Structure and preparation method of aromatic acid zinc difunctional acrylic resin

Abstract

The invention discloses a preparation method of aromatic acid-based zinc acrylate resin with antifouling and self-polishing double-effect synergy. The preparation method comprises the following process steps: (1) synthesizing aromatic acid-based basic zinc salt; and (2) polymerization preparation of the zinc acrylate resin. The vinyl monomer is introduced into the synthesized resin, so that the flexibility, film-forming property and stability of the polymer are improved. Aromatic acid compounds are introduced into the synthesized resin, so that the resin is endowed with antifouling property and is environment-friendly. According to the resin material, a graded hydrolysis mechanism is established through molecular design: in a seawater environment, zinc ions and sodium ions in a side chain on the surface of the resin are exchanged to trigger surface hydrolysis, so that a controllable self-polishing function is realized; meanwhile, the aromatic acid compound grafted on the side chain is continuously and slowly released along with hydrolysis of the ester group, and a synergistic effect of preventing attachment of fouling organisms is generated. A real sea hanging plate experiment verifies that the static antifouling period is 180 days or above, and the anti-fouling performance is good and is prolonged by 50% or above compared with that of conventional zinc acrylate resin. The difunctional resin prepared by the invention provides an innovative solution with environmental adaptability and long-acting protective property for a marine antifouling coating.

Description

Technical Field

[0001] The present invention relates to the field of marine antifouling resins, and more specifically, to an aromatic acid-based zinc acrylate resin, a method for preparing the aromatic acid-based zinc acrylate resin, and the marine cladding performance of the aromatic acid-based zinc acrylate resin. Background Art

[0002] Wuxi self-polishing marine antifouling coating is a special type of coating that is commonly used in the marine antifouling field to reduce biofouling. The following is a detailed description of its advantages and disadvantages. Advantages: (1) Automatic renewal of antifouling effect. The metal ions in the acrylic acid metal salt resin in the coating formula can undergo ion exchange with the sodium ions in seawater and hydrolyze, continuously forming a smooth surface. This helps reduce the ability of organisms to attach and maintain the antifouling properties of the coating without the need for frequent cleaning or maintenance. (2) Long-term protection. Self-polishing coatings are generally able to provide a long protection period, reducing frequent ship or equipment maintenance. This reduces maintenance costs and downtime, which is very attractive for commercial shipping and marine equipment operations. (3) Applicable to different environments. Self-polishing antifouling resins can be adjusted to different marine environments and water temperatures to ensure that their performance is maintained under various conditions. This makes it suitable for a variety of different marine environments around the world. (4) Environmental protection. Self-polishing antifouling resins generally reduce biofouling, thereby reducing the need for antifouling cleaning agents and chemicals, helping to reduce negative impacts on the environment.

[0003] Self-polishing antifouling coatings are a type of antifouling coating that can meet both good antifouling performance and environmental requirements. However, the resin in the formulation itself does not possess biocidal properties. Antifouling is primarily achieved through the use of antifouling agents. Self-polishing properties alone cannot achieve long-term or static antifouling.

[0004] Currently, there are five methods for preparing acrylic acid metal salt resins: (1) Yao Baoshu et al. (CN03130372.2) used acrylic acid and acrylic acid ester prepolymers to react with unsaturated fatty acids and divalent metal alkaline compounds to synthesize hydrolyzable resins. This method is prone to exchange reactions between carboxyl groups and organic acids, resulting in a continuous increase in polymer viscosity and even gelation. (2) Yu Liangmin et al. (CN200310105495.6) first synthesized a zinc or copper basic salt of an organic acid, then synthesized a carboxyl-containing acrylic resin, and then reacted the zinc or copper basic salt of an organic acid with the carboxyl-containing acrylic resin to obtain a zinc or copper acrylic resin. The disadvantage of this method is that a large amount of basic salts may cause the hydrolysis of the ester group in the acrylic resin prepolymer, resulting in a gel-like state. (3) Shi Liyi et al. (CN201110048903.3) first synthesized a zinc or copper small molecule monomer, and then free radical polymerized it with an acrylic acid soft or hard monomer initiator to produce a zinc or copper acrylic resin. The disadvantage of this method is that zinc acrylate or copper small molecule monomers may agglomerate during the polymerization process or precipitate at the bottom of the equipment, resulting in poor stability and repeatability during the preparation process. (4) Wang Xianxian et al. (CN201210545640.1) first synthesized a polyacrylic acid resin solution with a carboxyl group, neutralized it with a sodium hydroxide aqueous solution to generate a sodium polyacrylate resin solution, then prepared an organic acid copper (zinc) chloride intermediate, and finally generated a polyacrylic acid copper (zinc) resin through an ion exchange reaction. After washing with water to remove impurities and distillation and dehydration, a polyacrylic acid copper (zinc) resin solution was finally obtained. The disadvantage of this method is that the synthesis process is relatively complicated and the stability of the product structure and performance is poor. (5) Yu Xueyan et al. (CN201410112406.9) first prepared a zinc acrylate small molecule monomer containing an unsaturated double bond at only one end, and then copolymerized it with other vinyl unsaturated monomers under the action of an initiator to prepare a zinc acrylate type self-polishing resin. The disadvantage of this method is that it is not easy to form a zinc acrylate resin with a high relative molecular weight.

[0005] Among the above preparation methods, we chose the second method. On this basis, we adopted a multiple-addition method and aromatic acid compounds with antifouling effect to reduce the amount of antifouling agent used or even eliminate it, making zinc acrylate resin suitable for long-term antifouling or static antifouling. Summary of the Invention

[0006] The invention provides a preparation method of an aromatic 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.

[0007] The structure of an aromatic acid-based zinc acrylate resin is characterized by using a structural formula such as Figure 1shown. wherein R1 is H or CH3; R2 is H, CH2 or CH=CH; R3 is H, 2-OH, 2-CH3, 2-OCH3, 2-F, 2-Cl, 2-Br, 2-CF3,2-NO2, 2-NH2,3-OH, 3-CH3, 3-OCH3, 3-Br, 3-F, 3-Cl, 3-CF3, 3-NO2, 3-NH2, 4-OH,4-CH3, 4-OCH3, 4-Br, 4-F, 4-Cl, 4-CF3, 4-NO2, 4-NH2, 2,4-diOH, 2,4-diCH3, 2,4-diOCH3, 2,4-diF, 2,4-diCl, 2,4-diBr, 3,5-diOH, 3,5-diCH3, 2,4-diOCH3, 2,4-diF,2,4-diCl, 2,4-diBr, 2-OH-3-OCH3, 3-F-4-OH, 3-Br-4-OH, 2-Cl-5-OH.

[0008] A method for preparing an aromatic acid-based zinc acrylate resin is characterized by the following steps: In a three-necked flask equipped with a mechanical stirrer, a solvent is added and heated to 70-95°C. Acrylate monomer and acrylic acid monomer are separately weighed and added to the solvent. An initiator is added at a ratio of 2.8-4.2% of the combined amount of acrylate monomers. After uniform mixing, the mixture is transferred to a constant pressure funnel and added dropwise to the flask. After the addition is complete, the reaction is continued for 3 hours. Then, an initiator is added at a ratio of 1.2-1.8% of the combined amount of acrylate monomers and the reaction is continued for 3-4 hours. The desired basic zinc salt is then weighed and added in several portions, with the molar ratio of basic zinc salt to acrylic acid monomer being 1:1-1.5. Upon completion of the reaction, a light yellow, transparent zinc acrylate resin is obtained. This is the aromatic acid-based zinc acrylate resin.

[0009] The acrylate monomers are at least two of methyl methacrylate, ethyl acrylate, and butyl acrylate, with their weight percentages representing 85% to 97.5% of the total monomer mixture. The acrylic acid monomers are at least one of acrylic acid and methacrylic acid, with their weight percentages representing 2.5% to 15% of the total monomer mixture. The initiator is azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptylonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, or a mixture thereof. The resin prepared by the above method serves as a key component of an antifouling coating.

[0010] The aromatic acid-based zinc acrylate resin of the present invention adopts a multiple-addition method and an aromatic acid compound with antifouling effect, so that the zinc acrylate resin itself has an antifouling effect and will not gel. DETAILED DESCRIPTION

[0011] In order to explain the present invention more clearly, the present invention is further described below in conjunction with preferred embodiments. Those skilled in the art should understand that the following specific description is illustrative rather than restrictive and should not be used to limit the scope of protection of the present invention.

[0012] The present invention is described in more detail with reference to the following examples.

[0013] Example 1

[0014] Synthesis of zinc m-hydroxybenzoate resin (A1, 2.5% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 48.75 g of methyl methacrylate, 48.75 g of butyl acrylate, 3.75 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 6.33 g of homemade basic zinc salt in two additions, 3 hours apart. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3379 (OH), 3020 (-CH=CH-), 2956,2935, 2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452 (CH2),1387 (CH3), 1163, 1068(COC), 765, 695 cm -1 .

[0015] Example 2

[0016] Synthesis of zinc m-hydroxybenzoate resin (A2, 5% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 47.50 g of methyl methacrylate, 47.50 g of butyl acrylate, 7.50 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 12.66 g of homemade basic zinc salt in two additions, 3 hours apart. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3379 (OH), 3020 (-CH=CH-), 2956, 2935, 2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452(CH2), 1387 (CH3), 1163, 1068(COC), 768, 690cm -1 .

[0017] Example 3

[0018] Synthesis of zinc m-hydroxybenzoate resin (A3, 7.5% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 46.25 g of methyl methacrylate, 46.25 g of butyl acrylate, 11.25 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 18.99 g of homemade basic zinc salt in two additions, 3 hours apart. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3379 (OH), 3020 (-CH=CH-), 2956, 2935, 2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452(CH2), 1387 (CH3), 1163, 1068(COC), 770, 690cm -1 .

[0019] Example 4

[0020] Synthesis of zinc m-hydroxybenzoate resin (A4, 10% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 45.00 g of methyl methacrylate, 45.00 g of butyl acrylate, 15 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 25.32 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3379 (OH), 3020 (-CH=CH-), 2956,2935, 2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452 (CH2),1387 (CH3), 1163, 1068(COC), 770, 695 cm -1 .

[0021] Example 5

[0022] Synthesis of zinc m-hydroxybenzoate resin (A5, 12.5% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 43.75 g of methyl methacrylate, 43.75 g of butyl acrylate, 18.75 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 31.65 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3379 (OH), 3020 (-CH=CH-), 2956, 2935, 2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452(CH2), 1387 (CH3), 1163, 1068(COC), 770, 690cm -1 .

[0023] Example 6

[0024] Synthesis of acrylic resin (abbreviated as A0, 0% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 50.00 g of methyl methacrylate, 50.00 g of butyl acrylate, and 3.21 g of azobisisobutyronitrile into the same beaker, add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours to obtain a colorless, transparent acrylic resin. IR (KBr) v: 2956, 2935, 2873 (CH), 1730 (C=O), 1452 (CH2), 1387 (CH3), 1163, 1068 (COC) cm -1 .

[0025] The marine antifouling resin of the present invention can be directly used as an antifouling paint and can be coated using a conventional coating method.

[0026] At a yacht marina in the shallow waters of Haikou Bay, Haikou City, the antifouling performance of the aromatic acid-based zinc acrylate resin of the present invention was tested in accordance with the national standard "Shallow Sea Immersion Test Method for Antifouling Paint Samples" (GB / T 5320-2007), during the peak growth period of fouling organisms (May to October). The antifouling performance of the resin was comprehensively evaluated based on the number of fouling organisms or the area covered. The test results are shown in the table below. Figure 2 .

[0027]

[0028] Results showed that the coating of zinc acrylate resin A5, with a 12.5% zinc content, cracked and fell off due to rapid polishing due to its high zinc content. The coating of zinc acrylate resin A4, with a 10% zinc content, exhibited high strength and uniform polishing, demonstrating excellent antifouling performance. The coating of zinc acrylate resin A3, with a 7.5% zinc content, showed only minimal barnacles. The coatings of zinc acrylate resins A2 and A1, with zinc contents below 7.5%, showed a small amount of fouling organisms. The amount of fouling organisms attached to the coating of zinc acrylate resin A0 was only slightly less than that of an unprotected blank. Therefore, we selected the zinc acrylate resin with a 10% zinc content as a reference to investigate whether aromatic acid compounds with different substituents have an impact on antifouling performance.

[0029] Example 7

[0030] Synthesis of zinc benzoate resin (B4, 10% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 45.00 g of methyl methacrylate, 45.00 g of butyl acrylate, 15 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 25.32 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3020 (-CH=CH-), 2955, 2935, 2870,1730 (C=O), 1608 (O-Zn-O), 1587, 1520 1492 (C=C), 1452 (CH2), 1387 (CH3),1163, 1068(COC), 768, 695 cm -1 .

[0031] Example 8

[0032] Synthesis of zinc o-hydroxybenzoate resin (abbreviated as C4, zinc content 10%): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 45.00 g of methyl methacrylate, 45.00 g of butyl acrylate, 15 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 25.32 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3379 (OH), 3020 (-CH=CH-), 2956, 2935, 2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452(CH2), 1387 (CH3), 1163, 1068(COC), 740 cm -1 .

[0033] Example 9

[0034] Synthesis of zinc p-hydroxybenzoate resin (abbreviated as D4, zinc content 10%): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 45.00 g of methyl methacrylate, 45.00 g of butyl acrylate, 15 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 25.32 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3379 (OH), 3020 (-CH=CH-), 2956, 2935, 2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452(CH2), 1387 (CH3), 1163, 1068(COC), 795cm -1 .

[0035] Example 10

[0036] Synthesis of zinc m-methylbenzoate resin (abbreviated as E4, zinc content 10%): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 45.00 g of methyl methacrylate, 45.00 g of butyl acrylate, 15 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 25.32 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3020 (-CH=CH-), 2956, 2935,2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452 (CH2), 1387(CH3), 1163, 1068(COC), 765, 695cm -1 .

[0037] Example 11

[0038] Synthesis of zinc m-methoxybenzoate resin (abbreviated as F4, zinc content 10%): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 45.00 g of methyl methacrylate, 45.00 g of butyl acrylate, 15 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 25.32 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3020 (-CH=CH-), 2956, 2935,2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452 (CH2), 1387(CH3), 1163, 1068(COC), 765, 690cm -1 .

[0039] Example 12

[0040] Synthesis of zinc m-fluorobenzoate resin (G4, 10% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 45.00 g of methyl methacrylate, 45.00 g of butyl acrylate, 15 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 25.32 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3020 (-CH=CH-), 2956, 2935,2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452 (CH2), 1387(CH3), 1163, 1068(COC), 770, 695 cm -1 .

[0041] Example 13

[0042] Synthesis of zinc m-chlorobenzoate resin (H4, 10% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 45.00 g of methyl methacrylate, 45.00 g of butyl acrylate, 15 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 25.32 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3020 (-CH=CH-), 2956, 2935,2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452 (CH2), 1387(CH3), 1163, 1068(COC), 770, 695cm -1 .

[0043] Example 14

[0044] Synthesis of zinc meta-bromobenzoate resin (abbreviated as I4, 10% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 45.00 g of methyl methacrylate, 45.00 g of butyl acrylate, 15 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 25.32 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3020 (-CH=CH-), 2956, 2935,2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452 (CH2), 1387(CH3), 1163, 1068(COC), 770, 695cm -1 .

[0045] Example 15

[0046] Synthesis of zinc p-hydroxyphenylacetic acid resin (J4, 10% zinc content): In a 1L three-necked flask equipped with a mechanical stirrer, add 100 mL of mixed solvent and heat to 85°C. Weigh 45.00 g of methyl methacrylate, 45.00 g of butyl acrylate, 15 g of methacrylic acid, and 3.21 g of azobisisobutyronitrile into the same beaker. Add the solvent, mix and dissolve evenly, transfer the mixture to a constant pressure funnel, and add it dropwise to the flask at a rate of 3-4 drops per second. After the addition is complete, continue the reaction for 3 hours. Then, add 1.38 g of azobisisobutyronitrile and continue the reaction for 3-4 hours. Then, add 25.32 g of homemade basic zinc salt in three 3-hour increments. Continue the reaction for 3-5 hours to obtain a light yellow, transparent zinc acrylate resin. IR (KBr) v: 3379 (OH), 3020 (-CH=CH-), 2956, 2935, 2873, 1730 (C=O), 1608 (O-Zn-O), 1587, 1518, 1492 (C=C), 1452(CH2), 1387 (CH3), 1163, 1068(COC), 795cm -1 .

[0047] The marine antifouling resin of the present invention can be directly used as an antifouling paint and can be coated using a conventional coating method.

[0048] At a yacht marina in the shallow waters of Haikou Bay, Haikou City, the antifouling performance of the aromatic acid-based zinc acrylate resin of the present invention was tested in accordance with the national standard "Shallow Sea Immersion Test Method for Antifouling Paint Samples" (GB / T 5320-2007), during the peak growth period of fouling organisms (May to October). The antifouling performance of the resin was comprehensively evaluated based on the number of fouling organisms or the area covered. The test results are shown in the table below. Figure 3 .

[0049]

[0050] Results showed that unsubstituted zinc benzoate resin B4 exhibited a small amount of biofouling organisms. Compared to zinc benzoate resin coatings C4 and D4 with ortho- and para-hydroxyl groups, zinc benzoate resin A4 with meta-hydroxyl groups exhibited no biofouling organisms and demonstrated the best antifouling efficacy. Zinc benzoate resins G4, H4, and I4 with meta-halogen (fluorine, chlorine, and bromine) groups exhibited only minimal biofouling organisms, demonstrating inferior antifouling efficacy. Zinc benzoate resins E4 and F4 with meta-methyl and methoxy groups exhibited only a small amount of biofouling organisms and demonstrated excellent antifouling efficacy. Zinc phenylacetate coating J4 with para-hydroxyl groups exhibited no biofouling organisms and demonstrated comparable antifouling efficacy to zinc benzoate resin D4 with para-hydroxyl groups, indicating that chain extension of aromatic acids enhances antifouling efficacy.

[0051] Therefore, different substituents and their positions have varying effects on the antifouling properties of aromatic acid-based zinc acrylate resins. Benzoate-based zinc acrylate resins substituted with meta-hydroxyl groups exhibit the best performance, followed by those substituted with meta-halogens (fluorine, chlorine, bromine), methyl, or methoxy groups. In particular, chain extension of the aromatic acid enhances the antifouling capabilities of aromatic acid-based zinc acrylate resins.

[0052] The aromatic acid-based zinc acrylate resin of the present invention is simple to synthesize, and the raw materials are inexpensive and readily available. Compared with conventional metal acrylate resins commonly used as film-forming materials in the prior art, the resin exhibits uniform release in seawater, a smooth coating that is less prone to cracking and falling off, and better antifouling properties. Without the addition of any antifouling agent, the antifouling resin exhibits a static antifouling period of over 180 days, demonstrating excellent antifouling performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 Structure of zinc aromatic acid bifunctional acrylic resin.

[0054] Figure 2 Static antifouling properties of zinc m-hydroxybenzoate resins with different zinc contents.

[0055] Figure 3 Static antifouling properties of aromatic acid zinc resins with different substituents.

Claims

1. An aromatic acid-based zinc acrylate resin with antifouling and self-polishing dual effects, characterized in that The structure of the resin is shown in Figure 1. . Among them: R1 is H or CH3; R2 is H, CH2 or CH=CH; R3 is H, 2-OH, 2-CH3, 2-OCH3, 2-F, 2-Cl, 2-Br, 2-CF3, 2-NO2, 2-NH2, 3-OH, 3-CH3, 3-OCH3, 3-F, 3-Cl, 3-Br, 3-CF3, 3-NO2, 3-NH2, 4-OH, 4-CH3, 4-OCH3, 4-F, 4-Cl, 4-Br, 4-CF3, 4-NO2, 4-NH2, 2,4-diOH, 2,4-diCH3, 2,4-diOCH3, 2,4-diF, 2,4-diCl, 2,4-diBr, 3,5-diOH, 3,5-diCH3, 3,5-diOCH3, 3,5-diF, 3,5-diCl, 3,5-diBr, 2-OH-3-OCH3, 3-F-4-OH, 3-Br-4-OH, or 2-Cl-5-OH.

2. The aromatic acid-based zinc acrylate resin according to claim 1, wherein the resin is prepared by condensation reaction of an aromatic acid basic zinc salt and an acrylic resin.

3. The basic zinc salt of aromatic acid according to claim 2, wherein the preparation method comprises mixing an aromatic acid compound, a hydroxide and zinc chloride in a molar ratio of 1-1.1:2-2.75:1-1.2 to obtain a basic zinc salt; wherein the hydroxide is selected from sodium hydroxide, potassium hydroxide or lithium hydroxide.

4. The acrylic resin according to claim 2, wherein the preparation method comprises the following steps: placing a mixed solvent in a three-necked flask equipped with a mechanical stirrer and heating it to 65-95°C. Acrylate monomer and acrylic acid monomer are separately weighed and added to the mixed solvent; an initiator is added at a rate of 2.8-4.2% based on the combined weight of the acrylate and acrylic acid monomers; the mixture is uniformly mixed, transferred to a constant pressure funnel, and then added dropwise to the flask. After the addition is complete, the reaction is continued for 3 hours; then, an initiator is added at a rate of 1.2-1.8% based on the combined weight of the acrylate and acrylic acid monomers; and the reaction is continued for 3-4 hours to obtain the acrylic resin.

5. The method for preparing the basic zinc salt of aromatic acid according to claim 3, wherein The aromatic acid compound is selected from benzoic acid, 2-hydroxybenzoic acid, 2-methylbenzoic acid, 2-methoxybenzoic acid, 2-fluorobenzoic acid, 2-chlorobenzoic acid, 2-bromobenzoic acid, 2-trifluoromethylbenzoic acid, 2-nitrobenzoic acid, 2-aminobenzoic acid, 3-hydroxybenzoic acid, 3-methylbenzoic acid, 3-methoxybenzoic acid, 3-fluorobenzoic acid, 3-chlorobenzoic acid, 3-bromobenzoic acid, 3-trifluoromethylbenzoic acid, 3-nitrobenzoic acid, 3-aminobenzoic acid, 4-hydroxybenzoic acid, 4-Methylbenzoic acid, 4-methoxybenzoic acid, 4-fluorobenzoic acid, 4-chlorobenzoic acid, 4-bromobenzoic acid, 4-trifluoromethylbenzoic acid, 4-nitrobenzoic acid, 4-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,4-dimethylbenzoic acid, 2,4-dimethoxybenzoic acid, 2,4-difluorobenzoic acid, 2,4-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dihydroxybenzoic acid, 3,5-dimethylbenzoic acid, 3,5-dimethoxybenzoic acid, 3,5-difluorobenzoic acid, 3,5-dichlorobenzoic acid, 3,5-dibromobenzoic acid, 2-hydroxy-3-methoxybenzoic acid, 3-fluoro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 2-chloro-5-hydroxybenzoic acid, phenylacetic acid, 2-hydroxyphenylacetic acid, 2-Methylphenylacetic acid, 2-methoxyphenylacetic acid, 2-fluorophenylacetic acid, 2-chlorophenylacetic acid, 2-bromophenylacetic acid, 2-trifluoromethylphenylacetic acid, 2-nitrophenylacetic acid, 2-aminophenylacetic acid, 3-hydroxyphenylacetic acid, 3-methylphenylacetic acid, 3-methoxyphenylacetic acid, 3-fluorophenylacetic acid, 3-chlorophenylacetic acid, 3-bromophenylacetic acid, 3-trifluoromethylphenylacetic acid, 3-nitrophenylacetic acid, 3-aminophenylacetic acid, 4-hydroxyphenylacetic acid, 4-methylphenylacetic acid, 4-methoxyphenylacetic acid, Aromatic acid compounds of 4-fluorophenylacetic acid, 4-chlorophenylacetic acid, 4-bromophenylacetic acid, 4-trifluoromethylphenylacetic acid, 4-nitrophenylacetic acid, 4-aminophenylacetic acid, 2,4-dihydroxyphenylacetic acid, 2,4-dimethylphenylacetic acid, 2,4-dimethoxyphenylacetic acid, 2,4-difluorophenylacetic acid, 2,4-dichlorophenylacetic acid, 2,4-dibromophenylacetic acid, 3,5-dihydroxyphenylacetic acid, 3,5-dimethylphenylacetic acid, 3,5-dimethoxyphenylacetic acid, 3,5-difluorophenylacetic acid, 3,5-dichlorophenylacetic acid, 3,5-dibromophenylacetic acid, 2-hydroxy-3-methoxyphenylacetic acid, 3-fluoro-4-hydroxyphenylacetic acid, 3-bromo-4-hydroxyphenylacetic acid, 2-chloro-5-hydroxyphenylacetic acid or p-coumaric acid.

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

7. The preparation method of aromatic acid-based zinc acrylate resin according to claim 2, characterized in that, The molar ratio of the basic zinc salt to the acrylic acid monomer is 1:1-1.

5. The basic zinc salt is added in several times, which can be two or three times and can be adjusted at any time according to the specific experimental conditions.

8. The aromatic acid-based zinc acrylate resin obtained by the preparation method according to any one of claims 1 to 7, characterized in that The number average molecular weight of the resin ranges from 9,000 to 14,000 g / mol, and the molecular weight distribution ranges from 1.0 to 2.

5.

9. The aromatic acid-based zinc acrylate resin obtained by the preparation method according to any one of claims 1 to 8, characterized in that When the resin is used as a marine antifouling coating, its static antifouling period is more than 180 days, and it has good antifouling performance.

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