阅读说明：本技术 一种自抛光乳液及其制备方法和应用 (Self-polishing emulsion and preparation method and application thereof ) 是由 周峰 裴小维 杨武芳 张建斌 于 2019-09-19 设计创作，主要内容包括：本发明提供了一种自抛光乳液及其制备方法和应用,属于海洋防污涂料技术领域。本发明提供的自抛光乳液,包括如下质量百分含量的制备原料：丙烯酸硅酯类单体5～30％,乙烯基不饱和单体10～40％,丙烯酸0.2～2％,松香5～20％,引发剂0.1～1％,乳化剂0.5～3％,碳酸氢钠0.01～0.1％,pH调节剂0.1～1％,余量为水。本发明提供的自抛光乳液完全是水性的,环境友好,其形成的漆膜力学性能好,自抛光速率稳定,且具有优异的耐水浸泡性。(The invention provides a self-polishing emulsion and a preparation method and application thereof, belonging to the technical field of marine antifouling coatings. The self-polishing emulsion provided by the invention comprises the following preparation raw materials in percentage by mass: 5-30% of acrylic silicone monomer, 10-40% of vinyl unsaturated monomer, 0.2-2% of acrylic acid, 5-20% of rosin, 0.1-1% of initiator, 0.5-3% of emulsifier, 0.01-0.1% of sodium bicarbonate, 0.1-1% of pH regulator and the balance of water. The self-polishing emulsion provided by the invention is completely aqueous and environment-friendly, and a formed paint film has good mechanical property, stable self-polishing rate and excellent water soaking resistance.)

1. The self-polishing emulsion is characterized by comprising the following preparation raw materials in percentage by mass:

5-30% of acrylic silicone monomer, 10-40% of vinyl unsaturated monomer, 0.2-2% of acrylic acid, 5-20% of rosin, 0.1-1% of initiator, 0.5-3% of emulsifier, 0.01-0.1% of sodium bicarbonate, 0.1-1% of pH regulator and the balance of water.

2. The self-polishing emulsion according to claim 1, wherein the silicone acrylate monomer comprises triisopropyl methacrylate and/or triisopropyl acrylate.

3. The self-polishing emulsion of claim 1, wherein the ethylenically unsaturated monomer comprises at least one of methyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, styrene, vinyl acetate, and vinyl pyridine.

4. The self-polishing emulsion of claim 1, wherein the initiator comprises a persulfate-based initiator;

the emulsifier comprises at least one of an anionic emulsifier, a cationic emulsifier and a nonionic emulsifier;

the pH regulator comprises ammonia water, and the mass concentration of the ammonia water is 25-28%.

5. The self-polishing emulsion according to any one of claims 1 to 4, wherein the pH of the self-polishing emulsion is from 6 to 8;

the average particle size of the latex particles in the self-polishing emulsion is 150-200 nm.

6. The method of preparing a self-polishing emulsion according to any one of claims 1 to 5, comprising the steps of:

mixing a silicon acrylate monomer, a vinyl unsaturated monomer, acrylic acid, rosin, an emulsifier and first part of water to obtain a component A;

mixing the initiator with the second part of water to obtain a component B;

mixing sodium bicarbonate, the rest water, part of the component A and part of the component B, and carrying out a first emulsion polymerization reaction on the obtained first reaction liquid to obtain a seed emulsion;

and dropwise adding the residual component A and the residual component B into the seed emulsion to obtain a second reaction solution, carrying out a second emulsion polymerization reaction, and then adding a pH regulator into the obtained system to obtain the self-polishing emulsion.

7. The preparation method according to claim 6, wherein the first part of water accounts for 73-78% of the total mass of water, and the second part of water accounts for 13-17% of the total mass of water;

the part A of the components accounts for 25-35% of the total mass of the component A;

the part B accounts for 12-17% of the total mass of the part B.

8. The preparation method according to claim 6 or 7, characterized in that the first emulsion polymerization reaction is in particular:

and reacting the first reaction solution for 70-120 min under the conditions of stirring and 80-81 ℃.

9. The method according to claim 8, wherein the second emulsion polymerization reaction is specifically:

the second reaction solution is reacted for 50-70 min at 80-81 ℃, and then reacted for 50-70 min at 87-89 ℃.

10. Use of the self-polishing emulsion according to any one of claims 1 to 5 or the self-polishing emulsion prepared by the preparation method according to any one of claims 6 to 9 as a film-forming material in an aqueous antifouling paint.

Technical Field

The invention relates to the technical field of marine antifouling coatings, and particularly relates to a self-polishing emulsion and a preparation method and application thereof.

Background

Marine biofouling presents a significant risk to the development of marine related fields, for example, fouling organisms can adhere to the surface of a ship body to accelerate corrosion, increase boundary resistance between the ship and fluid, reduce navigation speed and increase energy consumption. Among the various anti-fouling technologies, the use of anti-fouling coatings is the most mature and cost effective method. Since the prohibition of organotin (TBT) -containing antifouling paints after 1/1 of 2008, International Maritime Organization (IMO) regulation, a variety of novel antifouling paint systems have been developed and introduced, with tin-free self-polishing antifouling paints and low surface energy antifouling paints being particularly attractive. However, these antifouling paints widely used at present are solvent-based paints, and a large amount of organic solvent is added as a diluent in the construction process, so that a large amount of organic volatile gas (VOC) is released, which causes serious pollution to the environment and damages the health of workers. Therefore, with the increasing awareness of environmental protection, the development of the antifouling paint with environmental protection, no toxicity and water-based property becomes the inevitable development direction of the antifouling paint in the future.

At present, few researches on water-based marine antifouling paint at home and abroad are reported, a composite antifouling agent system which mainly takes water-based resin as a base material and cuprous oxide plus an organic antifouling agent has lower VOC content (less than 200g/L) compared with solvent-based antifouling paint, has an antifouling period of 6 months, and is mainly applied to the field of marine culture. In the composite antifouling agent system, a part of the composite antifouling agent system takes aqueous emulsion as a base material, and the composite antifouling agent has low VOC but no self-polishing performance; and the other part of the antifouling paint is water-soluble self-polishing resin which is a pseudo-aqueous resin, wherein the water-soluble self-polishing resin is used as a base material, the water solubility of the resin is improved by reacting acrylic acid in a main chain with an amine compound or ammonia water to form a salt, and more organic solvents still exist in the resin, so that the antifouling paint has higher VOC content.

Disclosure of Invention

The self-polishing emulsion provided by the invention is completely aqueous and environment-friendly, and a formed paint film has good mechanical property, stable self-polishing rate and excellent water soaking resistance.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a self-polishing emulsion which comprises the following preparation raw materials in percentage by mass:

5-30% of acrylic silicone monomer, 10-40% of vinyl unsaturated monomer, 0.2-2% of acrylic acid, 5-20% of rosin, 0.1-1% of initiator, 0.5-3% of emulsifier, 0.01-0.1% of sodium bicarbonate, 0.1-1% of pH regulator and the balance of water.

Preferably, the silicone acrylate monomer comprises triisopropyl methacrylate and/or triisopropyl acrylate.

Preferably, the ethylenically unsaturated monomer includes at least one of methyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, styrene, vinyl acetate, and vinyl pyridine.

Preferably, the initiator comprises a persulfate-based initiator;

the emulsifier comprises at least one of an anionic emulsifier, a cationic emulsifier and a nonionic emulsifier;

the pH regulator comprises ammonia water, and the mass concentration of the ammonia water is 25-28%.

Preferably, the pH value of the self-polishing emulsion is 6-8;

the average particle size of the latex particles in the self-polishing emulsion is 150-200 nm.

The invention provides a preparation method of the self-polishing emulsion in the technical scheme, which comprises the following steps:

mixing a silicon acrylate monomer, a vinyl unsaturated monomer, acrylic acid, rosin, an emulsifier and first part of water to obtain a component A;

mixing the initiator with the second part of water to obtain a component B;

mixing sodium bicarbonate, the rest water, part of the component A and part of the component B, and carrying out a first emulsion polymerization reaction on the obtained first reaction liquid to obtain a seed emulsion;

and dropwise adding the residual component A and the residual component B into the seed emulsion to obtain a second reaction solution, carrying out a second emulsion polymerization reaction, and then adding a pH regulator into the obtained system to obtain the self-polishing emulsion.

Preferably, the first part of water accounts for 73-78% of the total mass of the water, and the second part of water accounts for 13-17% of the total mass of the water;

the part A of the components accounts for 25-35% of the total mass of the component A;

the part B accounts for 12-17% of the total mass of the part B.

Preferably, the first emulsion polymerization reaction is specifically:

and reacting the first reaction solution for 70-120 min under the conditions of stirring and 80-81 ℃.

Preferably, the second emulsion polymerization reaction is specifically:

the second reaction solution is reacted for 50-70 min at 80-81 ℃, and then reacted for 50-70 min at 87-89 ℃.

The invention provides application of the self-polishing emulsion in the technical scheme or the self-polishing emulsion prepared by the preparation method in the technical scheme as a film forming material in a water-based antifouling paint.

The invention provides a self-polishing emulsion which comprises the following preparation raw materials in percentage by mass: 5-30% of acrylic silicone monomer, 10-40% of vinyl unsaturated monomer, 0.2-2% of acrylic acid, 5-20% of rosin, 0.1-1% of initiator, 0.5-3% of emulsifier, 0.01-0.1% of sodium bicarbonate, 0.1-1% of pH regulator and the balance of water. After the self-polishing emulsion provided by the invention forms a film to form a paint film, the acrylic silicon ester on the surface of the self-polishing emulsion is hydrolyzed in seawater and then stripped under the shearing action of seawater, so that the surface self-polishing is realized, and the self-renewal capacity is good. Meanwhile, in the self-polishing emulsion provided by the invention, under the synergistic action of the components, the pinky incense exists in the form of emulsion micelle, and the self-polishing emulsion can be uniformly distributed in a paint film in the film forming process and can be slowly dissolved in alkaline seawater to form a micro-channel, so that when the self-polishing emulsion is used as a film forming material in an aqueous antifouling paint, the self-polishing emulsion is beneficial to the seepage of an antifouling agent. In addition, the self-polishing emulsion provided by the invention is completely aqueous, does not contain VOC (volatile organic compounds) or toxic agents such as TBT (tert-butyl terephthalate), has uniform particle size of emulsion particles in the self-polishing emulsion, excellent stability, good film-forming property, excellent water soaking resistance, environmental friendliness, simple preparation method and convenient construction, and is suitable for industrial production and application. The results of the examples show that the self-polishing emulsion provided by the invention can achieve a paint film adhesion level of 1 after film formation, the flexibility of 1mm, the impact resistance of more than 50 kg-cm, no foaming and falling after being soaked in artificial seawater for 30 days, the self-polishing rate of the paint film is stable, and the average polishing rate is about 0.47-0.59 mu m/day.

Drawings

FIG. 1 is a graph showing the appearance of the self-polishing emulsion of example 1;

FIG. 2 is a graph showing the average particle size distribution of latex particles in the self-polishing emulsion of example 1;

FIG. 3 is an SEM image of the self-polishing emulsion of example 1.

Detailed Description

The invention provides a self-polishing emulsion which comprises the following preparation raw materials in percentage by mass:

5-30% of acrylic silicone monomer, 10-40% of vinyl unsaturated monomer, 0.2-2% of acrylic acid, 5-20% of rosin, 0.1-1% of initiator, 0.5-3% of emulsifier, 0.01-0.1% of sodium bicarbonate, 0.1-1% of pH regulator and the balance of water.

In the invention, the raw materials for preparing the self-polishing emulsion comprise 5-30% of acrylic silicone monomers, preferably 8-18% by mass. In the present invention, the silicone acrylate-based monomer preferably includes triisopropyl methacrylate and/or triisopropyl acrylate. After the self-polishing emulsion provided by the invention forms a film to form a paint film, the acrylic silicon ester on the surface of the self-polishing emulsion is hydrolyzed in seawater and then stripped under the shearing action of seawater, so that the surface self-polishing is realized, and the self-renewal capacity is good.

In the invention, the raw material for preparing the self-polishing emulsion comprises 10-40% of vinyl unsaturated monomer, preferably 20-30% by mass. In the present invention, the ethylenically unsaturated monomer preferably includes at least one of methyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, styrene, vinyl acetate and vinyl pyridine, more preferably one of the following mixtures:

the mass ratio of butyl acrylate, methyl methacrylate and styrene in the mixture is preferably (25-35) to (45-55): (15-18), more preferably (28-30): (47-50): (16-17);

the mixture of butyl acrylate, hydroxyethyl methacrylate, methyl methacrylate, styrene and vinyl acetate, wherein the mass ratio of butyl acrylate, hydroxyethyl methacrylate, methyl methacrylate, styrene and vinyl acetate in the mixture is preferably (18-22): (4-6): (40-50): (8-12): (6-7), more preferably 20: 5: 45: 10: 6.5;

the mass ratio of butyl acrylate, butyl methacrylate, methyl methacrylate, styrene and vinyl pyridine in the mixture is preferably (13-17): (8-12): (48-55): (13-17): (4-6), more preferably 15: 10: 51.5: 15: 5;

the mixture of butyl acrylate, methyl methacrylate, styrene and vinyl acetate, wherein the mass ratio of butyl acrylate, methyl methacrylate, styrene and vinyl acetate in the mixture is preferably (25-30): (45-55): (8-12): (9-13), more preferably 27: 50: 10: 11.

in the invention, the vinyl unsaturated monomer can adjust the glass transition temperature of the self-polishing emulsion, and is beneficial to improving the physical and chemical properties of the self-polishing emulsion.

In the invention, the raw material for preparing the self-polishing emulsion comprises 0.2-2% of acrylic acid by mass percentage, preferably 0.3-1%. In the invention, the acrylic acid can improve the hydrophilicity of latex particles in the self-polishing emulsion, and is beneficial to improving the dispersion stability of the self-polishing emulsion.

In the invention, the raw material for preparing the self-polishing emulsion comprises 5-20% of rosin, preferably 10-15% by mass. In the self-polishing emulsion provided by the invention, the pinky incense exists in the form of emulsion droplet micelles under the synergistic effect of the components, and the pinky incense can be uniformly distributed in a paint film in the film forming process of the self-polishing emulsion, can be slowly dissolved in alkaline seawater to form a micro-channel, and is favorable for the seepage of an antifouling agent.

In the invention, the raw materials for preparing the self-polishing emulsion comprise 0.1-1% of initiator by mass percentage, and preferably 0.2-0.5%. In the present invention, the initiator preferably includes a persulfate-based initiator, and more preferably includes ammonium persulfate or potassium persulfate.

In the invention, the raw materials for preparing the self-polishing emulsion comprise 0.5-3% of emulsifier by mass percentage, and preferably 0.8-1.6%. In the present invention, the emulsifier preferably includes at least one of an anionic emulsifier, a cationic emulsifier, and a nonionic emulsifier; the anionic emulsifier preferably comprises sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate, the cationic emulsifier preferably comprises dodecyl ammonium chloride and/or hexadecyl trimethyl ammonium bromide, and the nonionic emulsifier preferably comprises at least one of emulsifier OP-10, emulsifier OP-15 and emulsifier T-20. In the present invention, the emulsifier can reduce the surface tension of water, emulsify monomers, and contribute to the improvement in the storage stability of the resulting self-polishing emulsion.

In the invention, the raw material for preparing the self-polishing emulsion comprises 0.01-0.1% of sodium bicarbonate, preferably 0.04-0.06% by mass. In the present invention, the sodium bicarbonate can adjust and buffer the pH of the self-polishing emulsion, which is beneficial to maintaining the stability of the self-polishing emulsion.

In the invention, the raw materials for preparing the self-polishing emulsion comprise 0.1-1% of pH regulator, preferably 0.2-0.4% by mass. In the invention, the pH regulator preferably comprises ammonia water, and the mass concentration of the ammonia water is preferably 25-28%. The pH value of the self-polishing emulsion is adjusted by using the pH adjusting agent, and the pH adjusting agent is matched with the pH adjusting buffer effect of the sodium bicarbonate, so that the self-polishing emulsion is favorably ensured to have excellent stability.

In the invention, the raw materials for preparing the self-polishing emulsion comprise the balance of water by mass percentage, and the water is preferably deionized water.

In the invention, the pH value of the self-polishing emulsion is preferably 6-8; the average particle size of the latex particles in the self-polishing emulsion is preferably 150-200 nm.

The invention provides a preparation method of the self-polishing emulsion in the technical scheme, which comprises the following steps:

mixing a silicon acrylate monomer, a vinyl unsaturated monomer, acrylic acid, rosin, an emulsifier and first part of water to obtain a component A;

mixing the initiator with the second part of water to obtain a component B;

mixing sodium bicarbonate, the rest water, part of the component A and part of the component B, and carrying out a first emulsion polymerization reaction on the obtained first reaction liquid to obtain a seed emulsion;

and dropwise adding the residual component A and the residual component B into the seed emulsion to obtain a second reaction solution, carrying out a second emulsion polymerization reaction, and then adding a pH regulator into the obtained system to obtain the self-polishing emulsion.

The component A is obtained by mixing acrylic silicone ester monomers, vinyl unsaturated monomers, acrylic acid, rosin, an emulsifier and first part of water. In the invention, the first part of water preferably accounts for 73-78%, more preferably 75% of the total mass of water. In the invention, the acrylic silicon ester monomer, the vinyl unsaturated monomer, the acrylic acid, the rosin, the emulsifier and the first part of water are mixed, preferably, the acrylic silicon ester monomer, the vinyl unsaturated monomer and the acrylic acid are uniformly stirred and mixed, then the rosin is added, stirred and dissolved until the solution is transparent, finally the emulsifier and the first part of water are added, and the mixture is stirred and mixed for 30-60 min at the temperature of 30-40 ℃ to obtain the component A.

The initiator is mixed with the second part of water to obtain the component B. In the invention, the second part of water preferably accounts for 13-17% of the total mass of water, and more preferably accounts for 15%. The initiator and the second part of water are mixed without special limitation, and the initiator and the second part of water can be fully mixed.

After the component A and the component B are obtained, the sodium bicarbonate, the residual water, the component A and the component B are mixed, and the obtained first reaction liquid is subjected to a first emulsion polymerization reaction to obtain the seed emulsion. In the invention, the part A component preferably accounts for 25-35% of the total mass of the A component, and more preferably accounts for 30%; the component B preferably accounts for 12-17% of the total mass of the component B, and more preferably accounts for 15%. In the invention, the sodium bicarbonate, the residual water, the part A component and the part B component are mixed, preferably, the sodium bicarbonate, the residual water and the part A component are mixed, stirred and mixed for 25-35 min at the temperature of 30-40 ℃, and then the part B component is added.

In the present invention, the first emulsion polymerization reaction is preferably: the first reaction solution is stirred and reacts for 70-120 min at the temperature of 80-81 ℃; specifically, in the first emulsion polymerization reaction process, when the reaction is carried out for 40-60 min under the conditions of stirring and 80-81 ℃, the system turns blue, and then the reaction is carried out for 30-60 min under the conditions of stirring and 80-81 ℃.

After the seed emulsion is obtained, the residual component A and the residual component B are dripped into the seed emulsion to obtain a second reaction solution, a second emulsion polymerization reaction is carried out, and then a pH regulator is added into the obtained system to obtain the self-polishing emulsion. In the invention, the residual component A and the residual component B are dropwise added into the seed emulsion, preferably, the heating temperature is maintained at 80-81 ℃, the residual component A is dropwise added into the seed emulsion, the dropwise addition is completed within 2h, and the residual component B is continuously supplemented in batches during the dropwise addition.

In the present invention, the second emulsion polymerization is preferably: the second reaction solution is reacted for 50-70 min at 80-81 ℃, and then reacted for 50-70 min at 87-89 ℃.

After the second emulsion polymerization reaction is completed, the temperature of the obtained system is preferably reduced to 50-55 ℃, then a pH regulator is dripped into the system, the pH value of the system is regulated to be within 6-8, and the obtained system is filtered and packaged to obtain the self-polishing emulsion.

The invention provides application of the self-polishing emulsion in the technical scheme or the self-polishing emulsion prepared by the preparation method in the technical scheme as a film forming material in a water-based antifouling paint. In the present invention, the water-based antifouling paint is preferably a water-based marine antifouling paint for ships, and the content of the self-polishing emulsion and other components in the water-based antifouling paint are not particularly limited, and technical solutions well known to those skilled in the art can be adopted.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.