A supramolecular self-assembly hydrophobic active agent

Abstract

The present invention relates to a supramolecular self-assembly hydrophobic active agent, and belongs to the field of supramolecular coordination chemistry, surface modification engineering and hydrophobic coating technology. In the present invention, 1,8-octanediamine and 4-aldehyde imidazole react to prepare a Schiff base ligand, which can form a supramolecular aggregate with the help of zinc ions in a solvent, and the aggregate electrically attracts 1H, 1H, 2H, 2H-perfluoro-1-alcohol to self-assemble into a supramolecular self-assembly hydrophobic active agent on its outside. The active agent can be applied in the field of hydrophobic coating, and the coating has the characteristics of imitating lotus leaf structure and hydrophobic wax, and has good hydrophobic properties.

Description

Technical Field

[0001] The invention relates to a supramolecular self-assembly hydrophobic active agent, and belongs to the field of surface modification engineering and hydrophobic coating. Background Art

[0002] Because droplets are difficult to settle on hydrophobic surfaces, these surfaces possess properties such as water repellency, anti-icing, anti-fogging, and self-cleaning. In the aerospace field, hydrophobic coatings on aircraft surfaces effectively prevent icing on the fuselage, ensuring flight performance and preventing air crashes. In transportation, hydrophobic coatings prevent glass fogging, ensuring clear vision and driving safety. In the electrical and electronics field, hydrophobic coatings prevent water accumulation on circuit boards, preventing short circuits and rusting of electronic components. In everyday life, hydrophobic coatings can prevent the bottoms of pots from sticking. Therefore, hydrophobic surfaces have a wide range of applications.

[0003] Imitation of lotus leaf structure has always been the research direction of researchers of hydrophobic coatings. The surface of lotus leaves has a dense micro-protrusion structure with a height of about 5 microns. Further magnification and observation can reveal that a layer of nano-scale papillae is attached to the surface of the micro-protrusions, with a height of about 200 nanometers. In addition, lotus leaves secrete a layer of biological wax on their surface to resist external invasion. It is precisely this characteristic of the combination of surface micro-nano composite structure and biological wax that gives lotus leaves unique hydrophobic properties, making it difficult for water droplets to stay on the surface of lotus leaves. In the process of rapid rolling down the surface, the droplets will carry away dust and debris on the surface, achieving self-cleaning. At present, the ideas for preparing hydrophobic surfaces are mostly focused on the preparation and coating of biological wax, mainly through perfluorinated compounds or other low surface energy materials. From the perspective of imitating the micro-nano structure of lotus leaves, it is more difficult because the structural construction requires fine design.

[0004] Early research mainly focuses on chemical synthesis methods, and fluoride is soluble in organic fluoride solvents because it is insoluble in water and conventional organic solvents. Therefore, when the material is subjected to hydrophobic surface treatment, it is necessary to infiltrate fluorinated organic solvents. This treatment method is considered to be not green enough because of the toxicity of the organic solvent and is restricted in application. Therefore, the preparation of green and environment-friendly water-based super-hydrophobic coatings using aqueous solvents as substitutes for volatile organic solvents is increasingly emerging. So far, some preparation methods have been explored, such as the wet chemical process of polymer-particle dispersions, electrochemical deposition, template method, etching method, sol-gel method and hydrothermal method. However, how to coat the substrate surface with a hydrophobic material having low surface energy and to make this material have the microscopic hydrophobic structure of imitating lotus leaves is a major problem at present. Summary of the Invention

[0005] The technology of this invention overcomes the shortcomings of existing technologies by abandoning traditional single covalent interactions and utilizing non-covalent interactions in supramolecular chemistry. Schiff base ligands are first synthesized using aldehyde groups and amino groups. The non-covalent interaction between imidazole and zinc ions is then used to achieve the self-assembly of the first layer of micelles. The electron-withdrawing effect of a perfluorinated compound is then used to achieve the self-assembly of the second layer of micelles, thereby constructing a nanoscale lotus leaf-inspired biomimetic structure. This biomimetic structural material is inherently hydrophobic and has a microscopic hydrophobic structure that mimics that of a lotus leaf, resulting in excellent hydrophobicity.

[0006] The technical solution of the present invention is:

[0007] A supramolecular self-assembly hydrophobic active agent, comprising a ligand, 1H,1H,2H,2H-perfluoro-1-ol, a zinc chloride crosslinking agent and anhydrous ethanol;

[0008] The zinc chloride cross-linking agent, the ligand, and 1H,1H,2H,2H-perfluoro-1-ol self-assemble into micelles and are dispersed in anhydrous ethanol;

[0009] The ratio of the zinc chloride cross-linking agent, the ligand, 1H,1H,2H,2H-perfluoro-1-alcohol and anhydrous ethanol is 1mmol:1-2mmol:1-3mmol:100ml.

[0010] The preparation method of the ligand is:

[0011] An anhydrous ethanol solution of 1,8-octanediamine, an anhydrous ethanol solution of 4-formylimidazole and glacial acetic acid are mixed for reaction, and the resulting product is dried in a vacuum oven at 85-95° C. for 4.5-5.5 hours after evaporating the solvent in a fume hood for 12-15 hours to obtain a ligand.

[0012] In the anhydrous ethanol solution of 1,8-octanediamine, the ratio of 1,8-octanediamine to anhydrous ethanol is 0.05 mol:20-30 ml;

[0013] In the anhydrous ethanol solution of 4-aldehyde imidazole, the ratio of 4-aldehyde imidazole to anhydrous ethanol is 0.1 mol: 15-25 ml;

[0014] The ratio of 1,8-octanediamine, 4-formylimidazole and glacial acetic acid is 0.05 mol:0.1 mol:3-5 ml.

[0015] The reaction temperature is 70-80°C and the reaction time is 4-5h.

[0016] A method for preparing a supramolecular self-assembled hydrophobic active agent, comprising the following steps:

[0017] The ethanol solution of the ligand, the anhydrous ethanol solution of 1H,1H,2H,2H-perfluoro-1-ol and the ethanol solution of zinc chloride are mixed and stirred to obtain a supramolecular self-assembled hydrophobic active agent.

[0018] The concentration of anhydrous ethanol of the ligand is 25 mmol / L;

[0019] The concentration of the anhydrous ethanol solution of zinc chloride is 25 mmol / L;

[0020] The concentration of the 1H,1H,2H,2H-perfluoro-1-ol anhydrous ethanol solution is 50 mmol / L;

[0021] The volume ratio of the zinc chloride ethanol solution, the ligand ethanol solution and the 1H,1H,2H,2H-perfluoro-1-ol anhydrous ethanol solution is 2:1-2:1-3.

[0022] An application of a supramolecular self-assembled hydrophobic active agent in the field of hydrophobic coatings comprises the following steps:

[0023] The substrate is immersed in the supramolecular self-assembly hydrophobic active agent, and after the immersion is completed, the substrate is taken out and dried to obtain a hydrophobic substrate modified by the supramolecular self-assembly hydrophobic active agent.

[0024] The immersion time is 0.5-1h.

[0025] Beneficial effects

[0026] The present invention utilizes the zinc ion coordination principle and the non-covalent interaction of low-surface-energy substances. First, 4-aldehyde imidazole and 1,8-octanediamine are used to synthesize a Schiff base ligand. Then, the imidazole group is coordinated with the zinc ion to achieve the first layer self-assembly. The electron-withdrawing effect of the perfluorinated compound is used to achieve the second layer self-assembly. Thus, a nano-scale lotus leaf biomimetic structure is constructed. The biomimetic structural material itself has hydrophobicity and also has a microscopic hydrophobic structure that imitates the lotus leaf, thus having good hydrophobicity. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 Schematic diagram of supramolecular self-assembled micelles;

[0028] Figure 2 This is a cryo-TEM image of micelles in water.

[0029] Figure 3 This is the contact angle test diagram of the substrate without hydrophobic treatment.

[0030] Figure 4 This is an SEM image of the lotus leaf structure on the substrate surface after surface modification with the active agent in Example 1.

[0031] Figure 5This is the contact angle test of the substrate after surface modification with the active agent in Example 1.

[0032] Figure 6 This is an SEM image of the lotus leaf structure on the substrate surface after surface modification with the active agent in Example 2.

[0033] Figure 7 This is the contact angle test of the substrate after surface modification with the active agent in Example 2. DETAILED DESCRIPTION

[0034] The present invention will be further described below by way of examples, but the examples do not limit the scope of protection of the present invention.

[0035] A supramolecular self-assembly hydrophobic active agent, comprising a ligand, 1H,1H,2H,2H-perfluoro-1-alcohol, a zinc chloride crosslinker and anhydrous ethanol; Figure 1 and Figure 2 As shown;

[0036] The zinc chloride cross-linking agent, the ligand, and 1H,1H,2H,2H-perfluoro-1-ol self-assemble into micelles and are dispersed in anhydrous ethanol;

[0037] The ratio of the zinc chloride cross-linking agent, the ligand, 1H,1H,2H,2H-perfluoro-1-alcohol and anhydrous ethanol is 1mmol:1-2mmol:1-3mmol:100ml.

[0038] A supramolecular self-assembly hydrophobic active agent. The preparation raw materials include main raw materials and auxiliary raw materials. The main raw materials include 1H,1H,2H,2H-perfluoro-1-ol, zinc chloride, 1,8-octanediamine, and 4-aldehyde imidazole. The auxiliary raw materials are catalysts and solvents.

[0039] The catalyst is glacial acetic acid and the solvent is anhydrous ethanol.

[0040] A method for preparing a ligand, comprising the following steps:

[0041] In the first step, 0.05 mol of 1,8-octanediamine was added to a beaker and dissolved in 25 ml of anhydrous ethanol to prepare an anhydrous ethanol solution of 1,8-octanediamine. The anhydrous ethanol solution of 1,8-octanediamine was then transferred to a 250 ml three-necked flask.

[0042] In the second step, 0.1 mol of 4-formylimidazole was added to a beaker and dissolved in 20 ml of anhydrous ethanol to prepare an anhydrous ethanol solution of 4-formylimidazole. The anhydrous ethanol solution of 4-formylimidazole was then transferred to a 25 ml constant pressure separatory funnel, and the separatory funnel was assembled into the three-necked flask described in the first step.

[0043] The third step is to heat and stir the three-necked flask until it reaches 70°C, then add 3-5 ml of glacial acetic acid, open the constant pressure separatory funnel, and allow the anhydrous ethanol solution of 4-aldehyde imidazole to be continuously added dropwise to the three-necked flask.

[0044] Step 4: After 5 hours of reaction, pour the product solution into a beaker, cover with plastic wrap, poke some holes in it, and place it in a fume hood to evaporate the solvent for 12-15 hours to obtain a viscous mixture of the ligand and glacial acetic acid.

[0045] In the fifth step, the viscous mixture obtained in the fourth step is placed in a vacuum oven and dried at 90° C. for 5 hours to remove the glacial acetic acid and obtain the ligand.

[0046] A method for preparing a supramolecular self-assembled hydrophobic active agent, comprising the following steps:

[0047] In the first step, 10 ml of a 25 mmol / L zinc chloride solution in anhydrous ethanol was added to a beaker, followed by a 25 mmol / L ligand solution in anhydrous ethanol (the volume ratio of the ligand solution to the zinc chloride solution was 1:1-2). The mixture was then stirred for 30 minutes and allowed to stand for 1 hour to obtain a preliminary coordination solution.

[0048] In the second step, a 50 mmol / L solution of 1H,1H,2H,2H-perfluoro-1-ol in anhydrous ethanol (the volume ratio of 1H,1H,2H,2H-perfluoro-1-ol to zinc chloride solution is 1:1-3) is added to the preliminary coordination solution obtained in the first step. Any solution less than 60 ml is made up with anhydrous ethanol. Stir for 10 minutes to obtain a supramolecular self-assembling hydrophobic active agent.

[0049] An application of a supramolecular self-assembled hydrophobic active agent in the field of hydrophobic coatings comprises the following steps:

[0050] In the first step, the substrate was immersed in the supramolecular self-assembled hydrophobic active agent and stirred continuously for 2 hours.

[0051] In the second step, the substrate is taken out and placed in a forced air oven for 2 hours to dry the anhydrous ethanol on the surface of the substrate to obtain a substrate modified with a supramolecular self-assembled hydrophobic active agent.

[0052] Example 1

[0053] A method for preparing a ligand, comprising the following steps:

[0054] In the first step, 0.05 mol of 1,8-octanediamine was added to a beaker and dissolved in 25 ml of anhydrous ethanol to prepare an anhydrous ethanol solution of 1,8-octanediamine. The anhydrous ethanol solution of 1,8-octanediamine was then transferred to a 250 ml three-necked flask.

[0055] In the second step, 0.1 mol of 4-formylimidazole was added to a beaker and dissolved in 20 ml of anhydrous ethanol to prepare an anhydrous ethanol solution of 4-formylimidazole. The anhydrous ethanol solution of 4-formylimidazole was then transferred to a 25 ml constant pressure separatory funnel, and the separatory funnel was assembled into the three-necked flask described in the first step.

[0056] The third step is to heat and stir the three-necked flask until it reaches 70°C, then add 5 ml of glacial acetic acid, open the constant pressure separatory funnel, and allow the anhydrous ethanol solution of 4-aldehyde imidazole to be continuously added dropwise to the three-necked flask.

[0057] Step 4: After 5 hours of reaction, the product solution was poured into a beaker, covered with plastic wrap, and some holes were pierced in the beaker. The beaker was placed in a fume hood to evaporate the solvent for 15 hours to obtain a viscous mixture of the ligand and glacial acetic acid.

[0058] In the fifth step, the viscous mixture obtained in the fourth step is placed in a vacuum oven and dried at 90° C. for 5 hours to remove the glacial acetic acid and obtain the ligand.

[0059] A method for preparing a supramolecular self-assembled hydrophobic active agent, comprising the following steps:

[0060] In the first step, 10 ml of a 25 mmol / L solution of zinc chloride in anhydrous ethanol was added to a beaker, followed by 20 ml of a 25 mmol / L solution of the ligand in anhydrous ethanol. The mixture was then stirred for 30 minutes and allowed to stand for 1 hour to obtain a preliminary coordination solution.

[0061] In the second step, 30 ml of a 50 mmol / L absolute ethanol solution of 1H,1H,2H,2H-perfluoro-1-ol was added to the preliminary coordination solution obtained in the first step and stirred for 10 minutes to obtain a supramolecular self-assembled hydrophobic active agent.

[0062] An application of a supramolecular self-assembled hydrophobic active agent in the field of hydrophobic coatings comprises the following steps:

[0063] In the first step, the substrate was immersed in the supramolecular self-assembled hydrophobic active agent and stirred continuously for 2 hours.

[0064] In the second step, the substrate is taken out and placed in a forced air oven for 2 hours to dry the anhydrous ethanol on the surface of the substrate to obtain a substrate modified with a supramolecular self-assembled hydrophobic active agent.

[0065] The contact angle test of the substrate without hydrophobic treatment is shown in the figure Figure 3 As shown, the contact angle is 73.3°; Figure 4 This is an SEM image of the lotus leaf structure on the substrate surface after surface modification with the active agent in Example 1. Figure 5 The contact angle of the substrate after surface modification by the surfactant in Example 1 was 158.8°. Figure 4It can be seen that the surface of the substrate modified by the active agent in Example 1 has a lotus leaf structure. Figure 5 It can be seen that the substrate after surface modification by the active agent in Example 1 has good hydrophobicity.

[0066] Example 2

[0067] A method for preparing a ligand, comprising the following steps:

[0068] In the first step, 0.05 mol of 1,8-octanediamine was added to a beaker and dissolved in 25 ml of anhydrous ethanol to prepare an anhydrous ethanol solution of 1,8-octanediamine. The anhydrous ethanol solution of 1,8-octanediamine was then transferred to a 250 ml three-necked flask.

[0069] In the second step, 0.1 mol of 4-formylimidazole was added to a beaker and dissolved in 20 ml of anhydrous ethanol to prepare an anhydrous ethanol solution of 4-formylimidazole. The anhydrous ethanol solution of 4-formylimidazole was then transferred to a 25 ml constant pressure separatory funnel, and the separatory funnel was assembled into the three-necked flask described in the first step.

[0070] The third step is to heat and stir the three-necked flask until it reaches 70°C, then add 5 ml of glacial acetic acid, open the constant pressure separatory funnel, and allow the anhydrous ethanol solution of 4-aldehyde imidazole to be continuously added dropwise to the three-necked flask.

[0071] Step 4: After 5 hours of reaction, the product solution was poured into a beaker, covered with plastic wrap, and some holes were pierced in the beaker. The beaker was placed in a fume hood to evaporate the solvent for 15 hours to obtain a viscous mixture of the ligand and glacial acetic acid.

[0072] In the fifth step, the viscous mixture obtained in the fourth step is placed in a vacuum oven and dried at 90° C. for 5 hours to remove the glacial acetic acid and obtain the ligand.

[0073] A method for preparing a supramolecular self-assembled hydrophobic active agent, comprising the following steps:

[0074] In the first step, 10 ml of a 25 mmol / L solution of zinc chloride in anhydrous ethanol was added to a beaker, followed by 10 ml of a 25 mmol / L solution of the ligand in anhydrous ethanol. The mixture was then stirred for 30 minutes and allowed to stand for 1 hour to obtain a preliminary coordination solution.

[0075] In the second step, 20 ml of a 50 mmol / L solution of 1H,1H,2H,2H-perfluoro-1-ol in anhydrous ethanol was added to the preliminary coordination solution obtained in the first step. An additional 20 ml of anhydrous ethanol was added, and the mixture was stirred for 10 minutes to obtain a supramolecular self-assembled hydrophobic active agent.

[0076] An application of a supramolecular self-assembled hydrophobic active agent in the field of hydrophobic coatings comprises the following steps:

[0077] In the first step, the substrate was immersed in the supramolecular self-assembled hydrophobic active agent and stirred continuously for 2 hours.

[0078] In the second step, the substrate is taken out and placed in a forced air oven for 2 hours to dry the anhydrous ethanol on the surface of the substrate to obtain a substrate modified with a supramolecular self-assembled hydrophobic active agent.

[0079] Figure 6 This is an SEM image of the lotus leaf structure on the substrate surface after surface modification with the active agent in Example 2. Figure 7 The contact angle of the substrate after surface modification by the active agent in Example 2 was 146.5°. Figure 6 It can be seen that the surface of the substrate modified by the active agent in Example 2 has a lotus leaf structure. Figure 7 It can be seen that the substrate after surface modification by the active agent in Example 2 has good hydrophobicity.

[0080] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A supramolecular self-assembly hydrophobic active agent, characterized in that: The supramolecular self-assembly hydrophobic active agent comprises a ligand, 1H,1H,2H,2H-perfluoro-1-alcohol, a zinc chloride cross-linking agent and anhydrous ethanol; The zinc chloride cross-linking agent, the ligand, and 1H,1H,2H,2H-perfluoro-1-ol self-assemble into micelles and are dispersed in anhydrous ethanol; The ratio of the zinc chloride crosslinker, the ligand, 1H,1H,2H,2H-perfluoro-1-ol and anhydrous ethanol is 1mmol:1-2mmol:1-3mmol:100ml; An anhydrous ethanol solution of 1,8-octanediamine, an anhydrous ethanol solution of 4-formylimidazole and glacial acetic acid are mixed for reaction, and the resulting product is dried in a vacuum oven at 85-95° C. for 4.5-5.5 hours after evaporating the solvent in a fume hood for 12-15 hours to obtain a ligand.

2. The supramolecular self-assembly hydrophobic active agent according to claim 1, characterized in that: In the anhydrous ethanol solution of 1,8-octanediamine, the ratio of 1,8-octanediamine to anhydrous ethanol is 0.05 mol:20-30 ml; In the anhydrous ethanol solution of 4-aldehyde imidazole, the ratio of 4-aldehyde imidazole to anhydrous ethanol is 0.1 mol: 15-25 ml; The ratio of 1,8-octanediamine, 4-formylimidazole and glacial acetic acid is 0.05 mol:0.1 mol:3-5 ml.

3. The supramolecular self-assembly hydrophobic active agent according to claim 1, characterized in that: The reaction temperature is 70-80°C and the reaction time is 4-5h.

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