field, namely the mass fraction of the concentrated nitric acid is 68%, and the mass fraction of the concentrated hydrochloric acid is 36-38%.
In the present invention, the ATRP initiator preferably includes 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon) propyl ester.
In the present invention, the volume ratio of the alcohol, tetraethyl orthosilicate, water, and mineral acid is preferably 12: (2-8): 1: (0.2 to 1), more preferably 12: (4-6): 1: (0.3 to 0.8); the mass ratio of the tetraethoxysilane to the ATRP initiator is preferably (3-100): 1, more preferably (20-80): 1, and even more preferably (40-60): 1.
In the present invention, said mixing of tetraethoxysilane, alcohol, water, mineral acid and ATRP initiator preferably comprises: stirring ethyl orthosilicate, alcohol, water and inorganic acid uniformly, and adding an ATRP initiator under the condition of stirring.
The invention has no special requirements on the specific stirring conditions, and can uniformly mix all the materials.
In the present invention, the hydrolysis process preferably comprises: and mixing the materials to obtain a mixed solution, stirring, and standing and aging.
In the present invention, the stirring time in the hydrolysis process is preferably 1 hour; the time for the standing aging is preferably 72 hours. The invention further promotes the full hydrolysis of the tetraethoxysilane by standing and aging. The stirring rate in the hydrolysis process is not particularly required in the present invention, and the stirring rate well known in the art can be adopted.
After the hydrolysis is completed, the obtained hydrolysate is coated on the surface of a substrate, and a wear-resistant and renewable polymer brush initiator coating is formed on the surface of the substrate.
The invention has no special requirements for the substrate, and any substrate required to prepare a polymer brush can be used. In an embodiment of the invention, the substrate is a glass sheet.
In the present invention, the coating is preferably dip coating. The dip coating preferably comprises: the substrate is immersed in the hydrolysate and then pulled upward. In the invention, the immersion time is preferably 20-30 s; the pulling rate is preferably 10 to 200mm/min, more preferably 30 to 150mm/min, and still more preferably 50 to 100 mm/min. The thickness of the wear-resistant renewable polymer brush initiator coating is controlled within a proper range by controlling the pulling speed. In the invention, the thickness of the initiator coating is preferably 50-100 nm, and more preferably 60-90 nm. In embodiments of the invention, the initiator coating has a thickness of 70nm, 75nm, 90nm or 95 nm.
In the hydrolysis process, tetraethoxysilane and ATRP initiator are hydrolyzed in alcohol/water solution, and after the solvent deposited on the surface of the matrix is volatilized, the hydrolysate of tetraethoxysilane and the hydrolysate of ATRP initiator are subjected to dehydration condensation to form an organic-inorganic hybrid initiator coating. The reaction formula is shown as formula 1:
the invention preferably promotes the volatilization of the alcohol solvent in the hydrolysate by naturally airing at room temperature.
The wear-resistant renewable polymer brush initiator coating prepared by the invention is an inorganic organic hybrid layer, has high strength and certain thickness, and therefore, has better wear resistance than the initiator layer assembled by traditional single molecules; meanwhile, more initiator molecules can be modified on the solid surface by a certain thickness, and even if the surface initiator molecules are worn away after being worn, the initiator in the initiator coating can still be exposed for re-initiation, so that the initiator coating has the characteristics of re-initiation and high strength. In addition, the invention utilizes the characteristic that the bonding strength of the silica sol obtained by hydrolyzing tetraethoxysilane and a substrate is high, and can form a silica sol layer on the surface of most substrates.
The invention provides a wear-resistant renewable polymer brush initiator coating prepared by the preparation method in the scheme. The invention has no special requirement on the thickness of the initiator coating and is determined by the preparation process.
The invention provides application of the wear-resistant renewable polymer brush initiator coating in the scheme in preparation of a polymer brush.
In the present invention, the method of application preferably comprises the steps of: dipping a substrate containing an abrasion resistant, renewable polymeric brush initiator coating into a composition comprising an ethylenic monomer, L-ascorbic acid, a catalyst, and 2,2-In the reaction solution of bipyridyl, ATRP reaction is carried out to form a polymer brush on the surface of a matrix; the catalyst is CuCl2Or CuBr2。
In the present invention, the ethylenic monomer is preferably 3-sulfopropyl methacrylate potassium salt, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, dimethylaminoethyl methacrylate, or trimethylammonium methacrylate; the solvent of the reaction solution is a mixed solution of water and methanol, and the volume ratio of the water to the methanol in the mixed solution is preferably 1: 1.
In the present invention, the concentration of the alkenyl monomer in the reaction solution is preferably 0.01 to 0.1g/mL, and more preferably 0.02 to 0.8 g/mL.
In the present invention, the mass ratio of the alkenyl monomer to the catalyst is preferably (5 to 200): 1, more preferably (30 to 170): 1, more preferably (50 to 150): 1; the mass ratio of the L-ascorbic acid to the catalyst is preferably (1-30): 1, more preferably (5-25): 1, more preferably (10 to 20): 1; the mass ratio of the 2, 2-bipyridine to the catalyst is preferably 2: 1.
in the invention, the L-ascorbic acid is a reducing agent, and the 2, 2-bipyridyl is a complex ligand. According to the invention, excessive ascorbic acid is used as a reducing agent, the ascorbic acid can continuously reduce divalent copper ions into monovalent copper in a solution, and the ATRP reaction is catalyzed to be carried out, so that the polymerization process can be carried out under the air condition without deoxidation.
In the invention, the ATRP reaction temperature is preferably room temperature, and the time is preferably 1-6 h, more preferably 2-5 h, and even more preferably 3-4 h.
After the ATRP reaction is completed, the substrate is preferably taken out, flushed with water, and dried by nitrogen to form the polymer brush on the surface of the substrate.
The abrasion resistant, renewable polymeric brush initiator coatings provided by the present invention, and methods of making and using the same, are described in detail below with reference to the examples, which should not be construed as limiting the scope of the invention.
SPMA described in the following examples and application examples represents 3-sulfopropyl methacrylate potassium salt monomer, SBMA represents [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, DMAEMA represents dimethylaminoethyl methacrylate, MATAC represents trimethylammonium methacrylate, Bpy represents 2, 2-bipyridine, and AA represents L-ascorbic acid.
Example 1
1. Respectively measuring 12mL of ethanol, 2mL of ethyl orthosilicate, 1mL of water and 0.2mL of concentrated nitric acid (mass fraction is 68%), adding the mixture into a beaker, uniformly stirring, adding 0.6mL of 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon) propyl ester under the stirring condition, stirring for one hour, and standing and aging for 72 hours to obtain a hydrolysate;
2. immersing a glass sheet with the thickness of 1.5 multiplied by 1.5cm into the hydrolysate for 20s at room temperature, then pulling out the glass sheet by a pulling machine at the speed of 20mm/min, and airing the glass sheet at room temperature to obtain the glass sheet with the initiator coating, wherein the thickness of the initiator coating is 70 nm. The static contact angle was found to be on average 64.0 + -0.5 deg., significantly higher than the static contact angle of the blank glass sheet of 40.2 + -0.3 deg., indicating that the initiator coating had covered the surface of the glass sheet.
Application example 1
The glass sheet containing the initiator coating obtained in example 1 was immersed in a solution containing 0.08g/mL SPMA, 8mg/mL AA, 0.8mg/mL CuCl2And 1.6mg/mL of Bpy mixed solvent of methanol and water (the volume ratio of the methanol to the water is 1:1), reacting for 2 hours at room temperature under a closed condition, flushing with water, and drying with nitrogen to obtain the glass sheet modified by the polymer brush.
Comparative example 1
A conventional vapor deposition initiator was used to prepare the polymer brush as follows:
ultrasonically cleaning a clean glass sheet for 20 minutes by using ethanol, and then treating the cleaned glass sheet for 3 minutes by using oxygen plasma; placing the treated glass sheet in a vacuum dryer, sucking 20 microliters of 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon) propyl ester by using a liquid-transferring gun and simultaneously dripping the propyl ester in the dryer, then pumping air out of the dryer by using an oil pump, controlling the air pressure to be 100-10 Pa, standing for 30min, then pumping air out by using the oil pump, and repeating the steps for 3 times; a conventional vapor deposition initiator coating can be obtained.
And (3) placing the glass sheet of the vapor deposition initiator in the solution of the application example 1 for reaction to obtain the grafted polymer brush glass surface.
And (3) performance characterization:
1. the initiator coating of example 1, after modification of the SPMA polymer brush, had a surface static contact angle of 3.4. + -. 0.2 ℃ which is significantly lower than that of the initiator coated glass slide, and the results are shown in FIG. 1.
2. The polymer brushes prepared in application example 1 and comparative example 1 were subjected to double-side grinding using silicone rubber balls under a load of 3N and a frequency of 2Hz, respectively, and the results are shown in fig. 2. FIG. 2 shows that the friction coefficient of the SPMA polymer brush layer initiated by the conventional initiator layer (corresponding to no silica sol in FIG. 2) in comparative example 1 can be maintained at 0.003-0.005 within 10000 cycles, while the low friction coefficient of the SPMA polymer brush layer initiated by the conventional initiator layer (corresponding to no silica sol in FIG. 2) in comparative example 1 is maintained for only 100 cycles under 3N load and 2Hz frequency, and after 100 cycles, the friction coefficient of the surface of the polymer brush initiated by the conventional initiator layer is sharply increased to 0.4, which indicates that the wear resistance of the polymer brush layer prepared by the conventional method is poor.
3. The SPMA polymer brush layers of application example 1 and comparative example 1 were abraded under a high load of 8N at 1Hz, and then placed in a reactive monomer solution, and the friction coefficient of the surface of the material was measured, and the results are shown in FIG. 3. As can be seen from FIG. 3, after the brush layer of SPMA polymer is worn away, the surface friction coefficient becomes large, and then the brush layer is placed in the reaction monomer solution, the initiator layer (corresponding to the silica sol in FIG. 3) provided by the present invention can still initiate polymerization again to modify SPMA to the surface, thereby obtaining an ultra-low friction coefficient, so that the process of "wear-reinitiation" can be repeated for many times, which shows that the initiator coating of the present invention has good wear resistance and can be initiated for many times; the initiator layer prepared in comparative example 1 by the conventional method (corresponding to fig. 2 without silica sol) does not have such an effect.
4. Referring to example 1 and application example 1, initiator coatings and polymer brushes were prepared on the surfaces of various solid materials (e.g., glass, plexiglass, aluminum, polycarbonate, polyimide, polyethylene terephthalate) and water was dropped on the surfaces of the obtained polymer brushes and bare materials, and the results are shown in fig. 4. As can be seen from FIG. 4, the initiator coating of the present invention applied on various surfaces can initiate the polymerization of the hydrophilic monomer SPMA, the surface becomes more hydrophilic, the water drop spreads more on the surface, and the water drop does not spread on the surface of the bare material. It is illustrated that the initiator coatings of the present invention can be applied to a variety of solid material surfaces and initiate polymerization of the SPMA surface.
Example 2
1. Respectively measuring 12mL of ethanol, 3m L ethyl orthosilicate, 1mL of water and 0.3mL of concentrated nitric acid (mass fraction is 68%), adding the mixture into a beaker, uniformly stirring, adding 0.1mL of 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon) propyl ester under the condition of rapid stirring, stirring for one hour, and standing and aging for 72 hours to obtain a hydrolysate;
2. immersing a glass sheet with the thickness of 1.5 multiplied by 1.5cm into the hydrolysate for 20s at room temperature, then pulling out the glass sheet by a pulling machine at the speed of 20mm/min, and airing the glass sheet at room temperature to obtain the glass sheet with the initiator coating, wherein the thickness of the initiator coating is 75 nm. The static contact angle was found to be on average 62.1 + -0.3 deg., significantly higher than the static contact angle of 40.2 deg. for the blank glass sheet.
Application example 2
The glass sheet containing the initiator coating obtained in application example 2 was immersed in a solution containing SBMA at 0.08g/mL, AA at 4mg/mL, and CuCl at 0.4mg/mL2And 0.8mg/mL of Bpy mixed solvent of methanol and water (the volume ratio of the methanol to the water is 1:1), reacting for 4 hours at room temperature under a closed condition, flushing with water, and drying with nitrogen to obtain the glass sheet containing the polymer brush coating.
The SBMA brush prepared in this application example had similar surface wetting properties, wear resistance, water lubricity, and reinitiability properties as in example 1.
Example 3
1. Respectively measuring 12mL of ethanol, 2m L ethyl orthosilicate, 1mL of water and 0.2mL of concentrated nitric acid (mass fraction is 68%), adding the mixture into a beaker, uniformly stirring, adding 0.3mL of 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon) propyl ester under the condition of rapid stirring, stirring for one hour, and standing and aging for 72 hours to obtain a hydrolysate;
2. immersing a glass sheet with the thickness of 1.5 multiplied by 1.5cm into the hydrolysate for 20s at room temperature, then pulling out the glass sheet by a pulling machine at the speed of 100mm/min, and airing the glass sheet at room temperature to obtain the glass sheet with the initiator coating, wherein the thickness of the initiator coating is 90 nm.
Application example 3
The glass flake with initiator coating obtained in example 3 was immersed in a solution containing 0.08g/mL DMAEMA, 4mg/mL AA, 0.4mg/mL CuCl2And 2.0mg/mL of Bpy in a mixed solvent of methanol and water (the volume ratio of the methanol to the water is 1:1), reacting for 6 hours at room temperature under a closed condition, flushing with water, and drying with nitrogen to obtain the glass sheet with the polymer brush coating.
The DMAEMA brush prepared in this application example had surface wetting properties, abrasion resistance, water lubricity, and re-initiation properties similar to those of example 1.
Example 4
1. Respectively measuring 12mL of ethanol, 5m L ethyl orthosilicate, 1mL of water and 1mL of concentrated nitric acid (mass fraction is 68%), adding the mixture into a beaker, uniformly stirring, adding 0.05mL of 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon) propyl ester under the condition of rapid stirring, stirring for one hour, and standing and aging for 72 hours to obtain a hydrolysate;
2. immersing a glass sheet with the thickness of 1.5 multiplied by 1.5cm into the hydrolysate for 20s at room temperature, then pulling out the glass sheet by a pulling machine at the speed of 200mm/min, and airing the glass sheet at room temperature to obtain the glass sheet with the initiator coating, wherein the thickness of the initiator coating is 90 nm.
Application example 4
The glass sheet containing the initiator coating obtained in example 4 was immersed in a solution containing 0.02g/mL MATAC, 4mg/mL AA, 0.4mg/mL CuCl2And 3.0mg/mL of Bpy in a mixed solvent of methanol and water (the volume ratio of the methanol to the water is 1:1), reacting for 6 hours at room temperature under a closed condition, flushing with water, and drying with nitrogen to obtain the glass sheet with the polymer brush coating.
The surface wetting properties, abrasion resistance, water lubricity, and reinitiability of the MATAC brush prepared in this application example were similar to those in example 1.
Example 5
1. Respectively measuring 12mL of ethanol, 8m L ethyl orthosilicate, 1mL of water and 1mL of concentrated nitric acid (mass fraction is 68%), adding the mixture into a beaker, uniformly stirring, adding 0.1mL of 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon) propyl ester under the condition of rapid stirring, stirring for one hour, and standing and aging for 72 hours to obtain a hydrolysate;
2. immersing a glass sheet with the thickness of 1.5 multiplied by 1.5cm into the hydrolysate for 20s at room temperature, then pulling out the glass sheet by a pulling machine at the speed of 100mm/min, and airing the glass sheet at room temperature to obtain the glass sheet with the initiator coating, wherein the thickness of the initiator coating is 95 nm.
Application example 5
The glass sheet containing the initiator coating obtained in example 5 was immersed in a solution containing 0.06g/mL SPMA, 4mg/mL AA, 0.4mg/mL CuCl2And 3.0mg/mL of Bpy in a mixed solvent of methanol and water (the volume ratio of methanol to water is 1:1), reacting for 1h at room temperature under a sealed condition, flushing with water, and drying with nitrogen to obtain the glass sheet containing the polymer brush coating.
The surface wetting properties, wear resistance, water lubricity, re-initiation properties of the SPMA brush prepared in this application example were similar to those of example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method for preparing an abrasion-resistant, renewable polymer brush initiator coating, comprising the steps of:
mixing ethyl orthosilicate, alcohol, water, inorganic acid and an ATRP (atom transfer radical polymerization) initiator, hydrolyzing, coating the obtained hydrolysate on the surface of a matrix, and forming a wear-resistant and renewable polymer brush initiator coating on the surface of the matrix; the ATRP initiator comprises 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon) propyl ester; the mass ratio of the ethyl orthosilicate to the ATRP initiator is (3-100): 1.
2. The method according to claim 1, wherein the volume ratio of the alcohol, tetraethyl orthosilicate, water, and mineral acid is 12: (2-8): 1: (0.2 to 1); the alcohol is a monohydric alcohol; the inorganic acid comprises concentrated nitric acid or concentrated hydrochloric acid.
3. The method for preparing according to claim 1, wherein the coating is performed by dip coating; the dip-coating pulling speed is 10-200 mm/min.
4. An abrasion-resistant renewable polymer brush initiator coating prepared by the preparation method of any one of claims 1 to 3.
5. Use of the abrasion-resistant renewable polymer brush initiator coating of claim 4 in the preparation of a polymer brush.
6. The application according to claim 5, characterized in that the method of application comprises the steps of: immersing a substrate containing an abrasion-resistant and renewable polymer brush initiator coating into a reaction solution containing an alkenyl monomer, L-ascorbic acid, a catalyst and 2, 2-bipyridyl to carry out ATRP reaction, and forming a polymer brush on the surface of the substrate; the catalyst is CuCl2Or CuBr2。
7. The use according to claim 6, wherein the ATRP reaction is carried out at room temperature for 1-6 h.
8. Use according to claim 6, wherein the ethylenic monomer is 3-sulfopropyl methacrylate potassium salt, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, dimethylaminoethyl methacrylate or trimethylammonium methacrylate; the mass ratio of the alkenyl monomer to the catalyst is (5-200): 1; the mass ratio of the L-ascorbic acid to the catalyst is (1-30): 1; the mass ratio of the 2, 2-bipyridyl to the catalyst is 2: 1; the solvent of the reaction solution is a mixed solution of water and methanol, and the volume ratio of the water to the methanol in the mixed solution is 1: 1; the concentration of the alkenyl monomer in the reaction solution is 0.01-0.1 g/mL.
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