阅读说明：本技术 水性涂料防污添加剂及其制备方法 (Antifouling additive for water-based paint and preparation method thereof ) 是由 李正香 于 2020-05-30 设计创作，主要内容包括：本发明提供了一种水性涂料防污添加剂,利用笼型聚倍半硅氧烷作为载体,负载氧化亚铜。在制备的过程中,以超临界二氧化碳作为反应介质,利用超临界流体的高扩散性、强的溶解性、优异的表面润湿性及强的渗透能力,促使部分铜离子渗透到筒状笼型结构中,经氢氧根离子原位沉淀得到氢氧化铜,再经葡萄糖原位还原得到氧化亚铜,然后被束缚在筒状笼型结构中,确保了防污添加剂的防污效果稳定、持久性。(The invention provides an antifouling additive for a water-based paint, which utilizes cage-type polysilsesquioxane as a carrier to load cuprous oxide. In the preparation process, supercritical carbon dioxide is used as a reaction medium, and by utilizing the high diffusivity, strong solubility, excellent surface wettability and strong permeability of a supercritical fluid, part of copper ions are promoted to permeate into the cylindrical cage-shaped structure, copper hydroxide is obtained through hydroxyl ion in-situ precipitation, cuprous oxide is obtained through glucose potential reduction, and then the copper hydroxide is bound in the cylindrical cage-shaped structure, so that the stability and the durability of the antifouling additive are ensured.)

1. A method for preparing an antifouling additive for a water-based paint, comprising:

(1) preparing a carrier emulsion: dispersing cage type polysilsesquioxane shown in a formula (I) in an organic solvent to obtain a solution with the mass concentration of 20-50%;

（I）

r is one or more of alkyl, amido, alkenyl and aryl;

(2) preparing a copper salt aqueous solution A, a sodium hydroxide aqueous solution B and a glucose solution C;

(3) putting the carrier emulsion, the copper salt aqueous solution A, the sodium hydroxide aqueous solution B and the glucose solution C into a high-pressure reaction kettle, wherein the volume ratio of the carrier emulsion to the copper salt aqueous solution A to the sodium hydroxide aqueous solution B to the glucose solution C is 3: 1: 1: 1.

(4) injecting supercritical carbon dioxide fluid into the high-pressure reaction kettle to 5-10MPa, then carrying out magnetic stirring, raising the temperature to 70-90 ℃ and reacting for 30-50 min;

(5) and (3) cooling to room temperature, then discharging supercritical carbon dioxide fluid, and cleaning, filtering and airing a reaction product to obtain the cage-type polysilsesquioxane-loaded cuprous oxide waterborne coating antifouling additive.

2. The method of claim 1, wherein the antifouling additive for water-based paint comprises: the organic solvent in the step (1) is selected from one or more of aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, alcohol, ketone, ether and alcohol ether.

3. The method of claim 2, wherein the antifouling additive for water-based paint comprises: the alicyclic hydrocarbon organic solvent includes but is not limited to cyclohexane, cyclohexanone, toluene cyclohexanone. The aliphatic hydrocarbon organic solvents include, but are not limited to, pentane, hexane, octane; the aromatic hydrocarbon organic solvent includes, but is not limited to, benzene, toluene, xylene; the alcoholic organic solvents include, but are not limited to, methanol, ethanol, isopropanol; the ketone organic solvents include, but are not limited to, acetone, methyl butanone, methyl isobutyl ketone; the ether organic solvents include, but are not limited to, ethyl ether, butyl ether, propylene oxide; the alcohol ether organic solvent includes, but is not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

4. The method of claim 1, wherein the antifouling additive for water-based paint comprises: in the cage type polysilsesquioxane shown in the formula (I), 8R groups are mutually independent and are selected from one of alkyl, amido, alkenyl and aryl, and the 8R groups can be completely different, mutually different or partially different.

5. The method of claim 1, wherein the antifouling additive for water-based paint comprises: in the step (2), the concentration of the copper salt aqueous solution A is 2-3mol/L, the concentration of the sodium hydroxide aqueous solution B is 4-6mol/L, and the concentration of the glucose solution C is 4-6 mol/L.

6. An aqueous paint antifouling additive prepared by the method of any one of claims 1 to 5.

Technical Field

The invention belongs to the field of water-based paint, and particularly relates to an antifouling additive for water-based paint and a preparation method thereof.

Background

In general, water-soluble paints are classified into water-soluble paints, water-reducible paints, and water-dispersible paints. As for the components, acrylic water-based paints, polyurethane water-based paints, and acrylic and polyurethane mixed water-based paints have been most studied.

In the water paint, besides the main paint component, various additives are usually added to make the paint obtain corresponding characteristics, such as hydrophobicity, flame retardancy, antifouling property, etc.

The water-based antifouling paint is widely applied to the fields of automobiles, ships, buildings and the like, and specifically comprises automobile windows, reversing image camera lenses, the outer surface of a ship body, the outer wall surface of a building and the like.

In the existing water-based antifouling paint, cuprous oxide is commonly used as an antifouling additive. However, the addition of cuprous oxide directly to an aqueous paint has disadvantages of poor binding property of cuprous oxide to the paint matrix, poor dispersion uniformity, unstable antifouling effect, and non-durability. Therefore, the selection of a suitable carrier to carry cuprous oxide, making cuprous oxide suitable for application to aqueous coatings as an efficient, durable antifouling additive, is a direction of interest to many researchers. However, studies on cage-type polysilsesquioxane as a carrier for cuprous oxide have been carried out. Therefore, the invention aims to provide the cage type polysilsesquioxane-loaded cuprous oxide water-based paint antifouling additive.

Disclosure of Invention

Aiming at the defects of the existing antifouling additive for cuprous oxide-based water-based paint, the invention provides the antifouling additive for the water-based paint, which takes cage-type polysilsesquioxane as a carrier to load cuprous oxide.

In one aspect, the present invention provides a method for preparing an antifouling additive for a water-based paint, comprising:

(1) preparing a carrier emulsion: dispersing cage type polysilsesquioxane shown in a formula (I) in an organic solvent to obtain a solution with the mass concentration of 20-50%;

（I）

r is one or more of alkyl, amido, alkenyl and aryl;

(2) preparing a copper salt aqueous solution A, a sodium hydroxide aqueous solution B and a glucose solution C;

(3) putting the carrier emulsion, the copper salt aqueous solution A, the sodium hydroxide aqueous solution B and the glucose solution C into a high-pressure reaction kettle, wherein the volume ratio of the carrier emulsion to the copper salt aqueous solution A to the sodium hydroxide aqueous solution B to the glucose solution C is 3: 1: 1: 1.

(4) injecting supercritical carbon dioxide fluid into the high-pressure reaction kettle to 5-10MPa, then carrying out magnetic stirring, raising the temperature to 70-90 ℃ and reacting for 30-50 min;

(5) and (3) cooling to room temperature, then discharging supercritical carbon dioxide fluid, and cleaning, filtering and airing a reaction product to obtain the cage-type polysilsesquioxane-loaded cuprous oxide waterborne coating antifouling additive.

Further, the organic solvent in step (1) is selected from one or more of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, ketones, ethers and alcohol ethers.

Wherein, the alicyclic hydrocarbon organic solvent includes but is not limited to cyclohexane, cyclohexanone and toluene cyclohexanone. The aliphatic hydrocarbon organic solvent includes but is not limited to pentane, hexane, octane. The aromatic hydrocarbon organic solvent includes but is not limited to benzene, toluene, xylene. The alcohol organic solvent includes but is not limited to methanol, ethanol, isopropanol. The ketone organic solvent includes, but is not limited to, acetone, methyl butanone, methyl isobutyl ketone. The ether organic solvent includes but is not limited to diethyl ether, butyl ether and propylene oxide. The alcohol ether organic solvent includes, but is not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

In the cage type polysilsesquioxane shown in the formula (I), 8R groups are mutually independent and are selected from one of alkyl, amido, alkenyl and aryl, and the 8R groups can be completely different, mutually different or partially different.

Further, in the step (2), the concentration of the copper salt aqueous solution A is 2-3mol/L, the concentration of the sodium hydroxide aqueous solution B is 4-6mol/L, and the concentration of the glucose solution C is 4-6 mol/L.

In another aspect, the invention provides an antifouling additive for water-based paint, which is prepared by the preparation method.

According to the invention, cage type polysilsesquioxane is used as a carrier to load cuprous oxide, and the obtained cuprous oxide-loaded waterborne paint antifouling additive carries R groups in the cage type polysilsesquioxane, and the R groups can promote the dispersion uniformity of the antifouling additive in a waterborne paint and the bonding stability of the antifouling additive and a paint matrix.

Wherein, the cage-shaped polysilsesquioxane is a cylindrical cage-shaped structure, and the hollow radius of the cylindrical cage-shaped structure is about 0.3 nm. The particle radius of the divalent copper ions is 0.073nm, which is about one fourth of the hollow radius of the cylindrical cage-shaped structure. In the preparation process, supercritical carbon dioxide is used as a reaction medium, and by utilizing the high diffusivity, strong solubility, excellent surface wettability and strong permeability of a supercritical fluid, part of copper ions are promoted to permeate into the cylindrical cage-shaped structure, copper hydroxide is obtained through in-situ precipitation of hydroxyl ions, cuprous oxide is obtained through reduction of glucose sites, and the cuprous oxide is bound in the cylindrical cage-shaped structure. That is, the antifouling additive in which cuprous oxide is supported on the cylindrical cage-like structure of cage-like polysilsesquioxane was obtained. Therefore, the antifouling effect of the antifouling additive of the present invention is more stable and durable.

Detailed Description

The present invention will be described in detail with reference to specific examples. These embodiments are merely some of the inventive content of the present invention, and not all of them. Other examples, which would be obtained by one of ordinary skill in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.