Lignin-based antifouling paint for ships and preparation method of lignin-based antifouling paint

Abstract

The invention belongs to the technical field of paint preparation, and particularly relates to lignin-based antifouling paint for ships and a preparation method of the lignin-based antifouling paint. The formula of the antifouling paint disclosed by the invention is a single-component formula and specifically comprises 20-25% of an alcohol-soluble lignin solution, 10-15% of butylated phenolic resin, 15-20% of pigment filler, 0.5-1% of fumed silica, 3-5% of a low-boiling-point aldehyde compound, 20-25% of a modified phenolic resin solution, 1-2% of fluorocarbon resin, 1-2% of aromatic amine, 10-15% of epoxy resin and 3-5% of a solvent. 0.5-1% of oxidized polyethylene wax slurry, and 1-2% of an organosilicon epoxy curing agent. During construction, 2-3% of ammonia water is added into the coating, the coating can be sprayed after being stirred for 30 minutes, the coating is cured for 7 days at normal temperature after being sprayed, the coating meets the standard GB / T 7789-2007, and microbial adsorption and coating abrasion cannot occur when the coating sails slowly or is soaked in seawater.

Description

Technical Field

[0001] The invention belongs to the technical field of paint preparation, and particularly relates to a lignin-based antifouling paint for ships and a preparation method thereof. Background Art

[0002] Antifouling paint in ship coatings has a non-negligible value for the use of ship coatings, which determines the degree of power loss of ships during driving. When ships are driving at low speed or docking at ports, algae are prone to growth and adsorption, and will gradually increase, resulting in increased power consumption during the ship's driving. In severe cases, the power cost increases by 1-2 times. Ships must enter the port to find a professional team to clean the attached organisms on the bottom of the ship. The biggest function of ship antifouling paint is to reduce the increase in power costs caused by the growth of barnacles and algae on the bottom of the ship when the ship is driving at low speed or docking at the port. Traditional ship coating design ideas use copper acrylate resin and metal salts of pyridinethione as coatings for painting. After painting, copper acrylate resin and pyridinethione are toxic to algae and barnacles. During driving, the coating gradually wears away or hydrolyzes to release resin and toxic substances, and the antifouling coating gradually becomes thinner. Now the world is restricting the use of such toxic substances. Akzo Nobel developed the first generation of silicon-containing antifouling paint in the 1980s. This type of coating uses a combination of silicone resins to form an antifouling paint. Although this type of antifouling paint uses low surface tension to reduce the adhesion of algae and barnacles, the recoating performance of this type of coating is poor.

[0003] Therefore, how to provide an antifouling paint for ships with excellent coating performance and good recoating performance is a technical problem that needs to be solved urgently by those skilled in the art. Summary of the invention

[0004] In view of this, the present invention discloses a lignin-based antifouling paint for ships and a preparation method thereof.

[0005] It should be noted that the lignin-based antifouling paint for ships disclosed in the present invention has the following excellent properties:

[0006] (1) The antifouling and sterilization of the chemical structure prevents the growth of microorganisms, but it can also prevent the toxic substances in the traditional acrylic copper antifouling paint from being continuously stripped and released into the seawater. The mechanism of traditional antifouling paint is that substances are continuously stripped and dissolved into the seawater, resulting in microorganisms adsorbed on the coating surface. They will also peel off from the ship as the coating peels off;

[0007] (2) The popular silicon-containing antifouling paint in recent years has the characteristics of low surface tension, and microorganisms and barnacles cannot firmly adhere. However, once the silicon-containing antifouling paint is partially scratched or damaged, it is difficult to re-coat. The antifouling paint prepared by the present invention has chemical structure antifouling and sterilization and recoatability. The surface structure of the coating contains organic fluorine segments and organic silicon segments, both of which have antifouling functions. It also contains Schiff bases, phenolic hydroxyl groups of phenolic aldehydes, hydroxymethyl groups and other highly reactive structures, so it can be re-coated.

[0008] In order to achieve the above object, the present invention adopts the following technical solution:

[0009] The first technical purpose of the present invention is to provide a lignin-based antifouling paint for ships, wherein the antifouling paint comprises the following components by mass percentage:

[0010] Alcohol soluble lignin solution 20-25%;

[0011] Butyl etherified phenolic resin 10-15%;

[0012] Pigments and fillers 15-20%;

[0013] Fumed silica 0.5-1%;

[0014] Low boiling point aldehyde compounds 3-5%;

[0015] Modified phenolic resin solution 20-25%;

[0016] Fluorocarbon resin 1-2%;

[0017] Aromatic amines 1-2%;

[0018] Epoxy resin 10-15%;

[0019] Solvent 3-5%;

[0020] Oxidized polyethylene wax slurry 0.5-1%;

[0021] Silicone epoxy curing agent 1-2%.

[0022] Optionally, the alcohol-soluble lignin solution is a lignin solution with a solid content of 50% dissolved in commercially available ethanol.

[0023] Optionally, the butylated phenolic resin adopts a phenolic resin with a lower degree of etherification, such as Shandong Shengquan's CR107 and CR113 with a solid content of 75-80%; the color filler adopts a corrosion-resistant filler, specifically a combination of 1250 mesh wollastonite powder, 800 mesh talcum powder, titanium dioxide, chrome green, iron red, and iron yellow to achieve covering and filling; the fumed silica adopts one of A200, R972, and R202.

[0024] Optionally, the low-boiling-point aldehyde compound has a flash point of ≤40°C and a boiling point of 45-75°C, specifically glyoxal, isobutyraldehyde, and n-butyraldehyde.

[0025] Optionally, the preparation method of the modified phenolic resin is as follows:

[0026] An ethanol-based basic phenolic resin is added into a reaction kettle, bisphenol S is added according to 10% of the mass of the ethanol-based basic phenolic resin, a zinc acetate catalyst is added according to 0.2-0.3% of the mass of the ethanol-based basic phenolic resin, 65% of p-hydroxybenzenesulfonic acid is added according to 0.1-0.2% of the mass of the ethanol-based basic phenolic resin, and 20% of butanol as a solvent based on the mass of the ethanol-based basic phenolic resin is added, and then the mixture is reacted at 90-100° C. for 40-50 minutes, and then a mixed solvent is added to prepare a phenolic resin with a solid content (mass) of 50%.

[0027] Furthermore, the ethanol-based basic phenolic resin is 2130 phenolic resin; and the mixed solvent is prepared by mixing ethylene glycol butyl ether and butanol in a mass ratio of 1:1.

[0028] It should be noted that the solid content test method calculates the mass solid content according to the residual mass tested at 105℃ / 60min, that is, a small amount of 3-10 grams of synthetic phenolic resin is taken to determine the mass m1, and then placed in an oven at 105℃ for 60 minutes to obtain the resin mass m2. When m2 / m1=50%, it is the modified phenolic resin for standby use.

[0029] Optionally, the fluorocarbon resin adopts Daikin GK570 resin with good weather resistance and containing alcoholic hydroxyl groups; the aromatic amine adopts meta-xylylenediamine, aniline, etc.; the epoxy resin adopts a small molecule epoxy resin with a functionality of 1.9-3, specifically Nan Ya's EL-128 resin, 170 resin, and EPALLOY 8240E phenolic epoxy resin.

[0030] Optionally, the solvent is an ester solvent, specifically butyl acetate and ethyl acetate; the oxidized polyethylene wax slurry is 202P or 202SP from Hemmings; the silicone epoxy curing agent is G-002, G-003, G-004 from Hangzhou Yipeng New Materials Co., Ltd.

[0031] It is worth noting that, in the present invention, alcohol lignin reacts with butylated phenolic formaldehyde, aldehydes and fillers through shear reaction, so that butylated phenolic resin reacts with lignin phenolic groups to form butylated phenolic formaldehyde containing lignin structure, and the phenolic formaldehyde contains butylated hydroxymethyl, hydroxymethyl and lignin structure; then the modified phenolic formaldehyde is introduced because the density of hydroxymethyl functional groups in the modified phenolic formaldehyde is large, the fluorocarbon resin is introduced because the hydroxymethyl of the phenolic formaldehyde can react with the hydroxyl of the fluorocarbon resin, so that the fluorocarbon structure is introduced into the modified phenolic formaldehyde and the butylated phenolic formaldehyde of the lignin structure, thereby improving the weather resistance of the phenolic resin, and the aromatic amine is introduced because the hydroxymethyl of the phenolic formaldehyde reacts with the aromatic amine to form a high The polar Schiff base structure reduces the hydroxymethyl content in the system and improves the stability of the coating. The Schiff base structure can catalyze the reaction of epoxy and phenolic hydroxyl groups, improving the poor alkali resistance caused by the excessive phenolic hydroxyl content in the system. The introduction of silicone epoxy curing agent is that the silicone epoxy curing agent has an amino structure and silicone segments. The amino group can react with the hydroxymethyl of the phenolic resin to achieve the successful access of the silicone chain to the phenolic structure. The entire coating resin part contains lignin structure, butylated hydroxymethyl structure, a small amount of incompletely reacted epoxy structure, phenolic hydroxyl reaction, Schiff base structure, fluorocarbon molecular chain structure, and silicone segments. The function of oxidized polyethylene wax slurry is to improve thixotropy. Adding ammonia water during construction can allow water to decapsulate the butylated structure in phenolic form to form a Schiff base structure, which further catalyzes the epoxy structure to react with the phenolic hydroxyl of phenolic form, and the decapsulated hydroxymethyl can react with the hydroxyl after the epoxy ring is opened continuously, and the hydroxymethyl can also react with the hydroxymethyl at room temperature, thereby achieving room temperature curing to form a high adhesion coating. There are fluorocarbon molecular segments and silicone segments with low surface tension on the surface of the coating, as well as highly polar Schiff base structures and a small amount of highly polar hydroxymethyl and hydroxyl structures. The Schiff base structure naturally has a bactericidal function. This coating has both the physical antifouling function of low surface tension of Akzo Nobel's silicone resin antifouling paint and the chemical structure antibacterial function of traditional antifouling paint.

[0032] The second technical purpose of the present invention is to provide a method for preparing the lignin-based antifouling paint for ships as described above, the method specifically comprising the following steps:

[0033] First, an alcohol-soluble lignin solution, a butylated phenolic resin, a pigment filler, a fumed silica and a low-boiling aldehyde compound are fully mixed and stirred at 45-55°C / 40-50min, a modified phenolic resin solution and a fluorocarbon resin are added to the mixed solution and stirred for 45-55°C / 30-40min, then an aromatic amine is added and stirred for 45-55°C / 30-4-min, then an epoxy resin and a solvent are added and stirred for 45-55°C / 30-40min, an oxidized polyethylene wax slurry and an organosilicon epoxy curing agent are added and stirred for 40-50°C / 30-40min, the solvent loss is determined and the solvent is supplemented, and finally the lignin-based antifouling paint for ships is obtained;

[0034] The supplementary mixed solvent is prepared by mixing ethylene glycol butyl ether and butyl acetate in a mass ratio of 1:1.

[0035] It should be noted that during construction, 2-3% ammonia water is added to the prepared lignin-based antifouling paint for ships, and the mixture is stirred for 20-30 minutes before spraying.

[0036] Moreover, the wet film is 120-180 microns, the dry film is 60-80 microns, and after curing at room temperature for 7 days, the test performance meets the coating standard GB / T 7789-2007, and there will be no microbial adsorption and coating wear during slow sailing or immersion in seawater; the coating surface tension is ≤30 dynes; the coating meets the 3.5% NaCl / -1.2V / 30d cathodic stripping test corrosion radius ≤8mm; ISO 2812 resistance to 40℃ seawater immersion / 6000h without change; ISO 725335℃ neutral salt spray test for 4032h without defects.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The invention adopts phenolic materials, lignin, epoxy resin, a small amount of fluorocarbon resin and amino-containing organic silicon resin as raw materials, and constructs an antifouling paint formula by combining a preparation process with a chemical reaction. A small amount of ammonia water is added and stirred before construction to control the wet film thickness to 120-180 microns and the dry film thickness to 60-80 microns. The cured coating surface has organic silicon resin segments and fluorocarbon resin segments with low surface tension, and the Schiff base structure formed by phenolic resin and aromatic amine has a natural bactericidal effect; the surface has a hydroxymethyl structure of the phenolic resin, an alcohol hydroxyl structure formed after the ring opening of the epoxy resin, and a lignin structure, so the coating has good recoatability; the organic silicon segments and the fluorocarbon segments give the coating a certain weather resistance, so the coating has the greatest feature of being bottom-surface integrated, while traditional antifouling paints require a matching primer, so the formula can effectively avoid heavy metal pollution and improve coating efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0040] Figure 1 This is the test result of using a 30 dyne dyne pen after the antifouling paint prepared with blue pigment was cured.

[0041] Figure 2 It is verified by re-coating the coating surface with silicone. DETAILED DESCRIPTION

[0042] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] The word "embodiment" used here as an "exemplary" does not necessarily mean that any embodiment described is superior to or better than other embodiments. Unless otherwise specified, the performance index tests in the embodiments of this application are performed using conventional test methods in the art. It should be understood that the terms described in this application are only used to describe specific implementation methods and are not used to limit the content disclosed in this application.

[0044] Unless otherwise specified, the technical and scientific terms used in this document have the same meanings as commonly understood by ordinary technicians in the technical field to which this application belongs; other experimental methods and technical means not specifically specified in this application refer to experimental methods and technical means commonly used by ordinary technicians in this field.

[0045] In order to better illustrate the content of the present application, numerous specific details are provided in the specific examples below. It should be understood by those skilled in the art that the present application can also be implemented without certain specific details. In the embodiments, some methods, means, instruments, equipment, etc. well known to those skilled in the art are not described in detail in order to highlight the main purpose of the present application.

[0046] Under the premise of no conflict, the technical features disclosed in the embodiments of the present application can be combined arbitrarily, and the resulting technical solutions belong to the contents disclosed in the embodiments of the present application.

[0047] The invention discloses a lignin-based antifouling paint for ships and a preparation method thereof.

[0048] In order to better understand the present invention, the present invention is further specifically described below through the following examples, but it should not be understood as a limitation of the present invention. Some non-essential improvements and adjustments made by technicians in this field based on the above invention content are also considered to fall within the protection scope of the present invention.

[0049] Example 1

[0050]

[0051]

[0052] Before construction, add 2-3% ammonia water to the paint and stir for 30 minutes, then spray it. The wet film thickness is 120-180 microns and the dry film thickness is 60-80 microns. After spraying on the metal substrate and curing at room temperature for 7 days, the coating meets the standard GB / T7789-2007, and there will be no microbial adsorption and coating wear during slow sailing or immersion in sea water; the coating surface tension is ≤30 dynes; the coating meets the 3.5% NaCl / -1.2V / 30d cathodic stripping test corrosion radius ≤8mm; ISO 2812 resistance to 40℃ seawater immersion / 6000h without change; ISO 725335℃ neutral salt spray test for 4032h without defects.

[0053] Example 2

[0054]

[0055]

[0056] Before construction, add 2-3% ammonia water to the paint and stir for 30 minutes, then spray it. The wet film thickness is 120-180 microns and the dry film thickness is 60-80 microns. After spraying on the metal substrate and curing at room temperature for 7 days, the coating meets the standard GB / T7789-2007, and there will be no microbial adsorption and coating wear during slow sailing or immersion in sea water; the coating surface tension is ≤30 dynes; the coating meets the 3.5% NaCl / -1.2V / 30d cathodic stripping test corrosion radius ≤8mm; ISO 2812 resistance to 40℃ seawater immersion / 6000h without change; ISO 725335℃ neutral salt spray test for 4032h without defects.

[0057] Example 3

[0058]

[0059]

[0060] Before construction, add 2-3% ammonia water to the paint and stir for 30 minutes, then spray it. The wet film thickness is 120-180 microns and the dry film thickness is 60-80 microns. After spraying on the metal substrate and curing at room temperature for 7 days, the coating meets the standard GB / T7789-2007, and there will be no microbial adsorption and coating wear during slow sailing or immersion in sea water; the coating surface tension is ≤30 dynes; the coating meets the 3.5% NaCl / -1.2V / 30d cathodic stripping test corrosion radius ≤8mm; ISO 2812 resistance to 40℃ seawater immersion / 6000h without change; ISO 725335℃ neutral salt spray test for 4032h without defects.

[0061] Example 4

[0062]

[0063]

[0064] Before construction, add 2-3% ammonia water to the paint and stir for 30 minutes, then spray it. The wet film thickness is 120-180 microns and the dry film thickness is 60-80 microns. After spraying on the metal substrate and curing at room temperature for 7 days, the coating meets the standard GB / T7789-2007, and there will be no microbial adsorption and coating wear during slow sailing or immersion in sea water; the coating surface tension is ≤30 dynes; the coating meets the 3.5% NaCl / -1.2V / 30d cathodic stripping test corrosion radius ≤8mm; ISO 2812 resistance to 40℃ seawater immersion / 6000h without change; ISO 725335℃ neutral salt spray test for 4032h without defects.

[0065] Example 5

[0066]

[0067] Before construction, add 2-3% ammonia water to the paint and stir for 30 minutes, then spray it. The wet film thickness is 120-180 microns and the dry film thickness is 60-80 microns. After spraying on the metal substrate and curing at room temperature for 7 days, the coating meets the standard GB / T7789-2007, and there will be no microbial adsorption and coating wear during slow sailing or immersion in sea water; the coating surface tension is ≤30 dynes; the coating meets the 3.5% NaCl / -1.2V / 30d cathodic stripping test corrosion radius ≤8mm; ISO 2812 resistance to 40℃ seawater immersion / 6000h without change; ISO 725335℃ neutral salt spray test for 4032h without defects.

[0068] Example 6

[0069]

[0070] Before construction, add 2-3% ammonia water to the paint and stir for 30 minutes, then spray it. The wet film thickness is 120-180 microns and the dry film thickness is 60-80 microns. After spraying on the metal substrate and curing at room temperature for 7 days, the coating meets the standard GB / T7789-2007, and there will be no microbial adsorption and coating wear during slow sailing or immersion in sea water; the coating surface tension is ≤30 dynes; the coating meets the 3.5% NaCl / -1.2V / 30d cathodic stripping test corrosion radius ≤8mm; ISO 2812 resistance to 40℃ seawater immersion / 6000h without change; ISO 725335℃ neutral salt spray test for 4032h without defects.

[0071] In addition, in order to further verify and illustrate the superiority of the lignin-based antifouling paint for ships provided by the present invention, the inventors also conducted the following experiments:

[0072] It should be noted that the reason why blue pigment is not used in the present invention is that the antifouling paint is an outdoor coating and the blue pigment is easy to change color after being exposed to the sun outdoors. Figure 1 , Figure 2 These are the experimental results involved in the preliminary test of the product of the present invention (prepared by any of the methods of the aforementioned Examples 1 to 6).

[0073] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A lignin-based antifouling paint for ships, characterized in that: The antifouling paint comprises the following components by mass percentage: Alcohol soluble lignin solution 20-25%; Butyl etherified phenolic resin 10-15%; Pigments and fillers 15-20%; Fumed silica 0.5-1%; Low boiling point aldehyde compounds 3-5%; Modified phenolic resin solution 20-25%; Fluorocarbon resin 1-2%; Aromatic amines 1-2%; Epoxy resin 10-15%; Solvent 3-5%; Oxidized polyethylene wax slurry 0.5-1%; Silicone epoxy curing agent 1-2%.

2. The lignin-based antifouling paint for ships according to claim 1, characterized in that: The alcohol-soluble lignin solution is a lignin solution with a solid content of 50% obtained by dissolving commercially available ethanol.

3. The lignin-based antifouling paint for ships according to claim 1, characterized in that: The butylated phenolic resin adopts a phenolic resin with a lower degree of etherification, such as Shandong Shengquan's CR107 and CR113 with a solid content of 75-80%; the color filler adopts a corrosion-resistant filler, specifically a combination of 1250 mesh wollastonite powder, 800 mesh talcum powder, titanium dioxide, chrome green, iron red, and iron yellow; the fumed silica adopts one of A200, R972, and R202.

4. The lignin-based antifouling paint for ships according to claim 1, characterized in that: The low-boiling-point aldehyde compound has a flash point of ≤40°C and a boiling point of 45-75°C, and specifically is glyoxal, isobutyraldehyde, and n-butyraldehyde.

5. The lignin-based antifouling paint for ships according to claim 1, characterized in that: The preparation method of the modified phenolic resin is as follows: The invention discloses a method for preparing a modified phenolic resin. The method comprises the following steps: adding an ethanol-based basic phenolic resin into a reaction kettle, adding bisphenol S according to 10% of the mass of the ethanol-based phenolic resin, adding a zinc acetate catalyst according to 0.2-0.3% of the mass of the ethanol-based phenolic resin, adding 65% of p-hydroxybenzenesulfonic acid according to 0.1-0.2% of the mass of the ethanol-based basic phenolic resin, adding 20% ​​of butanol as a solvent, reacting at 90-100° C. for 40-50 minutes, and then adding a mixed solvent to prepare a modified phenolic resin with a solid content of 50%.

6. The lignin-based antifouling paint for ships according to claim 5, characterized in that: The ethanol-based basic phenolic resin is 2130 phenolic resin; the mixed solvent is prepared by mixing ethylene glycol butyl ether and butanol in a mass ratio of 1:

1.

7. The lignin-based antifouling paint for ships according to claim 1, characterized in that: The fluorocarbon resin adopts Daikin GK570 resin with good weather resistance and containing alcohol hydroxyl groups; the aromatic amines include meta-xylylenediamine and aniline; the epoxy resin adopts a small molecule epoxy resin with a functionality of 1.9-3, specifically Nan Ya's EL-128 resin, 170 resin, and EPALLOY8240E phenolic epoxy resin.

8. The lignin-based antifouling paint for ships according to claim 1, characterized in that: The solvent is an ester solvent, specifically butyl acetate and ethyl acetate; the oxidized polyethylene wax slurry is 202P or 202SP from Hemmings; the organosilicon epoxy curing agent is G-002, G-003, G-004 from Hangzhou Yipeng New Materials Co., Ltd.

9. A method for preparing a lignin-based antifouling paint for ships as claimed in claim 1, characterized in that: The method specifically comprises the following steps: First, an alcohol-soluble lignin solution, a butylated phenolic resin, a pigment filler, a fumed silica and a low-boiling aldehyde compound are fully mixed and stirred at 45-55°C / 40-50min, a modified phenolic resin solution and a fluorocarbon resin are added to the mixed solution and stirred for 45-55°C / 30-40min, then an aromatic amine is added and stirred for 45-55°C / 30-4-min, then an epoxy resin and a solvent are added and stirred for 45-55°C / 30-40min, an oxidized polyethylene wax slurry and an organosilicon epoxy curing agent are added and stirred for 40-50°C / 30-40min, the solvent loss is determined and the solvent is supplemented, and finally the lignin-based antifouling paint for ships is obtained; The supplementary mixed solvent is prepared by mixing ethylene glycol butyl ether and butyl acetate in a mass ratio of 1:

1.

10. The method for preparing the lignin-based antifouling paint for ships according to claim 9, characterized in that: During construction, 2-3% ammonia water is added to the prepared lignin-based antifouling paint for ships, and the mixture is stirred for 20-30 minutes before spraying.

Images