CN112409916A - Preparation method of bionic super-hydrophobic acrylate modified polyurethane/nanoparticle composite coating - Google Patents
Preparation method of bionic super-hydrophobic acrylate modified polyurethane/nanoparticle composite coating Download PDFInfo
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Abstract
A preparation method of a bionic super-hydrophobic acrylate modified polyurethane/nanoparticle composite coating belongs to the technical field of synthesis and modification of waterborne polyurethane. The super-hydrophobic coating prepared by the invention is composed of a first component of acrylate modified polyurethane and a second component of modified silicon dioxide nano particles, wherein the first component is acrylate modified polyurethane emulsion prepared by taking organic silicon polyol, polyisocyanate, acrylate, a small molecular chain extender, a catalyst, a neutralizer, an acrylate coupling agent and water as raw materials. The super-hydrophobic functional coating with a lotus leaf-like micro-nano rough surface structure is constructed by spraying acrylate modified polyurethane emulsion and modified silicon dioxide nano particle dispersion on a base material. The surface of the membrane has a hydrophobic micro-nano structure by a spraying method, so that the physical hydrophobic property of the surface of the membrane is enhanced; since the hydrophobic groups migrate to the surface when the polydimethylsiloxane is introduced and dried and cured, the matrix material of the membrane is chemically modified to increase hydrophobicity. The lotus leaves are used as the inspiration to prepare the waterborne polyurethane coating, the rough surface is endowed while the surface energy is low, so that the waterborne polyurethane coating has super-strong hydrophobic property, the rolling angle of the water contact angle can reach 156-162 degrees and is 3-5 degrees, and the wear resistance is excellent.
Description
Technical Field
The invention belongs to the field of super-hydrophobic material manufacturing, and relates to a preparation method of bionic super-hydrophobic acrylate modified polyurethane/nanoparticles.
Background
In recent years, superhydrophobic materials have occupied more and more important areas in the fields of self-cleaning, ice and snow adhesion prevention, fluid drag reduction and the like, and therefore, researches have been increasingly conducted by researchers. Meanwhile, the super-hydrophobic material has wide application prospect in the fields of life and science and technology of people due to the unique performance, so that the super-hydrophobic material is concerned by people in recent years. By researching the internal mechanism of the formation of the natural super-hydrophobic surface, a plurality of theoretical bases are provided for artificially constructing the super-hydrophobic surface, and more design ideas are provided for people in the aspects of artificially developing and researching multifunctional super-hydrophobic materials. At present, most of methods for artificially preparing the super-hydrophobic coating have complex process and expensive equipment, and the mechanical property of the coating is poor, so that the lasting super-hydrophobic effect is difficult to achieve, therefore, the method has very important significance in researching and preparing the super-hydrophobic coating which is cheap and easy to obtain in the industry, has excellent mechanical property and can be widely applied. However, in the preparation process of the waterborne polyurethane, a hydrophilic chain extender is mostly needed to form an emulsion in water, so that the waterborne polyurethane is very easy to swell and even dissolve by water, and the application range of the waterborne polyurethane is greatly influenced, so that the waterborne polyurethane material is urgently needed to realize super-hydrophobicity at present, and the blank of the super-hydrophobic waterborne polyurethane in the industry is filled.
The traditional waterborne polyurethane coating is researched and improved in the aspects of environmental protection and hydrophobicity, and has the following patent application numbers: the CN201910220226.5 environment-friendly water-based two-component polyurethane coating is widely applied to the surface coating of various automobiles, carriages of passenger cars, locomotive heads, electric equipment, automobile parts, instruments and meters and the like. Application of patent No.: CN201710763936.3 prepares a fluorosilane modified polyurethane hydrophobic film, which can be applied to the fields of self-cleaning and waterproof materials because of excellent hydrophobicity and simple preparation method.
However, a coating suitable for a substrate with higher requirement on wear resistance is still to be developed, so that the improvement of the wear resistance of the super-hydrophobic coating is the first problem to be solved for preparing the waterborne polyurethane super-hydrophobic coating. The invention solves the problem of low bonding strength of the traditional super-hydrophobic coating by synthesizing the acrylate modified polyurethane/nano particle composite coating. Widens the application of the waterborne polyurethane coating which can be used as a super-hydrophobic coating for self-cleaning surfaces and various substrates in the future.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly and durable super-hydrophobic aqueous polyurethane coating. The problem of poor water resistance of the waterborne polyurethane is solved, and the preparation of the super-hydrophobic waterborne polyurethane coating with good durability, which is modified by the waterborne polyurethane in both physical and chemical ways, is realized.
The invention provides modified silicon dioxide nano particles to improve the hydrophobic property of a coating, and utilizes acrylate modification to improve the comprehensive property of the coating.
The invention provides a preparation method of a bionic super-hydrophobic acrylate modified polyurethane/nanoparticle coating, which comprises the following steps and conditions:
(1) first component preparation of acrylate modified polyurethane aqueous emulsion
a. Preparation of acrylate-modified polyurethane polymers
Uniformly mixing diisocyanate, organic silicon polyol, hydrophilic chain extender, catalyst and micromolecular chain extender according to the mass ratio of 100:60-70:6-8:0.1-0.3:0.5-1, putting the mixture into a four-neck flask, putting the four-neck flask into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, and preserving the heat for 2-4 hours. After the polymerization reaction is finished and the temperature of the system is reduced to room temperature, adding an acrylate coupling agent, wherein the molar ratio of hydroxyl in the acrylate coupling agent to residual isocyanic acid radical in the system is 1:5, and heating to 85 ℃ for reaction for 4 hours. And after the system is cooled to room temperature, adding n-butylamine to remove isocyanic acid radical, heating to 60 ℃, and continuing to react for 1 h. Adding an acrylate monomer and an azo initiator in a mass ratio of 100:10:0.2 to diisocyanate into the end-capped PU prepolymer, and stirring at 30 ℃ for 20 min to obtain an acrylate modified organic silicon polyurethane polymer; the diisocyanate is isophorone diisocyanate, the organic silicon polyol is polydimethylsiloxane diol, the hydrophilic chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, the micromolecule chain extender is 1, 4-butanediol, the acrylate coupling agent is glycerol methacrylate, the acrylate monomer is hydroxyethyl methacrylate, and the azo initiator is azodiisobutyronitrile;
b. preparation of acrylic ester modified polyurethane aqueous emulsion
Cooling the acrylate modified polyurethane prepared in the step (1) a to 50 ℃, adding triethylamine in the same molar ratio with the hydrophilic chain extender for neutralization, adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the acrylate modified polyurethane polymer is 6:4, and stirring at a high speed for emulsification to obtain the acrylate modified polyurethane aqueous emulsion;
(2) second component base catalytic modified SiO2Preparation of nanoparticles
Uniformly mixing ethanol, ammonia water, high-purity water and ethyl orthosilicate according to a molar ratio of 100:2-3:3-4: 2-3. The solution was stirred vigorously at 40 ℃ for 12 hours. Then, an alkylsiloxane was added in a mass ratio of 4:1 to ethyl orthosilicate. After stirring for 12 hours, the reaction was carried out at 75 ℃ for 2 hours. Finally, the resulting mixture was sonicated for 30 minutes to produce a uniform stable suspension of modified silica nanoparticles. The alkyl siloxane is perfluorodecyl triethoxysilane;
(3) preparation of waterborne polyurethane composite coating
The volume ratio of the first component of acrylic ester modified polyurethane aqueous emulsion to the second component of alkali-catalyzed silica nano-particles is 100: 9, mixing for 10 minutes, and performing ultrasonic dispersion for 30-50 minutes to obtain the waterborne polyurethane composite coating.
Has the advantages that:
1. the invention completely adopts water as a dispersion medium, does not use any organic solvent, metal catalyst and emulsifier in the preparation process, and accords with the concept of green environmental protection.
2. The waterborne polyurethane has hydrophobic property by adopting a mode of in-situ polymerization of polydimethylsiloxane, and is a chemical modification method; the other condition that the hydrophobic modified waterborne polyurethane has a rough surface by a spraying method and has super hydrophobicity is the physical method. The two components have synergistic effect, so that the hydrophobicity of the waterborne polyurethane is further enhanced to form a super-hydrophobic coating.
3. The method solves the problems to be solved urgently in the super-hydrophobic industry: the durability of the super-hydrophobic membrane is the problem, and the micro-nano structure of the common super-hydrophobic membrane is easily damaged by external environmental factors, so that the hydrophobicity of the membrane is reduced and even lost. According to the invention, due to the modification of the silicon dioxide nano particles, the adhesive force of the coating is improved, and the super-hydrophobicity is ensured to be not lost.
Detailed Description
Example 1
(1) First component preparation of acrylate modified polyurethane aqueous emulsion
a. Preparation of acrylate-modified polyurethane polymers
Uniformly mixing diisocyanate, organic silicon polyol, a hydrophilic chain extender, a catalyst and a micromolecular chain extender according to the mass ratio of 100:60:6:0.1:0.5, putting the mixture into a four-neck flask, putting the four-neck flask into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, and preserving the heat for 2-4 hours. After the polymerization reaction is finished and the temperature of the system is reduced to room temperature, adding an acrylate coupling agent, wherein the molar ratio of hydroxyl in the acrylate coupling agent to residual isocyanic acid radical in the system is 1:5, and heating to 85 ℃ for reaction for 4 hours. And after the system is cooled to room temperature, adding n-butylamine to remove isocyanic acid radical, heating to 60 ℃, and continuing to react for 1 h. Adding an acrylate monomer and an azo initiator in a mass ratio of 100:10:0.2 to diisocyanate into the end-capped PU prepolymer, and stirring at 30 ℃ for 20 min to obtain an acrylate modified organic silicon polyurethane polymer; the diisocyanate is isophorone diisocyanate, the organic silicon polyol is polydimethylsiloxane diol, the hydrophilic chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, the micromolecule chain extender is 1, 4-butanediol, the acrylate coupling agent is glycerol methacrylate, the acrylate monomer is hydroxyethyl methacrylate, and the azo initiator is azodiisobutyronitrile;
b. preparation of acrylic ester modified polyurethane aqueous emulsion
Cooling the organic silicon fluorine-containing acrylate polyurethane prepared in the step (1) a to 50 ℃, adding triethylamine in a molar ratio equal to that of the hydrophilic chain extender into the organic silicon fluorine-containing acrylate polyurethane for neutralization, adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the acrylate modified polyurethane polymer is 6:4, and stirring at a high speed for emulsification to obtain the acrylate modified polyurethane aqueous emulsion;
(2) second component base catalytic modified SiO2Preparation of nanoparticles
Uniformly mixing ethanol, ammonia water, high-purity water and ethyl orthosilicate according to a molar ratio of 100:2:3: 2. The solution was stirred vigorously at 40 ℃ for 12 hours. Then, an alkylsiloxane was added in a mass ratio of 4:1 to ethyl orthosilicate. Stirring was carried out for 12 hours and then for 2 hours at 75 ℃. Finally, the resulting mixture was sonicated for 30 minutes to produce a uniform stable suspension of modified silica nanoparticle nanoparticles. The alkyl siloxane is perfluorodecyl triethoxysilane;
(3) preparation of waterborne polyurethane composite coating
The volume ratio of the first component of acrylic ester modified polyurethane aqueous emulsion to the second component of alkali-catalyzed silica nano-particles is 100: 9, mixing for 10 minutes, and performing ultrasonic dispersion for 30-50 minutes to obtain the waterborne polyurethane composite coating;
the method for measuring the anti-friction performance of the prepared bionic super-hydrophobic acrylate modified polyurethane/nanoparticle coating comprises the following steps: the method comprises the steps of placing 1000-mesh sand paper on a water-based polyurethane coating, enabling a water-based polyurethane fiber film to be in direct contact with the sand paper, placing a 50g weight on the sand paper, pulling the sand paper at a constant speed, keeping the coated fiber film attached to the sand paper, and measuring a contact angle of the water-based polyurethane fiber film after the sand paper moves for 20 cm. This procedure was repeated three times and the average water contact angle of the polyurethane coating of a biomimetic superhydrophobic nanomaterial prepared in example 1 was 158.4 °.
Example 2
(1) First component preparation of acrylate modified polyurethane aqueous emulsion
a. Preparation of acrylate-modified polyurethane polymers
Uniformly mixing diisocyanate, organic silicon polyol, a hydrophilic chain extender, a catalyst and a micromolecular chain extender according to the mass ratio of 100:65:7:0.2:0.6, putting the mixture into a four-neck flask, putting the four-neck flask into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, and preserving the heat for 2-4 hours. After the polymerization reaction is finished and the temperature of the system is reduced to room temperature, adding an acrylate coupling agent, wherein the molar ratio of hydroxyl in the acrylate coupling agent to residual isocyanic acid radical in the system is 1:5, and heating to 85 ℃ for reaction for 4 hours. And after the system is cooled to room temperature, adding n-butylamine to remove isocyanic acid radical, heating to 60 ℃, and continuing to react for 1 h. Adding an acrylate monomer and an azo initiator in a mass ratio of 100:10:0.2 to diisocyanate into the end-capped PU prepolymer, and stirring at 30 ℃ for 20 min to obtain an acrylate modified organic silicon polyurethane polymer; the diisocyanate is isophorone diisocyanate, the organic silicon polyol is polydimethylsiloxane diol, the hydrophilic chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, the micromolecule chain extender is 1, 4-butanediol, the acrylate coupling agent is glycerol methacrylate, the acrylate monomer is hydroxyethyl methacrylate, and the azo initiator is azodiisobutyronitrile;
b. preparation of acrylic ester modified polyurethane aqueous emulsion
Cooling the organic silicon fluorine-containing acrylate polyurethane prepared in the step (1) a to 50 ℃, adding triethylamine in a molar ratio equal to that of the hydrophilic chain extender into the organic silicon fluorine-containing acrylate polyurethane for neutralization, adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the acrylate modified polyurethane polymer is 6:4, and stirring at a high speed for emulsification to obtain the acrylate modified polyurethane aqueous emulsion;
(2) second component base catalytic modified SiO2Preparation of nanoparticles
Uniformly mixing ethanol, ammonia water, high-purity water and ethyl orthosilicate according to the mass ratio of 100:2.5:3.5: 2.5. The solution was stirred vigorously at 40 ℃ for 12 hours. Then, an alkylsiloxane was added in a mass ratio of 4:1 to ethyl orthosilicate. Stirring was carried out for 12 hours and then for 2 hours at 75 ℃. Finally, the resulting mixture was sonicated for 30 minutes to produce a uniform stable suspension of modified silica nanoparticle nanoparticles. The alkyl siloxane is perfluorodecyl triethoxysilane;
(3) preparation of waterborne polyurethane composite coating
The volume ratio of the first component of acrylic ester modified polyurethane aqueous emulsion to the second component of alkali-catalyzed silica nano-particles is 100: 9, mixing for 10 minutes, and performing ultrasonic dispersion for 30-50 minutes to obtain the waterborne polyurethane composite coating
By using the determination method of example 1, the average water contact angle of the bionic super-hydrophobic acrylate modified polyurethane/nanoparticle coating prepared in example 2 is 160.6 °.
Example 3
(1) First component preparation of acrylate polyurethane aqueous emulsion
a. Preparation of acrylate-modified polyurethane polymers
Uniformly mixing diisocyanate, organic silicon polyol, a hydrophilic chain extender, a catalyst and a micromolecular chain extender according to the mass ratio of 100:70:8:0.3:1, putting the mixture into a four-neck flask, putting the four-neck flask into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, and preserving the heat for 2-4 hours. After the polymerization reaction is finished and the temperature of the system is reduced to room temperature, adding an acrylate coupling agent, wherein the molar ratio of hydroxyl in the acrylate coupling agent to residual isocyanic acid radical in the system is 1:5, and heating to 85 ℃ for reaction for 4 hours. And after the system is cooled to room temperature, adding n-butylamine to remove isocyanic acid radical, heating to 60 ℃, and continuing to react for 1 h. Adding an acrylate monomer and an azo initiator in a mass ratio of 100:10:0.2 to diisocyanate into the end-capped PU prepolymer, and stirring at 30 ℃ for 20 min to obtain an acrylate modified organic silicon polyurethane polymer; the diisocyanate is isophorone diisocyanate, the organic silicon polyol is polydimethylsiloxane diol, the hydrophilic chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, the micromolecule chain extender is 1, 4-butanediol, the acrylate coupling agent is glycerol methacrylate, the acrylate monomer is hydroxyethyl methacrylate, and the azo initiator is azodiisobutyronitrile;
b. preparation of acrylic ester modified polyurethane aqueous emulsion
Cooling the acrylate modified polyurethane prepared in the step (1) a to 50 ℃, adding triethylamine in the same molar ratio with the hydrophilic chain extender for neutralization, adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the acrylate modified polyurethane polymer is 6:4, and stirring at a high speed for emulsification to obtain the acrylate modified polyurethane aqueous emulsion;
(2) second component base catalytic modified SiO2Preparation of nanoparticles
Uniformly mixing ethanol, ammonia water, high-purity water and tetraethoxysilane according to a molar ratio of 100:3:4: 3. The solution was stirred vigorously at 40 ℃ for 12 hours. Then, an alkylsiloxane was added in a mass ratio of 4:1 to ethyl orthosilicate. Stirring was carried out for 12 hours and then for 2 hours at 75 ℃. Finally, the resulting mixture was sonicated for 30 minutes to produce a uniform stable suspension of modified silica nanoparticle nanoparticles. The alkyl siloxane is perfluorodecyl triethoxysilane;
(3) preparation of waterborne polyurethane composite coating
The volume ratio of the first component of acrylic ester modified polyurethane aqueous emulsion to the second component of alkali-catalyzed silica nano-particles is 100: 9, mixing for 10 minutes, and performing ultrasonic dispersion for 30-50 minutes to obtain the waterborne polyurethane composite coating
By using the determination method of example 1, the average water contact angle of the bionic super-hydrophobic acrylate modified polyurethane/nanoparticle coating prepared in example 2 is 158 °.
Claims (4)
1. A preparation method of a bionic super-hydrophobic acrylate modified polyurethane/nanoparticle coating is characterized by comprising the following steps:
(1) first component preparation of acrylate modified polyurethane aqueous emulsion
a. Preparation of acrylate-modified polyurethane polymers
Diisocyanate, organic silicon polyol, hydrophilic chain extender, catalyst and micromolecular chain extender are uniformly mixed according to the mass ratio of 100:0-70:6-8:0.1-0.3:0.5-1, the mixture is placed into a four-mouth flask, the four-mouth flask is placed into a constant-temperature water tank, nitrogen is introduced into the system while stirring, the temperature is kept at 70 ℃, the temperature is kept for 2-4 hours, after the polymerization reaction is finished and the system is cooled to the room temperature, acrylate coupling agent is added, the molar ratio of hydroxyl in the acrylate coupling agent to residual isocyanate in the system is 1:5, the temperature is increased to 85 ℃ for reaction for 4 hours, n-butylamine is added after the system is cooled to the room temperature to eliminate the isocyanate, the temperature is increased to 60 ℃ for continuous reaction for 1 hour, acrylate monomer and azo initiator with the mass ratio of 100:10:0.2 to diisocyanate are added into the blocked PU prepolymer, stirring for 20 min at 30 ℃ to obtain an acrylate modified polyurethane polymer; the diisocyanate is isophorone diisocyanate, the organic silicon polyol is polydimethylsiloxane diol, the hydrophilic chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, the micromolecule chain extender is 1, 4-butanediol, the acrylate coupling agent is glycerol methacrylate, the acrylate monomer is hydroxyethyl methacrylate, and the azo initiator is azodiisobutyronitrile;
b. preparation of acrylic ester modified polyurethane aqueous emulsion
Cooling the acrylate modified polyurethane prepared in the step (1) a to 50 ℃, adding triethylamine in the same molar ratio with the hydrophilic chain extender for neutralization, adding deionized water after 0.5-1 hour, wherein the adding amount of the deionized water is 6:4 of the mass ratio of the acrylate modified polyurethane polymer, and stirring at a high speed for emulsification to obtain the acrylate modified polyurethane aqueous emulsion;
(2) preparation of second component base catalytic modified silicon dioxide nano particle
Uniformly mixing ethanol, ammonia water, high-purity water and ethyl orthosilicate according to a molar ratio of 100:2-3:3-4: 2-3;
vigorously stirring the solution at 40 ℃ for 12 hours, then adding alkyl siloxane with the mass ratio of 4:1 to ethyl orthosilicate, stirring for 12 hours, then reacting at 75 ℃ for 2 hours, and finally carrying out ultrasonic treatment on the obtained mixture for 30 minutes to generate uniform and stable modified silicon dioxide nanoparticle suspension liquid, wherein the alkyl siloxane is perfluorodecyl triethoxysilane;
(3) preparation of waterborne polyurethane composite coating
The volume ratio of the first component of acrylic ester modified polyurethane aqueous emulsion to the second component of alkali-catalyzed silica nano-particles is 100: 9, mixing for 10 minutes, and performing ultrasonic dispersion for 30-50 minutes to obtain the waterborne polyurethane composite coating.
2. The preparation method of the bionic super-hydrophobic acrylate modified polyurethane/nanoparticle coating according to claim 1, characterized by comprising the following steps and conditions:
(1) first component preparation of acrylate modified polyurethane aqueous emulsion
a. Preparation of acrylate-modified polyurethane polymers
Uniformly mixing diisocyanate, organic silicon polyol, a hydrophilic chain extender, a catalyst and a micromolecular chain extender according to the mass ratio of 100:60:6:0.1:0.5, putting the mixture into a four-neck flask, putting the four-neck flask into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, and preserving the heat for 2-4 hours;
after the polymerization reaction is finished and the system is cooled to room temperature, adding an acrylate coupling agent, wherein the molar ratio of hydroxyl in the acrylate coupling agent to residual isocyanic acid radical in the system is 1:5, heating to 85 ℃ for reaction for 4 hours, adding n-butylamine to remove the isocyanic acid radical after the system is cooled to room temperature, heating to 60 ℃ for continuous reaction for 1 hour, adding an acrylate monomer and an azo initiator which have the mass ratio of 100:10:0.2 to diisocyanate into the blocked PU prepolymer, and stirring at 30 ℃ for 20 minutes to obtain an acrylate modified organic silicon polyurethane polymer; the diisocyanate is isophorone diisocyanate, the organic silicon polyol is polydimethylsiloxane diol, the hydrophilic chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, the micromolecule chain extender is 1, 4-butanediol, the acrylate coupling agent is glycerol methacrylate, the acrylate monomer is hydroxyethyl methacrylate, and the azo initiator is azodiisobutyronitrile;
b. preparation of acrylic ester modified polyurethane aqueous emulsion
Cooling the acrylate modified polyurethane prepared in the step (1) a to 50 ℃, adding triethylamine in the same molar ratio with the hydrophilic chain extender for neutralization, adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the acrylate modified polyurethane polymer is 6:4, and stirring at a high speed for emulsification to obtain the acrylate modified polyurethane aqueous emulsion;
(2) second component base catalytic modified SiO2Preparation of nanoparticles
Uniformly mixing ethanol, ammonia water, high-purity water and ethyl orthosilicate according to a molar ratio of 100:2:3:2, vigorously stirring the solution at 40 ℃ for 12 hours, then adding alkyl siloxane with a mass ratio of 4:1 to the ethyl orthosilicate, stirring for 12 hours, reacting at 75 ℃ for 2 hours, and finally carrying out ultrasonic treatment on the obtained mixture for 30 minutes to generate uniform and stable modified silicon dioxide nanoparticle suspension, wherein the alkyl siloxane is perfluorodecyl triethoxysilane;
(3) preparation of waterborne polyurethane composite coating
The volume ratio of the first component of acrylic ester modified polyurethane aqueous emulsion to the second component of alkali-catalyzed silica nano-particles is 100: 9, mixing for 10 minutes, and performing ultrasonic dispersion for 30-50 minutes to obtain the waterborne polyurethane composite coating.
3. The preparation method of the bionic super-hydrophobic acrylate modified polyurethane/nanoparticle coating according to claim 1, characterized by comprising the following steps and conditions:
(1) first component preparation of acrylate modified polyurethane aqueous emulsion
a. Preparation of acrylate-modified polyurethane polymers
Diisocyanate, organic silicon polyol, hydrophilic chain extender, catalyst and micromolecular chain extender are uniformly mixed according to the mass ratio of 100:65:7:0.2:0.6, put into a four-neck flask, placing the four-mouth flask into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the temperature for 2-4 hours, after the polymerization reaction is finished and the system is cooled to room temperature, adding an acrylate coupling agent, wherein the molar ratio of hydroxyl in the acrylate coupling agent to residual isocyanic acid radical in the system is 1:5, heating to 85 ℃ for reaction for 4 hours, adding n-butylamine to remove the isocyanic acid radical after the system is cooled to room temperature, heating to 60 ℃ for continuous reaction for 1 hour, adding an acrylate monomer and an azo initiator which have the mass ratio of 100:10:0.2 to diisocyanate into the blocked PU prepolymer, and stirring at 30 ℃ for 20 minutes to obtain an acrylate modified organic silicon polyurethane polymer; the diisocyanate is isophorone diisocyanate, the organic silicon polyol is polydimethylsiloxane diol, the hydrophilic chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, the micromolecule chain extender is 1, 4-butanediol, the acrylate coupling agent is glycerol methacrylate, the acrylate monomer is hydroxyethyl methacrylate, and the azo initiator is azodiisobutyronitrile;
b. preparation of acrylic ester modified polyurethane aqueous emulsion
Cooling the acrylate modified polyurethane prepared in the step (1) a to 50 ℃, adding triethylamine in the same molar ratio with the hydrophilic chain extender for neutralization, adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the acrylate modified polyurethane polymer is 6:4, and stirring at a high speed for emulsification to obtain the acrylate modified polyurethane aqueous emulsion;
(2) second component base catalytic modified SiO2Preparation of nanoparticles
Uniformly mixing ethanol, ammonia water, high-purity water, tetraethoxysilane and 100:2.5:3.5:2.5 molar ratio, violently stirring the solution at 40 ℃ for 12 hours, adding alkyl siloxane with the mass ratio of 4:1 to the tetraethoxysilane, stirring for 12 hours, reacting at 75 ℃ for 2 hours,
finally, the resulting mixture was sonicated for 30 minutes to produce a uniform and stable suspension of modified silica nanoparticles, the alkylsiloxane being perfluorodecyltriethoxysilane;
(3) preparation of waterborne polyurethane composite coating
The volume ratio of the first component of acrylic ester modified polyurethane aqueous emulsion to the second component of alkali-catalyzed silica nano-particles is 100: 9, mixing for 10 minutes, and performing ultrasonic dispersion for 30-50 minutes to obtain the waterborne polyurethane composite coating.
4. The preparation method of the bionic super-hydrophobic acrylate modified polyurethane/nanoparticle coating according to claim 1, characterized by comprising the following steps and conditions:
(1) first component preparation of acrylate modified polyurethane aqueous emulsion
a. Preparation of acrylate-modified polyurethane polymers
Uniformly mixing diisocyanate, organic silicon polyol, hydrophilic chain extender, catalyst and micromolecular chain extender according to the mass ratio of 100:70:8:0.3:1, putting into a four-neck flask, placing the four-mouth flask into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the temperature for 2-4 hours, after the polymerization reaction is finished and the system is cooled to room temperature, adding an acrylate coupling agent, wherein the molar ratio of hydroxyl in the acrylate coupling agent to residual isocyanic acid radical in the system is 1:5, heating to 85 ℃ for reaction for 4 hours, adding n-butylamine to remove the isocyanic acid radical after the system is cooled to room temperature, heating to 60 ℃ for continuous reaction for 1 hour, adding an acrylate monomer and an azo initiator which have the mass ratio of 100:10:0.2 to diisocyanate into the blocked PU prepolymer, and stirring at 30 ℃ for 20 minutes to obtain an acrylate modified organic silicon polyurethane polymer; the diisocyanate is isophorone diisocyanate, the organic silicon polyol is polydimethylsiloxane diol, the hydrophilic chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, the micromolecule chain extender is 1, 4-butanediol, the acrylate coupling agent is glycerol methacrylate, the acrylate monomer is hydroxyethyl methacrylate, and the azo initiator is azodiisobutyronitrile;
b. preparation of acrylic ester modified polyurethane aqueous emulsion
Cooling the acrylate modified polyurethane prepared in the step (1) a to 50 ℃, adding triethylamine in the same molar ratio with the hydrophilic chain extender for neutralization, adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the acrylate modified polyurethane polymer is 6:4, and stirring at a high speed for emulsification to obtain the acrylate modified polyurethane aqueous emulsion;
(2) second component base catalytic modified SiO2Preparation of nanoparticles
Uniformly mixing ethanol, ammonia water, high-purity water and tetraethoxysilane according to a molar ratio of 100:3:4:3, violently stirring the solution at 40 ℃ for 12 hours, then adding alkyl siloxane with a mass ratio of 4:1 to the tetraethoxysilane, stirring for 12 hours, reacting at 75 ℃ for 2 hours,
finally, the resulting mixture was sonicated for 30 minutes to produce a uniform and stable suspension of modified silica nanoparticles, the alkylsiloxane being perfluorodecyltriethoxysilane;
(3) preparation of waterborne polyurethane composite coating
The volume ratio of the first component of acrylic ester modified polyurethane aqueous emulsion to the second component of alkali-catalyzed silica nano-particles is 100: 9, mixing for 10 minutes, and performing ultrasonic dispersion for 30-50 minutes to obtain the waterborne polyurethane composite coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113831829A (en) * | 2021-09-28 | 2021-12-24 | 上海发电设备成套设计研究院有限责任公司 | Polyurethane anti-icing coating and preparation method and application thereof |
| CN114479120A (en) * | 2022-01-25 | 2022-05-13 | 太原理工大学 | Acrylate modified polyurethane adhesive hydrogel material and preparation method thereof |
| CN115558349A (en) * | 2022-10-28 | 2023-01-03 | 重庆交通大学 | Self-cleaning composite air purification coating and coating thereof |
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| CN109370408A (en) * | 2018-10-11 | 2019-02-22 | 河北工业大学 | The compound method for preparing super-hydrophobic coat of the inorganic nano-particle of aqueous polyurethane and hydrophobically modified |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109370408A (en) * | 2018-10-11 | 2019-02-22 | 河北工业大学 | The compound method for preparing super-hydrophobic coat of the inorganic nano-particle of aqueous polyurethane and hydrophobically modified |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113831829A (en) * | 2021-09-28 | 2021-12-24 | 上海发电设备成套设计研究院有限责任公司 | Polyurethane anti-icing coating and preparation method and application thereof |
| CN113831829B (en) * | 2021-09-28 | 2023-07-14 | 上海发电设备成套设计研究院有限责任公司 | Polyurethane anti-icing paint and preparation method and application thereof |
| CN114479120A (en) * | 2022-01-25 | 2022-05-13 | 太原理工大学 | Acrylate modified polyurethane adhesive hydrogel material and preparation method thereof |
| CN114479120B (en) * | 2022-01-25 | 2023-06-27 | 太原理工大学 | Acrylic ester modified polyurethane adhesive hydrogel material and preparation method thereof |
| CN115558349A (en) * | 2022-10-28 | 2023-01-03 | 重庆交通大学 | Self-cleaning composite air purification coating and coating thereof |
| CN115558349B (en) * | 2022-10-28 | 2024-01-19 | 重庆交通大学 | Self-cleaning composite air purification paint and coating thereof |
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