Acrylic acid metal salt resin containing rosin and rosin derivative quaternary ammonium salt as well as preparation method and application of acrylic acid metal salt resin

Abstract

The invention provides acrylic acid metal salt resin containing rosin and rosin derivative quaternary ammonium salt as well as a preparation method and application thereof, and relates to the technical field of organic polymer materials. The acrylic acid metal salt resin is prepared by the following preparation method: rosin, maleic anhydride, p-toluenesulfonic acid and acetic acid are mixed, heated and subjected to reflux reaction to obtain maleopimaric acid; the preparation method comprises the following steps: mixing maleopimaric acid, alcohol and N, N-dimethylethylenediamine, and heating to obtain a product precursor; mixing and reacting the product precursor with tetrahydrofuran and bromoethane to obtain rosin-derived quaternary ammonium salt; the preparation method comprises the following steps: 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 for polymerization to obtain a resin prepolymer; and adding a metal-containing compound, rosin, small-molecular organic acid, a solvent and rosin-derived quaternary ammonium salt, mixing and reacting to obtain the acrylic acid metal salt resin with antibacterial and anti-protein adsorption properties.

Description

Technical Field

[0001] The invention relates to the technical field of organic polymer materials, and in particular to an acrylic acid metal salt resin containing rosin and a rosin-derived quaternary ammonium salt, and a preparation method and application thereof. Background Art

[0002] Marine pollution is one of the main challenges faced by humans in the process of developing marine resources. It easily appears on the surface of various underwater structures, increasing the navigation resistance and fuel consumption of ships, accelerating metal corrosion, and causing huge economic losses and environmental impacts. Therefore, marine pollution seriously restricts people's development and utilization of the ocean and becomes a major problem facing human marine activities.

[0003] Antifouling coating is an economical, effective and widely used method to prevent marine biofouling. Self-polishing coating has become the most commonly used method to inhibit marine fouling due to its remarkable effect, convenient construction and economical price. Due to its serious harm to the environment, organotin (TBT) self-polishing coating, known as the "special effect weapon", was banned. Since then, the development of environmentally friendly antifouling coating has become a research focus.

[0004] Acrylic acid metal salt resin is the main Wuxi self-polishing material and one of the most effective marine antifouling materials. At present, zinc / copper acrylate resin has been widely used, such as Jotun Sea Quantum series, Intersmooth 365SPC, etc. Wuxi self-polishing antifouling coatings must be matched with parameters such as docking intervals and ship speeds to achieve ideal antifouling effects. Many foreign brands, such as Jotun and Hempel, have subdivided their self-polishing antifouling coatings into multiple categories, but the existing acrylic acid metal salt resins have weak antibacterial properties and poor anti-protein adsorption performance and poor green environmental protection.

[0005] Rosin is a rich biomass resource with high yield. With its excellent natural properties of antibacterial, antimicrobial and anti-protein adsorption, it has been widely used in antifouling coatings for a long time. And the derivatives obtained by chemical modification using it as raw material have been widely used in flavors and fragrances, 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 using the hydrogenated phenanthrene ring structure and carboxyl group of rosin resin acid, functional substituents and special functional groups are introduced through chemical modification, and rosin-derived quaternary ammonium salt compounds with good antibacterial activity and biocompatibility can be prepared. This quaternary ammonium salt compound not only shows efficient bactericidal performance, but is also environmentally friendly, non-toxic and has good biocompatibility. It has great development potential to develop antibacterial coatings as a bactericide. It can not only effectively improve the antibacterial properties of acrylic metal salt resins, but also open up new ways for the high-value utilization of rosin, and has broad application prospects.

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

[0007] The purpose of the present invention is to provide an acrylic acid metal salt resin containing rosin and rosin-derived quaternary ammonium salt, and a preparation method and application thereof, so as to solve the problems that the existing acrylic acid metal salt resin has weak antibacterial performance, poor anti-protein adsorption performance and poor green environmental protection.

[0008] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0009] The present invention provides an acrylic acid metal salt resin containing rosin and a quaternary ammonium salt derived from rosin. The structure of the acrylic acid metal salt resin containing rosin and a quaternary ammonium salt derived from rosin is as follows:

[0010]

[0011] Wherein, 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 CH3, -(CH2) 11 CH3, -(CH2) 17 CH3;

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

[0014] 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;

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

[0016] The present invention also provides a method for preparing an acrylic acid metal salt resin containing rosin and a rosin-derived quaternary ammonium salt, comprising the following steps:

[0017] 1) mixing rosin, maleic anhydride, p-toluenesulfonic acid and acetic acid, heating and refluxing to obtain maleopimaric acid; mixing maleopimaric acid, an alcohol solvent and N,N-dimethylethylenediamine, heating and reacting to obtain a product precursor; mixing the product precursor with tetrahydrofuran and ethyl bromide to react to obtain a rosin-derived quaternary ammonium salt;

[0018] 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;

[0019] 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;

[0020] There is no limitation on the order of step 1) and step 2).

[0021] Preferably, 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;

[0022] The temperature of the heating reflux reaction is 100-140° C. and the time is 12-24 hours.

[0023] Preferably, 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;

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

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

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

[0027] The molar ratio of the product precursor to ethyl bromide is 100:100-125;

[0028] In the process of preparing the rosin-derived quaternary ammonium salt, the reaction temperature is 40 to 60° C. and the reaction time is 12 to 24 hours.

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

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

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

[0032] The amount of the solvent added is 75-125% of the 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) includes 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 the rosin, the quaternary ammonium salt of the rosin derivative and the small molecule organic acid in step 3) is 50-90:1-30:0-30;

[0039] The ratio of the amount of the metal compound-containing substance to the total amount of rosin, rosin derivative quaternary ammonium salt and small molecular 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, quaternary ammonium salt of rosin derivatives 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 an application 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 novel acrylic metal salt resin containing rosin and rosin-derived quaternary ammonium salt, which has excellent antibacterial properties and anti-protein adsorption properties.

[0049] (2) The rosin is mainly used in the acrylic acid metal salt resin containing rosin and rosin-derived quaternary ammonium salt of the present invention, which is rich in natural resources and environmentally friendly. The acrylic acid metal salt resin of the invention shows excellent antifouling effect in the marine environment, with an antifouling period of more than 240 days, and has good application prospects in the field of marine antifouling. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 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 micrograph 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 results of the antibacterial performance test of the acrylic acid metal salt resins prepared in Examples 1 to 3 and Comparative Examples 1 to 2 are shown in FIG. Figure 4 (A) is a 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 protein adsorption resistance test of the acrylic acid metal salt resins prepared in Examples 1 to 3 and Comparative Examples 1 to 2 are shown in FIG. Figure 5 (A) is the standard curve of protein concentration-absorbance. Figure 5 (B) is a statistical graph of anti-protein adsorption rate;

[0055] Figure 6 The figure is a test result diagram of the actual marine antifouling effect test of the acrylic acid metal salt resin prepared in Examples 1 to 3 and Comparative Examples 1 to 2. DETAILED DESCRIPTION

[0056] The present invention provides an acrylic acid metal salt resin containing rosin and a quaternary ammonium salt derived from rosin. The structure of the acrylic acid metal salt resin containing rosin and a quaternary ammonium salt derived from rosin 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, and R6 are independently selected from -H, -CH3;

[0061] R4 is selected from the group consisting 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.

[0062] Among them, 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, and n, x, y, and z are all integers.

[0063] The present invention also provides a method for preparing an acrylic acid metal salt resin containing rosin and a rosin-derived quaternary ammonium salt, comprising the following steps:

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

[0065] 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;

[0066] 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;

[0067] There is no limitation on the order of step 1) and step 2).

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

[0069] In the present invention, the rosin in step 1) is preferably reacted with acetic acid after condensation reflux heating, and the temperature of condensation reflux heating is preferably 170-190°C, and can be selected from 170°C, 175°C, 180°C, 185°C, and 190°C; the time of condensation reflux heating is preferably 3-5h, and can be selected from 3h, 3.5h, 5h, 4.5h, and 5h. The purpose of condensation reflux heating is to isomerize the various configurations contained in the rosin into L-pimaric acid, so that L-pimaric acid can react with maleic anhydride. A temperature below 170°C is not conducive to the transformation of the configuration, and a temperature above 190°C is prone to blackening of the rosin.

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

[0071] In the present invention, the temperature of the heating reflux reaction in step 1) is 100-140°C, preferably 105-135°C, more preferably 110-130°C, and more preferably 115-125°C; the time is 12-24h, preferably 14-20h, and more preferably 14-16h. At 120-130°C, the rosin and maleic anhydride can react well, and the reaction time of 14-16h can ensure the yield. Too short a reaction time will lead to low yield, and too long a time will not significantly improve the yield.

[0072] In the present invention, the molar ratio of 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; the mass ratio of maleopimaric acid to alcohol solvent is 1:10-20, preferably 1:12-18, further preferably 1:14-16, and more preferably 1:15.

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

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

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

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

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

[0078] In the present invention, after the heating reflux reaction in step 1) is completed, the step of separating and purifying maleopimaric acid is further included, specifically: cooling the mixed reactants and standing for 1 to 4 hours, washing the precipitate with acetic acid, and recrystallizing to obtain maleopimaric acid.

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

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

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

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

[0083] In the present invention, the temperature of the polymerization reaction in step 2) is 75-110°C, preferably 80-105°C, more preferably 85-100°C, and more preferably 90-95°C; the time of the polymerization reaction is 2-6h, preferably 3-5h, more preferably 3.5-4.5h, and more preferably 4h; the atmosphere of the polymerization reaction is an inert atmosphere, specifically one or more of helium atmosphere, argon atmosphere, neon atmosphere or nitrogen atmosphere. An inert atmosphere can remove oxygen from 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; too high a reaction temperature will cause the active species to fail.

[0084] In the present invention, 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, isooctyl acrylate, laurate acrylate and octadecyl acrylate.

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

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

[0087] In the present invention, the solvent in step 2) includes one or more of toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, n-butanol and isobutanol.

[0088] In the present invention, the monomer mixture, initiator, solvent and chain transfer agent in step 2) are preferably mixed in the following manner: firstly, the monomer and the initiator are mixed to obtain a monomer mixture containing the initiator, and then the solvent, the chain transfer agent and 10-20wt% of the monomer mixture containing the initiator are added to the reaction vessel, and the reaction is carried out at the reaction temperature for 10-30min; the remaining monomer mixture containing the initiator is divided into 5-15 portions, and one portion is added every 10-20min, and the reaction is continued for 2-6h after all the monomer mixture containing the initiator is added. The main purpose of adding the monomer mixture into the reaction in multiple portions is to avoid agglomeration caused by excessive single addition or explosion caused by excessive local temperature; after the reaction is completed, a light yellow transparent viscous acrylic prepolymer is obtained; this process is the formation process of the main chain of the acrylic resin.

[0089] In the present invention, acrylic acid mainly participates in polymerization to form the main chain of 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 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 acrylic resin prepolymer, and give the resin flexibility 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, 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, further 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 derivatives and small molecule organic acid is 0.5 to 2:1, preferably 0.8 to 1.8:1, further 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 mixed reaction in step 3) is 75-110°C, preferably 80-105°C, more preferably 85-100°C, and more preferably 90-95°C; the time is 2-6h, preferably 2.5-5.5h, more preferably 3-5h, and more preferably 3.5-4.5h. The reaction endpoint is when no distilled water is removed.

[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 invention, the small molecule organic acid in step 3) includes one or more of lactic acid, benzoic acid, cyclopentane 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.

[0097] In the present invention, 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 invention also provides an application of the acrylic acid metal salt resin containing rosin and rosin-derived quaternary ammonium salt as an antifouling coating.

[0099] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0100] Example 1

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

[0102] Under nitrogen atmosphere, rosin was heated under condensation reflux at 180°C 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 condensed and refluxed at 120°C for 20h, then cooled and allowed to stand for 3h, and the product was washed with acetic acid and recrystallized to obtain maleopimaric acid.

[0103] Maleopimaric acid was dissolved in ethanol, N,N-dimethylethylenediamine was added dropwise, and the mixture was heated at 80°C for 4 hours. After standing and cooling, the product precipitated to obtain a product precursor, in which the amount of ethanol was 15 times the mass of maleopimaric acid, and the amount of N,N-dimethylethylenediamine was 105% of the molar amount of maleopimaric acid.

[0104] The product precursor is dissolved in tetrahydrofuran, ethyl bromide is added, and the reaction is heated at 50°C for 20 hours 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 ethyl bromide is 105% of the molar amount of the precursor;

[0105] (2) Preparation of resin prepolymer:

[0106] 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 an initiator azobisisobutyronitrile based on the weight of the monomer mixture is added to the monomer mixture, and the mixture is mixed evenly to obtain a monomer mixture containing an initiator.

[0107] In a three-necked flask, add a mixed solvent (mixed by xylene and n-butanol in a mass ratio of 4:1) according to 100% of the weight of the monomer mixture, add a chain transfer agent dodecyl mercaptan according to 0.8% of the total weight of the reactants, add 15% of the monomer mixture containing an initiator, and stir evenly; introduce nitrogen into the three-necked flask for 15 minutes, and at the same time, control the reaction temperature of the reaction mixture at 85°C under nitrogen protection for 20 minutes, divide the remaining 85% of the monomer mixture containing the initiator into 9 parts, add one part every 15 minutes, and continue to react for 4 hours after the addition is completed to obtain a resin prepolymer.

[0108] (3) Preparation of 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 the 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 to the rosin-derived quaternary ammonium salt prepared in step (1) is 80:20, the molar ratio of zinc oxide to the total amount of rosin and the rosin-derived quaternary ammonium salt is 1:1, the amount of the solvent added is equal to the total weight of zinc oxide, rosin and the rosin-derived quaternary ammonium salt, and the solvents used in this step are all mixed solvents of xylene, n-butanol and butyl acetate, and the mass ratio of the three is xylene: n-butanol: butyl acetate = 4:1:11. The reaction temperature is controlled at 90°C for 4h, and the reaction is carried out 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 recorded as RN-Zn-1.

[0110] The present invention uses a BrukerAVANCE III 600 nuclear magnetic resonance spectrometer produced by Bruker Corporation of Germany to test the rosin-derived quaternary ammonium salt prepared in step (1). The characterization results are shown in FIG. Figure 1 ,from Figure 1 It can be seen that the NMR peaks of methine a (δ=5.38, -CH=), methylene b (δ=3.64, -CH2-), methyl e (δ=3.04, -CH3) and methine g (δ=2.63, -CH=) correspond one to one with the rosin-derived quaternary ammonium salt molecules, proving the successful synthesis of the quaternary ammonium salt molecules.

[0111] The synthesized zinc acrylate resin was characterized using a SU8010 scanning electron microscope from Hitachi, Japan. The characterization results are shown in Figure 2 ,from Figure 2 It can be seen that 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 from Thermo Fisher Scientific, USA. The characterization results are shown in Figure 3 ,from Figure 3 It can be seen that C, N, O, Zn and Br elements are definitely present in the resin, proving that rosin and rosin-derived quaternary ammonium salt molecules are successfully introduced into the resin system.

[0113] Example 2

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

[0115] Under nitrogen atmosphere, rosin was heated under condensation reflux at 180°C 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 condensed and refluxed at 120°C for 20h, then cooled and allowed to stand for 3h, and the product was washed with acetic acid and recrystallized to obtain maleopimaric acid.

[0116] Maleopimaric acid was dissolved in ethanol, N,N-dimethylethylenediamine was added dropwise, and the mixture was heated at 80°C for 4 hours. After standing and cooling, the product precipitated to obtain a product precursor, in which the amount of ethanol was 15 times the mass of maleopimaric acid, and the amount of N,N-dimethylethylenediamine was 105% of the molar amount of maleopimaric acid.

[0117] The product precursor is dissolved in tetrahydrofuran, ethyl bromide is added, and the reaction is heated at 50°C for 20 hours 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 ethyl bromide is 105% of the molar amount of the precursor;

[0118] (2) Preparation of resin prepolymer:

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

[0120] In a three-necked flask, add xylene as a solvent at 100% by weight of the monomer mixture, add dodecyl mercaptan as a chain transfer agent at 0.8% by weight of the total reactants, add 15% of a monomer mixture containing an initiator, and stir evenly; introduce nitrogen into the three-necked flask for 15 minutes, and at the same time, control the reaction temperature of the reaction mixture at 85°C under nitrogen protection for 20 minutes, divide the remaining 85% of the monomer mixture containing the initiator into 9 portions, add one portion every 15 minutes, and continue to react for 4 hours after the addition is completed to obtain a resin prepolymer.

[0121] (3) Preparation of 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 the 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 to the rosin-derived quaternary ammonium salt prepared in step (1) is 80:20, the molar ratio of zinc oxide to the total amount of rosin and the rosin-derived quaternary ammonium salt is 1:1, the amount of the solvent added is equal to the total weight of zinc oxide, rosin and the rosin-derived quaternary ammonium salt, and the solvents used in this step are all mixed solvents of xylene, n-butanol and butyl acetate, and the mass ratio of the three is xylene: n-butanol: butyl acetate = 4:1:11. The reaction temperature is controlled at 90°C for 4h, and the reaction is carried out 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 recorded as RN-Zn-2.

[0123] Example 3

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

[0125] Under nitrogen atmosphere, rosin was heated under condensation reflux at 180°C 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 condensed and refluxed at 120°C for 20h, then cooled and allowed to stand for 3h, and the product was washed with acetic acid and recrystallized to obtain maleopimaric acid.

[0126] Maleopimaric acid was dissolved in ethanol, N,N-dimethylethylenediamine was added dropwise, and the mixture was heated at 80°C for 4 hours. After standing and cooling, the product precipitated to obtain a product precursor, in which the amount of ethanol was 15 times the mass of maleopimaric acid, and the amount of N,N-dimethylethylenediamine was 105% of the molar amount of maleopimaric acid.

[0127] The product precursor is dissolved in tetrahydrofuran, ethyl bromide is added, and the reaction is heated at 50°C for 20 hours 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 ethyl bromide is 105% of the molar amount of the precursor;

[0128] (2) Preparation of resin prepolymer:

[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 an initiator azobisisobutyronitrile based on the weight of the monomer mixture is added to the monomer mixture, and the mixture is mixed evenly to obtain a monomer mixture containing an initiator.

[0130] In a three-necked flask, add a mixed solvent (mixed by xylene and n-butanol in a mass ratio of 4:1) according to 100% of the weight of the monomer mixture, add a chain transfer agent dodecyl mercaptan according to 0.8% of the total weight of the reactants, add 15% of the monomer mixture containing an initiator, and stir evenly; introduce nitrogen into the three-necked flask for 15 minutes, and at the same time, control the reaction temperature of the reaction mixture at 85°C under nitrogen protection for 20 minutes, divide the remaining 85% of the monomer mixture containing the initiator into 9 parts, add one part every 15 minutes, and continue to react for 4 hours after the addition is completed to obtain a resin prepolymer.

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

[0132] The resin prepolymer, zinc oxide, rosin, the rosin-derived quaternary ammonium salt prepared in step (1), benzoic acid and 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 to the rosin-derived quaternary ammonium salt prepared in step (1) and 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, 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, and the mass ratio of the three is xylene: n-butanol: butyl acetate = 4:1:11. The reaction temperature is controlled at 90°C for 4h, and the reaction is carried out 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 recorded as RN-Zn-3.

[0133] Example 4

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

[0135] Under nitrogen atmosphere, rosin was heated under condensation reflux at 180°C 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 condensed and refluxed at 120°C for 20h, then cooled and allowed to stand for 3h, and the product was washed with acetic acid and recrystallized to obtain maleopimaric acid.

[0136] Maleopimaric acid was dissolved in ethanol, N,N-dimethylethylenediamine was added dropwise, and the mixture was heated at 80°C for 4 hours. After standing and cooling, the product precipitated to obtain a product precursor, in which the amount of ethanol was 15 times the mass of maleopimaric acid, and the amount of N,N-dimethylethylenediamine was 105% of the molar amount of maleopimaric acid.

[0137] The product precursor is dissolved in tetrahydrofuran, ethyl bromide is added, and the reaction is heated at 50°C for 20 hours 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 ethyl bromide is 105% of the molar amount of the precursor;

[0138] (2) Preparation of resin prepolymer:

[0139] 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 an initiator azobisisobutyronitrile based on the weight of the monomer mixture is added to the monomer mixture, and the mixture is mixed evenly to obtain a monomer mixture containing an initiator.

[0140] In a three-necked flask, add xylene as a solvent at 100% by weight of the monomer mixture, add dodecyl mercaptan as a chain transfer agent at 0.8% by weight of the total reactants, add 15% of a monomer mixture containing an initiator, and stir evenly; introduce nitrogen into the three-necked flask for 15 minutes, and at the same time, control the reaction temperature of the reaction mixture at 85°C under nitrogen protection for 20 minutes, divide the remaining 85% of the monomer mixture containing the initiator into 9 portions, add one portion every 15 minutes, and continue to react for 4 hours after the addition is completed 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 to 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, 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, rosin-derived quaternary ammonium salt and lactic acid, and the solvent used in this step is a mixed solvent of xylene and butyl acetate, and the mass ratio of the two is xylene: butyl acetate = 1:2. The reaction temperature is controlled at 90°C for 4h, and the reaction is carried out 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 recorded as RN-Zn-4.

[0143] Example 5

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

[0145] Under nitrogen atmosphere, rosin was heated under condensation reflux at 180°C 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 condensed and refluxed at 120°C for 20h, then cooled and allowed to stand for 3h, and the product was washed with acetic acid and recrystallized to obtain maleopimaric acid.

[0146] Maleopimaric acid was dissolved in ethanol, N,N-dimethylethylenediamine was added dropwise, and the mixture was heated at 80°C for 4 hours. After standing and cooling, the product precipitated to obtain a product precursor, in which the amount of ethanol was 15 times the mass of maleopimaric acid, and the amount of N,N-dimethylethylenediamine was 105% of the molar amount of maleopimaric acid.

[0147] The product precursor is dissolved in tetrahydrofuran, ethyl bromide is added, and the reaction is heated at 50°C for 20 hours 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 ethyl bromide is 105% of the molar amount of the precursor;

[0148] (2) Preparation of resin prepolymer:

[0149] 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 an initiator azobisisobutyronitrile based on the weight of the monomer mixture is added to the monomer mixture, and the mixture is mixed evenly to obtain a monomer mixture containing an initiator.

[0150] In a three-necked flask, add xylene as a solvent at 100% by weight of the monomer mixture, add dodecyl mercaptan as a chain transfer agent at 0.8% by weight of the total reactants, add 15% of a monomer mixture containing an initiator, and stir evenly; introduce nitrogen into the three-necked flask for 15 minutes, and at the same time, control the reaction temperature of the reaction mixture at 85°C under nitrogen protection for 20 minutes, divide the remaining 85% of the monomer mixture containing the initiator into 9 portions, add one portion every 15 minutes, and continue to react for 4 hours after the addition is completed 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 the solvent are mixed, the total amount of zinc oxide and copper hydroxide added is 1 times the molar amount of acrylic acid and methacrylic acid, the molar ratio of zinc oxide to copper hydroxide is 1:1, the molar ratio of rosin to the rosin-derived quaternary ammonium salt prepared in step (1) is 80:20, the molar ratio of the total amount of zinc oxide and copper oxide to the total amount of rosin and the rosin-derived quaternary ammonium salt is 1:1, the amount of the solvent added is equal to the total weight of zinc oxide, copper hydroxide, rosin and the rosin-derived quaternary ammonium salt, the solvents used in this step are all mixed solvents of xylene, n-butanol and butyl acetate, and the mass ratio of the three is xylene: n-butanol: butyl acetate = 4:1:11. The reaction temperature is controlled at 90°C for 4h, and the reaction is carried out 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 acrylic zinc copper resin, which is recorded as RN-Zn / Cu.

[0153] Comparative Example 1

[0154] The difference between this comparative example and Example 1 is that no rosin-derived quaternary ammonium salt is added in step (3). The prepared zinc acrylate resin is denoted as R-Zn-1

[0155] Comparative Example 2

[0156] The difference between this comparative example and Example 1 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. The prepared zinc acrylate resin is denoted as RZ n -2.

[0157] The antibacterial and anti-protein adsorption capabilities of the coatings of the acrylic acid metal salt resins prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 2 were tested, and the specific test methods and results are as follows:

[0158] Preparation of application sample plate: First, take a PVC plate (5*5cm) and grind it to increase the roughness to facilitate sample attachment. After cleaning and drying the PVC plate, apply the resin samples of Examples 1 to 3 and Comparative Examples 1 to 2 on the PVC plate at a coating amount of 0.1 g / cm 2 , apply 3 times with an interval of 16 hours, dry naturally for 3 days, and dry in a 45℃ oven for 3 days before testing.

[0159] The antibacterial experiment was conducted using Escherichia coli and marine bacteria (both provided by the Microbiology Laboratory of the School of Life Sciences of Ocean University of China). First, the bacteria used were activated for 24 hours, and this process was completed in a 37°C incubator. The culture medium and agar were prepared and sterilized at high temperature. The bacteria were cultured in the culture medium for 24 hours, and then the bacterial solution was diluted. At a wavelength of 600nm on the UV absorption photometer, the absorbance of the fixed bacterial solution was 0.3. Then, 1ml of the bacterial solution was added dropwise to the sample plate coated with the polymer, covered with a PE film, placed in a culture dish (d=10cm) and sealed with a sealing film, and placed in a 37°C shaking incubator for 24 hours. Then, rinse repeatedly with 10ml of saline to ensure that the bacteria on the surface of the coating were completely rinsed off, and the rinse solution was collected as the bacterial stock solution. Then, the bacterial stock solution was diluted with saline to obtain multiple gradients of diluted bacterial solution. Take 100 μL of the diluted bacterial solution and evenly smear it on the surface of the agar solid culture medium. Repeat the smearing until the bacterial solution is completely absorbed. Then, place the solid culture medium in a 37°C shaking incubator and culture it for 24 hours. After the culture is completed, the photos of each group of colonies are as follows: Figure 4 As shown in (B) in the figure. The items used in the above antibacterial experiments were all sterilized at high temperature, and the above process was carried out in a sterile clean bench. The antibacterial experiment used pure ABS board as the blank control group, and three groups of parallel experiments were performed to obtain the average value.

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

[0161] N=(1-N i / N c )×100% (1)

[0162] Where N i is the average colony count of the experimental samples, N C is the average colony number of the control group.

[0163] The calculation results of the inhibition rate are as follows: Figure 4 As shown in (A), the results show that compared with the blank and comparative examples 1 to 2, Examples 1 to 3 having rosin and rosin-derived quaternary ammonium salts have significantly better antibacterial effects, and the antibacterial effects are all above 98%, which are obvious.

[0164] The initial attachment of proteins to the surface marks the beginning of the attachment of marine fouling organisms, which highlights the necessity of evaluating the anti-protein adsorption properties of resin coatings. The resin coatings of Examples 1 to 3 and Comparative Examples 1 to 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 0.05 mg / ml bovine serum albumin (BSA) solution. Then, the pre-soaked resin coating was immersed in 30 ml of BSA solution, with the resin-coated side of the sample plate facing down, and allowed to float in the BSA solution for 24 hours. After soaking, rinse the coating surface with 10 ml of BSA solution, and collect the rinse liquid into the original soaking solution. Add another 20 ml of PBS to the soaking solution. Extract 1 ml from the mixed solution and mix with 10 ml of Coomassie Brilliant Blue working solution. According to Figure 5 The concentration of BSA was calculated using the standard curve shown in (A).

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

[0166] C=C i / C0×100% (2)

[0167] Where C0 is the concentration of unused BSA solution, C i is the concentration of protein not attached to the coating.

[0168] The calculation results of the anti-protein adsorption rate are as follows: Figure 5 As shown in (B), from Figure 5 It can be seen that compared with the blank sample and comparative examples 1 to 2, the anti-protein adsorption effect of embodiments 1 to 3 is significantly improved, from 43.02% of the blank, 57.88% and 56.23% of comparative examples 1 to 2 to more than 80%, and the effect is very significant.

[0169] The antifouling performance of the acrylic acid metal salt resin prepared in Examples 1 to 5 of the present invention and Comparative Examples 1 to 2 was tested on the real sea hanging board. The specific test method and results are as follows:

[0170] The acrylic acid metal salt resins prepared in Examples 1 to 5 of the present invention and Comparative Examples 1 to 2 were respectively used as marine antifouling materials for coating, and their antifouling performance was tested according to the national standard "Antifouling Paint Sample Shallow Sea Immersion Test Method" (GB / T5370-2007). The test results are as follows: Figure 6 shown.

[0171] The test period is 240 days from October 2023 to July 2024, during which the marine biological coverage is observed at four different times. The first time period is 0 days of immersion in the sea, the second time period is 30 days of immersion in the sea, the third time period is 60 days of immersion in the sea, and the fourth time period is 240 days of immersion in the sea.

[0172] Depend on Figure 6 It can be seen that after 60 days of the real sea experiment, the blank control group was completely covered with marine fouling organisms, comparative examples 1 to 2 also had more biological mucosa, examples 1 to 2 had almost no fouling attachment, and example 3 had a small amount of mucosa, but the resin surface was in good condition and could be used normally; after 240 days of the real sea experiment, the surface of the blank control group was still completely covered with marine organisms, the biological mucosa of comparative examples 1 to 2 continued to increase, example 1 still had almost no fouling attachment, and examples 2 to 3 had a small amount of biological mucosa attachment.

[0173] The above-mentioned real sea hanging board test results show that, compared with the blank board and the comparative example, the acrylic acid metal salt resin of the present invention has excellent antifouling activity, and the antifouling effect can reach 240 days. In particular, the resin represented by Example 1 still has a very clean surface after 240 days.

[0174] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

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; R2H、、、-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; 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, characterized in that: The following steps are involved: 1) mixing rosin, maleic anhydride, p-toluenesulfonic acid and acetic acid, heating and refluxing to obtain maleopimaric acid; mixing maleopimaric acid, an alcohol solvent and N,N-dimethylethylenediamine, heating and reacting to obtain a product precursor; mixing the product precursor with tetrahydrofuran and ethyl bromide to react 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 limitation on the order of step 1) and step 2).

3. The method for preparing a metal acrylate resin containing rosin and a rosin-derived quaternary ammonium salt according to claim 2, characterized in that: 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 temperature of the heating reflux reaction 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, characterized in that: 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; In the process of preparing the product precursor, the heating reaction temperature is 70-100°C and the heating reaction time is 2-5h; 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 to 60° C. and the reaction time is 12 to 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 initiator is added in an amount of 0.8 to 3.2% by weight of the monomer mixture; The chain transfer agent is added in an amount of 0.2 to 2.0% by weight of the monomer mixture; The amount of the solvent added is 75-125% of the 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, characterized in that: 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, isooctyl acrylate, laurate 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 one or more of n-dodecyl mercaptan, tert-dodecyl mercaptan and 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-containing substance to the total amount of rosin, rosin derivative quaternary ammonium salt and small molecular organic acid is 1:0.5-2.0; 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, quaternary ammonium salt of rosin derivatives 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 acrylic acid metal salt resin containing rosin and a quaternary ammonium salt derived from rosin as claimed in claim 1 or the acrylic acid metal salt resin containing rosin and a quaternary ammonium salt derived from rosin as claimed in claims 2 to 9 as an antifouling coating.

Images