Structure of heterocyclic acid zinc acrylic acid self-polishing antifouling resin and preparation method of heterocyclic acid zinc acrylic acid self-polishing antifouling resin

Abstract

The invention relates to a preparation method of heterocyclic acid zinc acrylate resin. The preparation method comprises two steps of monomer mixture preparation and zinc acrylate resin synthesis. By introducing the acrylate monomer, the flexibility, the film-forming property and the thermal stability of the polymer are remarkably improved; low-toxicity zinc ions are adopted to replace traditional copper-containing resin, so that potential environmental risks caused by copper ion aggregation are effectively avoided; meanwhile, heterocyclic compound monomers containing nitrogen, sulfur and oxygen are introduced, so that the resin is endowed with diversified biological activity. The resin has the self-polishing characteristic and the antifouling function, the preparation process steps are simplified, the raw material cost is low, and industrial production is easy. Experiments prove that the resin has remarkable inhibitory activity on marine bacteria and algae, and shallow sea hanging plate tests show that the static antifouling time efficiency can reach 6 months. The resin provided by the invention has practical application value and industrialization potential in the field of marine antifouling materials.

Description

Technical Field

[0001] The present invention relates to the field of marine antifouling resins, and more specifically, to a method for preparing a heterocyclic acid-based zinc acrylate resin. The invention also relates to the antibacterial and antialgae properties and marine antifouling properties of the heterocyclic acid-based zinc acrylate resin. The invention is particularly suitable for the development of environmentally friendly polymer materials for antifouling coatings on ships. Background Art

[0002] Marine biofouling refers to the phenomenon in the marine environment where organisms attach to surfaces and form communities. These organisms typically include microorganisms, algae, mollusks, corals, sponges, and marine life. They attach to the surfaces of various man-made and natural objects, including ship hulls, coastal facilities, marine equipment, underwater pipelines, buoys, etc.

[0003] The main hazards of biofouling include reduced efficiency, increased maintenance costs, the spread of harmful substances, bioinvasion, and damage to marine ecosystems. To mitigate the harm of biofouling, scientists and engineers have adopted various methods, including antifouling coatings, ultrasonic equipment, chemical treatments, and biofouling prevention technologies, to reduce the number and impact of attached organisms. These methods help improve the efficiency of marine equipment and vessels and reduce adverse impacts on marine ecosystems. Currently, antifouling coatings are the most widely used, simple, and cost-effective method.

[0004] Although organotin antifouling materials have been banned worldwide, their self-polishing antifouling properties are still widely used. Primarily using a polyacrylic resin / Cu2O system, these coatings offer easy application and a high cost-effectiveness. They currently command over 90% of the global antifouling coating market. They primarily consist of polymer resins, antifouling agents, pigments, fillers, additives, and solvents, with the polymer resins and antifouling agents being the most critical components. The resin is the antifouling coating's matrix, providing mechanical strength, adhesion, and controlled release of the antifouling agent, while the antifouling agent acts to repel and kill fouling organisms.

[0005] In the field of self-polishing antifouling materials, tin-free self-polishing materials such as copper polyacrylate, zinc polyacrylate, and polyacrylate silane polymers have been developed by replacing tin with relatively low-toxic elements (such as copper and zinc). Copper polyacrylate coatings hydrolyze to form sodium salts and basic copper carbonate, zinc polyacrylate coatings produce sodium salts through ion exchange, and polyacrylate silane coatings hydrolyze to form sodium salts. These salts slowly dissolve in seawater and are polished away by the erosion of the water. Compared to polyacrylate silane coatings, copper polyacrylate and zinc polyacrylate coatings have significantly faster polishing rates. Because the copper and zinc ions produced by copper polyacrylate and zinc polyacrylate resins are far less effective against fouling than organotin, and polyacrylate silane resins have no antifouling effect at all, these antifouling coatings must contain large amounts of the toxic antifouling agent (40%-50%) cuprous oxide, as well as some auxiliary organic antifouling agents, to ensure effective antifouling.

[0006] In order to meet the needs of environmental protection and static antifouling, polyacrylate zinc resin is the first choice, and bioactive heterocyclic compounds are grafted on the side chain to give it both self-polishing and antifouling properties. Summary of the Invention

[0007] The invention provides a preparation method of a heterocyclic acid-based zinc acrylate resin and application thereof. The resin is directly used as an antifouling coating with good antifouling performance and self-polishing performance.

[0008] The structure of a heterocyclic acid-based zinc acrylate resin is characterized by being represented by a structural formula, wherein R1 is H or CH3; and R2 is the acid radical of 2-furancarboxylic acid, thiophene-2-carboxylic acid, pyrrole-2-carboxylic acid, pyrazole-3-carboxylic acid, triazole-3-carboxylic acid, thiazole-4-carboxylic acid, 2-(1-imidazolyl)-acetic acid, 2-pyridinecarboxylic acid, 2-pyrone-5-carboxylic acid, benzofuran-2-carboxylic acid, benzothiophene-2-carboxylic acid, piperic acid, indole-2-carboxylic acid, 2-(3-oxobenzo[d]isothiazol-2(3H)-yl)acetic acid or coumarin-3-carboxylic acid.

[0009] A method for preparing a heterocyclic acid-based zinc acrylate resin is characterized by being implemented in the following steps: adding a small amount of a mixed solvent to a three-necked flask and heating it to 80-90°C. Transferring the monomer mixture to a constant pressure funnel and slowly adding it dropwise to the flask. After the dropwise addition is complete, the reaction is continued for 3 hours. Subsequently, a portion of the initiator is added, and the reaction is continued for 3-4 hours. Next, a homemade basic heterocyclic zinc salt is weighed and added to the reaction system in several portions. After all the additions are complete, the reaction is continued for 3 hours to obtain a colorless, transparent zinc acrylate resin. This is the heterocyclic acid-based zinc acrylate resin.

[0010] The acrylate monomers are at least two of methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, or butyl acrylate, and their weight percentage accounts for 80%-100% of the total monomer mixture. The acrylic acid monomer is at least one of acrylic acid and methacrylic acid, and its weight percentage accounts for 2.5%-15% of the total monomer mixture. The initiator is azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, or benzoyl peroxide, or a mixture thereof, and its weight percentage accounts for 2%-6% of the total monomer mixture. The resin prepared by the above method is used as a key component of the antifouling coating.

[0011] The heterocyclic acid-based zinc acrylate resin of the present invention adopts a multiple-addition method and contains nitrogen-containing, sulfur-containing and oxygen-containing heterocyclic compound monomers with antifouling effects, so that the zinc acrylate resin itself has antifouling effects and will not gel. DETAILED DESCRIPTION

[0012] In order to more clearly illustrate the present invention, it will be further described below in conjunction with preferred embodiments. For those skilled in the art, it should be understood that the following description is only for illustrative purposes and not for limiting the scope of the present invention.

[0013] The present invention is described in more detail with examples below.

[0014] Example 1

[0015] Preparation of monomer mixture

[0016] 11.25 g of methyl methacrylate, 11.25 g of butyl acrylate, 2.5 g of methacrylic acid, and 0.8 g (4.59% of the total monomer mixture, 70% added first) of initiator were weighed into a beaker, and a mixed solvent of xylene and n-butanol (volume ratio 4:1) was added and stirred to obtain a monomer mixture.

[0017] Example 2

[0018] Synthesis of Heterocyclic Acid-Based Zinc Acrylate Resin A

[0019] Add 50 mL of the mixed solvent to a 250 mL three-necked flask and heat to 80-90°C with mechanical stirring and a reflux device. Transfer the monomer mixture to a constant pressure funnel and slowly add it dropwise to the flask over a 2-3 hour period. After the addition is complete, continue the reaction for 3 hours. Subsequently, add 0.35 g of initiator and continue the reaction for 3-4 hours. Next, weigh the homemade basic furanoic acid zinc salt and add it to the reaction system in three portions at 2-hour intervals. After the addition is complete, continue the reaction for 3 hours to obtain colorless, transparent zinc acrylate resin. IR (KBr) v: 3020 (-CH=CH-), 2960, 2933, 2874, 1730 (C=O), 1602 (O-Zn-O), 1454 (CH2), 1383 (CH3), 1163, 1068 (COC) cm -1 .

[0020] Example 3

[0021] Synthesis of Heterocyclic Acid-Based Zinc Acrylate Resin B

[0022] Add 50 mL of the mixed solvent to a 250 mL three-necked flask and heat to 80-90°C with mechanical stirring and a reflux device. Transfer the monomer mixture to a constant pressure funnel and slowly add it dropwise to the flask over a 2-3 hour period. After the addition is complete, continue the reaction for 3 hours. Subsequently, add 0.35 g of initiator and continue the reaction for 3-4 hours. Next, weigh the homemade basic thiophenecarboxylic acid zinc salt and add it to the reaction system in three portions at 2-hour intervals. After the addition is complete, continue the reaction for 3 hours to obtain colorless, transparent zinc acrylate resin. IR (KBr) v: 3020 (-CH=CH-), 2960, 2933, 2874, 1730 (C=O), 1602 (O-Zn-O), 1454 (CH2), 1383 (CH3), 1163, 1068 (COC) cm -1 .

[0023] Example 4

[0024] Synthesis of Heterocyclic Acid-Based Zinc Acrylate Resin C

[0025] Add 50 mL of the mixed solvent to a 250 mL three-necked flask and heat to 80-90°C with mechanical stirring and a reflux device. Transfer the monomer mixture to a constant pressure funnel and slowly add it dropwise to the flask over a 2-3 hour period. After the addition is complete, continue the reaction for 3 hours. Subsequently, add 0.35 g of initiator and continue the reaction for 3-4 hours. Next, weigh the homemade basic zinc pyrrolidone salt and add it to the reaction system in three portions every 2 hours. After the addition is complete, continue the reaction for 3 hours to obtain colorless, transparent zinc acrylate resin. IR (KBr) v: 3350 (NH), 3020 (-CH=CH-), 2960, 2933, 2874, 1730 (C=O), 1602 (O-Zn-O), 1454 (CH2), 1383 (CH3), 1160, 1070 (COC) cm -1 .

[0026] Example 5

[0027] Synthesis of heterocyclic acid-based zinc acrylate resin D.

[0028] Add 50 mL of the mixed solvent to a 250 mL three-necked flask, heat to 80-90°C, and equip with a mechanical stirrer and a condensing reflux device. Transfer the mixed solution of the monomer mixture to a constant pressure funnel and slowly add it dropwise to the flask. The addition time should be controlled within 2-3 hours. After the addition is completed, continue the reaction for 3 hours. Subsequently, add 0.35 g of initiator and keep the reaction going for 3-4 hours. Next, weigh the homemade basic pyrazole-3-carboxylic acid zinc salt 3 times and add it to the reaction system every 2 hours. After all the additions are completed, the reaction continues for 3 hours to finally obtain a colorless and transparent zinc acrylate resin. IR (KBr) v: 3285 (NH), 3061 (-CH=CH-), 2960,2933, 2874, 1730 (C=O), 1602 (O-Zn-O), 1454 (CH2), 1383 (CH3), 1165, 1070(COC) cm -1 .

[0029] Example 6

[0030] Synthesis of heterocyclic acid-based zinc acrylate resin E.

[0031] Add 50 mL of the mixed solvent to a 250 mL three-necked flask, heat to 80-90°C, and equip with a mechanical stirrer and a condensing reflux device. Transfer the mixed solution of the monomer mixture to a constant pressure funnel and slowly add it dropwise to the flask. The addition time should be controlled within 2-3 hours. After the addition is completed, continue the reaction for 3 hours. Subsequently, add 0.35 g of initiator and keep the reaction going for 3-4 hours. Next, weigh the homemade basic triazole-3-carboxylic acid zinc salt 3 times and add it to the reaction system every 2 hours. After all the additions are completed, the reaction continues for 3 hours to finally obtain a colorless and transparent zinc acrylate resin. IR (KBr) v: 3310(NH), 3020 (-CH=CH-),2960, 2933, 2874, 1730 (C=O), 1602 (O-Zn-O), 1454 (CH2), 1383 (CH3), 1163,1068(COC) cm -1 .

[0032] Example 7

[0033] Synthesis of heterocyclic acid-based zinc acrylate resin F.

[0034] Add 50 mL of the mixed solvent to a 250 mL three-necked flask and heat to 80-90°C with mechanical stirring and a reflux device. Transfer the monomer mixture to a constant pressure funnel and slowly add it dropwise to the flask over a 2-3 hour period. After the addition is complete, continue the reaction for 3 hours. Subsequently, add 0.35 g of initiator and continue the reaction for 3-4 hours. Next, weigh the homemade basic thiazole-4-carboxylic acid zinc salt and add it to the reaction system in three portions every 2 hours. After the addition is complete, continue the reaction for 3 hours to obtain colorless, transparent zinc acrylate resin. IR (KBr) v: 3020 (-CH=CH-), 2960, 2933, 2874, 1730 (C=O), 1602 (O-Zn-O), 1454 (CH2), 1383 (CH3), 1163, 1070 (COC) cm -1 .

[0035] Example 8

[0036] Synthesis of heterocyclic acid-based zinc acrylate resin G.

[0037] Add 50 mL of the mixed solvent to a 250 mL three-necked flask, heat to 80-90°C, and equip it with a mechanical stirrer and a condensing reflux device. Transfer the mixed solution of the monomer mixture to a constant pressure funnel and slowly add it dropwise to the flask. The addition time should be controlled within 2-3 hours. After the addition is completed, continue the reaction for 3 hours. Subsequently, add 0.35 g of initiator and keep the reaction going for 3-4 hours. Next, weigh the homemade basic zinc piperonate three times and add it to the reaction system every 2 hours. After all the additions are completed, the reaction continues for 3 hours to finally obtain a colorless and transparent zinc acrylate resin. IR (KBr) v: 3020 (-CH=CH-), 2960, 2933, 2874,1730 (C=O), 1602 (O-Zn-O), 1515, 1492 (C=C),1454 (CH2), 1383 (CH3), 1163, 1068(COC), 877, 845cm -1 .

[0038] Example 9

[0039] Synthesis of heterocyclic acid-based zinc acrylate resin H.

[0040] Add 50 mL of the mixed solvent to a 250 mL three-necked flask, heat to 80-90°C, and equip it with a mechanical stirrer and a condenser reflux device. Transfer the mixed solution of the monomer mixture to a constant pressure funnel and slowly add it dropwise to the flask. The addition time should be controlled within 2-3 hours. After the addition is completed, continue the reaction for 3 hours. Subsequently, add 0.35 g of initiator and keep the reaction going for 3-4 hours. Next, weigh the homemade basic indole-2-carboxylic acid zinc salt 3 times and add it to the reaction system every 2 hours. After all the additions are completed, the reaction continues for 3 hours to finally obtain a colorless and transparent zinc acrylate resin. IR (KBr, ) v: 3349 (NH), 3020 (-CH=CH-), 2960, 2933, 2874, 1730 (C=O), 1602 (O-Zn-O), 1515, 1492 (C=C), 1454 (CH2), 1383 (CH3), 1163, 1068(COC), 740 cm -1 .

[0041] Example 10

[0042] The antibacterial performance of the prepared heterocyclic acid-based zinc acrylate resin AH was tested using the absorbance method. The inhibition rates of the eight resins against Staphylococcus aureus, Vibrio corallilyticus and Vibrio parahaemolyticus were tested in 12 hours. The results are shown in Table 1. Figure 2 .

[0043]

[0044] The results showed that the antibacterial performance of the prepared heterocyclic acid zinc acrylate resin AH was as high as over 97%, indicating that the prepared heterocyclic acid zinc acrylate resin AH can significantly inhibit the growth of marine bacteria.

[0045] Example 11

[0046] The anti-algae performance of the prepared heterocyclic zinc acrylate resin AH was tested by absorbance method. The inhibition rate of 8 kinds of resins on Chlorella vulgaris, Isochrysis galbana and Chaetoceros spiralis in 7 days was tested respectively. The results are shown in Figure 3 .

[0047]

[0048] The results showed that the algae inhibition performance of the prepared heterocyclic acid-based zinc acrylate resin AH was as high as over 95%, indicating that the prepared heterocyclic acid-based zinc acrylate resin AH can significantly inhibit the growth of marine algae.

[0049] The heterocyclic zinc acrylate resin AH prepared above can be used directly as an antifouling coating. Conventional coating methods were used for application. The antifouling performance of the heterocyclic zinc acrylate resin AH containing the present invention was tested at a yacht marina in the shallow waters of Haikou Bay, Haikou City, according to the national standard "Shallow Sea Immersion Test Method for Antifouling Paint Samples" (GB / T 5320-2007). The antifouling performance was tested from May to October, the peak growth period for fouling organisms. The results showed that uncoated epoxy resin panels were heavily infested with organisms such as barnacles, mussels, lime worms, oysters, bryozoans, and brown algae. However, only a small amount of marine animals and plants adhered to the epoxy resin panels coated with the heterocyclic zinc acrylate resin AH provided by the present invention. This demonstrates the excellent antifouling performance of the heterocyclic zinc acrylate resin AH provided by the present invention.

[0050] The heterocyclic acid-based zinc acrylate resin provided by the present invention has a simple synthesis method and uses inexpensive and readily available raw materials. Compared with conventional metal acrylate resins commonly used as film-forming materials in the prior art, the resin of the present invention can be evenly released in seawater, and the coating is smooth and not prone to cracking or falling off, exhibiting superior antifouling performance. Furthermore, the use of different heterocyclic acids to prepare the antifouling resin adds diversification to the development of resins. Without the addition of any antifouling agent, the antifouling resin can maintain a static antifouling period of up to six months. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 The structure of a heterocyclic acid-based zinc acrylate self-polishing antifouling resin.

[0052] Figure 2 The inhibition rates of 8 resins against Staphylococcus aureus, Vibrio corallilyticus and Vibrio parahaemolyticus in 12 h.

[0053] Figure 3 The inhibition rates of 8 resins on Chlorella vulgaris, Isochrysis galbana and Chaetoceros spiralis at 7 days.

Claims

1. A heterocyclic acid-based zinc acrylate self-polishing antifouling resin, characterized in that The structure of the resin is shown in Figure 1: wherein R1 is H or CH3; and R2 is an acid radical of 2-furancarboxylic acid, thiophene-2-carboxylic acid, pyrrole-2-carboxylic acid, pyrazole-3-carboxylic acid, triazole-3-carboxylic acid, thiazole-4-carboxylic acid, 2-(1-imidazolyl)-acetic acid, 2-pyridinecarboxylic acid, 2-pyrone-5-carboxylic acid, benzofuran-2-carboxylic acid, benzothiophene-2-carboxylic acid, piperic acid, indole-2-carboxylic acid, 2-(3-oxobenzo[d]isothiazol-2(3H)-yl)acetic acid, or coumarin-3-carboxylic acid. The heterocyclic acid-based zinc acrylate resin has a number average molecular weight in the range of 10,000-15,000 g / mol and a molecular weight distribution in the range of 1.0-2.

0.

2. The heterocyclic acid-based zinc acrylate self-polishing antifouling resin according to claim 1, wherein the resin is prepared by condensing a basic zinc salt of a heterocyclic acid with an acrylic resin, wherein the molar ratio of the basic zinc salt of a heterocyclic acid to the acrylic acid monomer is 1:1-1.

5.

3. The basic zinc salt of heterocyclic acid according to claim 2, wherein the preparation method comprises mixing a heterocyclic acid compound, a hydroxide and zinc chloride in a molar ratio of 1.0-1.2:2.0-3.0:1.0-1.5 to obtain the basic zinc salt of heterocyclic acid.

4. The acrylic resin according to claim 2, wherein the preparation method comprises adding an acrylate monomer and an acrylic acid monomer to a mixed solvent in a three-necked flask equipped with a mechanical stirrer, adding an initiator, heating to 65-95°C, and continuing the reaction for 3-4 hours to obtain the acrylic resin. The mass ratio of the acrylate monomer, acrylic acid monomer, and free radical initiator is 80-100:0-20:2-6.

5. The preparation method of the heterocyclic acid-based zinc acrylate self-polishing antifouling resin according to claim 2, characterized in that, The heterocyclic acid basic zinc salt is added in batches, which can be two or three times and can be adjusted at any time according to the specific experimental conditions. After all the addition is completed, the reaction is continued for 3-5 hours to finally obtain a colorless and transparent heterocyclic acid-based zinc acrylate resin.

6. The heterocyclic acid compound according to claim 3, which is selected from 2-furancarboxylic acid, thiophene-2-carboxylic acid, pyrrole-2-carboxylic acid, pyrazole-3-carboxylic acid, triazole-3-carboxylic acid, thiazole-4-carboxylic acid, 2-(1-imidazolyl)-acetic acid, 2-pyridinecarboxylic acid, 2-pyrone-5-carboxylic acid, benzofuran-2-carboxylic acid, benzothiophene-2-carboxylic acid, piperic acid, indole-2-carboxylic acid, 2-(3-oxobenzo[d]isothiazol-2(3H)-yl)acetic acid or coumarin-3-carboxylic acid; and the hydroxide is one selected from sodium hydroxide, potassium hydroxide or lithium hydroxide.

7. The method for preparing acrylic resin according to claim 4, wherein The acrylate monomers are one or more acrylate monomers selected from methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate or butyl acrylate, and the acrylic acid monomer is one selected from methacrylic acid or acrylic acid monomers; the mixed solvent is one or more solvents selected from xylene, n-butanol, toluene or butyl acetate; the free radical initiator is one selected from azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate or benzoyl peroxide.

8. The heterocyclic acid-based zinc acrylate resin obtained by the preparation method according to any one of claims 1 to 7, characterized in that When the resin is used directly as a marine antifouling coating, its static antifouling effect can reach 6 months.

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