阅读说明：本技术 一种双组份耐磨超疏水涂料的制备方法及应用 (Preparation method and application of double-component wear-resistant super-hydrophobic coating ) 是由 胡吉明 赵越 于 2021-08-27 设计创作，主要内容包括：本发明公开了一种双组份耐磨超疏水涂料的制备方法及应用。该方法以常用的传统树脂(如环氧树脂)为树脂骨架,以经官能团化的金属有机框架(MOF)材料作为纳米颗粒(提供涂层内的粗糙结构),以经官能团化的硅油作为低表面能物质,并采用异氰酸酯类物质作为上述组分的交联固化剂,制备得到经室温快速固化的耐磨超疏水涂层。本发明的涂层可简易涂制在金属、织物、玻璃、木头等各类基底上,使其实现超疏水。涂层固化后自上而下都有粗糙结构,磨损后表面仍能露出新的可实现超疏水效应的表面,耐磨性优异。(The invention discloses a preparation method and application of a two-component wear-resistant super-hydrophobic coating. The method takes common traditional resin (such as epoxy resin) as a resin framework, takes a functionalized Metal Organic Framework (MOF) material as nanoparticles (providing a rough structure in a coating), takes functionalized silicone oil as a low surface energy substance, and takes an isocyanate substance as a crosslinking curing agent of the components to prepare the wear-resistant super-hydrophobic coating which is rapidly cured at room temperature. The coating of the invention can be simply coated on various substrates such as metal, fabric, glass, wood and the like, so that the super-hydrophobicity is realized. After the coating is cured, the coating has a rough structure from top to bottom, and after the coating is worn, a new surface capable of realizing a super-hydrophobic effect can be exposed on the surface, so that the wear resistance is excellent.)

1. A preparation method of a two-component wear-resistant super-hydrophobic coating is characterized in that,

preparing a component A: weighing 0.1-5 g of resin, 0.1-20 g of functionalized Metal Organic Framework (MOF) powder and 0.5-10 g of functionalized silicone oil, weighing 5-50 mL of organic solvent, refluxing at high temperature for a period of time, and cooling to room temperature for later use;

preparing a component B: 0.1-10 mL of isocyanate substances;

before use, the two components are stirred and mixed evenly for use;

the resin in the component A is one or more of epoxy resin, alkyd resin, polyurethane resin and polyurea resin;

the functionalized MOF material in the component A is an aminated, carboxylated or hydroxylated MOF material;

the functional group silicone oil in the component A is one or more of aminated, carboxylated, hydroxylated and epoxidized silicone oil.

2. The preparation method of claim 1, wherein the organic solvent in the component A is one or more of toluene, xylene, butyl acetate and ethyl acetate.

3. The process according to claim 1, wherein the reflux temperature of the high temperature reflux of the component A is 50 to 150 ℃ and the reflux time is 0.5 to 10 hours.

4. The preparation method of claim 1, wherein the isocyanate-based material of the component B is one or more of diisocyanate-based materials or triisocyanate-based materials, and the diisocyanate-based materials comprise hexamethylene diisocyanate, isophorone diisocyanate, and phenyl diisocyanate; the triisocyanate species include phenyl triisocyanate.

5. The method of claim 1, wherein the A, B mixture temperature is between room temperature and 100 ℃.

6. A two-component abrasion-resistant super-hydrophobic coating comprising the component a and the component B according to claim 1.

7. A two-component wear-resistant super-hydrophobic coating, which is characterized by being obtained by uniformly mixing the component A and the component B according to claim 1.

8. The application of the two-component wear-resistant super-hydrophobic coating is characterized in that the super-hydrophobic coating is formed on a substrate by brushing or spraying, and the substrate comprises metal, fabric, glass and wood.

9. The use of claim 8, wherein the superhydrophobic coating has a rough structure from top to bottom after the coating is cured, and the surface can still expose a new surface capable of realizing the superhydrophobic effect after being worn, so that the wear resistance is excellent.

Technical Field

The invention relates to the field of super-hydrophobic coatings and solid surface wettability, in particular to a preparation method and application of a double-component wear-resistant super-hydrophobic coating.

Technical Field

In nature, super-hydrophobic phenomenon is ubiquitous, self-cleaning of lotus leaf surface, free galloping of water strider on water surface, and the like. In general, a surface having a contact angle with a water droplet of more than 150 ° and a rolling angle of less than 10 ° is referred to as a superhydrophobic surface. The construction of the super-hydrophobic surface mainly comprises two major ways of constructing a rough structure on a low-surface-energy substance and modifying the low-surface-energy substance on the rough surface. Until now, researchers have developed many methods for preparing superhydrophobic surfaces, such as hydrothermal methods, etching methods, sol-gel methods, electrodeposition methods, templating methods, and the like. These methods are often complicated in steps or harsh in experimental conditions, or require power-up, template addition, etc. Therefore, it is very important to develop a simple and easy technique for preparing a superhydrophobic surface in one step.

The polymer coating is widely applied in daily life, and is widely applied to various aspects such as metal coating protection, home decoration, article decoration and the like. The low surface energy coating on the market at present is mainly fluorocarbon coating, contains fluorine element, and has poor environmental protection. Common low surface energy coatings coat surfaces that are only as hydrophobic (contact angle greater than 100 °) and are difficult to achieve superhydrophobic grades.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a preparation method and application of a two-component wear-resistant super-hydrophobic coating.

The invention develops a fluorine-free super-hydrophobic coating which can be coated on various substrates such as metal, fabric, glass, wood and the like by a brushing or spraying method similar to common coatings to construct a super-hydrophobic coating. The preparation method comprises the steps of pre-grafting common traditional resins, such as epoxy resin (providing a coating framework), organic framework compound (MOF) nanoparticles (providing a micro-nano coarse structure for a coating), functionalized silicone oil (providing low surface energy) and the like, and rapidly curing the composite components by utilizing the characteristic that isocyanate groups can rapidly react with active groups such as amino groups, hydroxyl groups, carboxyl groups and the like at room temperature and high temperature. After the coating is cured, a paint film is provided with components with a rough structure and low surface energy from top to bottom, and after the paint film is worn, a new surface can be exposed on the surface to continuously exert the super-hydrophobic effect, so that the wear resistance is excellent.

A preparation method of a two-component wear-resistant super-hydrophobic coating,

preparing a component A: weighing 0.1-5 g of resin, 0.1-20 g of functionalized Metal Organic Framework (MOF) powder and 0.5-10 g of functionalized silicone oil, weighing 5-50 mL of organic solvent, refluxing at high temperature for a period of time, and cooling to room temperature for later use;

preparing a component B: 0.1-10 mL of isocyanate substances;

before use, the two components are stirred and mixed evenly for use;

the resin in the component A is one or more of epoxy resin, alkyd resin, polyurethane resin and polyurea resin;

the functionalized MOF material in the component A is an aminated, carboxylated or hydroxylated MOF material;

the functional group silicone oil in the component A is one or more of aminated, carboxylated, hydroxylated and epoxidized silicone oil.

The organic solvent in the component A is one or more of toluene, xylene, butyl acetate and ethyl acetate.

The reflux temperature of the high-temperature reflux of the component A is 50-150 ℃, and the reflux time is 0.5-10 hours.

The isocyanate substance of the component B is one or more of diisocyanate substance or triisocyanate substance, and the diisocyanate substance comprises hexamethylene diisocyanate, isophorone diisocyanate and phenyl diisocyanate; the triisocyanate species include phenyl triisocyanate.

In the preparation method, the mixing temperature of the A, B two components is room temperature-100 ℃.

The double-component wear-resistant super-hydrophobic coating comprises a component A and a component B.

The double-component wear-resistant super-hydrophobic coating is obtained by uniformly mixing the component A and the component B.

The application of the two-component wear-resistant super-hydrophobic coating is to brush or spray the two-component wear-resistant super-hydrophobic coating on a substrate to form a super-hydrophobic coating, wherein the substrate comprises metal, fabric, glass and wood.

The super-hydrophobic coating has a rough structure from top to bottom after the coating is cured, a new surface capable of realizing the super-hydrophobic effect can be exposed on the surface after the coating is abraded, and the wear resistance is excellent.

The invention has the beneficial effects that:

(1) the coating is simple in coating method, and is suitable for common brush coating and spray coating methods. The A and B components can be quickly cured at room temperature after being mixed, and the practical application is easy.

(2) The super-hydrophobic coating does not contain fluorine, does not cause fluorine pollution, and has excellent environmental protection performance.

(3) The paint can be coated on various substrates such as metal, fabric, glass, wood and the like, and has excellent adhesive force.

(4) After the coating is cured, the coating has a rough structure from top to bottom, and a new surface capable of realizing a super-hydrophobic effect can be exposed on the surface after the coating is worn, so that the coating has excellent wear resistance.

Drawings

FIG. 1 is a schematic diagram of the grafting and curing reactions of the resin epoxy resin, the functionalized MOF amino-group UiO-66, the functionalized silicone oil amino-group PDMS, and the isocyanate hexamethylene diisocyanate.

FIG. 2a is the surface SEM topography of the super-hydrophobic coating prepared in example 1.

FIG. 2b is a sectional SEM appearance of the ITO glass coated with the super-hydrophobic coating prepared in example 1.

Detailed Description

The technical solution of the present invention is further described below by using specific examples, but the scope of the present invention is not limited thereto.

The coating comprises two components A and B:

the component A comprises: weighing 0.1-5 g of traditional resin, 0.1-20 g of functionalized Metal Organic Framework (MOF) powder and 0.5-10 g of functionalized silicone oil, weighing 5-50 mL of organic solvent, refluxing at high temperature for a period of time, and cooling to room temperature for later use.

The component B comprises: 0.1-10 mL of isocyanate.

Before use, the two components are stirred and mixed evenly for use.

The traditional resin in the component A is one or more of epoxy resin, alkyd resin, polyurethane resin, polyurea resin and the like.

The functionalized MOF material in the component A is an aminated, carboxylated or hydroxylated MOF material.

The functionalized silicone oil in the component A is one or more of aminated silicone oil, carboxylated silicone oil, hydroxylated silicone oil, epoxidized silicone oil and the like.

The organic solvent in the component A is one or more of toluene, xylene, butyl acetate, ethyl acetate and the like.

The reflux temperature of the high-temperature reflux of the component A is 50-150 ℃, and the reflux time is 0.5-10 hours.

The isocyanate substance of the component B is one or more of diisocyanate substances (such as hexamethylene diisocyanate, isophorone diisocyanate, phenyl diisocyanate and the like) or triisocyanate substances (such as phenyl triisocyanate) and the like. A. The temperature of the mixed reaction of the two components B is room temperature to 100 ℃.

Example 1

The traditional resin in the component A is selected to be epoxy resin, and the functionalized MOF material is selected to be NH₂-UiO-66, the functionalized silicone oil is a silicone amide oil, the organic solvent is xylene: butyl acetate =7:3, the reflux temperature of the high-temperature reflux is 80 ℃, the reflux time is 1 hour, and the isocyanate in the component B is hexamethylene diisocyanate. The curing temperature of the two components after mixing is room temperature (25 ℃).

The component A comprises: 1 g of epoxy resin, 5 g of NH were weighed₂-UiO-66, 3 g of silicon amide oil, 20 mL of organic solvent (xylene: butyl acetate =7:3) is measured, refluxed for 1 hour at 80 ℃, and cooled to room temperature for later use.

The component B comprises: 5mL of hexamethylene diisocyanate.

Mixing the components A and B, stirring for 10 minutes at room temperature, brushing, curing for 2 hours at room temperature, and testing. The reaction principle is shown in figure 1, and amino and epoxy react for ring-opening reaction in the reflux process of the component A. And after the component B is mixed, amino and hydroxyl react with isocyanate groups to form a network structure, and the nano particles and the low-surface-energy substance are grafted into the coating network structure.

And (3) morphology characterization: FIG. 2a shows the surface SEM appearance of the super-hydrophobic coating, which is a rough porous structure with good crosslinking integrity. FIG. 2b is a SEM (scanning electron microscope) appearance of a section of ITO glass coated with a super-hydrophobic coating, and it can be seen that rough porous structures are all arranged from top to bottom. This top-down coarse structure is of great benefit to the abrasion resistance of the superhydrophobic coating.

And (3) testing results: the contact angle of the water drop is 165 degrees, and the rolling angle is 1 degree. After being soaked in water for 7 days, the coating is not peeled off at all, and the contact angle is 156 degrees and the rolling angle is 4 degrees after being dried. After 10 m of friction with a weight of 100 g using 2000-mesh sandpaper, the contact angle was 151 DEG and the rolling angle was 6 deg. After the coating was applied to TC4 titanium alloy by brush, the amount of Bovine Serum Albumin (BSA) adsorbed was 422. mu.g/cm in 24 hours^-2Reduced to 26. mu.g/cm^-2Protein adsorption is the first step of marine biofouling, and the effective reduction of protein adsorption indicates that the effect of preventing biofouling is achieved.

Example 2

The traditional resin in the component A is selected to be epoxy resin, and the functionalized MOF material is NH₂-ZIF-7, the functionalized silicone oil is hydroxylated silicone oil, the organic solvent is toluene: ethyl acetate =4:6, the reflux temperature of the high-temperature reflux is 90 ℃, the reflux time is 3 hours, and the isocyanate substance of the component B is isophorone diisocyanate in the diisocyanate substances. The curing temperature of the two components after mixing is room temperature (25 ℃).

The component A comprises: weighing 2 g of epoxy resin and 6 g of NH₂-ZIF-7, 4 g of hydroxylated silicone oil, 25mL of organic solvent (toluene: ethyl acetate =4: 6) was weighed out, refluxed at 90 ℃ for 4 hours, and cooled to room temperature for later use.

The component B comprises: 6 mL of isophorone diisocyanate.

Mixing the components A and B, stirring for 15 minutes at room temperature, brushing, curing for 3 hours at room temperature, and testing.

And (3) testing results: the contact angle of the water drop is 160 degrees, and the rolling angle is 2 degrees. After being soaked in water for 7 days, the coating is not peeled off at all, and the contact angle is 153 degrees and the rolling angle is 5 degrees after being dried. After 10 m of friction with 2000-mesh sandpaper by a weight of 100 g, the contact angle is 150 degrees and the rolling angle is 8 degrees. After the coating was applied to TC4 titanium alloy by brush, the amount of Bovine Serum Albumin (BSA) adsorbed was from 420. mu.g/cm in 24 hours^-2Reduced to 54. mu.g/cm^-2。

Example 3

The traditional resin in the component A is selected to be polyurethane, the functionalized MOF material is HO-UiO-66, the functionalized silicone oil is hydroxylated silicone oil, and the organic solvent is xylene: ethyl acetate =5:5, the reflux temperature of the high-temperature reflux is 70 ℃, the reflux time is 5 hours, and the isocyanate substance of the component B is hexamethylene diisocyanate in the diisocyanate substances. The curing temperature of the two components after mixing is 45 ℃.

The component A comprises: 2 g of polyurethane resin, 6 g of HO-UiO-66 and 5 g of hydroxylated silicone oil are weighed, 30 mL of organic solvent (xylene: ethyl acetate =5: 5) is weighed, reflux is carried out for 3 hours at 85 ℃, and the mixture is cooled to room temperature for standby.

The component B comprises: 4 mL of hexamethylene diisocyanate.

Mixing the components A and B, stirring for 10 minutes at room temperature, brushing, curing at 45 ℃ for 2 hours, and testing.

And (3) testing results: the contact angle of the water drop is 158 degrees, and the rolling angle is 5 degrees. After being soaked in water for 7 days, the coating is not peeled off at all, and after being dried, the contact angle is 151 degrees and the rolling angle is 9 degrees. After the sheet was rubbed with a 100 g weight of 2000-mesh sandpaper for 8.3 m, the contact angle was 150 ° and the rolling angle was 9 °. After the coating was applied to TC4 titanium alloy by brush, the amount of Bovine Serum Albumin (BSA) adsorbed was from 421. mu.g/cm in 24 hours^-2Reduced to 75 μ g/cm^-2。

Example 4

Selecting the traditional resin in the component A as polyurea resin and selecting the functional MOF material as NH₂-UiO-66, the silicone oil capable of being modified is silicone amide oil, and the organic solvent is toluene: butyl acetate =8:2, reflux temperature of high temperature reflux is 75 ℃, reflux time is 2 hoursThe isocyanate substance of the component B is phenyl diisocyanate in diisocyanate substances. The curing temperature of the two components after mixing is 60 ℃.

The component A comprises: 2.5 g of polyurea resin, 8 g of NH were weighed₂-UiO-66, 5 g of silicon amide oil, 15 mL of organic solvent (toluene: butyl acetate =8: 2) is measured, refluxed for 5 hours at 95 ℃, and cooled to room temperature for later use.

The component B comprises: 4 mL of phenyl diisocyanate.

Mixing the components A and B, stirring for 10 minutes at room temperature, brushing, curing at 60 ℃ for 2 hours, and testing.

And (3) testing results: the contact angle of the water drop is 159 degrees, and the rolling angle is 4 degrees. After being soaked in water for 7 days, the coating is not peeled off at all, and the contact angle is 152 degrees and the rolling angle is 7 degrees after being dried. After 9.4 m of friction using 2000-mesh sandpaper with a weight of 100 g, the contact angle was 150 DEG and the rolling angle was 8 deg. After the coating was applied to TC4 titanium alloy by brush, the amount of Bovine Serum Albumin (BSA) adsorbed was from 421. mu.g/cm in 24 hours^-2Reduced to 35. mu.g/cm^-2。

Example 5

Selecting the traditional resin in the component A as polyurea resin and selecting the functional MOF material as NH₂-ZIF-9, the functionalized silicone oil is a carboxyl terminated silicone oil, and the organic solvent is xylene: butyl acetate =6:4, the reflux temperature of the high-temperature reflux is 85 ℃, the reflux time is 6 hours, and the isocyanate substance of the component B is phenyl triisocyanate in the triisocyanate substances. The curing temperature of the two components after mixing is 80 ℃.

The component A comprises: weighing 3 g of polyurea resin and 8 g of NH₂-ZIF-9, 6 g of carboxy terminated silicone oil, weighing 35 mL of organic solvent (xylene: butyl acetate =6: 4), refluxing for 6 hours at 65 ℃, and cooling to room temperature for later use.

The component B comprises: 5mL of phenyl triisocyanate.

Mixing the components A and B, stirring for 10 minutes at room temperature, brushing, curing at 80 ℃ for 1 hour, and testing.

And (3) testing results: the contact angle of the water drop is 154 degrees, and the rolling angle is 5 degrees. After being soaked in water for 7 days, the coating is not peeled off at all, and the contact angle is 149 degrees and the rolling angle is 11 degrees after being dried. Use 2000After the sandpaper is subjected to load friction of 7.6 m by a weight of 100 g, the contact angle is 150 degrees, and the rolling angle is 8 degrees. After the coating was applied to TC4 titanium alloy by brush, the amount of Bovine Serum Albumin (BSA) adsorbed was 422. mu.g/cm in 24 hours^-2Reduced to 64. mu.g/cm^-2。