CN112680103B - Ultrahigh-strength hydrophobic antifogging coating composition and application thereof - Google Patents
Ultrahigh-strength hydrophobic antifogging coating composition and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of coatings, and particularly relates to an ultrahigh-strength hydrophobic antifogging coating composition and application thereof. The antifogging coating composition is prepared from the following raw materials in parts by weight: 100 parts of resin-based polymerized monomer, 1-3 parts of modified silicon carbide crystal whisker, 1-3 parts of photoinitiator, 0.1-0.3 part of flatting agent and 0.3-0.5 part of defoaming agent; the resin matrix comprises 60-80 parts of silicon acrylate oligomer and 20-40 parts of silicon acrylate monomer. The polymeric monomer in the paint is a mixture of the silicon-containing acrylate oligomer and the silicon-containing acrylate monomer, and has excellent water resistance, light resistance and hydrophobicity; modified silicon carbide crystal whisker is added, and can be uniformly dispersed in a coating system to play an excellent role in enhancing mechanical properties, and the cured coating has ultrahigh strength, scratch resistance and hydrophobicity and plays an excellent antifogging effect; the coating of the invention is applied to the surfaces of glasses, automobile glass, bathroom mirrors, goggles and swimming goggles.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an ultrahigh-strength hydrophobic antifogging coating composition and application thereof.
Background
Ultraviolet (UV) curing is an advanced technology of surface treatment of materials emerging in the 60's of the 20 th century, and is collectively referred to as radiation curing along with Electronic Book (EB) curing. The photo-curing coating is a coating which uses ultraviolet light to decompose a photoinitiator in a coating composition to generate active free radicals or cationic active centers, and initiates free radical polymerization or cationic polymerization of monomers and resin, so that a coating is cured. The ultraviolet curing coating does not contain organic volatile matters, is environment-friendly, and has high curing speed and high production efficiency. In a plurality of ultraviolet light curing coatings, the acrylic resin has light color, high transparency, brightness, fullness, color retention, light retention, strong adhesive force and corrosion resistance, and has excellent light resistance and outdoor aging resistance as the main absorption peak of light is outside the solar spectrum range. However, pure acrylic resin has low mechanical strength and hardness, and has poor acid and alkali resistance due to ester bonds in the molecule.
The transparent material has a light transmittance of 80% or more for visible light having a wavelength of 400 to 800 nm. Glass is the most commonly used inorganic transparent material. In the daily use process, the surface of the glass is easy to be atomized and dewed, thereby influencing the use of the glass. The fogging phenomenon of glass brings a lot of troubles to people and even can cause huge economic loss to people. For example, in cold seasons with low air temperature, the fogging of the glasses and various protective masks affects the sight of people, thereby obstructing people's travel; the windshield of the automobile is fogged, which can cause huge potential safety hazard for people in driving trips. Therefore, it is a very important subject to be studied to prevent fogging and condensation of glass. The antifogging material is a functional coating for slowing down or preventing the atomization or condensation phenomenon on the surface of the transparent substrate. Generally, antifogging coatings are mainly classified into inorganic-system antifogging coatings, organic-system antifogging coatings, and organic-inorganic hybrid-system antifogging coatings. Surface coating with anti-fogging coatings is a more common method for eliminating fogging: firstly, use hydrophilic polymer coating, reduce water at the contact angle (theta) of material surface, water takes place to spread and the film ization, has reduced diffuse reflection, and light can pass the material betterly. However, the hydrophilic polymer coating may form hydrogen bonds or strong polar bonds, has high room temperature viscosity and poor leveling property, is not easy to spread uniformly, and has poor corrosion resistance; secondly, the hydrophobic polymer coating is used to increase theta of water on the surface of the material, and the water is difficult to stay on the surface due to the action of gravity after water drops are formed on the surface of the material, so as to achieve the aim of preventing fog. In order to improve the performances of the traditional antifogging coating such as water resistance, poor strength and the like and meet zero VOC emission as far as possible, the UV photocuring technology and the organic-inorganic composite technology are adopted, so that the prepared coating has the advantages of excellent antifogging performance, excellent adhesive force, ultrahigh strength, good water resistance and good anti-reflection effect, and the preparation process is green and environment-friendly.
Disclosure of Invention
In order to solve the problems of poor water resistance, limited scratch resistance and unstable long-term mechanical property of the existing antifogging coating, the invention discloses an ultrahigh-strength hydrophobic antifogging coating composition and application thereof, wherein a polymerization monomer in a coating used by the coating is a mixture of a silicon-containing acrylate oligomer and a silicon-containing acrylate monomer, and the ultrahigh-strength hydrophobic antifogging coating composition has excellent water resistance, light resistance and hydrophobicity; modified silicon carbide crystal whisker is added, and can be uniformly dispersed in a coating system to play an excellent role in enhancing mechanical properties, and the prepared coating has ultrahigh strength, scratch resistance and hydrophobicity and plays an excellent antifogging effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the ultrahigh-strength hydrophobic antifogging coating composition is prepared from the following raw materials in parts by weight:
the resin-based polymerization monomer comprises the following components in parts by weight:
60-80 parts of silicon-containing acrylate oligomer
20-40 parts of silicon-containing acrylate monomer.
Preferably, the modified silicon carbide crystal whisker is acrylic acid surface grafted silicon carbide crystal whisker, the length is 0.1-0.5 mm, and the diameter is 0.5-3 μm.
Preferably, the preparation method of the acrylic acid surface grafted silicon carbide crystal whisker comprises the following steps:
(1) weighing a certain amount of silicon carbide, placing the silicon carbide in a round-bottom flask, dropwise adding 98% concentrated sulfuric acid under the condition of ice-water bath, ultrasonically dispersing for 0.5-1h to obtain a silicon carbide suspension solution, dropwise adding distilled water under vigorous stirring in the ice-water bath, then adding HNO3, heating to 105-110 ℃ under the protection of nitrogen, stirring for reacting for 3-5h, cooling, and filtering;
(2) adjusting the pH value of the clear liquid obtained in the step (1) to 10-12 by using a NaOH solution with the mass fraction of 10%, so that a large amount of suspended matters appear in the solution, finally changing the solution into an opaque solution, standing for 3-4h to completely precipitate, centrifuging for 10-15min at the rotating speed of 5000-8000 r/min by using a centrifuge to obtain a modified solid, washing and centrifuging the solid by using a 1mol/L NaOH solution, repeating for 3 times, repeatedly washing the solid by using methanol to be neutral, centrifuging, collecting the solid, and performing vacuum drying at room temperature to obtain loose powder, namely the silicon carbide with the hydroxyl-rich surface;
(3) adding silicon carbide with rich hydroxyl groups on the surface and deionized water into a round-bottom flask, stirring to uniformly disperse the silicon carbide with rich hydroxyl groups on the surface, adding bifunctional acrylate, stirring uniformly, adding ammonium persulfate and triethylamine under stirring, introducing nitrogen to remove oxygen, reacting for 5-8h at 60-80 ℃, washing, and drying to obtain corresponding acrylic acid modified silicon carbide;
wherein, in the step (1), the mass ratio of the silicon carbide to the 98% concentrated sulfuric acid is 10:0.1-0.5, the mass ratio of the silicon carbide to the distilled water is 1:15-20, and the mass ratio of the silicon carbide to the HNO3 is 12: 1; in the step (3), the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the deionized water is 1:15-20, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the bifunctional acrylate is 1:3-5, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the ammonium persulfate is 1:0.1, and the mass ratio of the ammonium persulfate to the triethylamine is 1: 3-5.
Preferably, the difunctional acrylate in the step (3) is one or more of 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and neopentyl glycol diacrylate.
Preferably, the silicon-containing acrylate oligomer is prepared by the following method: adding the hydroxyl-terminated polysiloxane and the aliphatic polyurethane acrylate oligomer into a reaction vessel according to the molar ratio of-OH to-NCO of 0.5-1:1, raising the temperature to 50-60 ℃ while stirring, adding dibutyltin dilaurate accounting for 0.3 percent of the total mass of the reactants and hydroquinone accounting for 0.01 percent of the total mass of the reactants, continuously stirring for reaction for 5-8 hours, and stopping to obtain the silicon-containing acrylate oligomer; the silicon-containing acrylate monomer is prepared by the following method: adding the hydroxyl-terminated polysiloxane and the acrylate monomer into a reaction vessel according to the mol ratio of 0.5-1:1, stirring and raising the temperature to 70-80 ℃ under the protection of nitrogen, adding dibutyltin dilaurate accounting for 0.5% of the total mass of reactants and hydroquinone accounting for 0.01% of the total mass of the reactants, continuously stirring and reacting for 5-8h, and stopping reaction to obtain the silicon-containing acrylate monomer.
Preferably, the aliphatic urethane acrylate oligomer is one or more of CN968 urethane acrylate, CN980 urethane acrylate, CN981 urethane acrylate, CN983 urethane acrylate, CN989 urethane acrylate, CN996 aliphatic urethane acrylate, CN9006 aliphatic urethane acrylate and CN9010 aliphatic urethane acrylate from sandoma corporation; the acrylate monomer is one or more of CD501 propylene oxide trimethylolpropane triacrylate, SR351 trimethylolpropane triacrylate, SR-306NS tripropylene glycol diacrylate, SR101 ethoxylated bisphenol A dimethacrylate and SR-423NS methacrylate isobornyl ester of Saedoma company.
Preferably, the photoinitiator is composed of a free radical initiator and a cationic initiator according to a mass ratio of 1-3: 3-1; the free radical initiator is one or more of hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide; the cation initiator is one or more of diaryl iodonium salt, triaryl sulfonium salt, aryl ferrocenium salt and aryl diazonium salt.
Preferably, the leveling agent is one or more of BYK-333 and BYK-358N, BG 2020; the defoaming agent is one or more of BYK052, BYK1797 and BYK 381.
Further, the ultrahigh-strength hydrophobic antifogging coating composition is prepared by the following method:
(1) sequentially adding a silicon-containing acrylate oligomer, a silicon-containing acrylate monomer and modified silicon carbide according to the weight parts, stirring at the rotating speed of 1000-1200r/min for 1-3h at room temperature, sequentially adding a flatting agent, a defoaming agent and a photoinitiator in the continuous stirring process, and uniformly mixing to prepare the ultrahigh-strength hydrophobic antifogging coating;
(2) and (2) smearing the ultrahigh-strength hydrophobic antifogging coating obtained in the step (1) on a base material, and curing the coating to form a film under UV illumination to obtain the ultrahigh-strength hydrophobic antifogging coating.
Further, an application of the ultrahigh-strength hydrophobic antifogging coating composition is disclosed, and the coating is applied to the surfaces of glasses, automobile glass, toilet glass and goggles.
The invention has the following beneficial effects:
the invention has the following beneficial effects:
(1) according to the ultrahigh-strength hydrophobic antifogging coating composition, a polymerization monomer in a coating used by the coating is a mixture of a silicon-containing acrylate oligomer and a silicon-containing acrylate monomer, the polysiloxane modified aliphatic polyurethane acrylate oligomer integrates comprehensive performances of hydroxy acrylic resin and polyurethane, and the hydrophobicity, the weather resistance, the pollution resistance and the ultraviolet light stability of the coating are further improved after siloxane modification.
(2) The ultrahigh strength hydrophobic antifogging coating composition is added with modified silicon carbide whisker, the surface grafting of acrylic group can ensure that the silicon carbide whisker has better compatibility with matrix resin, the modified silicon carbide whisker can be better dispersed in a coating system, and the ultrahigh strength hydrophobic antifogging coating composition has the advantages of length of 0.1-0.5 mm, diameter of 0.5-3 mu m, length-diameter ratio of micro-nano size and extreme anisotropy, and can be bonded with acrylate of a matrix in the photocuring process, so that the modified silicon carbide whisker forms a compact bonded network structure in the coating curing process, the coating is endowed with ultrahigh mechanical strength, good hardness and toughness and low curing shrinkage.
(3) According to the ultrahigh-strength hydrophobic antifogging coating composition, siloxane on a matrix resin main chain can be cracked to form a large number of silane free radicals under the action of a cationic photoinitiator, the reaction speed of the generated macromolecular free radicals and an acrylate monomer can be increased by 1-2 orders of magnitude, an interpenetrating network structure is formed by curing, the hydrophobic performance of the cured coating is greatly improved, the ultrahigh mechanical strength is realized, the scratch resistance is realized, and the long-term protection effect on a substrate is realized.
(4) The ultrahigh-strength hydrophobic antifogging coating composition disclosed by the invention can be applied to the surfaces of glasses, automobile glass, toilet glass and goggles by adopting processes such as spraying, slow drawing, dip coating, roller coating and the like, and is simple to operate, environment-friendly and pollution-free.
Detailed Description
The present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.
Example 1
The ultrahigh-strength hydrophobic antifogging coating composition is prepared from the following raw materials in parts by weight:
100 parts of resin-based polymerization monomer, 2 parts of modified silicon carbide crystal whisker, 2 parts of initiator consisting of 1-hydroxycyclohexyl phenyl ketone and diaryl iodonium salt according to the mass ratio of 1:2, 2 parts of leveling agent BYK-3330.2 and 0520.4 parts of defoaming agent BYK.
The resin-based polymerization monomer comprises the following components in parts by weight:
80 portions of silicon-containing acrylate oligomer
And 20 parts of silicon-containing acrylate monomer.
The silicon-containing acrylate oligomer is prepared by the following method: adding hydroxypropyl-terminated polysiloxane and CN968 polyurethane acrylate of Sadoma company into a reaction vessel according to the molar ratio of-OH to-NCO of 0.5:1, raising the temperature to 50-60 ℃ while stirring, adding dibutyltin dilaurate accounting for 0.3 percent of the total mass of reactants and hydroquinone accounting for 0.01 percent of the total mass of the reactants, and continuously stirring for reacting for 5-8 hours to obtain the silicon-containing acrylate oligomer; the silicon-containing acrylate monomer is prepared by the following method: adding the hydroxypropyl-terminated polysiloxane and SR-306NS tripropylene glycol diacrylate into a reaction vessel according to the molar ratio of 0.5:1, stirring and raising the temperature to 70-80 ℃ under the protection of nitrogen, adding dibutyltin dilaurate accounting for 0.5 percent of the total mass of reactants and hydroquinone accounting for 0.01 percent of the total mass of the reactants, continuously stirring and reacting for 5-8 hours, and stopping to obtain the silicon-containing acrylate monomer.
The preparation method of the acrylic acid surface grafted silicon carbide crystal whisker comprises the following steps:
(1) weighing a certain amount of silicon carbide, placing the silicon carbide into a round-bottom flask, and dripping 98 percent of the silicon carbide under the condition of ice-water bathUltrasonically dispersing concentrated sulfuric acid for 0.5-1h to obtain silicon carbide suspension, adding distilled water while vigorously stirring in ice water bath, and adding HNO3Heating to 105-110 ℃ under the protection of nitrogen, stirring for reaction for 3-5h, cooling and filtering;
(2) adjusting the pH value of the clear liquid obtained in the step (1) to 10-12 by using a NaOH solution with the mass fraction of 10%, so that a large amount of suspended matters appear in the solution, finally changing the solution into an opaque solution, standing for 3-4h to completely precipitate, centrifuging for 10-15min at the rotating speed of 5000-8000 r/min by using a centrifuge to obtain a modified solid, washing and centrifuging the solid by using a 1mol/L NaOH solution, repeating for 3 times, repeatedly washing the solid by using methanol to be neutral, centrifuging, collecting the solid, and performing vacuum drying at room temperature to obtain loose powder, namely the silicon carbide with the hydroxyl-rich surface;
(3) adding silicon carbide with hydroxyl-rich surface and deionized water into a round-bottom flask, stirring to uniformly disperse the silicon carbide with hydroxyl-rich surface, adding 1, 6-hexanediol diacrylate, stirring uniformly, adding ammonium persulfate and triethylamine under stirring, introducing nitrogen to remove oxygen, reacting at 60-80 ℃ for 5-8h, washing, and drying to obtain acrylic acid modified silicon carbide with the corresponding length of 0.1mm and the diameter of 0.5 mu m;
wherein, in the step (1), the mass ratio of the silicon carbide to the 98% concentrated sulfuric acid is 10:0.3, the mass ratio of the silicon carbide to the distilled water is 1:20, and the silicon carbide and the HNO are3The mass ratio of (A) to (B) is 12: 1; in the step (3), the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the deionized water is 1:20, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the 1, 6-hexanediol diacrylate is 1:5, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the ammonium persulfate is 1:0.1, and the mass ratio of the ammonium persulfate to the triethylamine is 1: 5.
Example 2
The ultrahigh-strength hydrophobic antifogging coating composition is prepared from the following raw materials in parts by weight:
100 parts of resin-based polymerization monomer, 1 part of modified silicon carbide crystal whisker, 1 part of initiator consisting of 2-hydroxy-2-methyl-1-phenyl-1-acetone and diaryliodonium salt according to the mass ratio of 2:1, 0.1 part of flatting agent BYK-358N and 78 parts of defoaming agent BYK 17970.3.
The resin-based polymerization monomer comprises the following components in parts by weight:
60 portions of silicon-containing acrylate oligomer
40 parts of silicon-containing acrylate monomer.
The silicon-containing acrylate oligomer is prepared by the following method: adding hydroxypropyl-terminated polysiloxane and CN981 polyurethane acrylate of Sadoma company into a reaction vessel according to the mol ratio of-OH to-NCO of 0.8:1, raising the temperature to 50-60 ℃ while stirring, adding dibutyltin dilaurate accounting for 0.3 percent of the total mass of reactants and hydroquinone accounting for 0.01 percent of the total mass of the reactants, and continuously stirring for reacting for 5-8 hours to obtain the silicon-containing acrylate oligomer; the silicon-containing acrylate monomer is prepared by the following method: adding hydroxypropyl terminated polysiloxane and CD501 propoxylated trimethylolpropane triacrylate into a reaction vessel according to the molar ratio of 0.8:1, under the protection of nitrogen, raising the temperature value to 70-80 ℃ while stirring, adding dibutyltin dilaurate accounting for 0.5 percent of the total mass of reactants and hydroquinone accounting for 0.01 percent of the total mass of the reactants, continuously stirring for reaction for 5-8 hours, and stopping to obtain the silicon-containing acrylate monomer.
The preparation method of the acrylic acid surface grafted silicon carbide crystal whisker comprises the following steps:
(1) weighing a certain amount of silicon carbide, placing in a round-bottom flask, dropwise adding 98% concentrated sulfuric acid under the condition of ice-water bath, ultrasonically dispersing for 0.5-1h to obtain silicon carbide suspension solution, dropwise adding distilled water under vigorous stirring in ice-water bath, and then adding HNO3Heating to 105-110 ℃ under the protection of nitrogen, stirring for reaction for 3-5h, cooling and filtering;
(2) adjusting the pH value of the clear liquid obtained in the step (1) to 10-12 by using a NaOH solution with the mass fraction of 10%, so that a large amount of suspended matters appear in the solution, finally changing the solution into an opaque solution, standing for 3-4h to completely precipitate, centrifuging for 10-15min at the rotating speed of 5000-8000 r/min by using a centrifuge to obtain a modified solid, washing and centrifuging the solid by using a 1mol/L NaOH solution, repeating for 3 times, repeatedly washing the solid by using methanol to be neutral, centrifuging, collecting the solid, and performing vacuum drying at room temperature to obtain loose powder, namely the silicon carbide with the hydroxyl-rich surface;
(3) adding silicon carbide with hydroxyl-rich surface and deionized water into a round-bottom flask, stirring to uniformly disperse the silicon carbide with hydroxyl-rich surface, adding dipropylene glycol diacrylate, stirring uniformly, adding ammonium persulfate and triethylamine under stirring, introducing nitrogen to remove oxygen, reacting at 60-80 ℃ for 5-8h, washing, and drying to obtain acrylic acid modified silicon carbide with the corresponding length of 0.3mm and the diameter of 1 micron;
wherein, in the step (1), the mass ratio of the silicon carbide to the 98% concentrated sulfuric acid is 10:0.1, the mass ratio of the silicon carbide to the distilled water is 1:15, and the silicon carbide and the HNO are3The mass ratio of (A) to (B) is 12: 1; in the step (3), the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the deionized water is 1:15, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the dipropylene glycol diacrylate is 1:4, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the ammonium persulfate is 1:0.1, and the mass ratio of the ammonium persulfate to the triethylamine is 1: 3.
Example 3
The ultrahigh-strength hydrophobic antifogging coating composition is prepared from the following raw materials in parts by weight:
100 parts of resin-based polymerization monomer, 3 parts of modified silicon carbide crystal whisker, 3 parts of initiator consisting of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and triaryl sulfonium salt according to the mass ratio of 3:1, 0.3 part of flatting agent BYK-358N and 78 parts of defoaming agent BYK 17970.5.
The resin-based polymerization monomer comprises the following components in parts by weight:
70 portions of silicon-containing acrylate oligomer
30 parts of silicon-containing acrylate monomer.
The silicon-containing acrylate oligomer is prepared by the following method: adding hydroxypropyl-terminated polysiloxane and CN996 urethane acrylate of the company Saedoma into a reaction vessel according to the mol ratio of-OH to-NCO of 1:1, raising the temperature to 50-60 ℃ while stirring, adding dibutyltin dilaurate accounting for 0.3 percent of the total mass of reactants and hydroquinone accounting for 0.01 percent of the total mass of the reactants, continuously stirring for reaction for 5-8 hours, and stopping to obtain the silicon-containing acrylate oligomer; the silicon-containing acrylate monomer is prepared by the following method: adding hydroxypropyl-terminated polysiloxane and SR-423NS isobornyl methacrylate into a reaction vessel according to the molar ratio of 1:1, stirring while raising the temperature to 70-80 ℃ under the protection of nitrogen, adding dibutyltin dilaurate accounting for 0.5 percent of the total mass of reactants and hydroquinone accounting for 0.01 percent of the total mass of the reactants, continuously stirring for reacting for 5-8 hours, and stopping reaction to obtain the silicon-containing acrylate monomer.
The preparation method of the acrylic acid surface grafted silicon carbide crystal whisker comprises the following steps:
(1) weighing a certain amount of silicon carbide, placing in a round-bottom flask, dropwise adding 98% concentrated sulfuric acid under the condition of ice-water bath, ultrasonically dispersing for 0.5-1h to obtain silicon carbide suspension solution, dropwise adding distilled water under vigorous stirring in ice-water bath, and then adding HNO3Heating to 105-110 ℃ under the protection of nitrogen, stirring for reaction for 3-5h, cooling and filtering;
(2) adjusting the pH value of the clear liquid obtained in the step (1) to 10-12 by using a NaOH solution with the mass fraction of 10%, so that a large amount of suspended matters appear in the solution, finally changing the solution into an opaque solution, standing for 3-4h to completely precipitate, centrifuging for 10-15min at the rotating speed of 5000-8000 r/min by using a centrifuge to obtain a modified solid, washing and centrifuging the solid by using a 1mol/L NaOH solution, repeating for 3 times, repeatedly washing the solid by using methanol to be neutral, centrifuging, collecting the solid, and performing vacuum drying at room temperature to obtain loose powder, namely the silicon carbide with the hydroxyl-rich surface;
(3) adding silicon carbide with hydroxyl-rich surface and deionized water into a round-bottom flask, stirring to uniformly disperse the silicon carbide with hydroxyl-rich surface, adding neopentyl glycol diacrylate, stirring uniformly, adding ammonium persulfate and triethylamine under stirring, introducing nitrogen to remove oxygen, reacting at 60-80 ℃ for 5-8h, washing, and drying to obtain acrylic acid modified silicon carbide with the corresponding length of 0.2mm and the diameter of 2 microns;
wherein, in the step (1), the mass ratio of the silicon carbide to the 98% concentrated sulfuric acid is 10:0.5, the mass ratio of the silicon carbide to the distilled water is 1:18, and the silicon carbide to the HNO3The mass ratio of (A) to (B) is 12: 1; in the step (3), the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the deionized water is 1:18, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the neopentyl glycol diacrylate is 1:3, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the ammonium persulfate is 1:0.1, and the mass ratio of the ammonium persulfate to the triethylamine is 1: 4.
Example 4
The ultrahigh-strength hydrophobic antifogging coating composition is prepared from the following raw materials in parts by weight:
100 parts of resin-based polymerized monomer, 3 parts of modified silicon carbide crystal whisker, 2 parts of initiator consisting of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and aryl diazonium salt according to the mass ratio of 1:3, 0.2 part of flatting agent BYK-358N and 17970.4 parts of defoaming agent BYK.
The resin-based polymerization monomer comprises the following components in parts by weight:
85 portions of silicon-containing acrylate oligomer
15 parts of silicon-containing acrylate monomer.
The silicon-containing acrylate oligomer is prepared by the following method: adding hydroxypropyl-terminated polysiloxane and CN9010 polyurethane acrylate of Sadoma company into a reaction vessel according to the molar ratio of-OH to-NCO of 0.9:1, raising the temperature to 50-60 ℃ while stirring, adding dibutyltin dilaurate accounting for 0.3 percent of the total mass of reactants and hydroquinone accounting for 0.01 percent of the total mass of the reactants, and continuously stirring for reacting for 5-8 hours to obtain the silicon-containing acrylate oligomer; the silicon-containing acrylate monomer is prepared by the following method: adding hydroxypropyl-terminated polysiloxane and SR101 ethoxylated bisphenol A dimethacrylate into a reaction vessel according to a molar ratio of 0.9:1, stirring while raising the temperature to 70-80 ℃ under the protection of nitrogen, adding dibutyltin dilaurate accounting for 0.5% of the total mass of reactants and hydroquinone accounting for 0.01% of the total mass of the reactants, continuously stirring for reacting for 5-8h, and stopping reaction to obtain the silicon-containing acrylate monomer.
The preparation method of the acrylic acid surface grafted silicon carbide crystal whisker comprises the following steps:
(1) weighing a certain amount of silicon carbide, placing in a round-bottom flask, dropwise adding 98% concentrated sulfuric acid under the condition of ice-water bath, ultrasonically dispersing for 0.5-1h to obtain silicon carbide suspension solution, dropwise adding distilled water under vigorous stirring in ice-water bath, and then adding HNO3Heating to 105-110 ℃ under the protection of nitrogen, stirring for reaction for 3-5h, cooling and filtering;
(2) adjusting the pH value of the clear liquid obtained in the step (1) to 10-12 by using a NaOH solution with the mass fraction of 10%, so that a large amount of suspended matters appear in the solution, finally changing the solution into an opaque solution, standing for 3-4h to completely precipitate, centrifuging for 10-15min at the rotating speed of 5000-8000 r/min by using a centrifuge to obtain a modified solid, washing and centrifuging the solid by using a 1mol/L NaOH solution, repeating for 3 times, repeatedly washing the solid by using methanol to be neutral, centrifuging, collecting the solid, and performing vacuum drying at room temperature to obtain loose powder, namely the silicon carbide with the hydroxyl-rich surface;
(3) adding silicon carbide with hydroxyl-rich surface and deionized water into a round-bottom flask, stirring to uniformly disperse the silicon carbide with hydroxyl-rich surface, adding tripropylene glycol diacrylate, stirring uniformly, adding ammonium persulfate and triethylamine under stirring, introducing nitrogen to remove oxygen, reacting at 60-80 ℃ for 5-8h, washing, and drying to obtain acrylic acid modified silicon carbide with the corresponding length of 0.5mm and the diameter of 3 mu m;
wherein, in the step (1), the mass ratio of the silicon carbide to the 98% concentrated sulfuric acid is 10:0.4, the mass ratio of the silicon carbide to the distilled water is 1:19, and the silicon carbide to the HNO3The mass ratio of (A) to (B) is 12: 1; in the step (3), the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the deionized water is 1:19, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the tripropylene glycol diacrylate is 1:4, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the ammonium persulfate is 1:0.1, and the mass ratio of the ammonium persulfate to the triethylamine is 1: 5.
An ultra-high strength hydrophobic anti-fog coating composition of examples 1-4 was prepared by the following method:
(1) sequentially adding a silicon-containing acrylate oligomer, a silicon-containing acrylate monomer and modified silicon carbide according to the weight parts, stirring at the rotating speed of 1000-1200r/min for 1-3h at room temperature, sequentially adding a flatting agent, a defoaming agent and a photoinitiator in the continuous stirring process, and uniformly mixing to prepare the ultrahigh-strength hydrophobic antifogging coating;
(2) and (2) smearing the ultrahigh-strength hydrophobic antifogging coating obtained in the step (1) on a base material, and curing the coating to form a film under UV illumination to obtain the ultrahigh-strength hydrophobic antifogging coating.
Comparative examples 1-4 are compared to example 1 with the following exceptions:
comparative example 1
100 parts of resin-based polymerization monomer, 2 parts of modified silicon carbide crystal whisker, 2 parts of initiator consisting of 1-hydroxycyclohexyl phenyl ketone and diaryl iodonium salt according to the mass ratio of 1:2, 2 parts of leveling agent BYK-3330.2 and 0520.4 parts of defoaming agent BYK.
The resin-based polymerization monomer comprises the following components in parts by weight:
80 portions of CN968 acrylic ester oligomer
20 parts of SR-306NS silicon-containing acrylate monomer.
The preparation method of the acrylic acid surface grafted silicon carbide crystal whisker comprises the following steps:
(1) weighing a certain amount of silicon carbide, placing in a round-bottom flask, dropwise adding 98% concentrated sulfuric acid under the condition of ice-water bath, ultrasonically dispersing for 0.5-1h to obtain silicon carbide suspension solution, dropwise adding distilled water under vigorous stirring in ice-water bath, and then adding HNO3Heating to 105-110 ℃ under the protection of nitrogen, stirring for reaction for 3-5h, cooling and filtering;
(2) adjusting the pH value of the clear liquid obtained in the step (1) to 10-12 by using a NaOH solution with the mass fraction of 10%, so that a large amount of suspended matters appear in the solution, finally changing the solution into an opaque solution, standing for 3-4h to completely precipitate, centrifuging for 10-15min at the rotating speed of 5000-8000 r/min by using a centrifuge to obtain a modified solid, washing and centrifuging the solid by using a 1mol/L NaOH solution, repeating for 3 times, repeatedly washing the solid by using methanol to be neutral, centrifuging, collecting the solid, and performing vacuum drying at room temperature to obtain loose powder, namely the silicon carbide with the hydroxyl-rich surface;
(3) adding silicon carbide with hydroxyl-rich surface and deionized water into a round-bottom flask, stirring to uniformly disperse the silicon carbide with hydroxyl-rich surface, adding 1, 6-hexanediol diacrylate, stirring uniformly, adding ammonium persulfate and triethylamine under stirring, introducing nitrogen to remove oxygen, reacting at 60-80 ℃ for 5-8h, washing, and drying to obtain acrylic acid modified silicon carbide with the corresponding length of 0.1mm and the diameter of 0.5 mu m;
wherein, in the step (1), the mass ratio of the silicon carbide to the 98% concentrated sulfuric acid is 10:0.3, the mass ratio of the silicon carbide to the distilled water is 1:20, and the silicon carbide and the HNO are3Quality of (1)The quantity ratio is 12: 1; in the step (3), the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the deionized water is 1:20, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the 1, 6-hexanediol diacrylate is 1:5, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the ammonium persulfate is 1:0.1, and the mass ratio of the ammonium persulfate to the triethylamine is 1: 5.
Comparative example 2 is compared to example 1 with the following exceptions: the silicon carbide crystal whisker is not modified.
Comparative example 3 is compared to example 1 with the following exceptions: the length of the prepared modified silicon carbide crystal whisker is 1mm, and the diameter is 4 mu m
Comparative example 4 was compared with example 1, except that: the initiator used was 1-hydroxycyclohexyl phenyl ketone only.
Performance testing
The inventors coated the ultrahigh strength hydrophobic antifogging coating prepared in the above examples 1-4 and comparative examples 1-4 on the surface of the glass sheet by dip coating. The front and back sides of the formed cured coating were irradiated with 4KW uv lamps for 10 seconds, respectively, and the results of the performance tests and evaluations were as shown in table 1 below:
TABLE 1
The abrasion resistance indexes in the table are:
wear resistance: the surface condition of the sample was observed after the sample was rubbed with 0000# steel wool (weight 1Kg) 3000 times.
X: the surface is completely polished, and the light transmittance is seriously reduced;
and (delta): the number of the scratches which are not milled but have the surface of more than 1cm is more than 30;
o: the number of the scar strips with the surface being more than 1cm is between 5 and 30;
very good: the number of the scars with the surface being more than 1cm is less than 5.
Adhesion force: the determination is carried out according to the national standard GB/T9286 marking test for paint films of colored paint and varnish.
As can be seen from the data in Table 1, the coating prepared by the scheme of the embodiment of the invention has good hydrophobicity, high hardness, good adhesion, particularly good mechanical property, and tensile strength of more than 34 MPa; excellent light transmission; the comparative examples, however, resulted in a decrease in the overall performance of the coating due to changes or lack of composition and key components.
In light of the above-described embodiments of the present invention, it is clear that many modifications and variations can be made by the worker skilled in the art without departing from the scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (7)
1. An ultra-high strength hydrophobic anti-fog coating composition characterized by: the composition is prepared from the following raw materials in parts by weight:
the resin-based polymerization monomer comprises the following components in parts by weight:
60-80 parts of silicon-containing acrylate oligomer
20-40 parts of a silicon-containing acrylate monomer;
the modified silicon carbide crystal whisker is acrylic acid surface grafted silicon carbide crystal whisker, the length is 0.1-0.5 mm, and the diameter is 0.5-3 μm;
the preparation method of the acrylic acid surface grafted silicon carbide crystal whisker comprises the following steps:
(1) weighing a certain amount of silicon carbide, placing in a round-bottom flask, dropwise adding 98% concentrated sulfuric acid under the condition of ice-water bath, ultrasonically dispersing for 0.5-1h to obtain silicon carbide suspension solution, dropwise adding distilled water under vigorous stirring in ice-water bath, and then adding HNO3 Heating to 105-110 ℃ under the protection of nitrogen, stirring for reaction for 3-5h, cooling and filtering;
(2) adjusting the pH value of the clear liquid obtained in the step (1) to 10-12 by using a NaOH solution with the mass fraction of 10%, so that a large amount of suspended matters appear in the solution, finally changing the solution into an opaque solution, standing for 3-4h to completely precipitate, centrifuging for 10-15min at the rotating speed of 5000-8000 r/min by using a centrifuge to obtain a modified solid, washing and centrifuging the solid by using a 1mol/L NaOH solution, repeating for 3 times, repeatedly washing the solid by using methanol to be neutral, centrifuging, collecting the solid, and performing vacuum drying at room temperature to obtain loose powder, namely the silicon carbide with the hydroxyl-rich surface;
(3) adding silicon carbide with rich hydroxyl groups on the surface and deionized water into a round-bottom flask, stirring to uniformly disperse the silicon carbide with rich hydroxyl groups on the surface, adding bifunctional acrylate, stirring uniformly, adding ammonium persulfate and triethylamine under stirring, introducing nitrogen to remove oxygen, reacting for 5-8h at 60-80 ℃, washing, and drying to obtain corresponding acrylic acid modified silicon carbide;
wherein, in the step (1), the mass ratio of the silicon carbide to the 98% concentrated sulfuric acid is 10:0.1-0.5, the mass ratio of the silicon carbide to the distilled water is 1:15-20, and the silicon carbide to the HNO3 The mass ratio of (A) to (B) is 12: 1; in the step (3), the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the deionized water is 1:15-20, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the bifunctional acrylate is 1:3-5, the mass ratio of the silicon carbide with rich hydroxyl groups on the surface to the ammonium persulfate is 1:0.1, and the mass ratio of the ammonium persulfate to the triethylamine is 1: 3-5;
the silicon-containing acrylate oligomer is prepared by the following method: adding the hydroxyl-terminated polysiloxane and the aliphatic polyurethane acrylate oligomer into a reaction vessel according to the molar ratio of-OH to-NCO of 0.5-1:1, raising the temperature to 50-60 ℃ while stirring, adding dibutyltin dilaurate accounting for 0.3 percent of the total mass of the reactants and hydroquinone accounting for 0.01 percent of the total mass of the reactants, continuously stirring for reacting for 5-8 hours, and stopping to obtain the silicon-containing acrylate oligomer; the silicon-containing acrylate monomer is prepared by the following method: adding the hydroxyl-terminated polysiloxane and the acrylate monomer into a reaction vessel according to the mol ratio of 0.5-1:1, stirring and raising the temperature to 70-80 ℃ under the protection of nitrogen, adding dibutyltin dilaurate accounting for 0.5% of the total mass of reactants and hydroquinone accounting for 0.01% of the total mass of the reactants, continuously stirring and reacting for 5-8h, and stopping reaction to obtain the silicon-containing acrylate monomer.
2. The ultra-high strength hydrophobic anti-fog coating composition according to claim 1, wherein: the difunctional acrylate in the step (3) is one or more of 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and neopentyl glycol diacrylate.
3. The ultra-high strength hydrophobic anti-fog coating composition according to claim 1, wherein: the aliphatic polyurethane acrylate oligomer is one or more of CN968 polyurethane acrylate, CN980 polyurethane acrylate, CN981 polyurethane acrylate, CN983 polyurethane acrylate, CN989 polyurethane acrylate, CN996 aliphatic polyurethane acrylate, CN9006 aliphatic polyurethane acrylate and CN9010 aliphatic polyurethane acrylate of Saedoma company; the acrylate monomer is one or more of CD501 propylene oxide trimethylolpropane triacrylate, SR351 trimethylolpropane triacrylate, SR-306NS tripropylene glycol diacrylate, SR101 ethoxylated bisphenol A dimethacrylate and SR-423NS methacrylate isobornyl ester of Saedoma company.
4. The ultra-high strength hydrophobic anti-fog coating composition according to claim 1, wherein: the photoinitiator is composed of a free radical initiator and a cationic initiator according to the mass ratio of 1-3: 3-1; the free radical initiator is one or more of hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide; the cation initiator is one or more of diaryl iodonium salt, triaryl sulfonium salt, aryl ferrocenium salt and aryl diazonium salt.
5. The ultra-high strength hydrophobic anti-fog coating composition according to claim 1, wherein: the leveling agent is one or more of BYK-333 and BYK-358N, BG 2020; the defoaming agent is one or more of BYK052, BYK1797 and BYK 381.
6. The ultra-high strength hydrophobic anti-fog coating composition according to claim 1, wherein: the preparation method comprises the following steps:
(1) sequentially adding a silicon-containing acrylate oligomer, a silicon-containing acrylate monomer and modified silicon carbide according to the weight parts, stirring at the rotating speed of 1000-1200r/min for 1-3h at room temperature, sequentially adding a flatting agent, a defoaming agent and a photoinitiator in the continuous stirring process, and uniformly mixing to prepare the ultrahigh-strength hydrophobic antifogging coating;
(2) and (2) smearing the ultrahigh-strength hydrophobic antifogging coating obtained in the step (1) on a base material, and curing the coating to form a film under UV illumination to obtain the ultrahigh-strength hydrophobic antifogging coating.
7. Use of an ultra-high strength hydrophobic anti-fog coating composition according to any of claims 1-6, wherein: the coating is applied to the surfaces of glasses, automobile glass, bathroom mirrors, goggles and swimming goggles.
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