Organocopper complex antifouling agent and preparation method thereof

Abstract

The application provides an organic copper ion complex antifouling agent and a preparation method thereof. The complex takes o-phenanthroline and imidazole monomers as main ligands, 1,10-phenanthroline as an auxiliary ligand, and forms an organic metal complex with copper ions. 1,10-phenanthroline and CuCl2 are added into 50-70 ml of a solvent in a reaction bottle, the ratio of 1,10-phenanthroline to CuCl2 is 1:1-1.5, the reaction temperature is controlled at 80-110 DEG C, the heating time is controlled at 2-3 h, then 1-1.4 mol of o-phenanthroline and imidazole monomers are added and stirring is continued for 2-3 h, after the reaction, cooling to room temperature, pouring into saturated NaClO4 aqueous solution, stirring for 20-40 min, collecting the precipitate by filtration, washing, drying in a vacuum drying oven, and recrystallizing in methanol. The organic copper ion complex antifouling agent can improve the antifouling performance of a coating, especially the antifouling performance on algae, and prolong the service life of the coating. The organic copper ion complex antifouling agent can be applied to the surface antifouling coating of marine engineering equipment and facilities such as marine ships, nuclear power platforms and oil production platforms, and can prevent and remove biological fouling.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of marine antifouling technology, and in particular to an organic copper ion complex antifouling agent and a preparation method thereof. BACKGROUND

[0002] The attachment of marine organisms can cause great harm to marine engineering equipment such as ships, nuclear power platforms and oil extraction platforms. The annual loss caused by marine biofouling is at least 3 billion US dollars worldwide. The attachment of marine organisms on nuclear power platforms and oil extraction platforms can induce and accelerate the corrosion of the metal surface of the equipment, leading to a decrease in strength and safety hazards, and shortening the service life of the equipment. The attachment and accumulation on the ship bottom not only increase the overall weight of the ship body but also make the ship body surface rough, causing sailing resistance to the ship, increasing the power of the ship body and fuel consumption. At present, inorganic compounds containing copper are mainly used as antifouling agents. Cuprous oxide is the most commonly used and traditional antifouling agent that can meet the current environmental requirements. However, copper-based antifouling agents have poor antifouling effect on algae, and require a large amount of leaching rate to effectively prevent algae. However, excessive copper ion leaching rate can also reduce the antifouling period of the antifouling paint, so organic antifouling agents are generally added to the coating formula containing cuprous oxide as the main antifouling agent to improve the antifouling performance of the coating and prolong the service life.

[0003] Patent CN102702821A relates to an antifouling agent for marine facilities, which is a complex formed by three (2-(N-oxide-pyridyl-2-sulfur) ethyl) amine and metal ions. The complex can form a nanometer particle suspension in a solvent, has stable properties, good antifouling effect, and is non-toxic or low-toxic. However, the preparation process is complex and not convenient for synthesis. CN114736221A discloses a rare earth-based complex marine antifouling agent and a preparation method thereof. The invention is composed of sodium pyrithione, acidic alpha-amino acid and soluble rare earth salt through ternary coordination. The rare earth elements are selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium. The invention reduces the repellency of marine organisms to the antifouling agent, increases the permeability of the antifouling agent, and better penetrates into cells, has strong antibacterial ability, long-lasting antibacterial efficacy and low ecological safety risk. However, some rare earth elements are too expensive, and the synthesis cost is high. SUMMARY

[0004] Therefore, the present application aims to provide an organic copper ion complex antifouling agent and a preparation method thereof to solve the problems of complex preparation process and high synthesis cost of organic metal ion complex antifouling agents in the prior art.

[0005] To achieve the above-mentioned purposes, the technical solution of the present application is as follows:

[0006] An organic copper ion complex antifouling agent, characterized in that the complex takes o-phenanthroline and imidazole monomers as main ligands, 1,10-phenanthroline as auxiliary ligands, and Cu 2+ The structure of the organic copper ion complex is as follows:

[0007]

[0008] R is a halogenated benzene ring.

[0009] Further, R is any one of R1, R2, R3:

[0010]

[0011] Further, when R is R2, the solvent used for synthesizing the organic copper ion complex II is one or two of the following: methanol, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, and trichloromethane.

[0012] Further, when R is R1 or R3, the solvent used for synthesizing the organic copper ion complexes I and III is one or two of the following: methanol, dimethyl sulfoxide, dimethylformamide, and tetrahydrofuran.

[0013] Compared with the prior art, the organic copper ion complex antifouling agent has the following advantages:

[0014] The o-phenanthroline and imidazole monomers are taken as main ligands, 1,10-phenanthroline is taken as auxiliary ligands, and halogen groups are introduced simultaneously, and Cu 2+ The organic Cu 2+ complex is formed. The organic Cu 2+ complex antifouling agent is added in the antifouling coating formula, which can improve the antifouling performance of the coating, especially the antifouling performance on algae, and prolong the service life of the coating. The organic Cu

[0015] The application further provides a preparation method of the organic copper ion complex antifouling agent, which comprises the following steps: 1,10-phenanthroline and CuCl2 are added into 50-70 ml of a solvent in a reaction bottle according to the molar amount, the ratio of the 1,10-phenanthroline and CuCl2 is 1:1-1.5, the reaction temperature is controlled at 80-110 DEG C, the heating time is controlled at 2-3 h, then 1-1.4 mol of o-phenanthroline and imidazole monomers are added and stirring is continued for 2-3 h, after the reaction, the mixture is cooled to room temperature, poured into saturated NaClO4 aqueous solution, stirred for 20-40 min, the precipitate is collected by filtration, washed, dried in a vacuum drying box, recrystallized in methanol, and the structure formula in the reaction process is shown in the following formula, and R in the organic copper ion complex I, II and III corresponds to R1, R2 and R3, respectively.

[0016]

[0017] 。

[0018] Further, the reaction is carried out under nitrogen atmosphere.

[0019] Further, the collected precipitate is washed with deionized water and ethanol.

[0020] Further, the amount of 1,10-phenanthroline added is 1 mol, and the amount of CuCl2 added is 1-1.5 mol.

[0021] Further, when R is R2, the solvent used for synthesizing the organic copper ion complex is one or two of the following: methanol, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, chloroform, and polyethylene glycol.

[0022] Further, when R is R1 or R3, the solvent used for synthesizing the organic copper ion complexes I and III is one or two of the following: methanol and dimethyl sulfoxide, dimethylformamide, and tetrahydrofuran.

[0023] The preparation method of the organic copper ion complex antifouling agent has the same advantages as the organic copper ion complex antifouling agent relative to the prior art, and will not be described here. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The infrared spectrum of the organic copper ion complex antifouling agent described in the embodiments of the present application is shown in the following figure:

[0025] Figure 2 The figure shows the anti-fouling performance of the organic copper ion complex antifouling agent described in the embodiments of the present application on Chlorella. DETAILED DESCRIPTION

[0026] In order to make the above-mentioned objects, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below with reference to the accompanying drawings.

[0027] As shown in the figure, an organic copper ion complex antifouling agent is formed by using o-phenanthroline and imidazole monomers as main ligands, 1,10-phenanthroline as auxiliary ligands, and Cu 2+ to form an organic metal complex, and the structure of the organic copper ion complex is as follows:

[0028]

[0029] wherein R is a halogenated benzene ring.

[0030] Further, R can be any one of R1, R2, and R3.

[0031]

[0032] Further, when R is R2, the solvent used in the synthesis of the organic copper ion complex II is one or two of methanol, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, chloroform, and polyethylene glycol.

[0033] Further, when R is R1 or R3, the solvent used in the synthesis of the organic copper ion complexes I and III is one or two of methanol and dimethyl sulfoxide, dimethylformamide, and tetrahydrofuran.

[0034] As part of the embodiments of the present application, a preparation method of the organic copper ion complex antifouling agent is also provided, comprising:

[0035] In a three-necked flask, 1 mol of 1,10-phenanthroline and 1-1.5 mol of CuCl2 are added to 50-70 ml of a solvent under nitrogen, the reaction temperature is controlled at 80-110°C, the heating time is controlled at 2-3 h, then 1-1.4 mol of phenanthroline and an imidazole monomer are added and stirring is continued for 2-3 h. After the reaction, the mixture is cooled to room temperature, poured into a saturated aqueous NaClO4 solution, stirred for 20-40 min, and then the precipitate is collected by filtration, washed with deionized water and ethanol three times each, dried in a vacuum drying oven, and recrystallized from methanol. The synthesis method is simple, and the organic Cu 2+ complex prepared has good antifouling performance.

[0036] The reaction process is shown in the following structural formula, and the organic Cu 2+ complex I, II, and III correspond to R1, R2, and R3, respectively.

[0037]

[0038] Example 1

[0039] The organic Cu 2+ complex I is synthesized as follows: In a three-necked flask, 1 mol of 1,10-phenanthroline and 1.1 mol of CuCl2 are added to 70 ml of a mixed solution of methanol and dimethyl sulfoxide (volume ratio 2:1) under nitrogen, the reaction temperature is controlled at 100°C, the heating time is controlled at 2 h, then 1.1 mol of phenanthroline and an imidazole monomer are added and stirring is continued for 3 h. After the reaction, the mixture is cooled to room temperature, poured into a saturated aqueous NaClO4 solution, stirred for 30 min, and then the precipitate is collected by filtration, washed with deionized water and ethanol three times each, dried in a vacuum drying oven, and recrystallized from methanol.

[0040] Example 2

[0041] The organic Cu 2+Complex II synthesis: 1 mol 1,10-phenanthroline, 1.1 mol CuCl2 were added into 60 ml methanol solvent under nitrogen in a flask, the reaction temperature was controlled at 80℃, the heating time was controlled at 3h, then 1.1 mol o-phenanthroline and imidazole monomer was added, and the stirring reflux was continued for 3h. After the reaction, it was cooled to room temperature, poured into saturated aqueous NaClO4 solution, stirred for 30 minutes, then the precipitate was collected by filtration, washed with deionized water, ethanol three times, and dried in a vacuum drying oven, and recrystallized in methanol.

[0042] Example 3

[0043] Organic Cu 2+ Complex III synthesis: 1 mol 1,10-phenanthroline, 1.1 mol CuCl2 were added into 50 ml mixed solution of methanol and dimethyl sulfoxide (volume ratio 1:1) under nitrogen in a flask, the reaction temperature was controlled at 110℃, the heating time was controlled at 3h, then 1.1 mol o-phenanthroline and imidazole monomer was added and the stirring was continued for 3h. After the reaction, it was cooled to room temperature, poured into saturated aqueous NaClO4 solution, stirred for 30 minutes, then the precipitate was collected by filtration, washed with deionized water, ethanol three times, and dried in a vacuum drying oven, and recrystallized in methanol.

[0044] Experimental Example 1

[0045] The organic copper ion complex antifouling agent obtained in the above examples was tested by infrared spectrum, as shown in Figure 1 The three spectra from bottom to top are the antifouling agents prepared by organic copper ion complexes I, II and III. Among them, 1659 cm -1 is the skeleton vibration of C=N, 1514 cm -1 , 1426 cm -1 is the benzene ring C=C skeleton vibration. 1086 cm -1 is the in-plane bending vibration of benzene ring CH, 844 cm -1 , 722 cm -1 is the out-of-plane bending vibration of benzene ring CH in the fingerprint area. It can be seen that the preparation method of the application successfully prepared the organic copper ion complex antifouling agent.

[0046] Experimental Example 2 Organic Cu 2+ Complex Antifouling Agent Analysis of Chlorella Anti-fouling Performance

[0047] 10mg Cu 2+ complex was dissolved in 1ml dimethyl sulfoxide to prepare 10mg / ml. An appropriate amount of solution was added to the conical flask of algal liquid, so that the Cu 2+The concentrations of the complex in the algal solution were 5 ppm, 10 ppm, and 30 ppm, with a blank control group also included. The absorbance values ​​of the algal solution in each conical flask were measured at 24, 72, 120, 168, and 240 h. The test data are shown below. Figure 2 As shown.

[0048] Figure 2 The Chlorella culture time-algal concentration curves show that complex I has a good inhibitory effect on Chlorella growth. At concentrations of 5 ppm, 10 ppm, and 30 ppm, the concentrations of Chlorella remained at their initial levels, indicating a good inhibitory effect. Complex II, at a concentration of 5 ppm, showed no inhibitory effect on Chlorella growth, consistent with the growth concentration curve of the control group. At concentrations of 10 ppm and 30 ppm, the concentrations of Chlorella remained at their initial levels at all times, indicating a significant inhibitory effect. Complex III, at 5 ppm, showed some inhibitory effect on growth, with distinct growth curves at 24, 72, and 120 hours. However, from 120 to 240 hours, the concentration of Chlorella remained essentially unchanged, reaching its growth limit, which was significantly lower than that of the control group. At concentrations of 10 ppm and 30 ppm, the concentration of Chlorella remained essentially unchanged, showing no significant growth.

[0049] Complexes I, II, and III all exhibit good growth-inhibiting effects on Chlorella. Complex I can prevent Chlorella from growing at a concentration of ≥5 ppm, while complexes II and III require a concentration of ≥10 ppm.

[0050] The complexes of this invention use o-phenanthroline-imidazole monomers as the main ligands and 1,10-phenanthroline as the auxiliary ligand, in conjunction with Cu. 2+ Organometallic complexes are formed. These antifouling agents not only possess excellent antifouling properties but are also easily synthesized. In application tests, they exhibited good inhibitory effects on the growth of Chlorella. Under a microscope, the antifouling agent clearly caused cell death and damage in Chlorella. This type of organic Cu... 2+ The complex is suitable for preparing antifouling coatings, which can be applied to equipment such as ships, marine aquaculture facilities, and marine nuclear power platforms and mining platforms to effectively prevent and inhibit marine fouling organisms.

[0051] While the present invention has been disclosed above, it is not limited thereto. Any person skilled in the art can make various modifications and alterations without departing from the spirit and scope of the invention; therefore, the scope of protection of the present invention should be determined by the scope defined in the claims.

Claims

1. An antifouling agent of an organic copper ion complex, characterized by, The complex takes o-phenanthroline and imidazole monomer as the main ligand, 1,10-phenanthroline as the auxiliary ligand, and Cu 2+ The organic copper ion complex is formed, and the structural formula of the organic copper ion complex is as follows: ； R is a halogenated benzene ring.

2. The antifouling agent according to claim 1, wherein R is any one of R1, R2, R3:

3. A method for preparing an antifouling agent of an organic copper ion complex, characterized by, comprising: In the reaction bottle, 1, 10-phenanthroline and CuCl2 are added into 50-70 ml of solvent in terms of the number of molar, the ratio of 1, 10-phenanthroline and CuCl2 is 1:1-1.5, the reaction temperature is controlled at 80-110℃, the heating time is controlled at 2-3 h, then 1-1.4 mol of o-phenanthroline and imidazole monomer is added and continue to stir for 2-3 h; after the reaction, it is cooled to room temperature, poured into saturated aqueous NaClO4 solution, stirred for 20-40 min, then the precipitate is collected by filtration, washed, dried in vacuum drying oven, recrystallized in methanol, the reaction process structure is shown as follows, and the organic copper ion complex I, II, III is obtained, wherein R corresponds to R1, R2, R3 respectively: ； 。 4. The method for preparing the organic copper ion complex antifouling agent according to claim 3, characterized in that, The reaction is carried out under nitrogen atmosphere.

5. The method for preparing the organic copper ion complex antifouling agent according to claim 3, characterized in that, The collected precipitate is washed with deionized water and ethanol.

6. The method for preparing the organic copper ion complex antifouling agent according to claim 3, characterized in that, The added amount of 1, 10-phenanthroline is 1 mol, and the added amount of CuCl2 is 1-1.5 mol.

7. The method for preparing the organic copper ion complex antifouling agent according to claim 3, characterized in that, When R is R2, the solvent used for synthesizing the organic copper ion complex is one or two of methanol, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, trichloromethane and polyethylene glycol.

8. The method for preparing the organocopper ion complex antifouling agent according to claim 3, characterized in that, When R is R1 or R3, the solvent used for synthesizing the organic copper ion complex I and III is one or two of methanol and dimethyl sulfoxide, dimethylformamide and tetrahydrofuran.

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