阅读说明：本技术 一种超强机械性能的超疏水油漆及其制备方法 (Super-hydrophobic paint with super-strong mechanical property and preparation method thereof ) 是由 夏帆 朱海 于 2019-12-11 设计创作，主要内容包括：本发明提供一种超强机械性能的超疏水油漆,由以下质量份的原料制得：环氧树脂1～10份,聚乙二醇0.4～2.4份,二氧化钛1～2.5份,1H,1H,2H,2H-全氟辛基三乙氧基硅烷1.6～5份,聚(N-异丙基丙烯酰胺)0.02～0.12份,氟硅烷0.1～1.2份,固化剂0.2～1.2份。本发明还提供了超疏水油漆的制备方法。本发明提供的超疏水油漆解决了响应性超润湿材料普遍的弱机械性能、不易在多种基材表面制备的技术问题。(The invention provides super-hydrophobic paint with super-strong mechanical property, which is prepared from the following raw materials in parts by mass: 1-10 parts of epoxy resin, 0.4-2.4 parts of polyethylene glycol, 1-2.5 parts of titanium dioxide, 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, 1.6-5 parts of poly (N-isopropylacrylamide), 0.02-0.12 part of fluorosilane and 0.2-1.2 parts of curing agent. The invention also provides a preparation method of the super-hydrophobic paint. The super-hydrophobic paint provided by the invention solves the technical problems that the general weak mechanical property of a responsive super-wetting material is not easy to prepare on the surfaces of various substrates.)

1. The super-hydrophobic paint with super-strong mechanical properties is characterized by being prepared from the following raw materials in parts by mass: 1-10 parts of epoxy resin, 0.4-2.4 parts of polyethylene glycol, 1-2.5 parts of titanium dioxide, 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, 1.6-5 parts of poly (N-isopropylacrylamide), 0.02-0.12 part of fluorosilane and 0.2-1.2 parts of curing agent.

2. The super-hydrophobic paint with super mechanical property according to claim 1, is characterized by being prepared from the following raw materials in parts by mass: 5 parts of epoxy resin, 2.0 parts of polyethylene glycol, 1.5 parts of titanium dioxide, 3.5 parts of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, 0.1 part of poly (N-isopropylacrylamide), 0.6 part of fluorosilane and 0.8 part of curing agent.

3. The super-hydrophobic paint with super mechanical property according to claim 1, is characterized by being prepared from the following raw materials in parts by mass: 8 parts of epoxy resin, 0.6 part of polyethylene glycol, 2.0 parts of titanium dioxide, 2.0 parts of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, 0.05 part of poly (N-isopropylacrylamide), 0.5 part of fluorosilane and 1.0 part of curing agent.

4. The paint with super-strong mechanical properties as claimed in any one of claims 1 to 3, wherein the curing agent is ethylenediamine, hexamethylenediamine or boron trifluoride.

5. The method for preparing the paint with super-strong mechanical properties according to any one of claims 1 to 3, which is characterized by comprising the following steps:

s1, weighing epoxy resin and polyethylene glycol, mixing, adding absolute ethyl alcohol, and magnetically stirring;

s2, adding absolute ethyl alcohol into the titanium dioxide, and magnetically stirring;

s3, mixing the solution obtained in the step S1 and the solution obtained in the step S2, then sequentially adding 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, poly (N-isopropylacrylamide), fluorosilane and curing agent, magnetically stirring and ultrasonically processing to obtain the super-hydrophobic paint.

Technical Field

The invention relates to the field of preparation and application of super-wetting responsive materials, in particular to super-hydrophobic paint with super-strong mechanical properties and a preparation method thereof.

Background

The Wettability (wetability) of the material is judged by a Water Contact Angle (WCA) of the surface, and can be divided into 4 types, namely, super-hydrophilic, hydrophobic and super-hydrophobic. When WCA <10 deg., the surface is said to be a super hydrophilic material; when 10 ° < WCA <90 °, the surface is a hydrophilic material; when 90 ° < WCA <150 °, the surface is a hydrophobic material; when WCA >150 deg., the surface is super-hydrophobic material. The microstructure construction and chemical composition modification of the surface are the main methods for preparing the material with special wettability at present.

Research on wetting materials has focused primarily on responsive wetting materials. The responsive wetting surface may enable a wettability transition, e.g. a reversible transition from (super) hydrophilic to (super) hydrophobic, (super) oleophobic to (super) hydrophilic, underwater (super) oleophobic to underwater (super) oleophilic, etc., when there is an external stimulus such as light, electricity, temperature, pH, solvent, magnetic field. These responsive wetting materials are also prepared by manipulating the surface roughness and chemical composition, but require the addition of a responsive substance or polymer. For example, a super-wetting material for synthesizing photoresponse, such as titanium dioxide, zinc oxide, and tungsten trioxide, which have photosensitivity; poly (N-isopropylacrylamide) having temperature sensitivity undergoes phase transition when the temperature changes, and changes in wettability can also be achieved. The intelligent response wettability material has great application prospect in the fields of self-cleaning, oil-water separation, micro-fluidic, drug loading, sensors, battery packaging and the like.

The material wettability can be reversibly switched by a surface response factor to an external stimulus. However, these materials have several disadvantages: (1) the responsive super-wetting material is often limited to laboratory preparation and is not suitable for large-scale production; (2) because the micro-nano structure on the surface of the obtained responsive super-wetting material is easy to wear and damage, and the super-wetting property of the surface is lost, it is difficult to simultaneously maintain the mechanical property and the super-wetting property of the surface; (3) the preparation of most responsive super-wetting materials often requires a special single substrate material, which adds difficulty to the universal application of the responsive super-wetting materials. Therefore, the development and research of the paint coating with super-wetting responsiveness and maintaining super-high mechanical performance have larger application prospect and higher practical value from the aspects of large-scale production, stability of mechanical performance and super-wetting performance and multi-material substrate application.

Disclosure of Invention

In view of the above, the invention provides a super-hydrophobic paint with super-strong mechanical properties and a preparation method thereof, and solves the technical problems that a responsive super-wetting material is generally weak in mechanical properties and is not easy to prepare on the surfaces of various substrates.

The invention provides super-hydrophobic paint with super-strong mechanical property, which is prepared from the following raw materials in parts by mass: 1-10 parts of epoxy resin, 0.4-2.4 parts of polyethylene glycol, 1-2.5 parts of titanium dioxide, 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, 1.6-5 parts of poly (N-isopropylacrylamide), 0.02-0.12 part of fluorosilane and 0.2-1.2 parts of curing agent.

Further, the feed additive is prepared from the following raw materials in parts by mass: 5 parts of epoxy resin, 2.0 parts of polyethylene glycol, 1.5 parts of titanium dioxide, 3.5 parts of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, 0.1 part of poly (N-isopropylacrylamide), 0.6 part of fluorosilane and 0.8 part of curing agent.

Further, the feed additive is prepared from the following raw materials in parts by mass: 8 parts of epoxy resin, 0.6 part of polyethylene glycol, 2.0 parts of titanium dioxide, 2.0 parts of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, 0.05 part of poly (N-isopropylacrylamide), 0.5 part of fluorosilane and 1.0 part of curing agent.

The curing agent may be any one of ethylenediamine, hexamethylenediamine, boron trifluoride, aromatic polyamine curing agents, modified aliphatic amine curing agents, and acid anhydride curing agents.

The invention also provides a preparation method of the super-hydrophobic paint with super-strong mechanical property, which comprises the following steps:

s1, weighing epoxy resin and polyethylene glycol, mixing, adding absolute ethyl alcohol, and magnetically stirring;

s2, adding absolute ethyl alcohol into the titanium dioxide, and magnetically stirring;

s3, mixing the solution obtained in the step S1 and the solution obtained in the step S2, then sequentially adding 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, poly (N-isopropylacrylamide), fluorosilane and curing agent, magnetically stirring and ultrasonically processing to obtain the super-hydrophobic paint.

In the steps, the epoxy resin is diluted by an ethanol solution and is changed into a mixed solution with lower viscosity after magnetic stirring treatment, the mixed solution is mixed and stirred with polyethylene glycol to regulate and control the surface energy, and then the mixed solution is mixed and stirred with fluoridized titanium dioxide composite particles to form a uniform suspension solution; mixing and stirring titanium dioxide nano particles by using an absolute ethyl alcohol solution, treating for about 1 hour by using a fluorosilane modifier, and performing stirring and ultrasonic cross operation to completely modify fluorosilane on the titanium dioxide nano particles.

The technical scheme provided by the invention has the beneficial effects that: the super-hydrophobic paint provided by the invention can be produced in a large scale; the super-hydrophobic paint provided by the invention overcomes the common problem that the conventional super-wetting material is weak in mechanical property, and the application range of the super-hydrophobic paint is greatly improved; the super-hydrophobic paint provided by the invention solves the problem of single property of super-wetting responsive materials, can be coated on different substrate materials such as metal sheets, glass sheets, plastic sheets, filter paper and woven fabrics, and greatly increases the universality of the application; the super-hydrophobic paint provided by the invention is subjected to mechanical damage of sanding, blade scratching and finger wiping, and the surface of the material still has stable super-wetting response property.

Drawings

FIG. 1 is a schematic diagram of the process for synthesizing a superhydrophobic paint of the present invention.

FIG. 2 is a scanning electron microscope image of a coating formed by the paint prepared in example 1.

FIG. 3 is a graph showing the change in wettability of the coating formed by the paint prepared in example 1 at various temperatures.

FIG. 4 is a graphical representation of the responsive wetting cycles at different temperatures for coatings formed on aluminum sheet substrates by spray painting the paint prepared in example 1.

FIG. 5(a) is a schematic view of sanding a coating layer formed of the paint prepared in example 1, FIG. 5(b) is a scanning electron microscope image of the coating layer after sanding, and FIG. 5(c) is a schematic view of super-wettability of the coating layer with temperature after sanding.

FIG. 6 is a graphical representation of the responsive wetting cycles at different temperatures for a coating formed from the paint prepared in example 1 after sanding.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.

The invention provides super-hydrophobic paint with super-strong mechanical property, which is prepared from the following raw materials in parts by mass: 1-10 parts of epoxy resin, 0.4-2.4 parts of polyethylene glycol, 1-2.5 parts of titanium dioxide, 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, 1.6-5 parts of poly (N-isopropylacrylamide), 0.02-0.12 part of fluorosilane and 0.2-1.2 parts of curing agent.

The epoxy resin has strong adhesiveness, so that the prepared paint can be coated on the surface of a substrate.

The titanium dioxide particles are composed of P25 titanium dioxide with the particle size of about 21nm and anatase titanium dioxide with the particle size of 200nm, and the mass ratio of the P25 titanium dioxide to the anatase titanium dioxide with the particle size of 200nm is 1.0-3.0: 1.

the poly (N-isopropyl acrylamide) is subjected to phase transition along with temperature change, and reversible temperature response from super-hydrophobicity to super-hydrophilicity is realized on the surface of the substrate.

The curing agent can be any one of ethylenediamine, hexamethylenediamine, boron trifluoride, aromatic polyamine curing agent, modified aliphatic amine curing agent or acid anhydride curing agent.

Referring to fig. 1, the present invention also provides a preparation method of the super-hydrophobic paint with super-strong mechanical properties, which comprises the following steps:

step S1, weighing 1-10 parts of epoxy resin and 0.4-2.4 parts of polyethylene glycol by mass, mixing, adding absolute ethyl alcohol, and magnetically stirring;

step S2, adding anhydrous ethanol into 1-2.5 parts by mass of titanium dioxide, and magnetically stirring;

and step S3, mixing the solution obtained in the step S1 with the solution obtained in the step S2, sequentially adding 1.6-5 parts by mass of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane, 0.02-0.12 part by mass of poly (N-isopropylacrylamide), 0.1-1.2 parts by mass of fluorosilane and 0.2-1.2 parts by mass of curing agent, and carrying out magnetic stirring and ultrasonic treatment to obtain the super-hydrophobic paint.

The super-hydrophobic paint and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples.