阅读说明：本技术 一种甜菜碱型离子液改性涂料及其制备方法和应用 (Betaine type ionic liquid modified coating and preparation method and application thereof ) 是由 周峰 裴小维 杨武芳 张建斌 于 2019-10-29 设计创作，主要内容包括：本发明提供了一种甜菜碱型离子液改性涂料及其制备方法和应用,属于海洋防污涂料技术领域。本发明提供的甜菜碱型离子液改性涂料,包括如下质量百分比的组分：甜菜碱型离子液改性乳液20～30％,松香乳液5～15％,防污剂20～30％,颜填料3～10％,水性助剂1～2％,成膜助剂0.5～1％,余量为水。本发明提供的甜菜碱型离子液改性涂料VOC含量超低(小于20g/L),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和防污性能。(The invention provides a betaine type ionic liquid modified coating as well as a preparation method and application thereof, belonging to the technical field of marine antifouling coatings. The invention provides a betaine type ionic liquid modified coating which comprises the following components in percentage by mass: 20-30% of betaine ionic liquid modified emulsion, 5-15% of rosin emulsion, 20-30% of antifouling agent, 3-10% of pigment and filler, 1-2% of water-based additive, 0.5-1% of film-forming additive and the balance of water. The betaine type ionic liquid modified coating provided by the invention has ultralow VOC content (less than 20g/L), is environment-friendly, and a formed paint film has good mechanical property, stable self-polishing rate, and excellent water soaking resistance and antifouling property.)

1. The betaine type ionic liquid modified coating is characterized by comprising the following components in percentage by mass:

20-30% of betaine ionic liquid modified emulsion, 5-15% of rosin emulsion, 20-30% of antifouling agent, 3-10% of pigment and filler, 1-2% of water-based additive, 0.5-1% of film-forming additive and the balance of water;

the betaine type ionic liquid modified emulsion comprises the following preparation raw materials in percentage by mass:

2-3% of betaine type ionic liquid monomer, 15-20% of acrylic silicon ester monomer, 30-40% of acrylic ester monomer, 0.5-1.5% of acrylic acid, 1-2% of emulsifier, 0.3-0.6% of initiator, 0.05-0.1% of sodium bicarbonate, 0.3-0.5% of pH regulator and the balance of water.

2. The betaine-type ionic liquid modified coating material according to claim 1, wherein the betaine-type ionic liquid monomer comprises 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt;

the acrylic silicon ester monomer comprises triisopropyl methacrylate silicon ester and/or triisopropyl acrylate silicon ester;

the acrylic ester monomer comprises one or more of methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and isobornyl methacrylate.

3. The betaine type ionic liquid modified coating according to claim 1, wherein the emulsifier is at least one of an anionic emulsifier, a cationic emulsifier, and a nonionic emulsifier;

the initiator is persulfate initiator;

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

4. The betaine type ionic liquid modified coating according to any one of claims 1 to 3, wherein the preparation method of the betaine type ionic liquid modified emulsion comprises the following steps:

mixing a betaine type ionic liquid monomer, an acrylic silicon ester monomer, an acrylic ester monomer, acrylic acid, an emulsifier and first part of water, and emulsifying to obtain a monomer emulsion;

dissolving an initiator in the second part of water to obtain an initiator aqueous solution;

stirring and mixing sodium bicarbonate, residual water, part of monomer emulsion and part of initiator aqueous solution, heating to 80-81 ℃, keeping the temperature, and continuously stirring for 50-100 min to obtain seed emulsion;

and dropwise adding the residual monomer emulsion and the residual initiator aqueous solution into the seed emulsion, heating to 87-89 ℃, preserving the temperature for 50-70 min, then cooling to 50-55 ℃, and adding a pH regulator into the obtained system to obtain the betaine type ionic liquid modified emulsion.

5. The betaine ionic liquid modified coating as claimed in claim 4, wherein the first part of water accounts for 10-15% of the total amount of water, and the mass concentration of the initiator aqueous solution is 5-10%;

the part of the monomer emulsion accounts for 25-35% of the total amount of the monomer emulsion;

the part of the initiator aqueous solution accounts for 12-18% of the total amount of the initiator aqueous solution.

6. The betaine ionic liquid modified coating according to claim 1, wherein the rosin emulsion is prepared from the following raw materials in parts by weight:

35-45 parts of rosin, 8-10 parts of a special rosin emulsifier and 45-55 parts of water.

7. The betaine type ionic liquid modified paint according to claim 1 or 6, wherein the preparation method of the rosin emulsion comprises the following steps:

melting rosin and mixing with a special emulsifier for rosin to obtain a water-in-oil system;

and (3) dropwise adding 88-92 ℃ hot water into a 98-102 ℃ water-in-oil system to obtain the rosin emulsion.

8. The betaine ionic liquid modified coating according to claim 1, wherein the antifouling agent comprises a primary antifouling agent and a secondary antifouling agent, the primary antifouling agent is cuprous oxide and/or copper powder, and the secondary antifouling agent is one or more of copper pyrithione, zinc pyrithione, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, diuron and zineb;

the pigment and filler comprises one or more of organic bentonite, iron oxide red, zinc oxide, calcium carbonate, barium sulfate, mica powder, quartz powder and talcum powder;

the water-based auxiliary agent comprises a water-based wetting dispersant, a water-based thickener, a water-based flatting agent and a water-based defoaming agent; the aqueous wetting dispersant is at least one of AC 8892, BYK156 and BYK152, the aqueous thickener is a mixture of DeuRheoWT-05A and hydroxyethyl cellulose, the aqueous leveling agent is at least one of WCT 2490, BYK375 and DC57, and the aqueous defoamer is at least one of DAPROAP7010, BYK025 and DC 65;

the coalescing agent comprises ethylene glycol ethyl ether and/or ethylene glycol butyl ether.

9. The preparation method of the betaine type ionic liquid modified coating as claimed in any one of claims 1 to 8, characterized by comprising the following steps:

mixing water, a water-based auxiliary agent, an antifouling agent and a pigment filler, and grinding to obtain an abrasive liquid;

and mixing the grinding material liquid with the betaine type ionic liquid modified emulsion, the rosin emulsion and the film-forming additive to obtain the betaine type ionic liquid modified coating.

10. Use of the betaine type ionic liquid modified paint according to any one of claims 1 to 8 or the betaine type ionic liquid modified paint prepared by the preparation method according to claim 9 as a marine antifouling paint.

Technical Field

The invention relates to the technical field of marine antifouling coatings, and particularly relates to a betaine type ionic liquid modified coating and a preparation method and application thereof.

Background

Marine biofouling is a serious hazard to ships, marine facilities and marine culture, and can cause the increase of the navigation resistance of the ships, accelerate the corrosion of the marine facilities and pollute the marine ecological environment. Among the many technologies for preventing marine biofouling, the use of antifouling coatings is the most cost effective approach. However, most of the commonly applied antifouling paints are solvent-based, the VOC content is higher than 400g/L, and organic solvents are added as thinner in the coating process, so that a large amount of organic solvents are released, the environment is polluted, and the health of construction personnel is also harmed. Therefore, the development of marine antifouling paint is heading towards the environment-friendly water-based paint.

At present, no mature environment-friendly water-based marine antifouling paint is applied to the market, and some reported water-based antifouling paint technologies generally have the bottleneck problems of high VOC content, short antifouling period (less than 6 months), poor water resistance and the like.

Disclosure of Invention

The betaine type ionic liquid modified coating provided by the invention is ultra-low in VOC content (less than 20g/L), environment-friendly, good in mechanical property of a formed paint film, stable in self-polishing rate, and excellent in water soaking resistance and antifouling property.

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

the invention provides a betaine type ionic liquid modified coating, which comprises the following components in percentage by mass:

20-30% of betaine ionic liquid modified emulsion, 5-15% of rosin emulsion, 20-30% of antifouling agent, 3-10% of pigment and filler, 1-2% of water-based additive, 0.5-1% of film-forming additive and the balance of water;

the betaine type ionic liquid modified emulsion comprises the following preparation raw materials in percentage by mass:

2-3% of betaine type ionic liquid monomer, 15-20% of acrylic silicon ester monomer, 30-40% of acrylic ester monomer, 0.5-1.5% of acrylic acid, 1-2% of emulsifier, 0.3-0.6% of initiator, 0.05-0.1% of sodium bicarbonate, 0.3-0.5% of pH regulator and the balance of water.

Preferably, the betaine type ionic liquid monomer comprises 3- [ N, N-dimethyl- [2- (2-methylpropane-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt;

the acrylic silicon ester monomer comprises triisopropyl methacrylate silicon ester and/or triisopropyl acrylate silicon ester;

the acrylic ester monomer comprises one or more of methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and isobornyl methacrylate.

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

the initiator is persulfate initiator;

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

Preferably, the preparation method of the betaine type ionic liquid modified emulsion comprises the following steps:

mixing a betaine type ionic liquid monomer, an acrylic silicon ester monomer, an acrylic ester monomer, acrylic acid, an emulsifier and first part of water, and emulsifying to obtain a monomer emulsion;

dissolving an initiator in the second part of water to obtain an initiator aqueous solution;

stirring and mixing sodium bicarbonate, residual water, part of monomer emulsion and part of initiator aqueous solution, heating to 80-81 ℃, keeping the temperature, and continuously stirring for 50-100 min to obtain seed emulsion;

and dropwise adding the residual monomer emulsion and the residual initiator aqueous solution into the seed emulsion, heating to 87-89 ℃, preserving the temperature for 50-70 min, then cooling to 50-55 ℃, and adding a pH regulator into the obtained system to obtain the betaine type ionic liquid modified emulsion.

Preferably, the first part of water accounts for 10-15% of the total amount of water, and the mass concentration of the initiator aqueous solution is 5-10%;

the part of the monomer emulsion accounts for 25-35% of the total amount of the monomer emulsion;

the part of the initiator aqueous solution accounts for 12-18% of the total amount of the initiator aqueous solution.

Preferably, the rosin emulsion is prepared from the following raw materials in parts by weight:

35-45 parts of rosin, 8-10 parts of a special rosin emulsifier and 45-55 parts of water.

Preferably, the preparation method of the rosin emulsion comprises the following steps:

melting rosin and mixing with a special emulsifier for rosin to obtain a water-in-oil system;

and (3) dropwise adding 88-92 ℃ hot water into a 98-102 ℃ water-in-oil system to obtain the rosin emulsion.

Preferably, the antifouling agent comprises a main antifouling agent and an auxiliary antifouling agent, wherein the main antifouling agent is cuprous oxide and/or copper powder, and the auxiliary antifouling agent is one or more of copper pyrithione, zinc pyrithione, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, diuron and zineb;

the pigment and filler comprises one or more of organic bentonite, iron oxide red, zinc oxide, calcium carbonate, barium sulfate, mica powder, quartz powder and talcum powder;

the water-based auxiliary agent comprises a water-based wetting dispersant, a water-based thickener, a water-based flatting agent and a water-based defoaming agent; the aqueous wetting dispersant is at least one of AC 8892, BYK156 and BYK152, the aqueous thickener is a mixture of DeuRheo WT-05A and hydroxyethyl cellulose, the aqueous leveling agent is at least one of WCT 2490, BYK375 and DC57, and the aqueous defoamer is at least one of DAPROAP7010, BYK025 and DC 65;

the coalescing agent comprises ethylene glycol ethyl ether and/or ethylene glycol butyl ether.

The invention provides a preparation method of the betaine type ionic liquid modified coating in the technical scheme, which comprises the following steps:

mixing water, a water-based auxiliary agent, an antifouling agent and a pigment filler, and grinding to obtain an abrasive liquid;

and mixing the grinding material liquid with the betaine type ionic liquid modified emulsion, the rosin emulsion and the film-forming additive to obtain the betaine type ionic liquid modified coating.

The invention provides an application of the betaine type ionic liquid modified coating in the technical scheme or the betaine type ionic liquid modified coating prepared by the preparation method in the technical scheme as a marine antifouling coating.

The invention provides a betaine type ionic liquid modified coating, which comprises the following components in percentage by mass: 20-30% of betaine ionic liquid modified emulsion, 5-15% of rosin emulsion, 20-30% of antifouling agent, 3-10% of pigment and filler, 1-2% of water-based additive, 0.5-1% of film-forming additive and the balance of water; the preparation method comprises the following steps of taking 100% of preparation raw materials of the betaine type ionic liquid modified emulsion, wherein the preparation raw materials of the betaine type ionic liquid modified emulsion comprise the following preparation raw materials in percentage by mass: 2-3% of betaine type ionic liquid monomer, 15-20% of acrylic silicon ester monomer, 30-40% of acrylic ester monomer, 0.5-1.5% of acrylic acid, 1-2% of emulsifier, 0.3-0.6% of initiator, 0.05-0.1% of sodium bicarbonate, 0.3-0.5% of pH regulator and the balance of water. According to the invention, the betaine type ionic liquid modified emulsion is prepared from the betaine type ionic liquid monomer and the acrylic silicon ester monomer, and is used as a film forming substance, so that the betaine type ionic liquid modified coating is endowed with excellent antifouling activity and self-polishing characteristic, and the antifouling period effect of the coating is remarkably improved; meanwhile, after the betaine type ionic liquid modified coating forms a paint film, the acrylic silicon ester monomer on the surface of the coating is hydrolyzed in water and then stripped under the action of water shearing, so that the surface is self-polished, and the coating has good self-renewal capacity; in addition, in the betaine type ionic liquid modified coating provided by the invention, under the synergistic effect of the components, the piny fragrance exists in the form of emulsion micelle, and the piny fragrance can be uniformly distributed in a paint film in the film forming process of the betaine type ionic liquid modified coating, can be slowly dissolved in alkaline seawater to form a micro-channel, so that the stable release of an antifouling agent is facilitated, and the antifouling performance is improved. Meanwhile, the betaine type ionic liquid modified coating provided by the invention has ultralow VOC content (less than 20g/L), does not contain toxic agents such as TBT (tert-butyl-tert-butyl) and the like, is environment-friendly, has good.

The results of the examples show that after the betaine type ionic liquid modified coating provided by the invention is formed into a film, the adhesive force of the paint film can reach 1 level, the flexibility can reach 1mm, the impact resistance is greater than 50 kg-cm, the paint film does not foam and fall off 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 0.29-0.40 mu m/day; after the south China sea area live sea static hanging plate is hung for 9 months, the surface of a paint film is still clean, the surface fouling area is less than 5%, and the paint film shows excellent anti-biofouling characteristic.

In addition, the betaine type ionic liquid modified coating provided by the invention is simple in preparation process and suitable for industrial scale-up production and application.