CN110628253A

CN110628253A - Environment-friendly super-hydrophobic antifouling paint and preparation method thereof

Info

Publication number: CN110628253A
Application number: CN201910929769.4A
Authority: CN
Inventors: 欧曙辉; 万励; 廖丽; 徐梦恬
Original assignee: ZHEJIANG HUAYU TECHNOLOGY Co Ltd
Current assignee: ZHEJIANG HUAYU TECHNOLOGY Co Ltd
Priority date: 2019-09-29
Filing date: 2019-09-29
Publication date: 2019-12-31

Abstract

The invention discloses an environment-friendly super-hydrophobic antifouling paint which comprises the following components in percentage by mass: 30-50% of a solvent; 40-55% of fluorine-silicon modified acrylic resin; 5-10% of organic silicon; 2-5% of nano silicon dioxide; 1-2% of an emulsifier; 1-2% of stabilizing agent. The invention also discloses a preparation method thereof, which comprises the following steps of S1: preparing a solvent in a mixing tank; s2: adding the fluorine-silicon modified acrylic resin into a mixing tank, heating and stirring; s3: adding organic silicon into a mixing tank, stirring and preserving heat for 1-2 hours; s4: uniformly mixing the nano silicon dioxide and the stabilizer, and adding the mixture into a mixing tank for stirring; s5: mixing the above solution with emulsifier, processing with colloid mill, cooling, and discharging. Has the advantages of excellent antifouling performance, less pollution, simple preparation process and low cost.

Description

Environment-friendly super-hydrophobic antifouling paint and preparation method thereof

Technical Field

The invention relates to the field of coatings, in particular to a hydrophobic antifouling coating.

Background

The low surface energy antifouling paint can be widely applied to the fields of building antifouling, marine antifouling, electrical appliance three-proofing paint, anti-icing and the like, and is a kind of functional paint with wide application. The common products in the market are few at present, and the existing products are often characterized as follows: 1. the small molecule organosilicon products cannot form effective coating thickness (namely cannot form continuous compact coating film), and have poor durability. 2. The paint product contains a large amount of benzene or alcohol organic solvent, which causes great pollution to the environment.

Therefore, it is a problem to be solved by those skilled in the art to improve the existing antifouling paint to overcome the above disadvantages.

Disclosure of Invention

The invention aims to provide an environment-friendly super-hydrophobic antifouling paint with excellent antifouling performance and less pollution.

The invention also aims to provide a preparation method of the environment-friendly super-hydrophobic antifouling paint, which has the advantages of simple preparation process and low cost.

In order to achieve the above purposes, the technical scheme adopted by the invention is as follows: the environment-friendly super-hydrophobic antifouling paint comprises the following components in percentage by mass:

30-50% of a solvent;

40-55% of fluorine-silicon modified acrylic resin;

5-10% of organic silicon;

2-5% of nano silicon dioxide;

1-2% of an emulsifier;

1-2% of stabilizing agent.

Preferably, the solvent is a mixed solution of n-butyl acetate and n-butanol.

Further, the mass ratio of n-butyl acetate to n-butanol in the solvent is 25: 75.

Preferably, the fluorine and silicon in the fluorine-silicon modified acrylic resin are 1-3% by mass.

Preferably, the particle diameter of the nano silicon dioxide is 20-100 nanometers.

A preparation method of an environment-friendly super-hydrophobic antifouling paint comprises the following steps:

s1: preparing a solvent in a mixing tank;

s2: adding the fluorine-silicon modified acrylic resin into a mixing tank, heating and stirring;

s3: adding organic silicon into a mixing tank, stirring and preserving heat for 1-2 hours;

s4: uniformly mixing the nano silicon dioxide and the stabilizer, and adding the mixture into a mixing tank for stirring;

s5: mixing the above solution with emulsifier, processing with colloid mill, cooling, and discharging.

Specifically, in the step S1, n-butyl acetate and n-butanol are added into a mixing tank according to the mass ratio of 25:75, and are uniformly stirred to form the solvent.

Preferably, in S2, the heating is performed to 90 to 120 ℃.

Compared with the prior art, the invention has the beneficial effects that: the antifouling property is good, the waterborne is pollution-free, and the application prospect is wide; and the preparation process is simple, the cost is low, and the method is suitable for wide popularization.

Drawings

FIG. 1 is a chemical reaction formula for synthesizing a fluorosilicone modified acrylic resin in a preferred embodiment of the present invention;

FIG. 2 is a spectrum chart for confirming the presence of a fluorosilicone modified acrylic resin according to a preferred embodiment of the present invention;

fig. 3 is a contact angle test chart of a preferred embodiment of the present invention.

Detailed Description

The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.

The environment-friendly super-hydrophobic antifouling paint of one preferred embodiment of the invention comprises the following components in percentage by mass: 48% of fluorine-silicon modified acrylic resin, 8% of organic silicon, 2% of nano silicon dioxide, 40% of solvent, 1% of emulsifier and 1% of stabilizer. Wherein the solvent is a mixed solution of n-butyl acetate and n-butanol, and the mass ratio of the n-butyl acetate to the n-butanol is 25: 75. The particle diameter of the selected nano-silica in this example is 30 + -5 nm. In the embodiment, the mass percentage of fluorine and silicon in the fluorine-silicon modified acrylic resin is 2%.

The preparation method of the environment-friendly super-hydrophobic antifouling paint comprises the following steps:

step 1: adding n-butyl acetate and n-butanol into a mixing tank according to the mass ratio of 25:75, and uniformly stirring to form a solvent.

Step 2: adding the fluorine-silicon modified acrylic resin into a mixing tank, heating to 100 ℃ and stirring.

And step 3: mixing the nano silicon dioxide and the stabilizing agent uniformly, and adding the mixture into a mixing tank for stirring.

And 4, step 4: mixing the above solution with emulsifier, processing with colloid mill, cooling, and discharging.

Wherein, the fluorine-silicon modified acrylic resin is a common material of the coating, and the preparation method is not described in detail. As shown in fig. 1, a synthetic reaction formula of the fluorosilicone modified acrylic resin is provided. The reaction formula is a synthetic process of fluorine-silicon modified acrylic resin: firstly, acrylic monomers (such as methyl methacrylate, acrylic acid and the like), organic silicon (such as vinyl trimethoxy silane and the like) and styrene are adopted to synthesize silicon-containing acrylic resin, and then fluorine-containing monomers are introduced to finally obtain the fluorine-silicon modified acrylic resin.

As shown in FIG. 2, a spectrum diagram illustrating that the substance synthesized by the above reaction formula is the target fluorosilicone modified acrylic resin is provided. Specifically, the method comprises the following steps: at 995cm^-1A characteristic absorption peak of Si-O bond appears; at 1240cm^-1At a position of 1150cm^-1Respectively show-CF₃and-CF₂Characteristic absorption peak of (A), indicating polymerizationThe fluorine silicon exists in the material, 1733cm^-1Characteristic absorption peak of C ═ O, 3447cm^-1The peak is the-OH stretching vibration peak of the acrylic acid carboxyl group, indicating that the polymer is an acrylic resin.

Generally, the higher the content of fluorine silicon in the fluorine-silicon modified acrylic resin is, the better the performance is, but with the increase of the content, the resin price is also higher, and when the contact angle reaches 110 degrees, the contribution value of the content to the contact angle is not obvious after the content is continuously increased. Therefore, in the embodiment, the fluorosilicone modified acrylic resin with 2% of fluorine and silicon in percentage by mass is selected, and at this content, the expected contact angle value is achieved, and the low-cost characteristic is achieved. As shown in fig. 3, a contact angle test chart of the present example is provided, which shows a contact angle of 108.3 °, has good hydrophobicity, and is expected.

In the prior art, xylene is usually selected as a coating solvent, but the dissolving capacity of the xylene to resin is general, and the sufficient dissolving time of the resin is 1.5 times of that of a mixed solvent of n-butyl acetate and n-butyl alcohol. In addition, the coating using xylene as a solvent has poor appearance and high cracking risk, and the compactness of the coating is influenced. The mixed solvent of n-butyl acetate and n-butanol has strong dissolving capacity and is volatilized in a gradient manner during drying, so that the uniformity and continuity of the coating are fully ensured.

The organosilicon that can be used in this example is only required to satisfy the silanes that contain a double bond in the molecular structure and can participate in the polymerization reaction. Such as: gamma-methacryloxypropyltrimethoxysilane, methylvinylchlorosilane, vinyltris (. beta. -methoxyethoxy) silane and the like can be used.

The stabilizer is preferably used in combination of an inorganic stabilizer and an organic stabilizer. After the composite emulsion is used, the charge repulsion among emulsion particles can be increased, the agglomeration is relieved, and the viscosity of the emulsion can be improved; from the above two aspects, the storage stability and the use stability of the emulsion can be improved. The inorganic and organic composite uses have synergistic effect, and the effect is better than that of single use. Wherein the inorganic stabilizer can be ammonium chloride, calcium chloride, etc.; the organic stabilizer may be polyvinyl alcohol, starch, carboxymethyl cellulose, etc.

In the embodiment, the emulsifier is selected from alkyl polyamines and quaternary ammonium salts, the effect is better, the emulsion prepared from the emulsifier has small and uniform particle size (the particle size range is concentrated in 1-5 mu m), the storage property is good (the emulsion breaking phenomena such as flocculation, caking and the like do not occur in the placing process), the drying speed is higher, and the requirements that the surface drying time is less than or equal to 4h and the actual drying time is less than or equal to 24h are met.

The environment-friendly super-hydrophobic antifouling paint produced by the components and the preparation method has the following properties:

color and appearance	Milky white color
		Contact angle (static, 5 μ L)	108.3°
Specific gravity, g/cm3	About 1.1
		Drying time, h	Surface dryness is less than or equal to 4; not more than 24 of full stem
Adhesion (cross-hatch method), grade	1
		Solids content of%	≥45
Impact strength, cm	≥50

The foregoing has described the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims

1. An environment-friendly super-hydrophobic antifouling paint is characterized in that: the composite material consists of the following components in percentage by mass:

2. the environment-friendly super-hydrophobic antifouling paint as claimed in claim 1, wherein: the solvent is a mixed solution of n-butyl acetate and n-butanol.

3. The environment-friendly super-hydrophobic antifouling paint as claimed in claim 2, wherein: the mass ratio of n-butyl acetate to n-butanol in the solvent is 25: 75.

4. The environment-friendly super-hydrophobic antifouling paint as claimed in claim 1, wherein: the fluorine and silicon mass percentage of the fluorine-silicon modified acrylic resin is 1-3%.

5. The environment-friendly super-hydrophobic antifouling paint as claimed in claim 1, wherein: the particle diameter of the nano silicon dioxide is 20-100 nanometers.

6. A method for preparing the environment-friendly superhydrophobic antifouling paint according to any one of claims 1 to 5, wherein: the method comprises the following steps:

s1: preparing a solvent in a mixing tank;

7. The method for preparing the environment-friendly super-hydrophobic antifouling paint according to claim 6, wherein the method comprises the following steps: in the S1, the n-butyl acetate and the n-butanol are added into a mixing tank according to the mass ratio of 25:75 and are stirred uniformly to form the solvent.

8. The method for preparing the environment-friendly super-hydrophobic antifouling paint according to claim 6, wherein the method comprises the following steps: in the step S2, the temperature is increased to 90-120 ℃.