CN115947886A - Fluorine-containing epoxy acrylate polymer, photocuring transparent super-hydrophobic coating and preparation method - Google Patents
Fluorine-containing epoxy acrylate polymer, photocuring transparent super-hydrophobic coating and preparation method Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 96
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 62
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000011737 fluorine Substances 0.000 title claims abstract description 60
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 52
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000000016 photochemical curing Methods 0.000 title abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 61
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- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 12
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- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- XNSIKGLUWHSURK-UHFFFAOYSA-N C(CC)[Si](OCC)(OCC)OCC.[O] Chemical compound C(CC)[Si](OCC)(OCC)OCC.[O] XNSIKGLUWHSURK-UHFFFAOYSA-N 0.000 claims 1
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- 229920000642 polymer Polymers 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 239000000377 silicon dioxide Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
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- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 238000010998 test method Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
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- 238000005096 rolling process Methods 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical group CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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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- 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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
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Abstract
The invention discloses a fluorine-containing epoxy acrylate polymer, a photocuring transparent super-hydrophobic coating and a preparation method thereof, belonging to the technical field of coatings. The fluorine-containing epoxy acrylate polymer is prepared by carrying out free radical polymerization reaction on glycidyl acrylate and perfluoropolyether acrylate; the preparation method is simple and easy to implement, low in raw material cost and beneficial to large-scale production, the fluorine-containing epoxy acrylate polymer, fluorinated nano silicon dioxide, epoxy resin and the like are compounded and used for coating, the UV curing characteristic is achieved, and the cured film has the characteristics of super-hydrophobicity, transparency, wear resistance, stability, good flexibility and the like.
Description
Technical Field
The invention relates to a photocuring transparent super-hydrophobic coating, and also relates to a fluorine-containing epoxy acrylate polymer and a preparation method thereof, and application of the fluorine-containing epoxy acrylate polymer in the photocuring transparent super-hydrophobic coating, belonging to the field of coatings.
Background
The surface of the super-hydrophobic material has excellent special performances such as hydrophobic performance, self-cleaning performance, oleophobic performance, low friction coefficient and the like, and the characteristics enable the super-hydrophobic material to have application prospects in various fields such as national defense and military industry, aerospace and aviation, consumer electronics and daily life production. In the prior technical scheme of the product, the light transmittance of the super-hydrophobic coating is low, so that the use of the super-hydrophobic coating is limited; therefore, the transparent super-hydrophobic material has both water drop adhesion resistance and excellent light transmittance, can be applied to the aspects of building curtain walls, doors and windows, vehicles, optical instruments, solar panels and the like, and has wider application prospect.
Although the super-hydrophobic material has a wide application prospect in real life, the current batch realization of the application of the super-hydrophobic coating has a plurality of difficulties and problems:
(1) The stability problem of the coating is the most important reason limiting the wide application of the superhydrophobic material. The adhesion ratio of the hydrophobic coating to the substrate is poor, the rough structure is very fragile, and the surface is easily damaged by mechanical action such as impact, friction and the like, so that the superhydrophobic property is lost.
(2) The longer the coating is exposed to the external environment, the more severe the contamination and the poorer the hydrophobic properties of the coating surface.
(3) The construction of superhydrophobic materials requires sufficient roughness of the surface, however, an increase in roughness reduces the light transmission of the material. Therefore, in the process of preparing the transparent superhydrophobic material, controlling the surface roughness is a key element.
(4) Raw materials, technologies and processing equipment used for preparing the super-hydrophobic surface are expensive, and the operation process is complex, so that the preparation cost is reduced by optimizing the preparation process.
The application of Chinese patent CN110669363A discloses a preparation method of a transparent super-hydrophobic coating. Adding a silicon precursor, a boron precursor and nano silicon dioxide powder into a solvent, stirring and mixing, performing ultrasonic dispersion to obtain a suspension, then adding glycerol to prepare a sol mixture, coating the sol mixture on a substrate, calcining, performing surface modification by using a low-surface-energy substance solution, and drying to obtain the super-hydrophobic coating. However, the low surface energy substance of the super-hydrophobic coating obtained by the invention is easy to wear, and is solidified by adopting a high-temperature calcination mode, so that the energy consumption is high and the pollution is large.
Chinese patent CN107254207A discloses an ultraviolet-curing super-hydrophobic transparent wear-resistant coating and a preparation method thereof: and adding an active fluorine monomer, an active diluent and a photoinitiator into the dispersion liquid containing the active nano particles, then uniformly coating the dispersion liquid on the transparent substrate subjected to the activation pretreatment in the first step, and curing under the action of ultraviolet energy to obtain the super-hydrophobic transparent wear-resistant coating. The invention adopts ultraviolet light for curing, has the characteristics of economy, energy conservation, environmental friendliness and the like, but the mechanical property of the coating is poor, and the persistence of the super-hydrophobic property is relatively common.
Therefore, the prepared super-hydrophobic coating with high mechanical stability, continuous super-hydrophobic performance, high transparency and flexibility has very wide application prospect.
Disclosure of Invention
Aiming at the defects that the super-hydrophobic coating in the prior art has insufficient mechanical stability and flexibility and can not continuously maintain the super-hydrophobic property, the invention aims to provide the fluorine-containing epoxy acrylate polymer which has the advantages of good flexibility, strong adhesive force, excellent chemical resistance and the like.
The second purpose of the invention is to provide a preparation method of the fluorine-containing epoxy acrylate polymer, which is simple and feasible, has low raw material cost and is beneficial to large-scale production.
The third purpose of the invention is to provide a photo-curing transparent super-hydrophobic coating, which comprises fluorine-containing epoxy acrylate polymer, has the advantages of UV curing, transparency, wear resistance, mechanical stability, good flexibility and the like, has the characteristics of self-cleaning surface, fog resistance, ice resistance and the like, and has good adhesive force to a base material.
The fourth purpose of the invention is to provide a preparation method of the photocuring transparent super-hydrophobic coating, which has the characteristics of high efficiency, wide adaptability, economy, energy conservation, environmental friendliness and the like.
In order to achieve the technical purpose, the invention provides a fluorine-containing epoxy acrylate polymer, which has a structural general formula shown as a formula I:
wherein,
m is 5 to 20; n is 10 to 20;
rf is K type perfluoropolyether.
Structural formula of Rf such as CF 3 CF 2 [OCF 2 CF(CF 3 )] n F, rf number average molecular weight of 1000 to 1200, n 5 to 7.
The invention also provides a preparation method of the fluorine-containing epoxy acrylate polymer, which is obtained by carrying out free radical polymerization reaction on glycidyl acrylate and perfluoropolyether acrylate;
the structural formula of the perfluoropolyether acrylate is shown as the formula II:
wherein Rf is K type perfluoropolyether. Rf structural formulae e.g. CF 3 CF 2 [OCF 2 CF(CF 3 )] n F, rf number average molecular weight of 1000 to 1200, n 5 to 7.
The free radical polymerization reaction between glycidyl acrylate and perfluoropolyether acrylate is shown as formula III:
the key technology of the invention is as follows: on one hand, glycidyl acrylate (GMA) is adopted as a raw material, acrylate double bonds with high activity in the GMA and perfluoropolyether acrylate (FEMA) terminal double bonds are utilized for free radical polymerization, and photocuring group epoxy groups can be introduced into the polymer through the GMA to enable the polymer to be crosslinked with a curing agent in a coating formula, so that the polymer has ultraviolet curing performance; on the other hand, fluorine-containing groups are introduced into the polymer through FEMA, so that the coating has lower surface free energy, and the hydrophobic property of the polymer is improved. In addition, the invention uses the azo-diethyl butyronitrile (AIBN) as a free radical initiator, the initiator can be decomposed to form an isobutyronitrile group at the temperature of over 60 ℃, the decomposition reaction is relatively stable, only 1 kind of free radicals are generated, the induced decomposition basically does not occur, the monomer conversion rate is high, and other impurities are not introduced.
In a preferred embodiment, the molar ratio of the glycidyl acrylate to the perfluoropolyether acrylate is 5 to 10, 1, the use amount of GMA to FEMA greatly affects the coating properties of the polymer, and if the relative amount of GMA is too small, the resin crosslinking degree of the polymer is low, the cured crosslinking point is small, the crosslinking density of the coating is insufficient, the impact resistance of the coating is poor, and if the relative amount of GMA is too high, the proportion of the introduced fluorine-containing group is too low, and the hydrophobicity is affected.
As a preferable scheme, the initiator is Azodiacetonitrile (AIBN), the addition amount of the initiator is 4-8% of the molar amount of the perfluoropolyether acrylate, 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 initiation is difficult, and the normal reaction is influenced.
As a preferable scheme, the temperature of the free radical polymerization reaction is 70-90 ℃ and the time is 2-6 h.
The invention provides a preparation method of a fluorine-containing epoxy acrylate polymer, which comprises the following specific steps:
GMA, FEMA, an initiator AIBN and tetrahydrofuran are sequentially added into a round-bottom flask, and nitrogen is continuously introduced to remove oxygen for 30min after sealing. Reacting for 2-6 h at 70-90 ℃ to obtain the fluorine-containing epoxy acrylate polymer. And (3) taking a proper amount of normal hexane by using a beaker, magnetically stirring, and dropwise adding the synthesized fluorine-containing epoxy acrylate polymer solution into a normal hexane vortex for purification. The n-hexane supernatant was decanted off and the precipitate was dried at 40 ℃.
The invention also provides a photocuring transparent super-hydrophobic coating which contains the fluorine-containing epoxy acrylate polymer.
As a preferable scheme, the light-cured transparent super-hydrophobic coating comprises the following components in parts by mass: 15-30 parts of fluorine-containing epoxy acrylate polymer; 15-30 parts of fluorinated silica dispersion; 20-40 parts of epoxy resin; 5-10 parts of a curing agent; 25-40 parts of a solvent.
In the UV coating, the fluorine-containing epoxy acrylate polymer has good flexibility, strong adhesive force and excellent chemical resistance, and can ensure that the coating has good photosensitive property and hydrophobic property. The fluorinated modified silicon dioxide can reduce the surface energy of silicon dioxide particles, and can weaken the intensity of UV irradiation absorbed by the ultraviolet curing coating when being added into the coating, thereby reducing the curing speed of the ultraviolet curing coating and obviously improving the hardness and adhesive force of ultraviolet curing. In addition, the proper epoxy resin can improve the alkali resistance of the UV coating and increase the adhesive capacity of the coating. Finally, the curing agent is added, so that the drying speed of the coating can be accelerated, and the hardness and the adhesion degree of a paint film of the UV coating can be increased, so that the stability and the corrosion resistance of the coating are improved.
As a preferred embodiment, the fluorinated silica dispersion is obtained by the following method: dispersing the nano silicon dioxide into an alcohol-water mixed solvent, adjusting the pH to be = 8-10, and then adding tridecafluorooctyl triethoxysilane and gamma-glycidyl ether oxypropyl triethoxysilane for hydrolysis reaction to obtain the nano silicon dioxide. Ultrasonic assistance can be adopted in the hydrolysis reaction process. The nano-silica is modified by a tridecafluorooctyltriethoxysilane coupling agent, hydroxyl groups on the surface of the silica are substantially replaced by the coupling agent, the surface hydrophobic property of nano-silica particles is improved, and the gamma-glycidyl ether oxypropyl triethoxysilane enables the nano-silica particles to be better dispersed in a solution, so that the fluorinated nano-silica dispersion liquid with super-hydrophobic property is obtained. Triethylamine may be used for pH adjustment. The alcohol-water mixed solvent is, for example, an alcohol-water solution having an alcohol concentration of 60 to 80% by mass. Alcohols such as ethanol.
As a preferable scheme, the particle size of the nano silicon dioxide is 100-1000 nm; more preferably 300 to 500nm; the mass ratio of the nano silicon dioxide, the tridecafluorooctyltriethoxysilane and the gamma-glycidoxypropyltriethoxysilane is 4-8:1-5:1-5 (further preferably 4-6:2-3:2-3); the transparency of the coating can be reduced when the particle size of the nano silicon dioxide is too large, and the mechanical strength of the micro-nano structure can be reduced when the particle size of the nano silicon dioxide is too small. And the relative content of epoxy groups and fluorine chains on the surface of the nano-silica particles can be adjusted by adjusting the mass ratio of the nano-silica, the tridecafluorooctyl triethoxysilane and the gamma-glycidoxypropyl triethoxysilane.
As a preferable scheme, the temperature of the hydrolysis reaction is 60-90 ℃ and the time is 2-5 h. The hydrolysis temperature directly affects the hydrolysis rate and thus the particle size of the modified silica.
As a preferable embodiment, the curing agent includes at least one of diethylenetriamine, phthalic anhydride, and 2-ethyl-4-methylimidazole.
As a preferable scheme, the solvent consists of butyl acetate and glycol methyl ether acetate according to the mass ratio of 1:1-2; further preferred are butyl acetate and ethylene glycol methyl ether acetate in a mass ratio of 1:1. Butyl acetate can effectively dissolve fluorine-containing epoxy acrylate, and ethylene glycol methyl ether acetate has larger polarity and can effectively disperse modified silicon dioxide particles.
The invention also provides a preparation method of the photocuring transparent super-hydrophobic coating, which comprises the following steps:
1) Adding fluorine-containing epoxy acrylate polymer and epoxy resin into a solvent for mixing to obtain a component A;
2) Carrying out ultrasonic treatment on the fluorinated silica solution to obtain a component B;
3) Mixing the component A and the component B to obtain a mixture;
4) Adding the curing agent into the mixture, stirring and filtering to obtain the curing agent.
Preferably, the mixing temperature is 30 to 50 ℃.
The photocuring transparent super-hydrophobic coating provided by the invention can be applied to the surface of glass. The method specifically comprises the following steps: the resulting coating was sprayed onto clear glass, dried at 100 ℃ for 10 minutes and then dried at 500mJ/cm 2 The dried coating is cured by the ultraviolet irradiation dose to form the ultraviolet-cured super-hydrophobic transparent wear-resistant coating.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) The fluorine-containing epoxy acrylate polymer prepared by the invention has good flexibility, strong adhesive force and excellent chemical resistance.
2) The preparation method of the fluorine-containing epoxy acrylate polymer provided by the invention is simple and feasible, has low raw material cost, and is beneficial to large-scale production.
3) According to the invention, the nano-silica particles with excellent dispersing ability and super-hydrophobic property are obtained by performing fluorination modification on the nano-silica particles, and can be better applied to UV coatings.
4) According to the photo-curing transparent super-hydrophobic coating provided by the invention, the mechanical strength of the super-hydrophobic coating can be improved by modifying a certain degree of cross-linking among organic components, and a part of high-shrinkage monomer is selected to participate in UV curing, so that the roughness and the hollow structure of the super-hydrophobic coating are enhanced; meanwhile, the super-hydrophobic transparent coating obtained by ultraviolet curing has the advantages of wear resistance, mechanical stability and flexibility of polymers.
Drawings
FIG. 1 is a contact angle test chart of the cured coating of example 1.
FIG. 2 is a scanning electron micrograph of the cured coating of example 1.
FIG. 3 is a nuclear magnetic hydrogen spectrum of the fluorine-containing epoxy acrylate polymer of example 1.
FIG. 4 is an infrared spectrum of a fluorine-containing epoxy acrylate polymer of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
In the following specific examples, the preparation of the fluorinated silica dispersion was carried out by the following method: adding 5g of nano silicon dioxide into a 100mL round-bottom flask, adding 50mL of 75% ethanol, magnetically stirring at normal temperature for 30min, then dropwise adding 0.5g of triethylamine, and adjusting the pH =9 of the solution after ultrasonic treatment; and (3) connecting a round-bottom flask containing reactants with a condenser pipe, putting the flask into a water bath kettle at 85 ℃, adding 2g of tridecafluorooctyltriethoxysilane and 2g of gamma-glycidoxypropyltriethoxysilane, and refluxing for 5 hours by magnetic stirring to obtain the fluorinated silica dispersion.
Example 1
14.2g of GMA (Rf number average molecular weight: 1100), 14.5g of FEMA, 0.9g of AIBN as an initiator and 20mL of tetrahydrofuran were sequentially charged into a round-bottomed flask, and after sealing, nitrogen was continuously introduced to remove oxygen for 30min. Heating to 80 ℃, reacting for 4 hours, taking 100mL of n-hexane in a beaker, magnetically stirring, dropwise adding the synthesized fluorine-containing polymer solution into n-hexane vortex for purification, pouring out the n-hexane supernatant, and drying the precipitate at 40 ℃ to obtain the purified fluorine-containing epoxy acrylate polymer.
The UV coating adopting the purified fluorine-containing epoxy acrylate polymer comprises the following components in parts by mass: 15 parts of fluorine-containing epoxy acrylate polymer; 15 parts of fluorinated silica dispersion liquid (with the particle size of 300 nm); 35 parts of epoxy resin (331J, dow chemical); 5 parts of diethylenetriamine; 30 parts of a solvent;
the preparation method of the UV coating comprises the following steps:
1) Adding fluorine-containing epoxy acrylate polymer and epoxy resin into a mixed solution of butyl acetate and ethylene glycol methyl ether acetate in a mass ratio of 1:1 as a solvent, and stirring and fully dissolving to obtain a component A;
2) Ultrasonically dispersing the fluorinated silicon dioxide solution for 30min to obtain a component B;
3) Mixing the component A and the component B, heating to 40 ℃, and stirring for 30min to obtain a mixture;
4) And adding the curing agent into the mixture, stirring for 2 hours, and filtering to obtain the UV coating.
The UV coating obtained was sprayed onto clear glass and dried at 100 ℃ for 10 minutes at a rate of 500mJ/cm 2 The dried coating is cured by the ultraviolet irradiation dose to form the ultraviolet-cured super-hydrophobic transparent wear-resistant coating.
Example 2
14.2g of GMA (Rf number average molecular weight: 1100), 14.5g of FEMA, 0.9g of AIBN as an initiator and 20mL of tetrahydrofuran were sequentially added to a round-bottomed flask, and after sealing, nitrogen was continuously introduced to remove oxygen for 30min. Heating to 80 ℃, reacting for 4h, containing 100mL of normal hexane by a beaker, magnetically stirring, dropwise adding the synthesized fluorine-containing polymer solution into a normal hexane vortex for purification, pouring off the normal hexane of a supernatant, and drying a precipitate at 40 ℃ to obtain the purified fluorine-containing epoxy acrylate polymer.
The UV coating adopting the fluorine-containing epoxy acrylate polymer comprises the following components in parts by mass: 15 parts of fluorine-containing epoxy acrylate polymer; 15 parts of fluorinated silica dispersion liquid (with the particle size of 300 nm); 30 parts of epoxy resin (331J, dow chemical); 5 parts of diethylenetriamine; 35 parts of a solvent.
The preparation method of the UV coating comprises the following steps:
1) Adding fluorine-containing epoxy acrylate polymer and epoxy resin into a mixed solution of butyl acetate and ethylene glycol methyl ether acetate in a mass ratio of 1:1 as a solvent, and stirring and fully dissolving to obtain a component A;
2) Ultrasonically dispersing the fluorinated silicon dioxide solution for 30min to obtain a component B;
3) Mixing the component A and the component B, heating to 40 ℃, and stirring for 30min to obtain a mixture;
4) And adding the curing agent into the mixture, stirring for 2 hours, and filtering to obtain the UV coating.
The UV coating obtained was sprayed onto clear glass and dried at 100 ℃ for 10 minutes at a rate of 500mJ/cm 2 The dried coating is cured by the ultraviolet irradiation dose to form the ultraviolet-cured super-hydrophobic transparent wear-resistant coating.
Example 3
14.2g of GMA (Rf number average molecular weight: 1100), 14.5g of FEMA, 0.9g of AIBN as an initiator and 20mL of tetrahydrofuran were sequentially charged into a round-bottomed flask, and after sealing, nitrogen was continuously introduced to remove oxygen for 30min. Heating to 80 ℃, reacting for 4h, containing 100mL of normal hexane by a beaker, magnetically stirring, dropwise adding the synthesized fluorine-containing polymer solution into a normal hexane vortex for purification, pouring off the normal hexane of a supernatant, and drying a precipitate at 40 ℃ to obtain the purified fluorine-containing epoxy acrylate polymer.
The UV coating adopting the fluorine-containing epoxy acrylate polymer comprises the following components in parts by mass: 25 parts of fluorine-containing epoxy acrylate polymer; 15 parts of fluorinated silica dispersion liquid (with the particle size of 300 nm); 30 parts of epoxy resin (331J, dow chemical); 5 parts of diethylenetriamine; and 25 parts of a solvent.
The preparation method of the UV coating comprises the following steps:
1) Adding fluorine-containing epoxy acrylate polymer and epoxy resin into a mixed solution of butyl acetate and ethylene glycol methyl ether acetate in a mass ratio of 1:1 as a solvent, and stirring and fully dissolving to obtain a component A;
2) Ultrasonically dispersing the fluorinated silicon dioxide solution for 30min to obtain a component B;
3) Mixing the component A and the component B, heating to 40 ℃, and stirring for 30min to obtain a mixture;
4) And adding the curing agent into the mixture, stirring for 2 hours, and filtering to obtain the UV coating.
The UV coating obtained was sprayed onto clear glass and dried at 100 ℃ for 10 minutes at a rate of 500mJ/cm 2 The ultraviolet radiation dose of the ultraviolet curing agent is used for curing the dried coating to form the ultraviolet curing super-hydrophobic transparent wear-resistant coating。
Example 4
14.2g of GMA (Rf number average molecular weight: 1100), 14.5g of FEMA, 0.9g of AIBN as an initiator and 20mL of tetrahydrofuran were sequentially added to a round-bottomed flask, and after sealing, nitrogen was continuously introduced to remove oxygen for 30min. Heating to 80 ℃, reacting for 4h, containing 100mL of normal hexane by a beaker, magnetically stirring, dropwise adding the synthesized fluorine-containing polymer solution into a normal hexane vortex for purification, pouring off the normal hexane of a supernatant, and drying a precipitate at 40 ℃ to obtain the purified fluorine-containing epoxy acrylate polymer.
The UV coating adopting the fluorine-containing epoxy acrylate polymer comprises the following components in parts by mass: 15 parts of fluorine-containing epoxy acrylate polymer; 15 parts of fluorinated silica dispersion liquid (with the particle size of 300 nm); 25 parts of epoxy resin (331J, dow chemical); 5 parts of diethylenetriamine; 40 parts of a solvent.
The preparation method of the UV coating comprises the following steps:
1) Adding a fluorine-containing epoxy acrylate polymer and epoxy resin into a solvent, wherein the mass ratio of butyl acetate to ethylene glycol monomethyl ether acetate is 1:1, stirring and fully dissolving the mixed solution to obtain a component A;
2) Ultrasonically dispersing the fluorinated silicon dioxide solution for 30min to obtain a component B;
3) Mixing the component A and the component B, heating to 40 ℃, and stirring for 30min to obtain a mixture;
4) And adding the curing agent into the mixture, stirring for 2 hours, and filtering to obtain the UV coating.
The UV coating obtained was sprayed onto clear glass and, after drying at 100 ℃ for 10 minutes, at a rate of 500mJ/cm 2 The dried coating is cured by the ultraviolet irradiation dose to form the ultraviolet-cured super-hydrophobic transparent wear-resistant coating.
Example 5
14.2g of GMA (Rf number average molecular weight: 1100), 14.5g of FEMA, 0.9g of AIBN as an initiator and 20mL of tetrahydrofuran were sequentially charged into a round-bottomed flask, and after sealing, nitrogen was continuously introduced to remove oxygen for 30min. Heating to 80 ℃, reacting for 4 hours, taking 100mL of n-hexane in a beaker, magnetically stirring, dropwise adding the synthesized fluorine-containing polymer solution into n-hexane vortex for purification, pouring out the n-hexane supernatant, and drying the precipitate at 40 ℃ to obtain the purified fluorine-containing epoxy acrylate polymer.
The UV coating adopting the fluorine-containing epoxy acrylate polymer comprises the following components in parts by mass: 15 parts of fluorine-containing epoxy acrylate polymer; 15 parts of fluorinated silica dispersion liquid (the particle size of nano-silica is 300 nm); 25 parts of epoxy resin (431, dow chemical); 5 parts of diethylenetriamine; 40 parts of a solvent.
The preparation method of the UV coating comprises the following steps:
1) Adding fluorine-containing epoxy acrylate polymer and epoxy resin into a mixed solution of butyl acetate and ethylene glycol methyl ether acetate in a mass ratio of 1:1 as a solvent, and stirring and fully dissolving to obtain a component A;
2) Ultrasonically dispersing the fluorinated silicon dioxide solution for 30min to obtain a component B;
3) Mixing the component A and the component B, heating to 40 ℃, and stirring for 30min to obtain a mixture;
4) And adding the curing agent into the mixture, stirring for 2 hours, and filtering to obtain the UV coating.
The UV coating obtained was sprayed onto clear glass and dried at 100 ℃ for 10 minutes at a rate of 500mJ/cm 2 The dried coating is cured by the ultraviolet irradiation dose to form the ultraviolet-cured super-hydrophobic transparent wear-resistant coating.
Example 6
The perfluoropolyether acrylate in the preparation of the fluorine-containing epoxy acrylate polymer was changed to 11.0g, and the remaining conditions were the same as in example 1.
Example 7
The particle size of the nano-silica in the fluorinated silica dispersion was changed to 100nm, and the remaining conditions were the same as in example 1.
Example 8
The particle size of the nano-silica in the fluorinated silica dispersion was changed to 800nm, and the remaining conditions were the same as in example 1.
Example 9 (as example 1 control)
The fluorinated silica dispersion in the UV coating component was changed to a silica dispersion, and the remaining conditions were the same as in example 1.
The UV coatings prepared in examples 1 to 9 were applied by spraying, and the UV coatings were diluted with a solvent (butyl acetate: ethylene glycol methyl ether acetate = 1:1) when the viscosity of the system was too high during the application, and the effects after UV curing are shown below:
TABLE 1 comparison of different UV coating effects
Hydrophobic Angle test method: the coating static contact angle was determined by a model JGW-360a contact angle apparatus. The volume of the test liquid is 2 mu L, the test environment is 24 +/-1 ℃, and the relative humidity is 45 +/-1%. The water drop tentacles were measured at 5 points and averaged.
The rolling angle test method comprises the following steps: the rolling angle is measured by an SDC-350 integral inclined contact angle measuring instrument, a liquid drop with the liquid volume of 2 mu L is placed on a test platform, the platform is slowly inclined, and the inclined angle of the platform when the liquid drop rolls is recorded.
The light transmittance test method comprises the following steps: the light transmittance is measured by a TH-110 type light transmittance haze meter, the constructed glass is placed on a test platform, a HOLD key of the instrument is pressed, the test can be started when the instrument passes through self calibration, and the test result is recorded.
The wear resistance test method comprises the following steps: the abrasion resistance test is measured by a ZJ-339-GSR type abrasion resistance tester, the constructed glass is fixed on the tester, the travel is set to be 60mm, the speed is set to be 60 times/minute, and the test result is recorded.
By comparing the data in example 6 and example 1, it can be seen that the hydrophobic angle after the coating is cured is remarkably reduced by reducing the amount of the fluorine monomer in the fluorine-containing epoxy acrylate polymer. It can be seen from examples 1, 7 and 8 that the increase of the particle size of the fluorinated nano-silica reduces the light transmittance of the coating, and the decrease of the particle size of the fluorinated nano-silica slightly reduces the wear resistance. The fluorinated silica particles can increase the hydrophobic angle of the coating. It can be seen from the data of examples 4 and 5 that the abrasion resistance is slightly reduced by using the epoxy resin with low shrinkage rate. Furthermore, fluorinated nanosilica with a particle size of 300nm is the preferred choice.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A fluorine-containing epoxy acrylate polymer characterized by: the structural general formula is shown as formula I:
wherein,
m is 5 to 20; n is 10 to 20;
rf is K type perfluoropolyether.
2. The method for preparing a fluorine-containing epoxy acrylate polymer according to claim 1, wherein: the acrylate is obtained by the free radical polymerization reaction of glycidyl acrylate and perfluoropolyether acrylate;
the structural formula of the perfluoropolyether acrylate is shown as the formula II:
wherein Rf is K-type perfluoropolyether.
3. The method for preparing a fluorine-containing epoxy acrylate polymer according to claim 2, wherein: the conditions of the free radical polymerization reaction are as follows:
the molar ratio of the glycidyl acrylate to the perfluoropolyether acrylate is 5-10;
taking azo-diethyl butyronitrile as an initiator, wherein the addition amount of the initiator is 4-8% of the molar amount of the perfluoropolyether acrylate; the temperature is 70-90 ℃ and the time is 2-6 h.
4. A light-cured transparent super-hydrophobic coating is characterized in that: comprising the fluorine-containing epoxy acrylate polymer according to claim 1.
5. The photo-curable transparent super-hydrophobic coating according to claim 4, wherein: the adhesive comprises the following components in parts by mass:
6. the photo-curable transparent super-hydrophobic coating according to claim 5, wherein: the fluorinated silica dispersion is obtained by the following method: dispersing the nano silicon dioxide into an alcohol-water mixed solvent, adjusting the pH to be = 8-10, and then adding tridecafluorooctyltriethoxysilane and gamma-glycidoxypropyltriethoxysilane for hydrolysis reaction to obtain the nano silicon dioxide.
7. The photo-curable transparent super-hydrophobic coating according to claim 6, wherein:
the particle size of the nano silicon dioxide is 100-1000 nm;
the mass ratio of the nano silicon dioxide, the tridecafluorooctyltriethoxysilane and the gamma-glycidyl ether oxygen propyl triethoxysilane is 4-8:1-5:1-5;
the temperature of the hydrolysis reaction is 60-90 ℃, and the time is 2-5 h.
8. The photo-curable transparent super-hydrophobic coating according to claim 5, wherein: the curing agent comprises at least one of diethylenetriamine, phthalic anhydride and 2-ethyl-4-methylimidazole.
9. The photo-curable transparent super-hydrophobic coating according to claim 5, wherein: the solvent consists of butyl acetate and glycol methyl ether acetate according to the mass ratio of 1:1-2.
10. The method for preparing a photocureable transparent super-hydrophobic coating of any one of claims 4 to 9, which is characterized by comprising the following steps: the method comprises the following steps:
1) Adding fluorine-containing epoxy acrylate polymer and epoxy resin into a solvent for mixing to obtain a component A;
2) Carrying out ultrasonic treatment on the fluorinated silica solution to obtain a component B;
3) Mixing the component A and the component B to obtain a mixture;
4) Adding the curing agent into the mixture, stirring and filtering to obtain the curing agent.
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| CN116904052A (en) * | 2023-08-03 | 2023-10-20 | 四川双特科技有限公司 | Electron beam curing fluorine-containing paint |
| CN117050243A (en) * | 2023-05-18 | 2023-11-14 | 湖南庆润新材料有限公司 | Fluorine-containing acrylate polymer, organic/inorganic hybrid self-cleaning anti-reflection coating, and preparation method and application thereof |
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| CN101307194B (en) * | 2008-06-27 | 2010-12-08 | 江苏科技大学 | Organic-inorganic hybridization ultraviolet cured paint for protecting metallic surface |
| KR101425897B1 (en) * | 2013-02-15 | 2014-08-13 | 화인폴리머 주식회사 | Superhydrophobic surface Nano Coating Composition for High Voltage Insulation and Production Method Therof |
| CN104804603B (en) * | 2015-04-24 | 2017-10-31 | 浙江大学 | A kind of super-hydrophobic ice-covering-proof coating with magnetic heating performance and preparation method thereof |
| CN106587075B (en) * | 2015-10-14 | 2019-06-28 | 香港理工大学 | The preparation method of super-hydrophobic silica particle and super-hydrophobic coat |
| CN106047090B (en) * | 2016-05-28 | 2019-03-26 | 晟通科技集团有限公司 | Compound UV photocureable coating of perfluoropolyether acrylate and preparation method thereof |
| CN106189706A (en) * | 2016-08-09 | 2016-12-07 | 河南大学 | A kind of super-hydrophobic resin-coated preparation method |
| CN106862039B (en) * | 2017-01-18 | 2020-05-22 | 华南理工大学 | Durable hydrophilic-super-hydrophobic bipolar self-cleaning composite membrane and preparation method thereof |
| CN106867359B (en) * | 2017-01-20 | 2019-10-11 | 常州大学 | A kind of fluorine-containing weather-proof anti-corrosion self stratifying coating of block propylene acid esters-epoxy resin and preparation method thereof |
| CN109851775A (en) * | 2019-02-21 | 2019-06-07 | 浙江诺诚技术发展有限公司 | A kind of anti-fingerprint agent and preparation method thereof of high perfluoropolyether content |
| CN112159506B (en) * | 2020-08-19 | 2023-01-10 | 浙江巨化技术中心有限公司 | Preparation method of multi-anchor brush-shaped perfluoropolyether anti-fingerprint agent |
| CN112745479B (en) * | 2020-12-14 | 2023-07-25 | 安徽庆润新材料技术有限公司 | Fluorine-containing epoxy acrylate oligomer, synthesis method, UV (ultraviolet) coating, preparation method and application thereof |
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| CN117050243B (en) * | 2023-05-18 | 2024-07-19 | 湖南庆润新材料有限公司 | Fluorine-containing acrylate polymer, organic/inorganic hybrid self-cleaning anti-reflection coating, and preparation method and application thereof |
| CN116904052A (en) * | 2023-08-03 | 2023-10-20 | 四川双特科技有限公司 | Electron beam curing fluorine-containing paint |
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