CN114479620A

CN114479620A - Antifouling and anticorrosive paint capable of being coated underwater and preparation method thereof

Info

Publication number: CN114479620A
Application number: CN202210216399.1A
Authority: CN
Inventors: 李江波; 王震宇; 韩恩厚; 吕晓明; 张良昌; 常峻玮
Original assignee: Institute of Corrosion Science and Technology
Current assignee: Institute of Corrosion Science and Technology
Priority date: 2022-03-07
Filing date: 2022-03-07
Publication date: 2022-05-13

Abstract

The invention belongs to the technical field of ocean engineering antifouling and anticorrosive coatings, and particularly relates to an ocean engineering structure antifouling and anticorrosive coating capable of being coated underwater and a preparation method thereof. The coating comprises A, B two components, wherein the weight of the component A is 3-6 times of that of the component B; the component A is prepared from epoxy resin, toughened epoxy resin, a halloysite pipe loaded with an antifouling agent, liquid rubber, an active diluent, a defoaming agent, a wetting dispersant, a thixotropic agent, a pigment filler and an adhesion promoter, and the component B is prepared from Mannich modified m-xylylenediamine and a polyether amine curing agent. The antifouling and anticorrosive paint is waterproof and moist, and has the advantages of no dispersion during construction, high adhesion and simple construction. The cured coating has excellent antifouling and anticorrosive performance, high flexibility, high impact resistance and high adhesion to the base material. The method can be used for antifouling, anticorrosion and repair engineering of sea-crossing bridges, drilling platforms, oil and gas pipelines, bridge steel piles, deep sea pastures, coastal power plants, ships and the like in marine environments.

Description

Antifouling and anticorrosive paint capable of being coated underwater and preparation method thereof

Technical Field

The invention belongs to the technical field of ocean engineering antifouling and anticorrosive coatings, and particularly relates to an underwater coating ocean engineering structure antifouling and anticorrosive coating and a preparation method thereof.

Background

Ocean engineering facilities, including various offshore steel structures and reinforced concrete structures, such as cross-sea bridges, ports and docks, coastal power plants, submarine pipelines, offshore platforms, marine vessels, and the like, are important infrastructure facilities for the safety and construction of state-of-affairs and civil engineering, national defense. The engineering facilities are large in quantity and wide in scope, and the investment is huge. The annual losses due to biofouling are difficult to estimate, and statistically, billions of dollars are invested each year in anti-fouling worldwide. In recent years, with the pace of ocean development and utilization accelerating, the threat of marine biofouling to ocean engineering facilities is becoming more and more serious, and therefore, how to reasonably and efficiently solve marine biofouling has great significance to national economic development and ocean equipment safety guarantee.

The coating of the antifouling paint on the surface of the ocean engineering facility is an economical and efficient method for solving the fouling problem, the traditional antifouling paint mainly comprises an organic tin type, a self-polishing type and a low surface energy type, but the organic tin type antifouling paint has high toxicity and is forbidden to be used by the international society, the self-polishing type antifouling paint is only suitable for ships capable of rapidly driving, and the efficiency of the ocean engineering facility in a static environment is reduced or even is ineffective. The low surface energy coating has a very low surface energy, on which marine organisms are difficult to attach, and even if the attachment is not firm, the coating is easy to fall off under the action of water flow or other external force. However, the materials generally have the defects of high cost, difficult construction, over-soft coating, low adhesive force, easy damage and the like, and the application of the materials is limited. In recent years, the introduction of natural antifouling agents such as capsaicin, alkaloid, maleimide and the like into paints is a major direction for the development of novel antifouling paints, and these antifouling agents are easily degradable, harmless to the environment and good in antifouling effect. However, the antifouling paint can not be long-acting and is frequently replaced when the paint is quickly released into seawater from the paint along with the scouring of the seawater. Therefore, the development of slow-release coatings with high efficiency and long action time is the focus and difficulty of the current anti-fouling coating research.

Ocean engineering facilities are also exposed to severe corrosive environments, and therefore, the coating is also required to have good corrosion resistance. At present, the common technology is to coat an anticorrosion primer (such as epoxy zinc-rich primer) on the surface of the ocean engineering structure, then coat an antifouling surface layer, and coat an intermediate layer between the anticorrosion primer and the antifouling surface layer. To increase the interaction force between the surface layer and the bottom layer, which undoubtedly increases the construction difficulty and the construction cost. In addition, the antifouling coating needs to be replaced regularly during the long-term use of marine engineering facilities along with the continuous release and complete consumption of the antifouling agent in the coating. However, these parts are generally located in the splash zone and the underwater region, and it is very difficult to replace the parts in an environment isolated from water. Meanwhile, the ocean engineering facilities are generally far away from the land, and the material transportation is difficult. Once the operation is stopped, huge economic losses are caused. Therefore, if a paint can be directly coated in water and achieve ideal antifouling and anticorrosion effects, the antifouling and anticorrosion paint is a breakthrough revolution for marine engineering facilities and has epoch-making significance.

Disclosure of Invention

The invention aims to provide an antifouling and anticorrosive paint capable of being coated underwater and a preparation method thereof. Water and damp environment resistance, no dispersion during construction, high adhesion and simple construction. The cured coating has excellent antifouling and anticorrosive performance, high flexibility, high impact resistance and high adhesion to base material.

In order to achieve the purpose, the invention adopts the technical scheme that:

an antifouling and anticorrosive paint capable of being coated underwater comprises A, B components, wherein the weight of the component A is 3-6 times that of the component B;

the component A is prepared from the following raw materials in parts by weight:

the component B is prepared from the following raw materials in parts by weight:

70-90 parts of Mannich modified m-xylylenediamine

10-30 parts of a polyether amine curing agent.

The antifouling and anticorrosive paint capable of being coated underwater comprises epoxy resin, wherein the epoxy resin is one or a mixture of more than two of bisphenol A epoxy resin E-44, bisphenol A epoxy resin E-51 and bisphenol F epoxy resin NPEF-170; the toughened epoxy resin is one or a mixture of polyurethane modified epoxy resin and acrylic acid modified epoxy resin.

The preparation process of the antifouling and anticorrosive coating capable of being coated underwater and the halloysite pipe loaded with the antifouling agent comprises the following steps: the method comprises the following steps of (1) adopting a halloysite nanotube as a carrier, improving the specific surface area and the cavity volume of the halloysite nanotube by using an etching method, and loading antifouling agent molecules on the halloysite nanotube by using a negative pressure solvent evaporation method; wherein the halloysite tube has a length of 0.5-1 μm and a specific surface area of 26m²The antifouling agent is sodium salicylate; in the halloysite pipe loaded with the antifouling agent, the weight percentage of the antifouling agent, namely the loading rate, is 20-30%.

The antifouling and anticorrosive paint capable of being coated underwater is characterized in that the liquid rubber is one or a mixture of more than two of liquid polysulfide rubber, hydroxyl-terminated silicon rubber and carboxyl-terminated nitrile rubber; the reactive diluent is a bifunctional epoxy diluent.

The antifouling and anticorrosive paint capable of being coated underwater has the reactive diluent being one or the mixture of neopentyl glycol diglycidyl ether and butanediol diglycidyl ether.

The anti-fouling and anti-corrosion coating capable of being coated underwater is characterized in that the defoaming agent is selected from a KMT-2233 defoaming agent or a BYK-05 defoaming agent; the wetting dispersant is Luborun Solsperse19000 dispersant; the thixotropic agent is BYK-1958 type bentonite; the pigment and filler is one or a mixture of more than two of titanium dioxide, superfine quartz powder, talcum powder, precipitated barium sulfate, sericite and acicular wollastonite powder; the adhesion promoter is a coupling agent KH-560.

The antifouling and anticorrosive paint capable of being coated underwater is characterized in that Mannich modified m-xylylenediamine is prepared from nonylphenol, m-xylylenediamine and 30-40 wt% formaldehyde aqueous solution, wherein the weight ratio of the nonylphenol to the m-xylylenediamine to the 30-40 wt% formaldehyde aqueous solution is (2-2.5) to (4-4.5) to 1; the polyether amine curing agent is Henschel polyether amine D2000.

A preparation method of an antifouling and anticorrosive paint capable of being coated underwater comprises the following specific steps:

the method comprises the following steps: mixing 24-34 parts of epoxy resin, 5-20 parts of toughened epoxy resin, 4-12 parts of liquid rubber and 2-6 parts of reactive diluent, and dispersing for 5-10 min at the rotating speed of 800-1000 r/min to obtain a mixed solution obtained in the first step;

step two: adding 8-15 parts of the halloysite tubes loaded with the antifouling agents into the mixed solution in the first step, and dispersing for 10-15 min at the rotating speed of 1000-1500 r/min to obtain mixed solution in the second step;

step three: adding 0.5-2 parts of wetting dispersant and 0.5-2 parts of thixotropic agent into the mixed solution in the second step, and dispersing for 5-10 min at the rotating speed of 500-800 r/min to obtain the mixed solution in the third step;

step four: adding 40-50 parts of pigment and filler into the mixed solution in the third step, and dispersing for 10-15 min at the rotating speed of 1000-1200 r/min to obtain the mixed solution in the fourth step;

step five: adding 0.5-2 parts of defoaming agent and 0.5-2 parts of adhesion promoter into the mixed solution obtained in the fourth step, and dispersing for 5-10 min at the rotating speed of 1000-1200 r/min to obtain mixed solution obtained in the fifth step;

step six: adding the mixed solution obtained in the fifth step into a three-roll grinder for grinding to obtain a component A of the antifouling and anticorrosive paint capable of being coated underwater;

step seven: mixing 70-90 parts of Mannich modified m-xylylenediamine and 10-30 parts of polyetheramine D2000, and stirring and dispersing at the rotating speed of 500-800 r/min for 5-10 min to obtain an antifouling and anticorrosive paint B component capable of being coated underwater;

step eight: the component A and the component B are mixed according to the weight ratio (3-6): 1, mixing and stirring uniformly to obtain the antifouling and anticorrosive paint capable of being coated underwater.

In the second step of the preparation method of the antifouling and anticorrosive paint capable of being coated underwater, the preparation process of the halloysite pipe loaded with the antifouling agent is as follows:

(1) adding 1-5 parts by weight of halloysite nanotubes into 100 parts of 1-3 mol/L sulfuric acid solution, stirring for 48 hours, filtering by using 0.1 mu m nitrocellulose filter paper, washing by using deionized water, and drying at 60-80 ℃ to obtain etched halloysite nanotubes;

(2) adding 1-5 parts by weight of etched halloysite nanotubes into 10 parts by weight of an antifouling agent saturated solution, mechanically stirring, and adjusting the pH value to 8 by using a potassium hydroxide aqueous solution with the concentration of 0.5-1.5 mol/L;

(3) and (3) drying the solution obtained in the step (2) in vacuum at 80-120 ℃ for 24h by adopting a negative pressure solvent evaporation method, washing antifouling agent molecules on the surface by using deionized water, and drying at 60-80 ℃ to obtain the halloysite tube loaded with the antifouling agent.

In the seventh step, the preparation process of the Mannich modified m-xylylenediamine is as follows:

(1) mixing nonyl phenol and m-xylylenediamine, and stirring for 5-10 min at 70-90 ℃;

(2) dripping 30-40 wt% of formaldehyde water solution into a mixed solution of nonyl phenol and m-xylylenediamine, heating to 80-120 ℃ after complete dripping, and carrying out condensation reflux for 4-6 h;

(3) and (4) vacuumizing and dehydrating for 20-30 min to obtain the Mannich modified m-xylylenediamine.

The principle of the invention is as follows: the specific surface area and the cavity volume of the halloysite nanotube are further improved by an etching method, and the loading rate of the antifouling agent molecules in the halloysite nanotube is obviously improved by combining a negative pressure solvent evaporation method. Adding the antifouling agent loaded halloysite nanotube into a coating matrix, and putting the coating matrix in serviceIn the process, the antifouling agent molecules in the halloysite can be slowly released into the matrix, so that the long-term antifouling performance of the coating is endowed. Meanwhile, Mannich modified m-xylylenediamine is selected as the curing agent, and C is contained in the curing agent molecule in the curing agent₉The high-hydrophobicity groups such as the aliphatic chain and the benzene ring can improve the hydrophobicity of the molecules, so that the high-hydrophobicity organic silicon polymer has good working performance in a wet interface and underwater application, and has good adhesive force with the surface of a base material.

Compared with the prior art, the invention has the following advantages:

(1) in the invention, firstly, the antifouling agent molecules are loaded in the halloysite nanotube, and then the halloysite nanotube is introduced into a coating system. Not only endows the coating with good antifouling performance, but also enables the antifouling agent to be slowly released from the halloysite nanotube, thereby achieving the long-term antifouling performance.

(2) At present, functional materials are loaded in halloysite, and a vacuum adsorption method is mainly adopted. However, the load factor of the vacuum adsorption method is not high, and the vacuum adsorption method needs to be carried out for a plurality of times of circulation, and the process is complex (such as Chinese patent CN 110307528A). In the invention, the halloysite nanotube is etched firstly, so that the specific surface area and the cavity volume of the halloysite nanotube are improved. Meanwhile, the traditional vacuum adsorption method is replaced by a method of evaporating the solvent under negative pressure. Therefore, the antifouling agent molecules have higher loading rate in the halloysite nanotubes, and the preparation process is simpler and more convenient. The loading rate of the antifouling agent in halloysite can reach 28.5 wt%.

(3) The invention aims at the problem that the traditional antifouling paint is limited in use because the parts of the marine engineering structure facility needing antifouling are generally positioned in a splash zone and an underwater zone and are often required to be constructed in water. Mannich modified m-xylylenediamine is used as a main curing agent, so that underwater construction of the antifouling paint is realized, and the antifouling paint has good adhesive force with a base material. The product has no solvent, low VOC and environmental protection, and can be applied to the antifouling, anticorrosion and restoration of engineering facilities which are in service in the marine environment for a long time.

(4) The halloysite tube has high specific surface area and cavity volume and high loading rate of antifouling agent molecules, can slowly release the antifouling agent molecules when being added into an anticorrosive coating, and can improve the long-term antifouling performance of the coating.

Drawings

FIG. 1 is a graph showing the release rate of molecules of the antifouling agent in examples 1 and 2. In the figure, the abscissa time (h) represents time, and the ordinate Release (%) represents Release rate.

Detailed Description

The present invention will be further understood with reference to the following specific examples, which are not intended to limit the invention.

Example 1

In this example, the preparation process of the antifouling and anticorrosive paint is as follows:

(1) preparation of antifouling agent-loaded halloysite tubes:

adding 1 part of halloysite nanotube into 100 parts of sulfuric acid solution with the concentration of 2mol/L according to parts by weight, stirring for 48 hours, filtering by using 0.1 mu m nitrocellulose filter paper, washing by using deionized water, and drying at 70 ℃ to obtain the etched halloysite nanotube. 1 part of the etched halloysite nanotubes was added to 10 parts of a saturated aqueous solution of sodium salicylate (. apprxeq.1.17 g/mL), mechanically stirred, and the pH was adjusted to 8 with an aqueous solution of potassium hydroxide at a concentration of 1 mol/L. And (3) drying the solution in vacuum at 100 ℃ for 24h, washing sodium salicylate molecules on the surface by using deionized water, and drying at 70 ℃ to obtain the halloysite tube HNT-SA-1 loaded with the antifouling agent.

(2) The preparation of the antifouling and anticorrosive paint capable of being coated underwater comprises the following steps:

according to parts by weight, firstly 25 parts of epoxy resin NPEF170, 12 parts of 102C-L high-elasticity epoxy resin of Hengchu technology (Thizhou) Co., Ltd., 5 parts of liquid polysulfide rubber and 4 parts of neopentyl glycol diglycidyl ether are mixed and dispersed for 5min at the rotating speed of 900 r/min. Then 10 parts of halloysite tube HNT-SA-1 loaded with the antifouling agent is added and dispersed for 15min at the rotating speed of 1500 r/min. Then 1 part of LubomoistSolsperse 19000 dispersant and 1 part of bentonite type BYK-1958 as thixotropic agent were added theretoDispersing for 5min at the rotating speed of 500 r/min. Then 10 parts of rutile type titanium dioxide with the granularity of 0.2-0.3 mu m, 11 parts of superfine quartz powder with the granularity of 1250 meshes, 10 parts of talcum powder with the granularity of 800 meshes and 10 parts of precipitated barium sulfate with the granularity of 400 meshes are added, and the mixture is dispersed for 15min at the rotating speed of 1200 r/min. Finally, adding 1 part of defoaming agent KMT-2233 and 1 part of coupling agent KH-560, dispersing for 10 minutes at the rotating speed of 1000r/min, adding a three-roll grinder to grind for one time to obtain the component A of the antifouling and anticorrosive paint A capable of being coated underwater₁。

Mixing 32 parts of nonyl phenol and 55 parts of m-xylylenediamine in parts by weight, stirring at 80 ℃ for 5min, dropwise adding 13 parts of 30 wt% formaldehyde aqueous solution, heating to 100 ℃ after complete dropwise addition, and carrying out condensation reflux for 4 h. And finally, dehydrating in vacuum for 20min to obtain the Mannich modified m-xylylenediamine m-MXDA-1. Mixing 75 parts of m-MXDA-1 modified m-xylylenediamine with 25 parts of Henstann polyether amine D2000 curing agent, stirring and dispersing at the rotating speed of 500r/min for 5min to obtain component B of the underwater coating antifouling and anticorrosive paint B₁。

Taking 80 parts of A by weight₁And 20 parts of B₁Mixing and stirring evenly to prepare the antifouling and anticorrosive paint C capable of being coated underwater₁。

The specific surface area and pore volume of the antifouling agent-loaded halloysite nanotubes before and after acid etching and in example 1 were tested using a physical adsorption tester. The specific surface area before etching was 26m²(ii)/g, pore volume 0.15 ml/g; the specific surface area after etching was 34m²The pore volume was 0.22ml/g, indicating that the acid etching method can increase the specific surface area and pore volume of the halloysite tube. The specific surface area of the loaded antifouling agent halloysite nanotube HNT-SA-1 is 18m²The pore volume was 0.17 ml/g. Indicating that the antifouling agent can be loaded into the halloysite nanotubes. The load rate of the antifouling agent is tested by adopting a thermal weight loss instrument, and the load rate can reach 28.5 wt%.

At room temperature, coating the surface with an antifouling and anticorrosive coating C₁After the iron sheet is soaked in the vibrio natriegens solution for 7 days (d), the stained area of the surface of the iron sheet is tested, and the stained area is 0.15%. Antifouling and anticorrosive coating capable of underwater coatingMaterial C₁Has good antifouling performance.

Example 2

(1) preparation of unetched antifouling agent-loaded halloysite tubes:

according to the weight portion, 1 portion of etched halloysite nanotube is added into 10 portions of sodium salicylate saturated aqueous solution (approximately equal to 1.17g/mL), mechanically stirred, and the pH value is adjusted to 8 by potassium hydroxide aqueous solution with the concentration of 1 mol/L. And (3) drying the solution in vacuum at 100 ℃ for 24h, washing sodium salicylate molecules on the surface by using deionized water, and drying at 70 ℃ to obtain the halloysite tube HNT-SA-2 loaded with the antifouling agent.

(2) Preparing the antifouling anticorrosive paint:

referring to the preparation method of the coating in example 1, except for replacing HNT-SA-1 of the halloysite pipe loaded with the antifouling agent with HNT-SA-2, the prepared underwater-coatable antifouling and anticorrosive coating has A component₂。

The specific surface area and pore volume of the antifouling agent-loaded halloysite nanotubes of example 2 were tested using a physical adsorption tester. The specific surface area of the loaded antifouling agent halloysite nanotube HNT-SA-2 is 18m²The pore volume was 0.13 ml/g. The loading rate of the antifouling agent is tested by adopting a thermal weight loss instrument, the loading rate is 18.5 wt% and is lower than that of HNT-SA-1 in the embodiment 1, and the loading rate of the etched halloysite nanotube can be obviously improved.

At room temperature, coating the surface with an antifouling and anticorrosive coating C₂After the iron sheet is soaked in the vibrio natriegens solution for 7 days, the stained area of the surface of the iron sheet is tested, and the stained area is 0.35%. Antifouling anticorrosive paint C capable of underwater coating₂Also has good antifouling properties, but weak antifouling properties.

Example 3

reference is made to the preparation of the coating in example 1, except that the antifoulant-loaded halloysite tube HNT-SA-1 is replaced byA component A of the prepared antifouling and anticorrosive coating capable of being coated underwater is A of halloysite pipe HNT which is not etched and is not loaded with antifouling agent₃。

At room temperature, coating the surface with an antifouling and anticorrosive coating C₃After the iron sheet is soaked in the vibrio natriegens solution for 7 days, the stained area of the surface of the iron sheet is tested, and the stained area is 45%. Visible, underwater coating antifouling and anticorrosive paint C₃The antifouling property of (A) is weak.

Example 4

referring to the preparation method of the dope in example 1, except for replacing 10 parts of the saturated aqueous solution of sodium salicylate (. apprxeq.1.17 g/mL) with 3 parts of the saturated aqueous solution of sodium salicylate, the underwater-coatable antifouling and anticorrosive dope A prepared has a component A₄。

At room temperature, coating the surface with an antifouling and anticorrosive coating C₃After the iron sheet is soaked in the vibrio natriegens solution for 7 days, the stained area of the surface of the iron sheet is tested, and the stained area is 0.13%. At room temperature, coating the surface with an antifouling and anticorrosive coating C₁And C₄The iron sheet is soaked in deionized water, and after a period of time, the concentration of salicylic acid released by the coating is calculated by adopting an ultraviolet spectrophotometer, and the result is shown in table 1, so that the release rate of the antifouling agent molecules can be slowed down and the service life of the antifouling coating can be prolonged by loading the antifouling agent molecules into the halloysite tube.

Example 5

In this embodiment, the preparation process of the antifouling and anticorrosive paint is as follows:

(1) preparation of antifouling agent-loaded halloysite tubes:

adding 2 parts by weight of halloysite nanotubes into 100 parts by weight of sulfuric acid solution with the concentration of 2mol/L, stirring for 48 hours, filtering by using 0.1 mu m nitrocellulose filter paper, washing by using deionized water, and drying at 70 ℃ to obtain etched halloysite nanotubes. 4 parts of etched halloysite nanotubes are added to 10 parts of a saturated aqueous solution of sodium salicylate (. apprxeq.1.17 g/mL), mechanically stirred and the pH adjusted to 8 with an aqueous solution of potassium hydroxide at a concentration of 1 mol/L. And (3) drying the solution in vacuum at 100 ℃ for 24h, washing sodium salicylate molecules on the surface by using deionized water, and drying at 70 ℃ to obtain the halloysite tube HNT-SA-3 loaded with the antifouling agent.

according to parts by weight, firstly 20 parts of epoxy resin NPEF170, 7 parts of epoxy resin E44, 10 parts of 102C-3 polyurethane modified epoxy resin of Hengchu technology (Tazhou) Co., Ltd., 5 parts of hydroxyl-terminated silicone rubber and 2 parts of butanediol diglycidyl ether are mixed and dispersed for 5min at the rotating speed of 900 r/min. Then 11 parts of halloysite tube HNT-SA-3 loaded with the antifouling agent is added and dispersed for 15min at the rotating speed of 1500 r/min. Then, 0.5 part of Lubo moist Solsperse19000 dispersant and 1 part of thixotropic agent BYK-1958 type bentonite were added thereto and dispersed at a rotation speed of 500r/min for 5 min. Then 12 parts of rutile type titanium dioxide with the granularity of 0.2-0.3 mu m, 8 parts of superfine quartz powder with the granularity of 1250 meshes, 11 parts of talcum powder with the granularity of 800 meshes and 12 parts of precipitated barium sulfate with the granularity of 400 meshes are added and dispersed for 15min at the rotating speed of 1200 r/min. Finally, 0.5 part of defoaming agent BYK-05 and 0.5 part of coupling agent KH-560 are added, dispersed for 10 minutes at the rotating speed of 1000r/min, and added into a three-roll grinder to grind for one time to obtain the component A of the antifouling and anticorrosive paint A capable of being coated underwater₅。

Mixing 30 parts of nonyl phenol and 56.5 parts of m-xylylenediamine in parts by weight, stirring at 80 ℃ for 5min, dropwise adding 13.5 parts of 30 wt% formaldehyde aqueous solution, heating to 100 ℃ after complete dropwise addition, and carrying out condensation reflux for 4 h. And finally, dehydrating in vacuum for 20min to obtain the Mannich modified m-xylylenediamine m-MXDA-2. 80 parts of m-MXDA-2 modified m-xylylenediamine and 20 parts of Henstann-polyetheramine D2000 curing agent are mixed, stirred and dispersed for 5min at the rotating speed of 500r/min to obtain a component B of the underwater coating antifouling and anticorrosive paint B₅。

Taking 78 parts of A by weight₅And 22 parts of B₅Mixing and stirring evenly to prepare the antifouling and anticorrosive paint C capable of being coated underwater₅。

The physical adsorption tester is adopted to load the antifouling agent halloysite nanotube H of example 5The specific surface area of NT-SA-3 was 19m²The pore volume was 0.18 ml/g. Indicating that the antifouling agent can be loaded into the halloysite nanotubes. The load rate of the antifouling agent is tested by adopting a thermal weight loss instrument, and the load rate can reach 26.4 wt%.

At room temperature, coating the surface with an antifouling and anticorrosive coating C₅After the iron sheet is soaked in a vibrio natriegens solution for 7 days, the fouling area of the surface of the iron sheet is tested, and the fouling area is 0.17%. Antifouling anticorrosive paint C capable of underwater coating₅Has good antifouling performance.

Example 6

(1) preparation of antifouling agent-loaded halloysite tubes:

adding 3 parts by weight of halloysite nanotubes into 100 parts by weight of sulfuric acid solution with the concentration of 2mol/L, stirring for 48 hours, filtering by using 0.1 mu m nitrocellulose filter paper, washing by using deionized water, and drying at 70 ℃ to obtain etched halloysite nanotubes. 5 parts of etched halloysite nanotubes are added to 10 parts of a saturated aqueous solution of sodium salicylate (. apprxeq.1.17 g/mL), mechanically stirred and the pH adjusted to 8 with an aqueous solution of potassium hydroxide at a concentration of 1 mol/L. And (3) drying the solution in vacuum at 100 ℃ for 24h, washing sodium salicylate molecules on the surface by using deionized water, and drying at 70 ℃ to obtain the halloysite tube HNT-SA-4 loaded with the antifouling agent.

according to parts by weight, 15 parts of epoxy resin NPEF170, 5 parts of epoxy resin E44, 8 parts of epoxy resin E51, 6 parts of 102C-3 polyurethane modified epoxy resin of Hengchu technology (Tazhou) Co., Ltd., 6 parts of carboxyl-terminated nitrile rubber and 3 parts of butanediol diglycidyl ether are mixed and dispersed for 5min at the rotating speed of 900 r/min. Then 13 parts of halloysite tube HNT-SA-4 loaded with the antifouling agent is added and dispersed for 15min at the rotating speed of 1500 r/min. 2 parts of LubomoistSolsperse 19000 dispersant and 1 part of bentonite BYK-1958 as a thixotropic agent were added thereto, and the mixture was dispersed at a rotation speed of 500r/min for 5 min. Then adding 9 parts of particle size of 0.2 to E0.3 mu m rutile type titanium dioxide, 8 parts of superfine quartz powder with the granularity of 1250 meshes, 11 parts of talcum powder with the granularity of 800 meshes and 12 parts of precipitated barium sulfate with the granularity of 400 meshes, and the materials are dispersed for 15min at the rotating speed of 1200 r/min. Finally, 1.5 parts of defoaming agent BYK-05 and 1.5 parts of coupling agent KH-560 are added, dispersed for 10 minutes at the rotating speed of 1000r/min, and added into a three-roll grinder to grind for one time to obtain the component A of the antifouling and anticorrosive paint A capable of being coated underwater₆。

Mixing 30 parts of nonyl phenol and 56 parts of m-xylylenediamine in parts by weight, stirring at 80 ℃ for 5min, dropwise adding 14 parts of 30 wt% formaldehyde aqueous solution, heating to 100 ℃ after complete dropwise addition, and carrying out condensation reflux for 4 h. And finally, dehydrating in vacuum for 20min to obtain the Mannich modified m-xylylenediamine m-MXDA-3. Mixing 76 parts of m-MXDA-3 modified m-xylylenediamine with 24 parts of Henstann polyether amine D2000 curing agent, stirring and dispersing at the rotating speed of 500r/min for 5min to obtain a component B of the solvent-free antifouling anticorrosive paint B capable of being coated underwater₆。

Taking 82 parts of A by weight₆And 18 parts of B₆Mixing and stirring evenly to prepare the antifouling and anticorrosive paint C capable of being coated underwater₆。

The specific surface area of the halloysite nanotube HNT-SA-4 loaded with the antifouling agent in example 6 is 18m by adopting a physical adsorption tester²The pore volume was 0.17 ml/g. Indicating that the antifouling agent can be loaded into the halloysite nanotubes. The load rate of the antifouling agent is tested by adopting a thermal weight loss instrument, and the load rate is 23.7 wt%.

At room temperature, coating the surface with a solvent-free antifouling anticorrosion paint C₆After the iron sheet is soaked in the vibrio natriegens solution for 7 days, the stained area of the surface of the iron sheet is tested, and the stained area is 0.16%. Antifouling anticorrosive paint C capable of underwater coating₆Has good antifouling performance.

The antifouling and anticorrosive coatings of examples 1, 5 and 6 were tested for their performance, and the results were as follows:

as can be seen from the performance test results in the above table, the antifouling and anticorrosive coatings which can be coated underwater in examples 1, 5 and 6 have good adhesion with the substrate during underwater construction, and the coatings are resistant to bending, impact and salt water immersion and are resistant to penetration of chloride ions. The raw materials adopted in the invention basically have no solvent, low VOC and environmental protection, so the product can be applied to the antifouling, anticorrosion and restoration of engineering facilities which are in service in marine environment for a long time.

As shown in fig. 1, from the release rate curves of the antifouling agent molecules in example 1 and example 2, it can be seen that the coating in both examples is capable of releasing the antifouling agent molecules, indicating that the antifouling agent molecules can be loaded into the halloysite nanotubes. However, the release amount of the antifouling agent in example 1 is more in the same time, which shows that the loading rate of the antifouling agent molecules can be remarkably improved by etching the halloysite nanotubes.

Claims

1. An antifouling and anticorrosive paint capable of being coated underwater is characterized by comprising A, B components, wherein the weight of the component A is 3-6 times that of the component B;

70-90 parts of Mannich modified m-xylylenediamine

10-30 parts of a polyether amine curing agent.

2. The antifouling anticorrosive paint capable of underwater coating according to claim 1, wherein the epoxy resin is one or a mixture of two or more of bisphenol a epoxy resin E-44, bisphenol a epoxy resin E-51 and bisphenol F epoxy resin NPEF-170; the toughened epoxy resin is one or a mixture of two of polyurethane modified epoxy resin and acrylic acid modified epoxy resin.

3. The underwater paintable antifouling anticorrosive paint according to claim 1, wherein the halloysite pipe loaded with the antifouling agent is prepared by the following process: the method comprises the following steps of (1) adopting a halloysite nanotube as a carrier, improving the specific surface area and the cavity volume of the halloysite nanotube by using an etching method, and loading antifouling agent molecules on the halloysite nanotube by using a negative pressure solvent evaporation method; wherein the halloysite tube has a length of 0.5-1 μm and a specific surface area of 26m²The antifouling agent is sodium salicylate; in the halloysite pipe loaded with the antifouling agent, the weight percentage of the antifouling agent, namely the loading rate, is 20-30%.

4. The antifouling paint which can be applied underwater according to claim 1, wherein the liquid rubber is one or a mixture of two or more of liquid polysulfide rubber, hydroxyl-terminated silicone rubber and carboxyl-terminated nitrile rubber; the reactive diluent is a bifunctional epoxy diluent.

5. The underwater paintable antifouling and anticorrosive paint according to claim 4, wherein the reactive diluent is one or a mixture of neopentyl glycol diglycidyl ether and butanediol diglycidyl ether.

6. The underwater paintable antifouling anticorrosive paint according to claim 1, wherein the antifoaming agent is selected from KMT-2233 antifoaming agent or BYK-05 antifoaming agent; the wetting dispersant is Luborun Solsperse19000 dispersant; the thixotropic agent is BYK-1958 type bentonite; the pigment and filler is one or a mixture of more than two of titanium dioxide, superfine quartz powder, talcum powder, precipitated barium sulfate, sericite and acicular wollastonite powder; the adhesion promoter is a coupling agent KH-560.

7. The antifouling and anticorrosive paint capable of being coated underwater according to claim 1, wherein the Mannich modified m-xylylenediamine is prepared from nonylphenol, m-xylylenediamine, and a 30-40 wt% formaldehyde aqueous solution, wherein the weight ratio of the nonylphenol, the m-xylylenediamine, and the 30-40 wt% formaldehyde aqueous solution is (2-2.5) to (4-4.5) to 1; the polyether amine curing agent is Henschel polyether amine D2000.

8. A method for preparing the antifouling and anticorrosive paint capable of being coated underwater according to any one of claims 1 to 7, which comprises the following steps:

step five: adding 0.5-2 parts of defoaming agent and 0.5-2 parts of adhesion promoter into the mixed solution in the step four, and dispersing for 5-10 min at the rotating speed of 1000-1200 r/min to obtain mixed solution in the step five;

9. The method for preparing an antifouling and anticorrosive paint which can be applied underwater according to claim 8, wherein in the second step, the halloysite pipe loaded with the antifouling agent is prepared by the following steps:

10. The method for preparing an underwater paintable antifouling and anticorrosive paint according to claim 8, wherein in step seven, the Mannich modified m-xylylenediamine is prepared as follows: