CN117050243A - Fluorine-containing acrylate polymer, organic/inorganic hybrid self-cleaning anti-reflection coating, and preparation method and application thereof - Google Patents
Fluorine-containing acrylate polymer, organic/inorganic hybrid self-cleaning anti-reflection coating, and preparation method and application thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 48
- 238000004140 cleaning Methods 0.000 title claims abstract description 47
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 44
- 239000011737 fluorine Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000058 polyacrylate Polymers 0.000 title description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002245 particle Substances 0.000 claims abstract description 42
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 35
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 35
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 23
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920006222 acrylic ester polymer Polymers 0.000 claims abstract description 20
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 19
- -1 acrylic ester Chemical class 0.000 claims abstract description 8
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 17
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- CKIXFRABPZURLY-UHFFFAOYSA-N triethoxy(3-isocyanopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC[N+]#[C-] CKIXFRABPZURLY-UHFFFAOYSA-N 0.000 claims description 9
- 239000006117 anti-reflective coating Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 5
- 238000007259 addition reaction Methods 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009396 hybridization Methods 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 239000011521 glass Substances 0.000 description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 16
- 239000000725 suspension Substances 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
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- 238000006243 chemical reaction Methods 0.000 description 5
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- 230000000694 effects Effects 0.000 description 5
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- 238000005299 abrasion Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical group CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C09D151/003—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 by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention discloses a fluorine-containing acrylic ester polymer, an organic/inorganic hybridization self-cleaning anti-reflection coating and a preparation method and application thereof, and belongs to the technical field of coatings. The fluorine-containing acrylic ester polymer is obtained by the free radical polymerization reaction of the hydroxyethyl methacrylate and the perfluoropolyether acrylic ester, and can be used for modifying nano silicon dioxide particles, so that the self-cleaning performance and excellent weather resistance and water resistance of the nano silicon dioxide particles can be endowed, the modified nano silicon dioxide particles are prepared into silica sol coating, and the silica sol coating is coated on the surface of a solar panel to form a film layer.
Description
Technical Field
The invention relates to a fluorine-containing acrylic ester polymer and an organic/inorganic hybrid self-cleaning anti-reflection coating, and also relates to a preparation method of the fluorine-containing acrylic ester polymer and the organic/inorganic hybrid self-cleaning anti-reflection coating, and further relates to application of the organic/inorganic hybrid self-cleaning anti-reflection coating, belonging to the technical field of coatings.
Background
The photovoltaic effect is one of the most direct ways to utilize solar energy, and solar panels are commonly used for this-conversion, but when light is irradiated onto the solar panels, about 8% of the sunlight is reflected by the glass cover plate thereon, which greatly reduces the conversion efficiency of the solar cells. In addition, for outdoor applications, the adsorption of dust, organic contaminants can lead to a substantial decrease in the light transmission of the glass cover plate. Therefore, the design and preparation of the film which can reduce the reflection of light on the surface of the glass and has the self-cleaning function are very important, and the film has wide application value.
At present, an antireflection film having a self-cleaning function is mainly obtained by the following several approaches. One is to plate a substance with low surface energy on the surface of the antireflection film to realize the super-hydrophobic self-cleaning function. For example, chinese patent (publication No. CN 110564187A) discloses a modified nano SiO 2 Colloid solution, then SiO is obtained by dipping and pulling method 2 A film. However, this often affects the transmittance of the anti-reflective film, and in addition, during use, the small molecules have low surface energy, which hydrolyze under severe conditions, losing hydrophobicity for a long period of time in outdoor applications, thus losing self-cleaning function. Another is to make the hydrophilic film more hydrophilic and the hydrophobic film more hydrophobic by increasing the surface roughness of the anti-reflective film. For example, chinese patent(publication No. CN 106892574A) discloses a method for preparing porous SiO by sol-gel method 2 A film. However, with the increase of roughness, light scattering is increased, which reduces light transmittance, affects optical performance of the film, and in severe natural environment, the coating has poor weather resistance, and can generate failure phenomena such as chalking, falling and the like after long-term use.
Disclosure of Invention
Aiming at the defects of insufficient flexibility, insufficient weather resistance, incapability of sustaining self-cleaning performance and the like of the self-cleaning anti-reflection coating in the prior art.
The first object of the present invention is to provide a fluoroacrylate polymer which has excellent properties of good hydrophobicity, good flexibility, strong adhesion, chemical resistance, etc.
The second aim of the invention is to provide a preparation method of the fluorine-containing acrylic ester polymer, which is simple and easy to implement, has low raw material cost and is beneficial to mass production.
The third object of the present invention is to provide an organic/inorganic hybrid self-cleaning anti-reflection coating, which mainly comprises modified nano silica particles, wherein the nano silica particles modified by using a fluoroacrylate polymer through a chemical grafting means have good stability, uniform particle size distribution, no influence on the light transmittance of the nano silica particles, and excellent hydrophobicity, weather resistance, chemical resistance and other properties of the nano silica particles, the modified nano silica particles easily form silica sol with good dispersibility in an organic solvent, and the cured film layer has high transmittance, excellent self-cleaning property and chemical stability, and can be applied to a solar panel surface coating.
The fourth object of the invention is to provide a preparation method of the organic/inorganic hybrid self-cleaning anti-reflection coating, which has the characteristics of high efficiency, wide adaptability, economy, energy conservation, environmental friendliness and the like.
The fifth purpose of the invention is to provide an application of the organic/inorganic hybrid self-cleaning anti-reflection coating, which is coated on the surface of a solar panel to form a film layer, so that the solar panel has high transmittance, continuous self-cleaning performance, hydrophobic, wear-resistant, weather-resistant and other performances.
In order to achieve the technical purpose, the invention provides a fluorine-containing acrylic ester polymer, the structural general formula of which is shown as formula I:
wherein,
m is 5-25; n is 12-20;
rf is a type K perfluoropolyether.
The fluorine-containing acrylate polymer is a linear copolymer formed by random copolymerization of hydroxyethyl methacrylate units and perfluoropolyether acrylate units, fluorine-containing groups are randomly distributed on side chains, the fluorine-containing groups can effectively improve the hydrophobic property and weather resistance of the copolymer, the free energy of the surface of a polymer cured film is reduced, the self-cleaning function is endowed, the service life is prolonged, and hydroxyl groups are randomly distributed on the side chains and can be used for grafting modification and crosslinking curing.
As a preferred embodiment, rf has the formula-CF (CF) 3 )[OCF 2 CF(CF 3 )] n OCF 2 CF 2 CF 3 Rf has a number average molecular weight of 1000 to 1200 and n is 4 to 6.
The invention also provides a preparation method of the fluorine-containing acrylic ester polymer, which is obtained by the free radical polymerization reaction of hydroxyethyl methacrylate and perfluoropolyether acrylic ester;
the structural formula of the perfluoropolyether acrylate is shown as formula II:
wherein Rf is a K-type perfluoropolyether.
The free radical polymerization reaction formula between the hydroxyethyl methacrylate and the perfluoropolyether acrylate is shown as a formula III:
according to the preparation method of the fluorine-containing acrylate polymer, on one hand, hydroxyethyl methacrylate (HEMA) is adopted as a raw material, acrylate double bonds with higher activity and double bonds at the tail end of perfluoropolyether acrylate (FEMA) are utilized to carry out free radical polymerization, hydroxyl groups can be introduced into side chains of a copolymer through HEMA monomers, so that the copolymer has grafting modification and crosslinking curing functions, on the other hand, fluorine-containing groups are introduced into the copolymer through FEMA, the hydrophobicity of the copolymer is improved, the surface free energy of the copolymer after curing is lower, and meanwhile, the chemical stability of the copolymer is improved. In addition, the invention uses the Azobisisobutyronitrile (AIBN) as a free radical initiator, the initiator can be decomposed to form isobutyronitrile groups at more than 60 ℃, the decomposition reaction is relatively stable, only 1 free radical is generated, the induction decomposition basically does not occur, the monomer conversion rate is high, and other impurities are not introduced.
As a preferred embodiment, the molar ratio of hydroxyethyl methacrylate to perfluoropolyether acrylate is 3-8:1. The usage amount of HEMA relative to FEMA has great influence on the film performance of the copolymer, if the usage amount of HEMA is too small, the curing and crosslinking points of the HEMA and the nano silica particles are small, the acting force between the polymer and the nano silica particles is poor, the polymer and the nano silica particles cannot be effectively prevented from being hydrolyzed, the weather resistance of the film is poor, the service life is influenced, and if the usage amount of HEMA is too high, the proportion of the introduced fluorine-containing groups is too low, and the hydrophobicity and other performances introduced by the fluorine-containing groups are influenced.
As a preferred embodiment, the conditions for the radical polymerization are: the azo diethyl nitrile is used as an initiator, the addition amount of the initiator is 4-8% of the molar amount of the perfluoropolyether acrylate, the temperature is 40-70 ℃ and the time is 9-15 h. The addition amount of the initiator is too large, the concentration of the initiator is increased, the polymerization rate is accelerated, the polymerization degree is reduced, and the addition amount of the initiator is too small, so that the initiator is not easy to initiate, and the normal operation of the reaction is affected.
The specific preparation method of the fluorine-containing acrylate polymer comprises the following steps: adding HEMA and FEMA into a polymerization tube according to a molar ratio of 3-8:1, adding 4-8% AIBN and a proper amount of THF as solvents according to the molar amount of the perfluoropolyether acrylate, and putting the mixture into a magnet. The polymerization tube is melted for three times by liquid nitrogen freezing, vacuumizing and nitrogen introducing, and then is sealed in a vacuum state. Placing the sealed polymerization tube into an oil bath at 40-70 ℃ for reaction for 9-15 h. The polymerization tube was opened, a small amount of THF was added to dissolve the polymer, which was precipitated in petroleum ether, and after standing for 1h, the liquid was poured out to obtain a viscous polymer, which was once again precipitated with petroleum ether, and then dried in a vacuum oven at 30 ℃.
The invention also provides an organic/inorganic hybrid self-cleaning anti-reflection coating, which comprises modified nano silica particles; the modified nano silicon dioxide particles are obtained by crosslinking nano silicon dioxide particles with the fluorine-containing acrylic ester polymer through isocyano propyl triethoxy siloxane.
The modified nano silicon dioxide particle surface in the organic/inorganic hybrid self-cleaning anti-reflection coating is modified by chemical grafting to form the fluorine-containing acrylic ester polymer, and the excellent performance of the fluorine-containing acrylic ester polymer is endowed to the nano silicon dioxide particle, so that the modified nano silicon dioxide particle has excellent chemical resistance and weather resistance, good mechanical property and hydrophobic property, and meanwhile, the modified silicon dioxide particle has lower refractive index, so that the light transmittance is greatly improved, and the solar energy loss is reduced. Meanwhile, compared with physical mixing, the action force between the nano silicon dioxide particles and the fluorine-containing acrylate polymer can be greatly enhanced through chemical bonding between the fluorine-containing acrylate polymer and the nano silicon dioxide particles, the continuous self-cleaning performance of the cured coating can be provided, and the service life of the cured coating is prolonged.
According to the modified nano silicon dioxide particles, the fluorine-containing acrylic ester polymer is grafted, a large number of perfluoropolyether flexible chains are uniformly distributed on the side chains of the fluorine-containing acrylic ester polymer, and the water impact resistance of the coating can be enhanced.
The organic/inorganic hybrid self-cleaning anti-reflection coating comprises a solvent, such as tetrahydrofuran, and can uniformly disperse the modified nano silicon dioxide particles to form silica sol (suspension).
As a preferred embodiment, the nano-silica particles have a particle diameter of 100 to 800nm. Further preferably 200 to 400nm, most preferably 300nm. Too large a particle size of the nano silica particles may decrease the transparency of the coating, and too small a particle size may decrease the mechanical strength of the micro-nano structure.
As a preferable scheme, the mass ratio of the nano silicon dioxide particles to the fluorine-containing acrylate polymer and the isocyano propyl triethoxy siloxane is 1:1.2-1.6:0.1-0.6. The interaction force between the nano silicon dioxide particles and the polymer, and the flexibility and impact resistance of the whole coating can be adjusted by adjusting the mass ratio of the nano silicon dioxide particles, the isocyano propyl triethoxy silane and the fluorine-containing polymer.
The invention also provides a preparation method of the organic/inorganic hybrid self-cleaning anti-reflection coating, which comprises the steps of adding isocyano propyl triethoxy silane into nano silicon dioxide particle dispersion liquid for hydrolysis condensation reaction, and then adding fluorine-containing acrylate polymer for addition reaction.
As a preferable embodiment, the conditions of the hydrolytic condensation reaction are: reacting for 6-10 h at 50-70 ℃.
As a preferred embodiment, the conditions of the addition reaction are: reacting for 4-8 h at 70-80 ℃.
The specific preparation method of the organic/inorganic hybrid self-cleaning anti-reflection coating comprises the following steps: slowly adding the nano silicon dioxide with the particle size of 100-800 nm into tetrahydrofuran solution, and stirring for 2h. And then the isocyano propyl triethoxy silane (the addition amount is 10 to 60 percent of the mass of the nano silicon dioxide) reacts for 6 to 10 hours at the temperature of 50 to 70 ℃. And then adding the fluorine-containing acrylic ester polymer into the solution (the addition amount is 120-160% of the mass of the nano silicon dioxide), and reacting for 4-8 h at 70-90 ℃ to obtain the fluorine-containing polymer grafted nano silicon dioxide particles.
The organic/inorganic hybrid self-cleaning anti-reflection coating can be applied to solar panels. The specific use process is as follows: the glass substrate (solar panel) was placed in an acetone solution and ultrasonically cleaned for 10min. The self-cleaning anti-reflection suspension prepared above was placed in a beaker. The cleaned glass substrate was vertically immersed in the suspension for 10 minutes, and then stably pulled at a constant rate of 100mm/min, and the resulting coating was heat-treated in ambient air at 160 ℃ for 1 hour, and then cooled to room temperature.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) The fluorine-containing acrylic ester polymer provided by the invention has the characteristics of good flexibility, strong adhesive force, chemical resistance, excellent water impact resistance and the like.
2) The preparation method of the fluorine-containing acrylic ester polymer provided by the invention is simple and feasible, has low raw material cost and is beneficial to large-scale production.
3) The organic/inorganic hybrid self-cleaning anti-reflection coating provided by the invention contains nano silicon dioxide which is obtained by grafting and modifying a fluorine-containing acrylic ester polymer, has uniform particle size distribution, can form stable silica sol after being dispersed in a solvent, has high transmittance and excellent self-cleaning performance after being cured, and can be applied to solar panels.
4) According to the invention, the fluorine-containing acrylic ester polymer is used for modifying the nano silicon dioxide particles through chemical grafting, the obtained modified nano silicon dioxide particles have good stability, the self-cleaning performance is endowed, the service life of the coating can be prolonged, and meanwhile, the modified nano silicon dioxide particles have low refractive index and better weather resistance, and can be better applied to solar panels.
Drawings
Fig. 1 is a graph of contact angle measurements of the cured coating prepared in example 1.
FIG. 2 is a scanning electron microscope image of the cured coating prepared in example 1.
FIG. 3 is a nuclear magnetic resonance spectrum of the fluoroacrylate polymer prepared in example 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
6.5g HEMA, 12.5g FEMA (the number average molecular weight of the perfluoropolyether chain is 1100), 0.8g AIBN and 40mL tetrahydrofuran are sequentially added into a round bottom flask, after sealing, the mixture is frozen by liquid nitrogen, vacuumized and melted by introducing nitrogen for three times, then heated to 60 ℃, reacted for 4 hours, 10mL THF is added to dissolve the polymer, the mixture is precipitated in petroleum ether, after standing for 1 hour, the liquid is poured out, the viscous polymer is obtained, and after once precipitation by petroleum ether, the mixture is put into a vacuum oven for drying at 30 ℃, and the product is the purified fluoroacrylate polymer.
10g of nanosilica (300 nm) was slowly added to 30mL of tetrahydrofuran solution and stirred for 2h. 4g of isocyanopropyltriethoxysilane are subsequently reacted at 60℃for 8h. Then 15g of fluorine-containing acrylic ester polymer is added into the solution to react for 6 hours at 80 ℃ to obtain the modified nano silicon dioxide particle suspension.
The glass substrate was placed in an acetone solution and ultrasonically cleaned for 10min. The self-cleaning anti-reflection suspension prepared above was placed in a beaker. The cleaned glass substrate was vertically immersed in the suspension for 10 minutes, and then stably pulled at a constant rate of 100mm/min. The resulting coating was heat treated in ambient air at 160 ℃ for 1 hour and then cooled to room temperature to form a self-cleaning anti-reflective coating.
Example 2
10.4g HEMA, 12.5g FEMA (perfluoropolyether chain number average molecular weight: 1100) and initiator 0.9g AIBN, 40mL tetrahydrofuran were added sequentially to a round bottom flask, and after sealing, the mixture was frozen by liquid nitrogen, evacuated and melted three times by nitrogen. Heating to 60 ℃, reacting for 4 hours, adding 10mL of THF to dissolve the polymer, precipitating in petroleum ether, standing for 1 hour, pouring out liquid to obtain a viscous polymer, precipitating once by petroleum ether, and drying in a vacuum oven at 30 ℃, thus obtaining the purified fluoroacrylate polymer.
10g of nanosilica (300 nm) was slowly added to 30mL of tetrahydrofuran solution and stirred for 2h. 4g of isocyanopropyltriethoxysilane are subsequently reacted at 60℃for 8h. Then adding 15g of fluorine-containing acrylate polymer into the solution, and reacting for 6 hours at 80 ℃ to obtain the fluorine-containing polymer grafted nano silicon dioxide particles.
The glass substrate was placed in an acetone solution and ultrasonically cleaned for 10min. The self-cleaning anti-reflection suspension prepared above was placed in a beaker. The cleaned glass substrate was vertically immersed in the suspension for 10 minutes, and then stably pulled at a constant rate of 100mm/min. The resulting coating was heat treated in ambient air at 160 ℃ for 1 hour and then cooled to room temperature to form a self-cleaning anti-reflective coating.
Example 3
4.0g HEMA, 12.5g FEMA (perfluoropolyether chain number average molecular weight: 1100) and initiator 0.7g AIBN, 40mL tetrahydrofuran were added sequentially to a round bottom flask, and after sealing, the mixture was frozen by liquid nitrogen, evacuated and melted three times by introducing nitrogen. Heating to 60 ℃, reacting for 4 hours, adding 10mL of THF to dissolve the polymer, precipitating in petroleum ether, standing for 1 hour, pouring out liquid to obtain a viscous polymer, precipitating once by petroleum ether, and drying in a vacuum oven at 30 ℃, thus obtaining the purified fluoroacrylate polymer.
10g of nanosilica (300 nm) was slowly added to 30mL of tetrahydrofuran solution and stirred for 2h. 4g of isocyanopropyltriethoxysilane are subsequently reacted at 60℃for 8h. Then adding 15g of fluorine-containing acrylate polymer into the solution, and reacting for 6 hours at 80 ℃ to obtain the fluorine-containing polymer grafted nano silicon dioxide particles.
The glass substrate was placed in an acetone solution and ultrasonically cleaned for 10min. The self-cleaning anti-reflection suspension prepared above was placed in a beaker. The cleaned glass substrate was vertically immersed in the suspension for 10 minutes, and then stably pulled at a constant rate of 100mm/min. The resulting coating was heat treated in ambient air at 160 ℃ for 1 hour and then cooled to room temperature to form a self-cleaning anti-reflective coating.
Example 4
6.5g HEMA, 12.5g FEMA (perfluoropolyether chain number average molecular weight: 1100) and initiator 0.8g AIBN, 40mL tetrahydrofuran were added sequentially to a round bottom flask, and after sealing, the mixture was frozen by liquid nitrogen, evacuated and melted three times by nitrogen. Heating to 60 ℃, reacting for 4 hours, adding 10mL of THF to dissolve the polymer, precipitating in petroleum ether, standing for 1 hour, pouring out liquid to obtain a viscous polymer, precipitating once by petroleum ether, and drying in a vacuum oven at 30 ℃, thus obtaining the purified fluoroacrylate polymer.
10g of nanosilica (300 nm) was slowly added to 30mL of tetrahydrofuran solution and stirred for 2h. 1g of isocyanopropyltriethoxysilane was subsequently reacted at 60℃for 8h. Then adding 15g of fluorine-containing acrylate polymer into the solution, and reacting for 6 hours at 80 ℃ to obtain the fluorine-containing polymer grafted nano silicon dioxide particles.
The glass substrate was placed in an acetone solution and ultrasonically cleaned for 10min. The self-cleaning anti-reflection suspension prepared above was placed in a beaker. The cleaned glass substrate was vertically immersed in the suspension for 10 minutes, and then stably pulled at a constant rate of 100mm/min. The resulting coating was heat treated in ambient air at 160 ℃ for 1 hour and then cooled to room temperature to form a self-cleaning anti-reflective coating.
Example 5
6.5g HEMA, 12.5g FEMA (perfluoropolyether chain number average molecular weight: 1100) and initiator 0.8g AIBN, 40mL tetrahydrofuran were added sequentially to a round bottom flask, and after sealing, the mixture was frozen by liquid nitrogen, evacuated and melted three times by nitrogen. Heating to 60 ℃, reacting for 4 hours, adding 10mL of THF to dissolve the polymer, precipitating in petroleum ether, standing for 1 hour, pouring out liquid to obtain a viscous polymer, precipitating once by petroleum ether, and drying in a vacuum oven at 30 ℃, thus obtaining the purified fluoroacrylate polymer.
10g of nanosilica (300 nm) was slowly added to 30mL of tetrahydrofuran solution and stirred for 2h. 4g of isocyanopropyltriethoxysilane are subsequently reacted at 60℃for 8h. Then adding 11g of fluorine-containing acrylate polymer into the solution, and reacting for 6 hours at 80 ℃ to obtain the fluorine-containing polymer grafted nano silicon dioxide particles.
The glass substrate was placed in an acetone solution and ultrasonically cleaned for 10min. The self-cleaning anti-reflection suspension prepared above was placed in a beaker. The cleaned glass substrate was vertically immersed in the suspension for 10 minutes, and then stably pulled at a constant rate of 100mm/min. The resulting coating was heat treated in ambient air at 160 ℃ for 1 hour and then cooled to room temperature to form a self-cleaning anti-reflective coating.
Example 6
The particle size of the nanosilica was changed to 100nm and the other conditions were the same as in example 1.
Example 7
The particle size of the nanosilica was changed to 800nm and the other conditions were the same as in example 1.
Comparative example 1
The modified nano-silica particles were prepared without adding isocyanatopropene triethoxysilane, and the other conditions were the same as in example 1.
Comparative example 2
The amount of the nanoparticle in example 1 was adjusted to 9.5g, and the remaining conditions were unchanged.
Comparative example 3
The amount of the nanoparticle in example 1 was adjusted to 12g, and the other conditions were unchanged.
The self-cleaning anti-reflection coating prepared in examples 1 to 7 and comparative example 1 is coated on a silicon wafer by adopting a spraying mode, the viscosity of the system is excessively high during construction, the system can be diluted by a solvent (butyl acetate: ethylene glycol methyl ether acetate=1:1), and the effect after ultraviolet light curing is shown as follows:
table 1 comparison of the effects of different UV coatings
Hydrophobic angle test method: the static contact angle of the coating was measured by a contact angle meter of the type JGW-360 a. The volume of the test liquid was 2. Mu.L, the test environment was 24.+ -. 1 ℃ and the relative humidity was 45.+ -. 1%. The drop antenna measures 5 points and takes the average value.
The roll angle testing method comprises the following steps: the roll angle was determined by an SDC-350 global tilt contact angle meter, placing a droplet of liquid volume 2. Mu.L on a test platform, tilting the platform slowly, recording the platform tilt angle as the droplet rolls off.
The light transmittance testing method comprises the following steps: the light transmittance is measured by a TH-110 type light transmittance haze meter, the glass after construction is placed on a test platform, a HOLD key of the meter is pressed down, the meter can start testing after self calibration, and the test result is recorded.
The abrasion resistance testing method comprises the following steps: the abrasion resistance test is determined by a ZJ-339-GSR abrasion resistance instrument, the constructed glass is fixed on the tester, the stroke is set to be 60mm, the speed is set to be 60 times/min, and the test result is recorded.
The comparison of the data in comparative example 1 and example 2 shows that the reduced proportion of fluoromonomer in the fluoroacrylate polymer significantly reduces the hydrophobic angle of the coating after curing. The particle size of the nano silicon dioxide is increased, the light transmittance of the paint is reduced, the particle size of the nano silicon dioxide is reduced, and the wear resistance is slightly reduced. By example 1 and comparative example 1, it can be seen that the coating prepared by chemically bonded silica particles, grafted with a polymer, is effective in enhancing the weather resistance and abrasion resistance of the coating.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A fluoroacrylate polymer characterized by: the structural general formula is shown in formula I:
wherein,
m is 5-25; n is 12-20;
rf is a type K perfluoropolyether.
2. A method of preparing a fluoroacrylate polymer of claim 1 wherein: the modified polyurethane is prepared from hydroxyethyl methacrylate and perfluoropolyether acrylate through free radical polymerization;
the structural formula of the perfluoropolyether acrylate is shown as formula II:
wherein Rf is a K-type perfluoropolyether.
3. A method of preparing a fluoroacrylate polymer in accordance with claim 2, wherein: the molar ratio of the hydroxyethyl methacrylate to the perfluoropolyether acrylate is 3-8:1.
4. A process for the preparation of a fluoroacrylate polymer according to claim 2 or 3, characterized in that: the conditions of the free radical polymerization reaction are as follows: the azo diethyl nitrile is used as an initiator, the addition amount of the initiator is 4-8% of the molar amount of the perfluoropolyether acrylate, the temperature is 40-70 ℃ and the time is 9-15 h.
5. An organic/inorganic hybrid self-cleaning anti-reflection coating, which is characterized in that: comprising modified nanosilica particles; the modified nano-silica particles are obtained by crosslinking nano-silica particles with the fluoroacrylate polymer according to claim 1 through isocyanatopropyl triethoxy siloxane.
6. An organic/inorganic hybrid self-cleaning antireflective coating according to claim 5, wherein: the particle size of the nano silicon dioxide particles is 100-800 nm.
7. An organic/inorganic hybrid self-cleaning antireflective coating according to claim 5 or 6, characterised in that: the mass ratio of the nano silicon dioxide particles to the fluorine-containing acrylic ester polymer to the isopropyl triethoxy siloxane is 1:1.2-1.6:0.1-0.6.
8. A method for preparing the organic/inorganic hybrid self-cleaning anti-reflection coating according to claim 5, 6 or 7, which is characterized in that: adding isocyano propyl triethoxy silane into the nano silicon dioxide particle dispersion liquid to carry out hydrolytic condensation reaction, and then adding fluorine-containing acrylic ester polymer to carry out addition reaction, thus obtaining the nano silicon dioxide particle dispersion liquid.
9. The method for preparing the organic/inorganic hybrid self-cleaning anti-reflection coating according to claim 8, which is characterized in that:
the conditions of the hydrolytic condensation reaction are as follows: reacting for 6-10 h at 50-70 ℃;
the conditions of the addition reaction are as follows: reacting for 4-8 h at 70-80 ℃.
10. Use of an organic/inorganic hybrid self-cleaning anti-reflective coating according to any one of claims 5 to 7, characterized in that: the coating is applied to the surface coating of the solar panel.
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