An acrylate metal salt resin containing rosin and rosin-derived quaternary ammonium salt, and a preparation method and application thereof

Abstract

The application provides an acrylic metal salt resin containing rosin and rosin-derived quaternary ammonium salt and a preparation method and application thereof, and relates to the technical field of organic polymer materials. The acrylic metal salt resin is prepared by the following preparation method: rosin, maleic anhydride, p-toluenesulfonic acid and acetic acid are mixed and heated to reflux to obtain maleopimaric acid; maleopimaric acid, alcohol and N, N-dimethylethylenediamine are mixed and heated to obtain a product precursor; the product precursor is mixed with tetrahydrofuran and bromoethane to obtain rosin-derived quaternary ammonium salt; acrylic ester monomers, acrylic acid and methacrylic acid are mixed to obtain a monomer mixture; the monomer mixture is mixed with an initiator, a solvent and a chain transfer agent to carry out polymerization and obtain a resin prepolymer; and then a metal-containing compound, rosin, a small-molecule organic acid, a solvent and rosin-derived quaternary ammonium salt are mixed to obtain the acrylic metal salt resin with antibacterial and anti-protein adsorption properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic polymer materials, and particularly relates to an acrylate metal salt resin containing rosin and rosin-derived quaternary ammonium salt, and a preparation method and application thereof. BACKGROUND

[0002] Marine biofouling is one of the main challenges in the process of human development of marine resources. It is prone to occur on the surface of various underwater structures, increases the sailing resistance and fuel consumption of ships, accelerates metal corrosion, and causes huge economic losses and environmental impact. Therefore, marine biofouling seriously limits the development and utilization of the ocean by human beings, and becomes a major problem faced by human marine activities.

[0003] Coating antifouling paint is an economic, effective and universally used method to prevent marine biofouling. Self-polishing coating is the most commonly used method to inhibit the generation of marine biofouling due to its remarkable effect, convenient construction and economy. The organic tin (TBT) self-polishing coating, which is called "special weapon" due to its serious harm to the environment, is banned. After that, the development of environmentally friendly antifouling paint becomes the research focus.

[0004] Acrylate metal salt resin is a main tin-free self-polishing material and one of the most effective marine antifouling materials at present. At present, zinc / copper acrylate resin has been widely used, for example, the series of Sea Quantum of ZOJON, Intersmooth 365SPC, etc. The tin-free self-polishing antifouling paint must be matched with parameters such as the interval of dock repair and the sailing speed of the ship to achieve the ideal antifouling period effect. Many foreign brands, such as ZOJON, HAIHONGLAO, etc., have subdivided their self-polishing antifouling paint into multiple categories, but the existing acrylate metal salt resin has the problems of weak antibacterial performance, poor protein adsorption resistance and poor green environmental protection.

[0005] Rosin is a rich biomass resource with high yield. It has been widely used in antifouling paint for a long time due to its excellent natural properties of antibacterial, antimicrobial and anti-protein adsorption. And the derivatives obtained by chemical modification of rosin as raw material have been widely used in the fields of essence and perfume, medicine and chemical industry. The main component of rosin is a mixture of resin acids containing hydrogenated phenanthrene ring structure, which has multiple chiral centers and good biological activity. By introducing functional substituents and special functional groups through chemical modification of the hydrogenated phenanthrene ring structure and carboxyl group of rosin resin acid, rosin-derived quaternary ammonium salt compounds with good antibacterial activity and biocompatibility can be prepared. Such quaternary ammonium salt compounds not only exhibit high bactericidal performance, but also are environmentally friendly and have no toxic side effects, and have good biocompatibility. Developing antibacterial coating by using them as bactericides has great development potential. Not only can the antibacterial performance of acrylate metal salt resin be effectively improved, but also a new way for high-value utilization of rosin is opened up, which has broad application prospects.

[0006] Therefore, it is of great significance to prepare a coating for marine antifouling by using rosin and rosin-derived quaternary ammonium salt compounds. SUMMARY

[0007] The present application aims to provide a rosin and rosin-derived quaternary ammonium salt-containing metal acrylate resin and its preparation method and application, so as to solve the problems of weak antibacterial performance, poor protein adsorption resistance and poor green environmental protection of the existing metal acrylate resin.

[0008] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0009] The present application provides a rosin and rosin-derived quaternary ammonium salt-containing metal acrylate resin, and the structure of the rosin and rosin-derived quaternary ammonium salt-containing metal acrylate resin is as follows:

[0010]

[0011] R1 is selected from -H, -CH3;

[0012] R2 is selected from -H, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2CH(CH3)2, -CH2CH2OH, -(CH2)3OH, -CH2CH2CH3, -(CH2)4OH, -(CH2)3CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 -(CH2) 11 -(CH2) 17 -(CH2)

[0013] R3, R5 and R6 are independently selected from -H and -CH3;

[0014] R4 is selected from the acid radicals of lactic acid, benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, rosin acid, dimeric rosin acid, disulfide rosin acid, proline, leucine, phenylalanine, arginine, salicylic acid, furoic acid and p-chlorobenzoic acid;

[0015] 40≤n≤90, 1≤x≤20, 10≤y≤20 and 1≤z≤20.

[0016] The present application also provides a preparation method of the rosin and rosin-derived quaternary ammonium salt-containing metal acrylate resin, which comprises the following steps:

[0017] 1) mixing and heating rosin, maleic anhydride, p-toluenesulfonic acid and acetic acid to reflux to obtain maleopimaric acid; mixing and heating maleopimaric acid, alcohol solvent and N,N-dimethyl ethylenediamine to obtain product precursor; mixing and heating product precursor, tetrahydrofuran and bromoethane to obtain rosin derivative quaternary ammonium salt;

[0018] 2) mixing acrylic ester monomer, acrylic acid and methacrylic acid to obtain monomer mixture, mixing and polymerizing monomer mixture, initiator, solvent and chain transfer agent to obtain resin prepolymer;

[0019] 3) mixing resin prepolymer prepared in step 2), metal-containing compound, rosin, small molecule organic acid, solvent and rosin derivative quaternary ammonium salt prepared in step 1) to obtain acrylic acid metal salt resin containing rosin and rosin derivative quaternary ammonium salt;

[0020] Step 1) and step 2) have no sequence limitation.

[0021] Preferably, the molar ratio of rosin, maleic anhydride and p-toluenesulfonic acid in step 1) is 100:75-125:5-20; the mass ratio of rosin to acetic acid is 100:50-200;

[0022] The temperature of the heating reflux reaction is 100-140℃, and the time is 12-24h.

[0023] Preferably, the molar ratio of maleopimaric acid to N,N-dimethyl ethylenediamine in step 1) is 100:100-125, and the mass ratio of maleopimaric acid to alcohol solvent is 1:10-20.

[0024] In the process of preparing product precursor, the temperature of heating reaction is 70-100℃, and the time of heating reaction is 2-5h;

[0025] The alcohol solvent includes one or more of ethanol, methanol and n-butanol.

[0026] Preferably, the mass ratio of product precursor to tetrahydrofuran in step 1) is 1:20-30.

[0027] The molar ratio of product precursor to bromoethane is 100:100-125.

[0028] In the process of preparing rosin derivative quaternary ammonium salt, the temperature of the reaction is 40-60℃, and the time of the reaction is 12-24h.

[0029] Preferably, the molar ratio of acrylic ester monomer, acrylic acid and methacrylic acid in step 2) is 40-90:10-20:10-40.

[0030] The amount of the initiator added is 0.8 to 3.2% by weight of the monomer mixture;

[0031] The added amount of the chain transfer agent is 0.2 to 2.0% by weight of the monomer mixture;

[0032] The amount of the solvent added is 75 to 125% by weight of the monomer mixture;

[0033] The polymerization reaction temperature is 75-110° C., the polymerization reaction time is 2-6 hours, and the polymerization reaction atmosphere is an inert atmosphere.

[0034] Preferably, the acrylic acid ester monomer in step 2) comprises one or more of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hydroxybutyl acrylate, isooctyl acrylate, laurate acrylate and octadecyl acrylate;

[0035] The initiator includes one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate and potassium persulfate;

[0036] The chain transfer agent includes one or more of n-dodecyl mercaptan, tert-dodecyl mercaptan and aliphatic mercaptan;

[0037] The solvent includes one or more of toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, n-butanol and isobutanol.

[0038] Preferably, the molar ratio of rosin, rosin derivative quaternary ammonium salt and small molecule organic acid in step 3) is 50-90:1-30:0-30;

[0039] The ratio of the amount of the metal compound to the total amount of rosin, rosin derivative quaternary ammonium salt and small molecule organic acid is 1:0.5-2.0;

[0040] The ratio of the sum of the amount of acrylic acid and methacrylic acid in the resin prepolymer to the total amount of the metal compound, rosin, rosin derivative quaternary ammonium salt and small molecular organic acid is 0.5 to 2:1;

[0041] The amount of the solvent added is 0.5 to 5 times the total mass of the metal compound, rosin, rosin derivative quaternary ammonium salt and small molecule organic acid;

[0042] The temperature of the mixed reaction is 75-110° C., and the time is 2-6 hours.

[0043] Preferably, the metal-containing compound in step 3) comprises one or more of zinc oxide, copper oxide, zinc hydroxide and copper hydroxide;

[0044] The small molecule organic acid includes one or more of lactic acid, benzoic acid, cyclohexane acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, rosin acid, dimerized rosin acid, disproportionated rosin acid, proline, leucine, phenylalanine, arginine, salicylic acid, furoic acid and p-chlorobenzoic acid;

[0045] The solvent includes one or more of toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, n-butanol and isobutanol.

[0046] The present invention also provides a use of the acrylic acid metal salt resin containing rosin and rosin-derived quaternary ammonium salt as an antifouling coating.

[0047] The present invention has at least the following beneficial effects:

[0048] (1) The present invention combines acrylic resin with rosin and rosin-derived quaternary ammonium salt compounds to prepare a new type of acrylic acid metal salt resin containing rosin and rosin-derived quaternary ammonium salt, which has excellent antibacterial properties and anti-protein adsorption properties.

[0049] (2) The present invention's metal acrylate resin containing rosin and a rosin-derived quaternary ammonium salt primarily utilizes rosin, which is abundant in natural resources and environmentally friendly. The invented metal acrylate resin exhibits excellent antifouling effects in marine environments, with an antifouling period exceeding 240 days, and has promising application prospects in the field of marine antifouling. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the rosin-derived quaternary ammonium salt prepared in Example 1;

[0051] Figure 2 This is a scanning electron microscope image of the zinc acrylate resin prepared in Example 1;

[0052] Figure 3 This is the full X-ray photoelectron spectrum of the zinc acrylate resin prepared in Example 1;

[0053] Figure 4 The graph is a result of testing the antibacterial properties of the acrylic acid metal salt resins prepared in Examples 1 to 3 and Comparative Examples 1 to 2. Figure 4 (A) is the statistical chart of the antibacterial rate against Escherichia coli and marine bacteria. Figure 4 (B) is a photo of the colony.

[0054] Figure 5The results of the anti-protein adsorption performance test of the metal acrylate resin prepared in Examples 1-3 and Comparative Examples 1-2 are shown in the following figures, Figure 5 (A) in the figure is a standard curve of protein concentration-absorbance, Figure 5 (B) in the figure is a statistical graph of the anti-protein adsorption rate.

[0055] Figure 6 The test results of the actual marine antifouling effect test of the metal acrylate resin prepared in Examples 1-3 and Comparative Examples 1-2 are shown in the following figures. DETAILED DESCRIPTION

[0056] The present application provides a metal acrylate resin containing rosin and rosin-derived quaternary ammonium salt, the structure of the metal acrylate resin containing rosin and rosin-derived quaternary ammonium salt is as follows:

[0057]

[0058] wherein R1 is selected from -H, -CH3;

[0059] R2 is selected from -H, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2CH(CH3)2, -CH2CH2OH, -(CH2)3OH, -CH2CH2CH3, -(CH2)4OH, -(CH2)3CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 17 CH3;

[0060] R3, R5, R6 are independently selected from -H, -CH3;

[0061] R4 is selected from the acid radicals of lactic acid, benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, dimeric abietic acid, disulfide abietic acid, proline, leucine, phenylalanine, arginine, salicylic acid, furoic acid, p-chlorobenzoic acid.

[0062] wherein 40≤n≤90, 1≤x≤20, 10≤y≤20, 1≤z≤20, preferably 50≤n≤85, 3≤x≤18, 12≤y≤18, 3≤z≤17, further preferably 55≤n≤80, 5≤x≤15, 13≤y≤17, 5≤z≤15, more preferably 60≤n≤75, 8≤x≤12, 14≤y≤16, 8≤z≤12, n, x, y, z are all integers.

[0063] The application also provides a preparation method of the rosin and rosin-derived quaternary ammonium salt-containing acrylic metal salt resin, comprising the following steps:

[0064] 1) mixing and heating rosin, maleic anhydride, p-toluenesulfonic acid and acetic acid to reflux to obtain maleopimaric acid; mixing and heating the maleopimaric acid, an alcohol solvent and N,N-dimethylethylene diamine to obtain a product precursor; mixing and reacting the product precursor with tetrahydrofuran and bromoethane to obtain a rosin-derived quaternary ammonium salt;

[0065] 2) mixing an acrylic ester monomer and methacrylic acid to obtain a monomer mixture, and mixing the monomer mixture with an initiator, a solvent and a chain transfer agent to perform a polymerization reaction to obtain a resin prepolymer;

[0066] 3) mixing the resin prepolymer prepared in step 2), a metal-containing compound, rosin, a small-molecule organic acid, a solvent and the rosin-derived quaternary ammonium salt prepared in step 1) to obtain the rosin and rosin-derived quaternary ammonium salt-containing acrylic metal salt resin;

[0067] Steps 1) and 2) are not limited in sequence.

[0068] In the application, the molar ratio of the rosin, maleic anhydride and p-toluenesulfonic acid in step 1) is 100:75-125:5-20, preferably 100:80-120:8-18, further preferably 100:90-110:10-15, and more preferably 100:95-105:12-13.

[0069] In the application, the rosin in step 1) is preferably reacted with acetic acid after condensation reflux heating, the temperature of the condensation reflux heating is preferably 170-190℃, and can be 170℃, 175℃, 180℃, 185℃ or 190℃; the time of the condensation reflux heating is preferably 3-5h, and can be 3h, 3.5h, 4.5h or 5h. The purpose of the condensation reflux heating is to convert various configurations of isomers in the rosin into levopimaric acid, and the levopimaric acid can react with maleic anhydride; the temperature lower than 170℃ is not conducive to the conversion of the configurations, and if higher than 190℃, the rosin is prone to blackening.

[0070] In the application, the mass ratio of the rosin to acetic acid in step 1) is 100:50-200, preferably 100:70-180, further preferably 100:100-150, and more preferably 100:120-130.

[0071] In the present application, the temperature of the heating reflux reaction in step 1) is 100-140℃, preferably 105-135℃, further preferably 110-130℃, and more preferably 115-125℃; and the time is 12-24h, preferably 14-20h, further preferably 14-16h. The reaction of the rosin and maleic anhydride can be well ensured at 120-130℃, and the yield can be ensured by the reaction time of 14-16h. The yield will be low if the reaction time is too short, and the yield will not be greatly improved if the reaction time is too long.

[0072] In the present application, the molar ratio of the maleopimaric acid to N,N-dimethylethylenediamine in step 1) is 100:100-125, preferably 100:105-120, further preferably 100:110-120, and more preferably 100:115-118; and the mass ratio of the maleopimaric acid to the alcohol solvent is 1:10-20, preferably 1:12-18, further preferably 1:14-16, and more preferably 1:15.

[0073] In the process of preparing the product precursor, the temperature of the heating reaction is 70-100℃, preferably 75-95℃, further preferably 80-90℃, and more preferably 85℃; and the time of the heating reaction is 2-5h, preferably 2.5-4.5h, further preferably 3-4h, and more preferably 3.5h.

[0074] In the present application, the alcohol solvent in step 1) includes one or more of ethanol, methanol and n-butanol.

[0075] In the present application, the mass ratio of the product precursor to tetrahydrofuran in step 1) is 1:20-30, preferably 1:22-28, further preferably 1:24-26, and more preferably 1:25.

[0076] In the present application, the molar ratio of the product precursor to bromoethane in step 1) is 100:100-125, preferably 100:105-120, further preferably 100:108-120, and more preferably 100:110-115.

[0077] In the present application, in the process of preparing the rosin-derived quaternary ammonium salt in step 1), the temperature of the reaction is 40-60℃, preferably 43-58℃, further preferably 45-55℃, and more preferably 48-53℃; and the time of the reaction is 12-24h, preferably 14-22h, further preferably 16-20h, and more preferably 18-20h.

[0078] In the present application, after the heating reflux reaction in step 1) is completed, a step of separating and purifying the maleopimaric acid is further included, specifically: the mixed reaction is cooled and left for 1-4 hours, the precipitate is washed and recrystallized with acetic acid to obtain the maleopimaric acid.

[0079] In the present application, the molar ratio of the acrylic ester monomer, acrylic acid and methacrylic acid in step 2) is 40-90: 10-20: 10-40, preferably 45-85: 12-18: 15-35, further preferably 50-80: 14-16: 20-30, and more preferably 60-70: 14-15: 25-28. If the amount of acrylic acid is low, the self-polishing performance of the resin will decrease, and good antifouling effect cannot be obtained; if the amount of acrylic acid is too high, the amount of metal and small-molecule organic acid participating in the dehydration condensation will be too much, the viscosity of the resin will be too large, and the reaction will be difficult to proceed normally. The methacrylic acid monomer has a similar effect as the acrylic acid monomer, but its effect is also reflected in improving the hardness of the resin and plays an important role in adjusting the hardness of the resin. If the amount of methacrylic acid monomer is lower than the range defined by the above molar ratio, the overall resin may be soft. If the amount of methacrylic acid monomer is higher than the range defined by the above molar ratio, the side chain will increase, the viscosity of the resin will be too large, and the resin will be prone to agglomeration and clumping, which will also affect the mechanical properties of the resin. Therefore, the appropriate molar ratio of the amount of methacrylic acid monomer to the acrylic ester monomer is 10-40: 40-90. If the amount of acrylic ester monomer is too low, the length and flexibility of the molecular chain of the resin cannot be well adjusted; if the amount of acrylic ester monomer is too high, the resin material of the present application will be too soft, which is not conducive to its film formation. Too little amount of initiator will result in incomplete polymerization of the acrylic resin and possible violent polymerization; too much amount of initiator will result in low viscosity and short molecular chain of the acrylic resin, which is not conducive to the adhesion and film formation of the resin.

[0080] In the present application, the amount of initiator added in step 2) is 0.8-3.2% of the weight of the monomer mixture, preferably 1-3%, further preferably 1.5-2.5%, and more preferably 1.8-2.2%.

[0081] In the present application, the amount of chain transfer agent added in step 2) is 0.2-2.0% of the weight of the monomer mixture, preferably 0.5-1.5%, further preferably 0.8-1.3%, and more preferably 1.0-1.2%.

[0082] In the present application, the amount of solvent added in step 2) is 75-125% of the weight of the monomer mixture, preferably 80-120%, further preferably 90-110%, and more preferably 95-105%.

[0083] In the present application, the temperature of the polymerization reaction in step 2) is 75-110°C, preferably 80-105°C, further preferably 85-100°C, and more preferably 90-95°C; the time of the polymerization reaction is 2-6h, preferably 3-5h, further preferably 3.5-4.5h, and more preferably 4h; and the atmosphere of the polymerization reaction is an inert atmosphere, specifically one or more of helium, argon, neon, or nitrogen. The inert atmosphere can remove oxygen in the reaction system, better reduce the occurrence of side reactions, and effectively improve the catalytic efficiency of the catalyst. Too low a reaction temperature is not conducive to initiating monomer polymerization; and too high a reaction temperature can cause active species to fail.

[0084] In the present application, the acrylic ester monomer in step 2) includes one or more of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hydroxybutyl acrylate, isooctyl acrylate, lauryl acrylate, and stearyl acrylate.

[0085] In the present application, the initiator in step 2) includes one or more of azobisisobutyronitrile, azobisisoheptyl nitrile, dimethyl azobisisobutyrate, benzoyl peroxide, t-butyl benzoyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate, and potassium persulfate.

[0086] In the present application, the chain transfer agent in step 2) includes one or more of n-dodecyl mercaptan, t-dodecyl mercaptan, and aliphatic mercaptan.

[0087] In the present application, the solvent in step 2) includes one or more of toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol.

[0088] In the present application, the mixing method of the monomer mixture, initiator, solvent, and chain transfer agent in step 2) is preferably first mixing the monomer and initiator to obtain a monomer mixture containing the initiator, then adding the solvent, chain transfer agent, and 10-20wt% of the monomer mixture containing the initiator into a reaction vessel, and reacting for 10-30min at the reaction temperature; dividing the remaining monomer mixture containing the initiator into 5-15 portions, adding one portion every 10-20min, and continuing to react for 2-6h after all the monomer mixture containing the initiator is added. The main purpose of dividing the monomer mixture into multiple portions is to avoid agglomeration or explosion caused by too large a single addition amount or too high a local temperature; and a light yellow transparent viscous acrylic acid prepolymer is obtained after the reaction is completed; this process is the formation process of the acrylic resin main chain.

[0089] In the present invention, acrylic acid mainly participates in polymerization to form the main chain of the acrylic resin prepolymer and participates in the subsequent dehydration condensation reaction with metal oxides or hydroxides; methacrylic acid mainly participates in polymerization to form the main chain of the acrylic resin prepolymer and can adjust the hardness of the resin material of the present invention; acrylate monomers also participate in polymerization to form the main chain of the acrylic resin prepolymer and impart flexibility to the resin and improve film-forming properties. The use of long-chain esters can increase the hydrophobicity of the resin.

[0090] In the present invention, the molar ratio of rosin, rosin derivative quaternary ammonium salt and small molecule organic acid in step 3) is 50-90:1-30:0-30, preferably 55-85:5-25:5-25, more preferably 60-80:10-20:10-20, and more preferably 65-75:12-15:15-18.

[0091] In the present invention, the ratio of the amount of the metal compound-containing substance in step 3) to the total amount of rosin, rosin derivative quaternary ammonium salt and small molecule organic acid is 1:0.5-2.0, preferably 1:0.8-1.8, more preferably 1:1.0-1.5, and more preferably 1:1.2.

[0092] In the present invention, the ratio of the sum of the amounts of acrylic acid and methacrylic acid in the resin prepolymer in step 3) to the total amount of the metal compound, rosin, quaternary ammonium salt of rosin derivative and small molecule organic acid is 0.5 to 2:1, preferably 0.8 to 1.8:1, more preferably 1 to 1.5:1, and more preferably 1.2 to 1.4:1.

[0093] In the present invention, the amount of the solvent added in step 3) is 0.5 to 5 times the total mass of the metal compound, rosin, rosin derivative quaternary ammonium salt and small molecule organic acid, preferably 1 to 4.5, more preferably 1.5 to 4, and more preferably 2 to 3.

[0094] In the present invention, the temperature of the mixing reaction in step 3) is 75-110°C, preferably 80-105°C, more preferably 85-100°C, and more preferably 90-95°C; and the reaction time is 2-6 hours, preferably 2.5-5.5 hours, more preferably 3-5 hours, and more preferably 3.5-4.5 hours. The reaction is terminated when no distilled water is released.

[0095] In the present invention, the metal-containing compound in step 3) includes one or more of zinc oxide, copper oxide, zinc hydroxide and copper hydroxide.

[0096] In the present application, the small molecule organic acid in step 3) includes one or more of lactic acid, benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, dimeric abietic acid, disulfated abietic acid, proline, leucine, phenylalanine, arginine, salicylic acid, furoic acid and p-chlorobenzoic acid.

[0097] In the present application, the solvent in step 3) includes one or more of toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, n-butanol and isobutanol.

[0098] The present application also provides the use of the above-mentioned rosin and rosin-derived quaternary ammonium salt-containing acrylic metal salt resin as an antifouling coating.

[0099] The technical solutions provided by the present application will be described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0100] Example 1

[0101] (1) Preparation of rosin-derived quaternary ammonium salt:

[0102] Under a nitrogen atmosphere, rosin was heated under condensation reflux at 180℃ for 3h. Thereafter, the reaction temperature was cooled and maleic anhydride, p-toluenesulfonic acid and acetic acid were added, wherein the molar ratio of maleic anhydride to rosin was 1:1, the amount of p-toluenesulfonic acid was 10% of the molar amount of rosin, and the mass of acetic acid was 110% of the mass of rosin. The reaction was carried out under condensation reflux at 120℃ for 20h, and then cooled and left to stand for 3h. The product was washed and recrystallized with acetic acid to obtain maleopimaric acid.

[0103] Maleopimaric acid was dissolved in ethanol, and N,N-dimethylethylene diamine was added dropwise. The reaction was heated at 80℃ for 4h, and the product was precipitated after standing and cooling to obtain the product precursor, wherein the amount of ethanol was 15 times the mass of maleopimaric acid, and the amount of N,N-dimethylethylene diamine was 105% of the molar amount of maleopimaric acid.

[0104] The product precursor was dissolved in tetrahydrofuran, and bromoethane was added. The reaction was heated at 50℃ for 20h to obtain the final product rosin-derived quaternary ammonium salt, wherein the amount of tetrahydrofuran used was 20 times the mass of the precursor, and the amount of bromoethane was 105% of the molar amount of the precursor.

[0105] (2) Preparation of resin prepolymer:

[0106] Butyl acrylate, ethyl acrylate, acrylic acid and methacrylic acid were mixed in a molar ratio of 30:40:15:15 to obtain a monomer mixture. Then, 1.2% of initiator azobisisobutyronitrile based on the weight of the monomer mixture was added to the monomer mixture, and mixed uniformly to obtain a monomer mixture containing an initiator.

[0107] In a three-necked flask, 100% of the mixed solvent (mixed by xylene and n-butanol with a mass ratio of 4:1) was added according to the weight of the monomer mixture, 0.8% of the chain transfer agent dodecyl mercaptan was added according to the total weight of the reactants, 15% of the monomer mixture containing the initiator was added, and stirring was uniform; nitrogen was introduced into the three-necked flask for 15 min, and the reaction temperature of the reaction mixture was controlled at 85°C under nitrogen protection for 20 min, the remaining 85% of the monomer mixture containing the initiator was divided into 9 portions, and each portion was added every 15 min, and after the addition was completed, the reaction was continued for 4 h to obtain a resin prepolymer.

[0108] (3) Preparation of a zinc acrylate resin containing rosin and rosin-derived quaternary ammonium salt:

[0109] The resin prepolymer, zinc oxide, rosin, the rosin-derived quaternary ammonium salt prepared in step (1), and a solvent were mixed, the amount of zinc oxide added was 1 times the molar amount of acrylic acid and methacrylic acid, the molar ratio of rosin to the rosin-derived quaternary ammonium salt prepared in step (1) was 80:20, the molar ratio of zinc oxide to the total amount of rosin and the rosin-derived quaternary ammonium salt was 1:1, and the amount of the solvent added was equal to the total weight of zinc oxide, rosin, and the rosin-derived quaternary ammonium salt. The solvent used in this step was a mixed solvent of xylene, n-butanol, and butyl acetate with a mass ratio of xylene:n-butanol:butyl acetate=4:1:11. The reaction temperature was controlled at 90°C for 4 h, and then the temperature was increased to the azeotropic temperature for dehydration until no distilled water was discharged, to obtain the zinc acrylate resin, which is denoted as RN-Zn-1.

[0110] The rosin-derived quaternary ammonium salt prepared in step (1) was tested using a nuclear magnetic spectrum tester of the model Bruker AVANCE III 600 from Bruker, Germany, and the characterization results are shown in Figure 1 As can be seen from Figure 1 , the methine a (δ=5.38, -CH=), the methylene b (δ=3.64, -CH2-), the methyl e (δ=3.04, -CH3), and the methine g (δ=2.63, -CH=) nuclear magnetic peaks correspond to the rosin-derived quaternary ammonium salt molecule one by one, proving the successful synthesis of the quaternary ammonium salt molecule.

[0111] The synthesized zinc acrylate resin was characterized using a scanning electron microscope of the model SU8010 from Hitachi, Japan, and the characterization results are shown in Figure 2 As can be seen from Figure 2 , the thickness of the resin coating is about 280 μm, and the cross section is uniform and smooth, which indicates that the resin coating is uniform from top to bottom.

[0112] The synthesized zinc acrylate resin was characterized using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer of Thermo Fisher Corporation, and the characterization results are shown in Table 1. Figure 3 As can be seen from Table 1, it is determined that C, N, O, Zn and Br elements exist in the resin, proving that the rosin and rosin-derived quaternary ammonium salt molecules are successfully introduced into the resin system. Figure 3

[0113] Example 2

[0114] (1) Preparation of rosin-derived quaternary ammonium salt:

[0115] The rosin was heated under condensation reflux at 180°C for 3h under a nitrogen atmosphere. Thereafter, the reaction temperature was cooled and maleic anhydride, p-toluenesulfonic acid and acetic acid were added, wherein the molar ratio of maleic anhydride to rosin was 1:1, the amount of p-toluenesulfonic acid was 10% of the molar amount of rosin, and the mass of acetic acid was 110% of the mass of rosin. The condensation reflux reaction was carried out at 120°C for 20h, and then cooled and stood for 3h. The product was washed and recrystallized with acetic acid to obtain maleopimaric acid.

[0116] The maleopimaric acid was dissolved in ethanol, and N,N-dimethyl ethylenediamine was added dropwise, and heated at 80°C for 4h. After standing and cooling, the product was precipitated to obtain the product precursor, wherein the amount of ethanol was 15 times the mass of maleopimaric acid, and the amount of N,N-dimethyl ethylenediamine was 105% of the molar amount of maleopimaric acid.

[0117] The product precursor was dissolved in tetrahydrofuran, and bromoethane was added, and heated at 50°C for 20h to obtain the final product rosin-derived quaternary ammonium salt, wherein the amount of tetrahydrofuran used was 20 times the mass of the precursor, and the amount of bromoethane was 105% of the molar amount of the precursor;

[0118] (2) Preparation of resin prepolymer:

[0119] Butyl acrylate, lauryl acrylate, acrylic acid and methacrylic acid were mixed in a molar ratio of 40:40:15:15 to obtain a monomer mixture; then, 1.2% of initiator azobisisobutyronitrile based on the weight of the monomer mixture was added to the monomer mixture, and mixed uniformly to obtain a monomer mixture containing an initiator.

[0120] ​In a three-necked flask, 100% of xylene was added as solvent based on the weight of the monomer mixture, 0.8% of chain transfer agent dodecyl mercaptan was added based on the total weight of the reactants, 15% of the monomer mixture containing initiator was added, and stirred uniformly; nitrogen was introduced into the three-necked flask for 15 min, and the reaction temperature of the reaction mixture was controlled at 85°C under nitrogen protection for 20 min, the remaining 85% of the monomer mixture containing initiator was evenly divided into 9 portions, and one portion was added every 15 min, and after the addition was completed, the reaction was continued for 4 h to obtain a resin prepolymer.

[0121] (3) Preparation of a zinc acrylate resin containing rosin and rosin-derived quaternary ammonium salt:

[0122] The resin prepolymer, zinc oxide, rosin, the rosin-derived quaternary ammonium salt prepared in step (1), and a solvent were mixed, the amount of zinc oxide added was 1 times the molar amount of acrylic acid and methacrylic acid, the molar ratio of rosin to the rosin-derived quaternary ammonium salt prepared in step (1) was 80:20, the molar ratio of zinc oxide to the total amount of rosin and the rosin-derived quaternary ammonium salt was 1:1, and the amount of the solvent added was equal to the total weight of zinc oxide, rosin, and the rosin-derived quaternary ammonium salt. The solvent used in this step was a mixed solvent of xylene, n-butanol, and butyl acetate, and the mass ratio of the three was xylene:n-butanol:butyl acetate = 4:1:11. The reaction temperature was controlled at 90°C for 4 h, and then dehydration was performed at the co-boiling temperature under the condition of a temperature of 90°C until no distilled water was discharged, to obtain the zinc acrylate resin, which is denoted as RN-Zn-2.

[0123] Example 3

[0124] (1) Preparation of a rosin-derived quaternary ammonium salt:

[0125] Under a nitrogen atmosphere, rosin was heated by condensation reflux at 180°C for 3 h. Thereafter, the reaction temperature was cooled and maleic anhydride, p-toluenesulfonic acid, and acetic acid were added, wherein the molar ratio of maleic anhydride to rosin was 1:1, the amount of p-toluenesulfonic acid was 10% of the molar amount of rosin, and the mass of acetic acid was 110% of the mass of rosin. Condensation reflux was performed at 120°C for 20 h, and then the product was washed and recrystallized with acetic acid after being cooled and standing for 3 h to obtain maleopimaric acid.

[0126] Maleopimaric acid was dissolved in ethanol, and N,N-dimethylethylene diamine was added dropwise, and the reaction was heated at 80°C for 4 h. The product was precipitated after standing and cooling to obtain a product precursor, wherein the amount of ethanol was 15 times the mass of maleopimaric acid, and the amount of N,N-dimethylethylene diamine was 105% of the molar amount of maleopimaric acid.

[0127] The product precursor is dissolved in tetrahydrofuran, bromoethane is added, and the reaction is heated at 50°C for 20h to obtain the final product rosin-derived quaternary ammonium salt, wherein the amount of tetrahydrofuran used is 20 times the mass of the precursor, and the amount of bromoethane is 105% of the molar amount of the precursor;

[0128] (2) Preparation of resin pre-polymer:

[0129] Butyl acrylate, ethyl acrylate, acrylic acid, and methacrylic acid are mixed in a molar ratio of 30:40:15:15 to obtain a monomer mixture; then, 1.2% of initiator azobisisobutyronitrile based on the weight of the monomer mixture is added to the monomer mixture, and the mixture is uniformly mixed to obtain a monomer mixture containing an initiator.

[0130] In a three-necked flask, 100% of a mixed solvent (obtained by mixing xylene and n-butanol in a mass ratio of 4:1) based on the weight of the monomer mixture is added, 0.8% of a chain transfer agent dodecyl mercaptan based on the total weight of the reactants is added, and 15% of the monomer mixture containing an initiator is added and stirred uniformly; nitrogen is introduced into the three-necked flask for 15 min, and the reaction temperature of the reaction mixture is controlled at 85°C under nitrogen protection for 20 min; the remaining 85% of the monomer mixture containing an initiator is divided into 9 equal parts, and each part is added every 15 min; after the addition is completed, the reaction is continued for 4h to obtain a resin pre-polymer.

[0131] (3) Preparation of rosin and rosin-derived quaternary ammonium salt-containing zinc acrylate resin:

[0132] The resin pre-polymer, zinc oxide, rosin, rosin-derived quaternary ammonium salt prepared in step (1), benzoic acid, and a solvent are mixed, the amount of zinc oxide added is 0.8 times the molar amount of acrylic acid and methacrylic acid, the molar ratio of rosin and rosin-derived quaternary ammonium salt prepared in step (1), benzoic acid is 60:15:25, the molar ratio of zinc oxide to the total amount of rosin, rosin-derived quaternary ammonium salt, and benzoic acid is 1:1, and the amount of the solvent added is equal to the total weight of zinc oxide, rosin, rosin-derived quaternary ammonium salt, and benzoic acid; the solvent used in this step is a mixed solvent of xylene, n-butanol, and butyl acetate in a mass ratio of xylene:n-butanol:butyl acetate = 4:1:11. The reaction temperature is controlled at 90°C for 4h, and then the temperature is raised to the azeotropic temperature for dehydration until no distilled water is discharged, to obtain the zinc acrylate resin, which is denoted as RN-Zn-3.

[0133] Example 4

[0134] (1) Preparation of rosin-derived quaternary ammonium salt:

[0135] The rosin was heated under condensation reflux at 180°C for 3h under nitrogen atmosphere. After that, the reaction temperature was cooled and maleic anhydride, p-toluenesulfonic acid and acetic acid were added, wherein the mole ratio of maleic anhydride to rosin was 1:1, the amount of p-toluenesulfonic acid was 10% of the mole amount of rosin, and the mass of acetic acid was 110% of the mass of rosin. The reaction was carried out under condensation reflux at 120°C for 20h, and then cooled and stood for 3h. The product was washed and recrystallized with acetic acid to obtain maleopimaric acid.

[0136] Maleopimaric acid was dissolved in ethanol, and N,N-dimethyl ethylenediamine was added dropwise. The reaction was heated at 80°C for 4h. After standing and cooling, the product was precipitated to obtain a product precursor, wherein the amount of ethanol was 15 times the mass of maleopimaric acid, and the amount of N,N-dimethyl ethylenediamine was 105% of the mole amount of maleopimaric acid.

[0137] The product precursor was dissolved in tetrahydrofuran, and bromoethane was added. The reaction was heated at 50°C for 20h to obtain the final product rosin-derived quaternary ammonium salt, wherein the amount of tetrahydrofuran used was 20 times the mass of the precursor, and the amount of bromoethane was 105% of the mole amount of the precursor;

[0138] (2) Preparation of resin prepolymer:

[0139] Butyl acrylate, ethyl acrylate, acrylic acid and methacrylic acid were mixed in a mole ratio of 30:40:15:15 to obtain a monomer mixture. Then, 1.2% of initiator azobisisobutyronitrile based on the weight of the monomer mixture was added to the monomer mixture, and mixed uniformly to obtain a monomer mixture containing an initiator.

[0140] In a three-necked flask, 100% of xylene was added as a solvent based on the weight of the monomer mixture, 0.8% of chain transfer agent dodecyl mercaptan was added based on the total weight of the reactants, and 15% of the monomer mixture containing an initiator was added, and stirred uniformly. Nitrogen was introduced into the three-necked flask for 15min, and the reaction temperature of the reaction mixture was controlled at 85°C under nitrogen protection for 20min. The remaining 85% of the monomer mixture containing an initiator was divided into 9 equal parts, and each part was added every 15min. After the addition was completed, the reaction was continued for 4h to obtain a resin prepolymer.

[0141] (3) Preparation of zinc acrylate resin containing rosin and rosin-derived quaternary ammonium salt:

[0142] The resin prepolymer, zinc oxide, rosin, the rosin-derived quaternary ammonium salt prepared in step (1), lactic acid and solvent are mixed, the amount of zinc oxide added is 1 times the molar amount of acrylic acid and methacrylic acid, the molar ratio of rosin, the rosin-derived quaternary ammonium salt prepared in step (1) and lactic acid is 70:20:10, the molar ratio of zinc oxide to the total amount of rosin, the rosin-derived quaternary ammonium salt and lactic acid is 1:1, the amount of the solvent added is equal to the total weight of zinc oxide, rosin, the rosin-derived quaternary ammonium salt and lactic acid, the solvent used in this step is a mixture of xylene and butyl acetate, the mass ratio of xylene to butyl acetate is 1:2. The reaction temperature is controlled at 90°C for 4h, then the temperature is raised to the azeotropic temperature for dehydration until no distilled water is discharged, and the zinc acrylate resin is obtained, which is recorded as RN-Zn-4.

[0143] Example 5

[0144] (1) Preparation of the rosin-derived quaternary ammonium salt:

[0145] Under a nitrogen atmosphere, rosin is heated by condensation reflux at 180°C for 3h. After that, the reaction temperature is cooled and maleic anhydride, p-toluenesulfonic acid and acetic acid are added, wherein the molar ratio of maleic anhydride to rosin is 1:1, the amount of p-toluenesulfonic acid is 10% of the molar amount of rosin, and the mass of acetic acid is 110% of the mass of rosin. The condensation reflux reaction is carried out at 120°C for 20h, and then the product is washed and recrystallized with acetic acid after being cooled and standing for 3h to obtain maleopimaric acid.

[0146] Maleopimaric acid is dissolved in ethanol, and N,N-dimethylethylene diamine is added dropwise, and the reaction is heated at 80°C for 4h. The product is precipitated after standing and cooling to obtain the product precursor, wherein the amount of ethanol is 15 times the mass of maleopimaric acid, and the amount of N,N-dimethylethylene diamine is 105% of the molar amount of maleopimaric acid.

[0147] The product precursor is dissolved in tetrahydrofuran, and bromoethane is added, and the reaction is heated at 50°C for 20h to obtain the final product, the rosin-derived quaternary ammonium salt, wherein the amount of tetrahydrofuran used is 20 times the mass of the precursor, and the amount of bromoethane is 105% of the molar amount of the precursor;

[0148] (2) Preparation of the resin prepolymer:

[0149] Butyl acrylate, ethyl acrylate, acrylic acid and methacrylic acid are mixed according to a molar ratio of 30:40:15:15 to obtain a monomer mixture; then, 1.2% of the initiator azobisisobutyronitrile based on the weight of the monomer mixture is added to the monomer mixture, and the mixture is uniformly mixed to obtain a monomer mixture containing an initiator.

[0150] In a three-necked flask, 100% of xylene was added as solvent based on the weight of the monomer mixture, 0.8% of chain transfer agent dodecyl mercaptan was added based on the total weight of the reactants, 15% of the monomer mixture containing initiator was added, and stirred uniformly; nitrogen was introduced into the three-necked flask for 15 min, and the reaction temperature of the reaction mixture was controlled at 85°C under nitrogen protection for 20 min, the remaining 85% of the monomer mixture containing initiator was divided into 9 portions, and each portion was added every 15 min, and after the addition was completed, the reaction was continued for 4 h to obtain a resin prepolymer.

[0151] (3) Preparation of zinc acrylate resin containing rosin and rosin-derived quaternary ammonium salt:

[0152] The resin prepolymer, zinc oxide, copper hydroxide, rosin, the rosin-derived quaternary ammonium salt prepared in step (1), and a solvent were mixed, the total amount of zinc oxide and copper hydroxide added was 1 times the molar amount of acrylic acid and methacrylic acid, the molar ratio of zinc oxide to copper hydroxide was 1:1, the molar ratio of rosin to the rosin-derived quaternary ammonium salt prepared in step (1) was 80:20, the molar ratio of the total amount of zinc oxide and copper oxide to the total amount of rosin and rosin-derived quaternary ammonium salt was 1:1, and the amount of the solvent added was equal to the total weight of zinc oxide, copper hydroxide, rosin, and rosin-derived quaternary ammonium salt. The solvent used in this step was a mixed solvent of xylene, n-butanol, and butyl acetate, and the mass ratio of the three was xylene:n-butanol:butyl acetate=4:1:11. The reaction temperature was controlled at 90°C for 4 h, and then the temperature was increased to the azeotropic temperature for dehydration until no distilled water was discharged, to obtain the zinc copper acrylate resin, which is denoted as RN-Zn / Cu.

[0153] Comparative Example 1

[0154] This comparative example is compared with Example 1, and the only difference is that no rosin-derived quaternary ammonium salt is added in step (3), and the zinc acrylate resin prepared is denoted as R-Zn-1.

[0155] Comparative Example 2

[0156] This comparative example is compared with Example 1, and the only difference is that the rosin-derived quaternary ammonium salt in step (3) is replaced by benzoic acid, and the molar ratio of rosin to benzoic acid is 80:20, and the zinc acrylate resin prepared is denoted as R-Z. n -2.

[0157] The antibacterial and anti-protein adsorption abilities of the coating layers of the metal acrylate resins prepared in Examples 1-3 and Comparative Examples 1-2 of the present application were tested, and the specific test methods and results are as follows:

[0158] Preparation of sample plate: first, take PVC plate (5*5cm), polish the PVC plate to increase roughness, which is beneficial for sample adhesion. After washing and drying the PVC plate, apply the resin samples of Examples 1-3 and Comparative Examples 1-2 on the PVC plate, the coating amount is 0.1g / cm 2 , apply 3 times, the interval time is 16h, naturally dry for 3 days, and then dry in 45℃ oven for 3 days before testing.

[0159] The bacteria used in the antibacterial experiment were activated for 24h at 37℃. The culture medium and agar were prepared and sterilized at high temperature. The bacteria were cultured in the culture medium for 24h, and then the bacterial solution was diluted. The absorbance of the bacterial solution was fixed at 0.3 at a wavelength of 600nm under ultraviolet absorption spectrophotometry. Then 1ml of the bacterial solution was added to the sample plate coated with the polymer, and a PE film was covered, placed in a culture dish (d=10cm) and sealed with a sealing film, and then placed in a 37℃ shaking incubator for 24h. Then it was washed repeatedly with 10ml of normal saline to ensure that the bacteria on the surface of the coating were completely washed off, and the washing liquid was collected as the bacterial stock solution. Then the bacterial stock solution was diluted with normal saline to obtain multiple gradient diluted bacterial solutions. 100μL of the diluted bacterial solution was evenly spread on the surface of the agar solid culture medium, and repeated until the bacterial solution was completely absorbed. Then the solid culture medium was placed in a 37℃ shaking incubator for 24h, and the photographs of the bacterial colonies of each group after incubation are shown in (B) of Figure 4 The above antibacterial experiment was performed on the sterilized articles, and the above process was performed in a sterile clean bench. The pure ABS plate was used as the blank control group, and three parallel experiments were performed to obtain the average value.

[0160] The bacteriostatic rate (N) was calculated according to the following formula (1):

[0161] N=(1-N i / N c )×100% (1)

[0162] In the formula, N i is the average number of colonies of the experimental sample, and N C is the average number of colonies of the control group.

[0163] The calculation results of the bacteriostatic rate are shown in (A) of Figure 4 The results show that, compared with the blank and Comparative Examples 1-2, Examples 1-3 with rosin and rosin-derived quaternary ammonium salt have significantly better bacteriostatic effect, and the bacteriostatic effect is more than 98%, which is obvious.

[0164] The initial adhesion of protein on the surface marks the beginning of the marine biofouling attachment, which highlights the necessity of evaluating the anti-protein adsorption properties of the resin coating. The resin coatings of Examples 1-3 and Comparative Examples 1-2 were immersed in phosphate buffered saline (PBS, pH = 7.2) for 2 hours. Subsequently, 20 mg of bovine serum albumin (BSA) was dissolved in 400 ml of PBS to prepare a bovine serum albumin (BSA) solution of 0.05 mg / ml. Then, the pre-soaked resin coating was immersed in 30 ml of the BSA solution with the side of the resin coating on the sample plate facing down, and the sample plate was allowed to float in the BSA solution for 24 hours. After the immersion, the coating surface was rinsed with 10 ml of the BSA solution, and the rinse was collected in the original soaking solution. 20 ml of PBS was further added to the soaking solution. 1 ml was taken from the mixed solution and mixed with 10 ml of a Coomassie brilliant blue working solution. The concentration of BSA was calculated according to the standard curve shown in (A) of Figure 5 .

[0165] The anti-protein adsorption rate (C) was calculated according to the following formula (2):

[0166] C = C i / C0x 100% (2)

[0167] wherein C0is the concentration of the unused BSA solution, and C i is the concentration of the protein not adhered to the coating.

[0168] The calculation results of the anti-protein adsorption rate are shown in (B) of Figure 5 , and it can be seen from Figure 5 that the anti-protein adsorption effect of Examples 1-3 is significantly improved compared to the blank sample and Comparative Examples 1-2, from 43.02% of the blank, 57.88% and 56.23% of Comparative Examples 1-2 to more than 80%, which is very significant.

[0169] The anti-fouling performance of the acrylic metal salt resin prepared according to Examples 1-5 and Comparative Examples 1-2 was tested on the actual marine panel, and the specific test method and results are as follows:

[0170] The acrylic metal salt resins prepared according to Examples 1-5 and Comparative Examples 1-2 were coated as marine anti-fouling materials, and their anti-fouling performance was tested according to the national standard "Anti-fouling paint panel shallow sea immersion test method" (GB / T5370-2007). The test results are shown in Figure 6 .

[0171] The test time is 240 days from October 2023 to July 2024, and the marine biological coverage is observed for 4 different time periods, the first time period is 0 days of sea immersion, the second time period is 30 days of sea immersion, the third time period is 60 days of sea immersion, and the fourth time period is 240 days of sea immersion.

[0172] By Figure 6 It can be seen that after 60 days of real sea experiment, the blank control group is completely covered with marine fouling organisms, and more biological mucosa appears in the comparative examples 1-2. The examples 1-2 have almost no fouling attachment, and the example 3 has a small amount of mucosa, but the resin surface state is good and can be used normally; after 240 days of real sea experiment, the surface of the blank control group is still completely covered with marine organisms, the biological mucosa of the comparative examples 1-2 continues to increase, the example 1 still has almost no any fouling attachment, and the examples 2-3 have a small amount of biological mucosa attachment.

[0173] From the above real sea hanging plate experiment results, it can be seen that the acrylic acid metal salt resin of the present application has excellent antifouling activity compared with the blank plate and the comparative examples, and the antifouling period can reach 240 days. Especially the resin represented by example 1, the surface is still very clean after 240 days.

[0174] The above is only a preferred embodiment of the present application, and it should be noted that for ordinary skilled persons in the technical field, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. An acrylic acid metal salt resin containing rosin and a rosin-derived quaternary ammonium salt, characterized in that: The structure of the acrylic acid metal salt resin containing rosin and rosin-derived quaternary ammonium salt is as follows: wherein R1 is selected from -H, -CH3; R2 is selected from -H, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2CH(CH3)2, -CH2CH2OH, -(CH2)3OH, -CH2CH2CH3, -(CH2)4OH, -(CH2)3CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 17 CH3; R3, R5, and R6 are independently selected from -H, -CH3; m1, m2, m3 are independently selected from Cu and / or Zn; R4 is selected from the group consisting of lactic acid, benzoic acid, cyclohexane acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, dimerized abietic acid, disproportionated abietic acid, proline, leucine, phenylalanine, arginine, salicylic acid, furoic acid, and p-chlorobenzoic acid; 40≤n≤90, 1≤x≤20, 10≤y≤20, 1≤z≤20.

2. The method for preparing a metal acrylate resin containing rosin and a rosin-derived quaternary ammonium salt according to claim 1, wherein: The following steps are involved: 1) Mixing rosin, maleic anhydride, p-toluenesulfonic acid, and acetic acid and heating them under reflux to obtain maleopimaric acid; mixing maleopimaric acid, an alcohol solvent, and N,N-dimethylethylenediamine and heating them to obtain a product precursor; and mixing the product precursor with tetrahydrofuran and ethyl bromide to obtain a rosin-derived quaternary ammonium salt; 2) mixing an acrylate monomer, acrylic acid, and methacrylic acid to obtain a monomer mixture, and mixing the monomer mixture with an initiator, a solvent, and a chain transfer agent to carry out a polymerization reaction to obtain a resin prepolymer; 3) mixing the resin prepolymer prepared in step 2), the metal-containing compound, rosin, a small molecule organic acid, a solvent, and the rosin-derived quaternary ammonium salt prepared in step 1) to obtain an acrylic acid metal salt resin containing rosin and the rosin-derived quaternary ammonium salt; There is no specific order for steps 1) and 2).

3. The method for preparing a metal acrylate resin containing rosin and a rosin-derived quaternary ammonium salt according to claim 2, wherein: In step 1), the molar ratio of rosin, maleic anhydride, and p-toluenesulfonic acid is 100:75-125:5-20; the mass ratio of rosin to acetic acid is 100:50-200; The heating reflux reaction temperature is 100-140° C., and the time is 12-24 hours.

4. The method for preparing a metal acrylate resin containing rosin and a rosin-derived quaternary ammonium salt according to claim 3, wherein: In step 1), the molar ratio of maleopimaric acid to N,N-dimethylethylenediamine is 100:100-125, and the mass ratio of maleopimaric acid to alcohol solvent is 1:10-20; During the preparation of the product precursor, the heating reaction temperature is 70-100°C and the heating reaction time is 2-5 hours; The alcohol solvent includes one or more of ethanol, methanol and n-butanol.

5. The method for preparing a metal acrylate resin containing rosin and a rosin-derived quaternary ammonium salt according to claim 3 or 4, characterized in that: The mass ratio of the product precursor to tetrahydrofuran in step 1) is 1:20-30; The molar ratio of the product precursor to ethyl bromide is 100:100-125; In the process of preparing the rosin-derived quaternary ammonium salt, the reaction temperature is 40-60° C. and the reaction time is 12-24 hours.

6. The method for preparing a metal acrylate resin containing rosin and a rosin-derived quaternary ammonium salt according to claim 5, characterized in that: In step 2), the molar ratio of the acrylic acid ester monomer, acrylic acid, and methacrylic acid is 40-90:10-20:10-40; The amount of the initiator added is 0.8-3.2% by weight of the monomer mixture; The added amount of the chain transfer agent is 0.2-2.0% by weight of the monomer mixture; The amount of the solvent added is 75-125% by weight of the monomer mixture; The polymerization reaction temperature is 75-110° C., the polymerization reaction time is 2-6 hours, and the polymerization reaction atmosphere is an inert atmosphere.

7. The method for preparing a metal acrylate resin containing rosin and a rosin-derived quaternary ammonium salt according to claim 6, wherein: The acrylic acid ester monomer in step 2) includes one or more of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hydroxybutyl acrylate, lauryl acrylate and octadecyl acrylate; The initiator includes one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate and potassium persulfate; The chain transfer agent includes an aliphatic mercaptan; The solvent includes one or more of toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, n-butanol and isobutanol.

8. The method for preparing a metal acrylate resin containing rosin and a rosin-derived quaternary ammonium salt according to claim 7, characterized in that: The molar ratio of rosin, rosin derivative quaternary ammonium salt and small molecule organic acid in step 3) is 50-90:1-30:0-30; The ratio of the amount of the metal compound to the total amount of rosin, rosin derivative quaternary ammonium salt and small molecule organic acid is 1:0.5-2.0; The ratio of the sum of the amounts of acrylic acid and methacrylic acid in the resin prepolymer to the total amount of the metal compound, rosin, rosin derivative quaternary ammonium salt and small molecular organic acid is 0.5 to 2:1; The amount of the solvent added is 0.5 to 5 times the total mass of the metal compound, rosin, rosin derivative quaternary ammonium salt and small molecule organic acid; The temperature of the mixed reaction is 75-110° C., and the time is 2-6 hours.

9. The method for preparing a metal acrylate resin containing rosin and a rosin-derived quaternary ammonium salt according to claim 8, characterized in that: The metal-containing compound in step 3) includes one or more of zinc oxide, copper oxide, zinc hydroxide and copper hydroxide; The small molecule organic acid includes one or more of lactic acid, benzoic acid, cyclohexane acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, rosin acid, dimerized rosin acid, disproportionated rosin acid, proline, leucine, phenylalanine, arginine, salicylic acid, furoic acid and p-chlorobenzoic acid; The solvent includes one or more of toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, n-butanol and isobutanol.

10. Use of the acrylate metal salt resin containing rosin and a rosin-derived quaternary ammonium salt as claimed in claim 1 or the acrylate metal salt resin containing rosin and a rosin-derived quaternary ammonium salt as claimed in any one of claims 2 to 9 as an antifouling coating.

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