CN110845952B - Fluorinated polyurethane coating and preparation method of super-hydrophobic coating - Google Patents
Fluorinated polyurethane coating and preparation method of super-hydrophobic coating Download PDFInfo
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- CN110845952B CN110845952B CN201911210127.5A CN201911210127A CN110845952B CN 110845952 B CN110845952 B CN 110845952B CN 201911210127 A CN201911210127 A CN 201911210127A CN 110845952 B CN110845952 B CN 110845952B
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- coating
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- fluorinated
- hydrophobic
- solvent
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- 239000011248 coating agent Substances 0.000 title claims abstract description 98
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
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- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 claims description 3
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
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- QMUNTDPZNPLSPB-UHFFFAOYSA-N 2,3-dihydroxypropyl 3,3,3-tris(sulfanyl)propanoate Chemical compound OCC(O)COC(=O)CC(S)(S)S QMUNTDPZNPLSPB-UHFFFAOYSA-N 0.000 claims description 2
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- JRLZYKZRJOLHIJ-UHFFFAOYSA-N 2-prop-1-enoxyoxolane Chemical group O1C(CCC1)OC=CC JRLZYKZRJOLHIJ-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
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- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention relates to a fluorinated polyurethane coating and a preparation method of a super-hydrophobic coating. Blending and dispersing the nano particles and the fluorinated polyurethane coating according to a certain proportion, then spraying, brushing or dipping on the surface of a base material, and after the solvent is volatilized, placing the coating in a 70 ℃ drying oven for heat treatment for 5 hours to obtain the super-hydrophobic coating. The coating has strong abrasion resistance, and after the coating is completely damaged, the super-hydrophobic performance of the coating can be recovered to a large extent in a short time through heating.
Description
Technical Field
The invention belongs to the technical field of super-hydrophobic coating materials, and relates to a fluorinated polyurethane coating and a preparation method of the super-hydrophobic coating.
Background
Inspired by the hydrophobic effect of lotus leaves, water flies, butterfly wings and the like in the nature, the artificial super-hydrophobic material is deeply researched and greatly developed, and has wide application prospect in the fields of self-cleaning, pollution prevention, deicing, fluid drag reduction and energy-saving transportation, oil-water separation and the like. According to the Wenzel-Cassie theory, it is generally believed that the achievement of superhydrophobic performance depends on the construction of micro-nano multilevel roughness structures and the use of low surface energy species. Common preparation methods for superhydrophobic surfaces are: etching, photoetching, 3D printing, chemical deposition, self-assembly, in-situ growth, in-situ reduction, microphase separation, nanoparticle stacking and the like. Because the micro-nano rough structure is mostly formed by low surface energy substances, the structures are easy to be worn and damaged, so that the service life of the coating is short, and the coating is difficult to be really widely applied. At the present stage, there are mainly three methods to overcome the above problems: 1. endowing the super-hydrophobic surface with self-repairing performance; 2. designing a high-strength super-hydrophobic coating with consistent internal and external structures, so that the exposed surface of the coating after the surface is damaged has a structure and surface energy similar to those of the original surface; 3. the relatively soft super-hydrophobic surface is designed to have certain impact resistance and friction resistance. At present, a great challenge still exists in comprehensively realizing the strategies. For example, the low surface energy segment has limited mobility, resulting in short repair cycle time, long repair time, and the like. The soft super-hydrophobic surface can also cause the micro-nano structure to be difficult to maintain. In addition, the introduced low surface energy component is difficult to be well blended and dispersed with other components, so that efficient preparation is difficult to realize, and the adhesion strength of the coating and the substrate is not ideal. In conclusion, the super-hydrophobic coating which is simple in preparation method, high in strength, self-repairing capability and high in substrate adhesion is designed and obtained, and the difficulty in the field is still high.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a fluorinated polyurethane coating and a preparation method of a super-hydrophobic coating.
Technical scheme
A preparation method of fluorinated polyurethane coating is characterized by comprising the following steps:
step 1, preparation of fluorinated thiol prepolymer: blending and dispersing a polyfunctional mercaptan compound and fluoroacrylate in a solvent, adding a photoinitiator, and reacting for 20-60 minutes under the conditions of ultraviolet illumination and normal temperature to obtain a fluorinated mercaptan prepolymer; the mass ratio of the multifunctional thiol compound to the fluoroacrylate to the solvent to the photoinitiator is 1: 0.8-2: 0.009-0.004;
step 2, preparing the fluorinated polyurethane coating: blending the dehydrated isocyanate and the polydiol compound according to the molar ratio of 2: 1-1.5, adding a solvent and a catalyst, and reacting at 50-80 ℃ for 2-4 hours to obtain a blended reactant; the mass ratio of the isocyanate to the polyether polyol, the solvent to the catalyst is 1: 0.5-1: 0-0.01; the polyglycol compound comprises a polyester diol or a polyether diol; the polyester dihydric alcohol is poly epsilon-caprolactone diol;
adding the fluorinated thiol prepolymer obtained in the step (1) into a blending reactant, adding a solvent to form a stable and well-dispersed suspension, and continuing to react for 0.5-2 hours; adding a binary chain extender, and continuing to react for 0.5-3 hours until the isocyanate is remained in the consumed system, so as to obtain the fluorinated polyurethane coating; the mass ratio of the fluorinated thiol prepolymer to the blending reaction product is 0.25-1: 1.
The polyfunctional thiol compounds include, but are not limited to: glycerol trimercaptopropionate, trimethylolpropane trimercaptopropyl ester, isocyanuric acid trimercaptocarboxylate, pentaerythritol tetramercaptopropionate, or dipentaerythritol hexa (3-mercaptopropionate).
The fluoroacrylate is a perfluoro (methyl) acrylate compound CH2CH (CH3) COO- (CH2)2- (CF2) nCF3, wherein n is a natural number of 3-10.
The solvent is acetone, dimethyl carbonate, N, N-dimethylacetamide or tetrahydrofuran, and the solvent needs to be subjected to dehydration treatment before use.
The photoinitiator comprises a UV photoinitiator: 1173. 184, 907, 369, 1490 and 1700.
The isocyanate is a difunctional isocyanate including, but not limited to: toluene diisocyanate, 4,4' -diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate or dimer acid diisocyanate.
The polyether diols include, but are not limited to, polyoxypropylene diol, tetrahydrofuran-oxypropylene copolyol, polytetrahydrofuran diol, or diols having different molecular weights.
Such catalysts include, but are not limited to: organotin catalysts and tertiary amine catalysts: dibutyltin dilaurate, stannous octoate, triethylamine or triethylenediamine.
The binary chain extenders include, but are not limited to: propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, neopentyl glycol, diethylamino glycol, ethylenediamine, N, N-dihydroxy (diisopropyl) aniline, hydrogenated bisphenol A, dimethylene phenyl diol, diethanolamine, diethylmethyl-phenylenediamine or 4,4' -methylidyne-bis (2-chloroaniline).
A method for preparing a super-hydrophobic coating by using the fluorinated polyurethane coating is characterized by comprising the following steps: blending and dispersing the nano particles and the fluorinated polyurethane coating, stirring for 10-30 minutes, and performing ultrasonic treatment for 2-10 minutes to obtain a super-hydrophobic coating; the mass ratio of the nano particles to the fluorinated polyurethane coating is 0.15-0.3: 1.
A method of applying the superhydrophobic coating, comprising: spraying or brushing the super-hydrophobic coating on the surface of the substrate, after the solvent is volatilized, placing the substrate at room temperature for 6-12 hours, and then placing the coated substrate in an oven at 80-120 ℃ for heat treatment for 3-6 hours to obtain the super-hydrophobic coating with self-repairing capability; the base material is non-woven fabric, chemical fiber cloth, steel, stone, glass, ceramic or plastic plate.
If less reactive chain extenders are used, such as 4,4' -methine-bis (2-chloroaniline), the remaining isocyanate is consumed by placing the coated substrate in an oven at 80-120 ℃ for curing. If no chain extender is added in the system (no chain extension reaction step), the coated base material is placed in a drying oven with the temperature of 110-120 ℃ for heat treatment for 3-6 hours, and the high-temperature self-crosslinking super-hydrophobic fluorinated polyurethane coating is obtained.
Advantageous effects
The invention provides a fluorinated polyurethane coating and a preparation method of a super-hydrophobic coating. According to the invention, the fluoroalkane chain segment containing a plurality of mercaptan functional groups is prepared through efficient mercaptan click reaction and is introduced into a polyurethane system, so that the reaction is efficiently carried out. The branched chain segments have stronger migration capability, and the self-repairing efficiency of the coating is improved. And then, uniformly dispersing the nano particles in the fluorinated polyurethane resin, wherein the obtained coating still maintains the structure and the chemical composition which are similar to those of the original surface after the surface of the coating is damaged. The polyurethane is used as a natural resin with high bonding strength, so that the super-hydrophobic coating has good substrate adhesion; the flexibility of the polyurethane enables the coating to have certain impact resistance. The invention provides a new idea and a new method for preparing the high-strength super-hydrophobic coating with the self-repairing capability.
Compared with the prior art, the invention has the advantages that:
1. fluorinated thiol prepolymers containing branched fluoroalkane segments and thiol functional groups are efficiently prepared by click chemistry and can be engineered into polyurethanes (or other resins) to provide low surface energy surfaces.
2. The fluorinated thiol prepolymer is quickly introduced into a polyurethane system through click chemistry, and the defect that a low-surface-energy component and other components are difficult to disperse efficiently, so that the reaction efficiency is low is overcome.
3. The molecular structure is strong in designability, and fluorinated polyurethane with different performances can be designed by changing the number of thiol functional groups of the fluorinated thiol prepolymer, the introduction amount of the fluorinated thiol prepolymer, the polyurethane formula, the selection of a chain extender and the like. The process has strong stability, good experiment repeating effect and no side reaction.
4. Flexible branched fluoroalkane chain segments are introduced through the multifunctional thiol compound, so that the coating has high surface migration capability and excellent self-repairing performance.
5. Fluorinated polyurethanes have been designed as superhydrophobic coatings with relatively little research. The technology provides a feasible preparation method of the fluorinated polyurethane-based super-hydrophobic coating with excellent performance.
6. The super-hydrophobic coating can be prepared on various base materials in a large range, and the base material has good adhesive force.
7. The super-hydrophobic coating has a contact angle to water of more than 160 degrees and a rolling angle of less than 5 degrees, and has good self-cleaning performance.
8. The coating has good friction resistance: the contact angle to water is still kept to be more than 150 degrees after 100 times of cyclic rubbing. The super-hydrophobic performance is still maintained after 2 hours of water drop impact test.
9. The coating has the self-repairing performance of super-hydrophobic property. The fluorine chain segment introduced by the coating has high migration capacity, so that the coating can quickly recover the damaged super-hydrophobic property after being heated for 1 hour at 135 ℃.
Drawings
FIG. 1 SEM images (with water contact angle images, respectively) of the surface (a) of the coating of example 1 and the surface (b) after 100 cycles of rubbing.
FIG. 2 is a graph showing the state of the contact angle of a water droplet of example 1 after 2 hours of impact.
FIG. 3 is a graph showing the adhesion of the coating in the cross-hatch test of example 1.
FIG. 4 is a graph of the water contact state after complete failure (acid etch) of the coating of example 1(a) and self-healing (b).
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the superhydrophobic effect of the superhydrophobic coating was characterized by measuring its contact angle and roll angle using a JC2000A model static hydrophobic angle measuring instrument. The super-hydrophobic abrasion resistance is characterized by a water drop impact test (0.4m, the volume of the water drop is 150 mu L, the impact speed is 3.1m/s), a cross-cut adhesion test method (ASTM D3359-. The pressure used in the constant pressure cyclic rubbing test was 10Kpa, the coating rubbing contact surface was 1000 mesh sandpaper, and the rubbing was performed 10 cm back and forth as one cycle.
Example 1: super-hydrophobic coating for coating glass surface
(1) Glass surface pretreatment: the glass plate was first soaked in 2.5M NaOH solution for 24 hours, taken out and sonicated in distilled water for 10 minutes. The glass plate was then immersed in 0.1M HCl solution for 15 minutes, and after removal, sonicated in distilled water and methanol for 10 minutes, respectively. And finally, washing the mixture for a plurality of times by using distilled water, and airing the mixture in an oven for later use.
(2) Preparation of fluorinated thiol prepolymer: into the reactor were added, in order, 4.89g of pentaerythritol tetramercaptopropionate, 10.56g of 2- (perfluorooctyl) ethyl methacrylate, 0.1g of 184 initiator, and 15g of acetone. The reaction was carried out under UV light and ambient temperature conditions for 40 minutes. The free radical addition mercaptan click reaction initiated by the photoinitiator has the characteristic of high-efficiency reaction, and infrared tests show that after the reaction is carried out for half an hour, infrared peaks of olefinic bonds completely disappear, which shows that the fluorinated mercaptan prepolymer is efficiently and successfully prepared. If the Michael nucleophilic addition mercaptan click reaction catalyzed by alkali is used, the residual alkali catalyst in the system can accelerate the subsequent chain extension reaction, so that the reaction is uncontrollable, flocculent compounds are generated, and the film cannot be formed. Free radical initiated thiol click chemistry facilitates coating application.
(3) Preparation of fluorinated polyurethane coating: to the new reactor, 0.174g of toluene diisocyanate (toluene diisocyanate), and poly-epsilon-caprolactone diol (M) which had been dehydrated were added in this ordern1000)0.6g, dehydrated acetone 0.58g, 1 drop of stannous octoate. The reaction was carried out at 50 ℃ for 2 hours. Then, 0.387g of the fluorinated thiol prepolymer prepared in (2) was taken and added to the reactor and acetone was added again until a well-dispersed suspension was obtained, and the reaction was continued at 50 ℃ for 2 h. Finally, 0.024g of chain extender 1, 4-butanediol is added, and the reaction is continued for 2 h. Because the molar ratio of the diisocyanate to the polyglycol is always kept between 1.5 and 2, the molecular weight and viscosity of the polyurethane prepolymer are lower, which is beneficial to the blending of the polyurethane prepolymer and the fluorinated thiol prepolymer and improves the reaction efficiency. Experiments show that when the molar ratio of the diisocyanate to the polyglycol is less than 1.5, the viscosity of the system is too high, acetone is difficult to effectively disperse the polyurethane, and even the gel phenomenon occurs. Infrared tests show that the fluorinated thiol prepolymer can react with the polyurethane prepolymer within a few minutes through a thiol click reaction of a michael nucleophilic addition mechanism, and the reaction time is greatly shortened compared with that of the traditional fluorinated polyurethane preparation.
(4) Preparing a super-hydrophobic coating: 0.194g of hydrophobic silica nanoparticles (-15 nm) is added into the reactor in (3), mechanically stirred for 10 minutes and ultrasonically treated for 5 minutes.
(5) And (4) spraying the super-hydrophobic coating prepared in the step (4) on the surface of the glass plate. After the solvent is volatilized, the mixture is placed in a normal temperature environment for 12 hours. And (3) placing the coated glass plate in a high-temperature oven at 80 ℃ for treatment for 3 hours to obtain the glass plate coated with the super-hydrophobic coating. The SEM image of the coating is shown in FIG. 1 (a).
(6) The super-hydrophobic performance, the friction resistance and the self-repairing performance of the coating are tested: the contact angle of the coating to water is 162 degrees, the rolling angle is 3 degrees, after 100 times of cyclic friction, the surface of the coating is not obviously damaged, an SEM picture after the cyclic friction is shown in figure 1(b), the contact angle is 157 degrees, and the rolling angle is 8 degrees. The contact angle of 152 deg. is maintained after 2 hours of drop impact testing. The cross-hatch test method showed good adhesion of the coating to the substrate (fig. 3). The contact angle of the surface of the coating after being completely abraded was reduced to 141 °, and the contact angle was restored to 159 ° by leaving the coating at 150 ℃ for 1 hour. After 5 rubbing cycles, the contact angle remained 155 deg.. The coating is soaked in acid solution for 12 hours, the contact angle of the coating is reduced to 118 degrees, the coating is self-repaired for 1 hour at the temperature of 150 ℃, and the contact angle is recovered to 153 degrees (figure 4)
Example 2: super-hydrophobic coating PET fiber cloth
(1) Preparation of fluorinated thiol prepolymer: into the reactor were added, in this order, trimethylolpropane trimercaptopropyl ester 3.98g, 2- (perfluorooctyl) ethyl methacrylate 5.18g, 184 initiator 0.08g, and acetone 7.33 g. The reaction was carried out under UV light and ambient temperature conditions for 40 minutes.
(2) Preparation of fluorinated polyurethane coating: 0.28g of 4,4' -dicyclohexylmethane diisocyanate (Md), dehydrated polytetrahydrofuran diol (M) was added to the new reactor in successionn1000)0.5g, dehydrated acetone 0.39g, 1 drop of dibutyltin dilaurate. The reaction was carried out at 60 ℃ for 2 hours. Then, 0.195g of the fluorinated thiol prepolymer prepared in (1) was added to the reactor and acetone was added further until a well-dispersed suspension was obtained, and the reaction was continued at 60 ℃ for 2 h. Finally, 0.037g of chain extender neopentyl glycol was added and the reaction was continued for 2 h.
(3) Preparing a super-hydrophobic coating: 0.137g of hydrophilic silica nanoparticles (-20 nm) was added to the reactor in (2), mechanically stirred for 20 minutes, and sonicated for 10 minutes.
(4) Diluting the super-hydrophobic coating prepared in the step (3) by 10 times with acetone. And (3) immersing the PET fiber cloth into the diluted super-hydrophobic coating for 5 minutes, taking out the PET fiber cloth, airing the PET fiber cloth at normal temperature, immersing the PET fiber cloth into the coating again, and circulating the steps for 3 times. And after the PET fiber cloth impregnated with the coating is dried for 12 hours at normal temperature, the PET fiber cloth is placed in a high-temperature oven at 100 ℃ for treatment for 5 hours, and the PET fiber cloth coated with the super-hydrophobic coating is obtained.
(5) The super-hydrophobic performance, the friction resistance and the self-repairing performance of the coating are tested: the coating has a contact angle to water of 158 degrees and a rolling angle of 6 degrees, the surface of the coating is not obviously damaged after 100 times of circulating friction, the contact angle to water is 152 degrees, and the rolling angle is 8 degrees. The contact angle 152 deg. was maintained after 2 hours of water impact testing. The contact angle of the surface of the coating after being completely abraded is reduced to 135 degrees, and the contact angle is recovered to 153 degrees after the coating is placed at 150 ℃ for 1 hour. After 5 rubbing cycles, the contact angle of the repaired coating still remains 152 degrees.
Example 3: super-hydrophobic coating PC surface (without chain extender)
(1) Preparation of fluorinated thiol prepolymer: 7.83g of dipentaerythritol hexa (3-mercaptopropionate), 20.72g of 2- (perfluorooctyl) ethyl methacrylate, 0.157g of 184 initiator and 57.1g of acetone were sequentially added to the reactor. The reaction was carried out under UV light and ambient temperature conditions for 40 minutes.
(2) Preparation of fluorinated polyurethane coating: into a new reactor, 0.22g of isophorone diisocyanate, water-removed polyoxypropylene diol (M)n1000)0.75g, 0.97g of dehydrated acetone, 1 drop of triethylamine. The reaction was carried out at 80 ℃ for 2 hours. Then, 0.97g of the fluorinated thiol prepolymer prepared in (1) was taken and added to the reactor and acetone was added again until a well-dispersed suspension was obtained, and the reaction was continued at 80 ℃ for 2 h.
(3) Preparing a super-hydrophobic coating: 0.394g of hydrophilic silica nanoparticles (. about.20 nm) was added to the reactor in (2), mechanically stirred for 30 minutes and sonicated for 2 minutes.
(4) And (4) spraying the super-hydrophobic coating prepared in the step (3) on the surface of a PC substrate. After the solvent is volatilized, the mixture is placed in a normal temperature environment for 12 hours. And (3) placing the coated glass plate in a high-temperature oven at 120 ℃ for treatment for 6 hours to obtain the PC plate coated with the super-hydrophobic coating.
(5) The super-hydrophobic performance, the friction resistance and the self-repairing performance of the coating are tested: the coating has a water contact angle of 162 degrees and a rolling angle of 4 degrees, the surface of the coating is not obviously damaged after 100 times of circulating friction, the water contact angle is 158 degrees and the rolling angle is 6 degrees. The contact angle of 155 deg. was maintained after 2 hours of the water impact test. The contact angle of the surface of the coating after being completely abraded is reduced to 142 degrees, and the contact angle is recovered to 155 degrees after the coating is placed at 150 ℃ for 1 hour. After 5 rubbing cycles, the contact angle remained 155 deg..
Example 4 (counter example 1):
the reaction sequence in examples 1-3 was changed by first reacting a fluorinated thiol prepolymer with a diisocyanate to obtain an isocyanate terminated fluorinated prepolymer, which was then reacted with a polyglycol compound by conventional urethane reaction. Because the blending and dispersing effect of the fluorinated prepolymer component and the polyglycol compound is poor, the reaction efficiency is not high, the molecular weight of the resin is low, and the prepared coating is waxy and has extremely poor mechanical strength. This example demonstrates the high efficiency of thiol click chemistry.
Example 5 (counter example 2):
the formulations in examples 1-3 were varied, without counting the formulation provided by the present invention, to obtain superhydrophobic resins using a thiol click reaction, a reaction of a fluorinated thiol prepolymer and a diisocyanate. The prepared coating has low molecular weight and poor mechanical strength, and the super-hydrophobic property of the coating is reduced because a large amount of hydrophilic urethane groups exist on the surface.
Example 6 (counter example 3):
the reaction sequence in examples 1-3 was changed by first adding a polyfunctional thiol compound to the polyurethane prepolymer and performing a thiol click reaction of michael nucleophilic addition, and then attempting to introduce the fluoroacrylate into the thiol polyurethane via a thiol-ene click reaction. Experiments prove that the multifunctional thiol compound and the polyurethane prepolymer are easy to gel under the efficient click reaction, so that the subsequent reaction cannot be carried out.
Claims (9)
1. A method of applying a superhydrophobic coating, comprising: spraying or brushing the super-hydrophobic coating on the surface of the substrate, placing the substrate at room temperature for 6-12 hours after the solvent is volatilized, and then placing the coated substrate in an oven at 80-120 ℃ for heat treatment for 3-6 hours to obtain the super-hydrophobic coating with self-repairing capability; the base material is non-woven fabric, chemical fiber cloth, steel, stone, glass, ceramic or plastic plate; the contact angle of the super-hydrophobic coating to water is more than 160 degrees, the rolling angle is less than 5 degrees, and the super-hydrophobic coating has good self-cleaning performance;
the preparation method of the super-hydrophobic coating comprises the following steps: blending and dispersing the nano particles and the fluorinated polyurethane coating, stirring for 10-30 minutes, and performing ultrasonic treatment for 2-10 minutes to obtain a super-hydrophobic coating; the mass ratio of the nano particles to the fluorinated polyurethane coating is 0.15-0.3: 1;
the preparation method of the fluorinated polyurethane coating comprises the following specific steps:
step 1, preparation of fluorinated thiol prepolymer: blending and dispersing a polyfunctional mercaptan compound and fluoroacrylate in a solvent, adding a photoinitiator, and reacting for 20-60 minutes under the conditions of ultraviolet illumination and normal temperature to obtain a fluorinated mercaptan prepolymer; the mass ratio of the multifunctional thiol compound to the fluoroacrylate to the solvent to the photoinitiator is 1: 0.8-2: 0.009-0.004;
step 2, preparing the fluorinated polyurethane coating: blending the dehydrated isocyanate and the polydiol compound according to the molar ratio of 2: 1-1.5, adding a solvent and a catalyst, and reacting at 50-80 ℃ for 2-4 hours to obtain a blended reactant; the mass ratio of the isocyanate to the polydiol compound, the solvent to the catalyst is 1: 0.5-1: 0-0.01; the polyglycol compound comprises a polyester diol or a polyether diol; the polyester dihydric alcohol is poly epsilon-caprolactone diol;
adding the fluorinated thiol prepolymer obtained in the step (1) into a blending reactant, adding a solvent to form a stable and well-dispersed suspension, and continuing to react for 0.5-2 hours; adding a binary chain extender, and continuing to react for 0.5-3 hours until the isocyanate is remained in the consumed system, so as to obtain the fluorinated polyurethane coating; the mass ratio of the fluorinated thiol prepolymer to the blending reaction product is 0.25-1: 1.
2. The method of applying a superhydrophobic coating of claim 1, wherein: the polyfunctional thiol compounds include, but are not limited to: glycerol trimercaptopropionate, trimethylolpropane trimercaptopropyl ester, isocyanuric acid trimercaptocarboxylate, pentaerythritol tetramercaptopropionate, or dipentaerythritol hexa (3-mercaptopropionate).
3. The method of applying a superhydrophobic coating of claim 1, wherein: the fluoroacrylate is CH2 =C(CH3 )COO-(CH2 )2 -(CF2 )n CF3 Wherein n is a natural number of 3 to 10.
4. The method of applying a superhydrophobic coating of claim 1, wherein: the solvent is acetone, dimethyl carbonate, N, N-dimethylacetamide or tetrahydrofuran, and the solvent needs to be subjected to dehydration treatment before use.
5. The method of applying a superhydrophobic coating of claim 1, wherein: the photoinitiator comprises a UV photoinitiator: 1173. 184, 907, 369, 1490 and 1700.
6. The method of applying a superhydrophobic coating of claim 1, wherein: the isocyanate is a difunctional isocyanate including, but not limited to: toluene diisocyanate, 4,4' -diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate or dimer acid diisocyanate.
7. The method of applying a superhydrophobic coating of claim 1, wherein: the polyether diol includes, but is not limited to, polyoxypropylene diol, tetrahydrofuran-oxypropylene copolyol, polytetrahydrofuran diol.
8. The method of applying a superhydrophobic coating of claim 1, wherein: such catalysts include, but are not limited to: dibutyltin dilaurate, stannous octoate, triethylamine or triethylenediamine.
9. The method of applying a superhydrophobic coating of claim 1, wherein: the binary chain extenders include, but are not limited to: propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, neopentyl glycol, diethylamino glycol, ethylenediamine, N, N-dihydroxy (diisopropyl) aniline, hydrogenated bisphenol A, dimethylene phenyl diol, diethanolamine, diethylmethyl-phenylenediamine or 4,4' -methylidyne-bis (2-chloroaniline).
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