A polymer coating with multifunctional self-cleaning function, preparation method and application thereof

Abstract

A polymer coating with multifunctional self-cleaning function has a chemical structure as follows: a solution of the polymer coating is coated on a clean solid surface to obtain an object with the polymer coating coated on the surface; the polymer coating coated on the object exhibits excellent hydrophilicity and can simply and effectively rinse off various oily stains on the coating with clean water without the help of detergent, and also has good anti-fog and anti-icing adhesion properties.

Description

Technical Field

[0001] The present invention belongs to the field of polymer chemical materials, and in particular relates to a polymer coating with multifunctional self-cleaning function, a preparation method thereof and an application thereof. Background Art

[0002] Solid surfaces contaminated with oil or laden with mist or ice are ubiquitous in many industrial processes and everyday life, presenting a host of challenges. The extensive use of detergents in traditional surface cleaning processes severely damages ecosystems and human health. The mist formed by droplets on surfaces can cause significant inconvenience in daily life and even lead to serious traffic accidents. Ice accumulation on various surfaces also poses significant challenges to building infrastructure, marine applications, aerospace, refrigeration, power transmission, telecommunications, and other industries.

[0003] Since traditional treatment of ice or oil adhered to the surface of equipment under certain conditions often requires a lot of manpower and material resources, is time-consuming, and has adverse effects on the environment, researchers have tried to use material modification to achieve surface self-cleaning. Conventional coatings with self-cleaning functions need to be constructed using surface micro-nano structures, but such self-cleaning coatings have problems such as cumbersome preparation processes and difficulty in cleaning accumulated oil in micro-nano structures. In recent years, hydrophilic coatings have played an important role in the field of self-cleaning by utilizing their hydration layers that can serve as physical barriers to achieve the effects of spreading water films on the surface to avoid fogging, easily resisting ice adhesion with the help of external forces, and cleaning oil pollutants under the action of water. They have shown great application potential.

[0004] Therefore, the preparation of a polymer coating with multifunctional self-cleaning functions such as anti-fog, anti-ice adhesion, and anti-oil pollution that can be coated on the surface of any object is of great significance for saving resources, protecting the environment, and reducing economic costs, bringing great convenience to people's daily lives. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, the present invention aims to provide a multifunctional self-cleaning polymer coating that can be formed on the surface of an object based on hydrogen bonding. By introducing tertiary amine groups with a specific carbon chain, this polymer utilizes hydrophobic forces to achieve the effect of coating any surface. Furthermore, the polymer chain retains a large number of sulfonate groups, which, upon contact with water, form a hydration layer that acts as a physical barrier. Consequently, this polymer coating exhibits excellent hydrophilicity, allowing various oily stains to be easily and effectively rinsed off with water alone, without the aid of detergents. It also exhibits excellent anti-fog and anti-icing properties.

[0006] Specifically, the first aspect of the present invention is to provide a polymer coating with multifunctional self-cleaning function, having a chemical structure as shown in Formula 1:

[0007]

[0008] Where R1 is a strong acid group - sulfonic acid group (-SO3), sulfuric acid group (-OSO3), benzenesulfonic acid group Any one of: R2 is C n H 2n group (n is an integer greater than or equal to 1); R3 is any one of methyl, ethyl, propyl, and butyl; M is Li + 、Na + , K + Any one of the metal cations; x and y are degrees of polymerization, each selected from an integer ranging from 30 to 2000, and the ratio of x:y ranges from 1.5 to 10.

[0009] The second aspect of the present invention is to provide a method for preparing the polymer coating and a method for coating the surface of a material according to the first aspect of the present invention, the steps comprising:

[0010] Step 1: Clean the solid surface to be coated to obtain a clean solid surface;

[0011] Step 2, preparing a strongly acidic aqueous solution of a strong electrolyte anion polymer, wherein the strong electrolyte anion polymer comprises any one of polyvinyl sulfonic acid or its salt, polyvinyl sulfate or its salt, and polystyrene sulfonic acid or its salt, and the pH range of the strongly acidic aqueous solution is 1.6 to 3;

[0012] Step 3: Prepare a mixed solution of an alkaline aqueous solution of a tertiary amine compound and an organic solvent, wherein the chemical structural formula of the tertiary amine compound is CH3(CH2): n N(R3)2, wherein n is an integer greater than or equal to 1, R3 is any one of methyl, ethyl, propyl, and butyl, and the pH range of the alkaline aqueous solution is 9 to 11;

[0013] Step 4: mixing the strongly acidic aqueous solution of the strong electrolyte anion polymer prepared in step 2 with the mixed solution containing the tertiary amine compound prepared in step 3, and hydrogen bonding the two to obtain a polymer coating solution having a chemical structure as shown in Formula 1 above after washing;

[0014] Step 5: coating the polymer coating solution prepared in step 4 on the clean solid surface obtained in step 1 to obtain a polymer coating having a chemical structure as shown in formula 1 above.

[0015] In the present invention, the solid material to be coated can be an inorganic non-metallic material, a metal product, a wood material, or a synthetic or natural polymer material. Specifically, the materials include: inorganic non-metallic materials such as single crystal silicon wafers, glass sheets, and silicon carbide; metal products such as stainless steel, iron and its alloys, magnesium and its alloys, titanium and its alloys, copper and its alloys, aluminum and its alloys, and zinc and its alloys; and synthetic or natural polymer materials such as polypropylene (PP), polystyrene (PS), polyurethane (PU), polyester (PET), polyethylene (PE), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polyacrylonitrile, rubber, cotton, and silk.

[0016] In the present invention, the weight average molecular weight of the strong electrolyte anion polymer is in the range of 5 to 1000 kDa, and the mass concentration of the strong electrolyte anion polymer strong acid aqueous solution is in the range of 0.2 to 20 mg / mL.

[0017] In the present invention, the above-mentioned strongly acidic aqueous solution with a pH of 1.6 to 3 is obtained by adjusting the pH value of a hydrochloric acid solution or a sulfuric acid solution.

[0018] In the present invention, the mass concentration of the tertiary amine compound in the mixed solution of step 3 is 0.2-20 mg / mL.

[0019] Preferably, the alkaline aqueous solution with a pH of 9 to 11 is obtained by adjusting the pH value with sodium hydroxide, potassium hydroxide or lithium hydroxide.

[0020] In the present invention, the organic solvent includes one or more of isopentane, n-pentane, petroleum ether, hexane, cyclohexane, cyclopentane, carbon tetrachloride, pentanediol or tetrahydrofuran.

[0021] In the present invention, the volume ratio of the organic solvent to the aqueous solution in the polymer coating solution is in the range of 2-9.

[0022] In the present invention, the coating method of the polymer coating solution includes dipping, spin coating, spraying, electrospinning or inkjet printing.

[0023] In the present invention, the coating time is 10 seconds to 80 minutes, the coating temperature is 10 to 50° C., and the number of coating times is one or more.

[0024] Preferably, the pH range of the strongly acidic aqueous solution of the strong electrolyte anionic polymer is 2-3.

[0025] Preferably, the mass concentration of the strong acidic aqueous solution of the strong electrolyte anion polymer is 0.5 to 10 mg / mL.

[0026] Preferably, the mass concentration of the tertiary amine compound in the mixed solution of alkaline aqueous solution / organic solvent is 0.5-10 mg / mL.

[0027] Preferably, the coating time is 10 seconds to 60 minutes, the coating temperature is preferably 15 to 40° C., and the coating times are preferably 4 to 8 times.

[0028] The third aspect of the present invention is to apply the polymer coating described in the first aspect of the present invention and the preparation method of the polymer coating described in the second aspect of the present invention and the method of coating the surface of a material in the field of self-cleaning of the surface of an object. Preferably, the self-cleaning field includes anti-oil pollution, anti-fog or anti-ice adhesion.

[0029] The present invention can achieve the following technical effects:

[0030] 1. The method for preparing the polymer coating and the method for coating the surface of a substance of the present invention are simple and easy to implement;

[0031] 2. The present invention can make the surface of the coated object exhibit excellent hydrophilicity. Without the help of detergent, various oily stains on the coating can be simply and effectively washed away with clean water alone. It also has good anti-fog and anti-icing adhesion properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is a comparison diagram of the self-cleaning effect of oil pollutants on the solid surface containing the polymer coating with multifunctional self-cleaning function of the present invention and the unmodified coating. DETAILED DESCRIPTION

[0033] In order to further understand the present invention, the preferred technical solutions of the present invention are described in detail with specific examples. The reagents and raw materials used in the following examples and test examples are all industrial pure commodities, and the equipment used are all commonly used equipment and devices in the field.

[0034] Example 1

[0035] Step 1: Treat the aluminum sheet in an oxygen environment of a plasma cleaning machine for 10 minutes to remove surface impurities and obtain a clean aluminum sheet surface;

[0036] Step 2: Prepare a 0.5 mg / mL, pH 2, and strongly acidic aqueous solution of polyvinyl potassium sulfate with a weight average molecular weight of 15 kDa using a 3 M hydrochloric acid solution;

[0037] Step 3: Prepare a 5 mg / mL, pH=11 alkaline aqueous solution of N,N-diethyltetradecamine using 1M KOH solution. Its chemical formula is CH3(CH2) 13 N(CH2CH3)2;

[0038] Step 4: mixing the alkaline aqueous solution of N,N-diethyltetradecamine prepared in step 3 with a pentanediol / tetrahydrofuran mixture in a volume ratio of 2:1 to obtain a mixed solution of N,N-diethyltetradecamine with a mass concentration of 2 mg / mL and an organic reagent / water volume ratio of 4;

[0039] Step 5: mixing the strongly acidic aqueous solution of potassium polyvinyl sulfate prepared in step 2 with the mixed solution of N,N-diethyltetradecamine prepared in step 4, and subjecting the two to hydrogen bonding for 2 hours. The mixture is then washed with a mixture of pentanediol and water at a volume ratio of 3 to obtain a polymer coating solution having the chemical structure shown in the following formula (x:y=10, organic reagent / water volume ratio is 3);

[0040]

[0041] Step 6: Inject the polymer coating solution obtained in step 5 at 30°C into a spray gun and spray it on the surface of the clean aluminum sheet obtained in step 1. The coating time is 1 minute. After drying, repeat the spraying 3 times to obtain a polymer coating with a chemical structure shown in the above formula formed based on hydrogen bonding.

[0042] Example 2

[0043] Step 1: Soak the silicon wafer in a hydrogen peroxide / concentrated sulfuric acid mixture (volume ratio of 1:3) at 90°C for 4 hours to remove surface impurities, and then ultrasonically clean the silicon wafer several times with ultrapure water to obtain a clean silicon wafer surface;

[0044] Step 2: Prepare a 2 mg / mL, pH 2.1, and strongly acidic aqueous solution of polyvinyl potassium sulfate with a weight average molecular weight of 10 kDa using a 1 M sulfuric acid solution;

[0045] Step 3: Prepare a 5 mg / mL, pH 10, alkaline aqueous solution of N,N-diethyloctylamine using a 1 M KOH solution. The chemical formula of the solution is CH3(CH2)7N(CH2CH3)2.

[0046] Step 4: mixing the alkaline aqueous solution of N,N-diethyloctylamine prepared in step 3 with pentanediol to obtain a mixed solution of N,N-diethyloctylamine with a mass concentration of 3 mg / mL and a pentanediol / water volume ratio of 4;

[0047] Step 5: mixing the strongly acidic aqueous solution of potassium polyvinyl sulfate prepared in step 2 with the mixed solution of N,N-diethyloctylamine prepared in step 4, subjecting the two to hydrogen bonding for 6 hours, and washing with a mixture of pentanediol and water at a volume ratio of 7 to obtain a polymer coating solution having a chemical structure shown in the following formula (x:y=8, pentanediol / water volume ratio of 7);

[0048]

[0049] Step 6: Soak the clean silicon wafer obtained in step 1 in the polymer coating solution obtained in step 5 at 30° C. for 40 minutes, repeat the soaking twice after drying, and obtain a polymer coating having a chemical structure shown in the above formula based on hydrogen bonding after drying.

[0050] Example 3

[0051] Step 1: Treat the wood in an oxygen environment of a plasma cleaning machine for 10 minutes to remove surface impurities and obtain a clean wood surface;

[0052] Step 2: Prepare a 10 mg / mL, pH=2.4, strongly acidic aqueous solution of 4 kDa weight-average molecular weight polyethylene sulfonate lithium and 12 kDa weight-average molecular weight polyethylene sulfuric acid (the molar ratio of the two polymers is 1:3) using 1 M sulfuric acid solution;

[0053] Step 3: Prepare a 5 mg / mL, pH 9.5, alkaline aqueous solution of N,N-dimethylpentylamine using 1 M LiOH solution. The chemical formula of the solution is CH3(CH2)4N(CH3)2.

[0054] Step 4: mixing the alkaline aqueous solution of N,N-dimethylpentylamine prepared in step 3 with a petroleum ether / methanol organic solvent in a volume ratio of 1:3 to obtain a mixed solution of N,N-dimethylpentylamine with a mass concentration of 1 mg / mL and an organic solvent / water volume ratio of 3;

[0055] Step 5: The strongly acidic aqueous solution of lithium polyvinyl sulfonate-polyvinyl sulfuric acid prepared in Step 2 is mixed with the mixed solution of N,N-dimethylpentylamine prepared in Step 4, and hydrogen bonding is carried out for 5 hours. The mixture is then washed with a methanol / water mixture having a volume ratio of 6 to obtain a polymer coating solution having the chemical structure shown in the following formula (x:y=3, organic reagent / water volume ratio is 6);

[0056]

[0057] Step 6: Inject the polymer coating solution prepared in step 5 at 20° C. into an inkjet printer and print on the clean wood surface obtained in step 1. The coating time is 20 minutes. After drying, the printing is repeated 5 times. After drying, a polymer coating with a chemical structure shown in the above formula formed based on hydrogen bonding is obtained.

[0058] Example 4

[0059] Step 1: Treat the polyester fiber in an oxygen environment of a plasma cleaning machine for 10 minutes to remove surface impurities and obtain a clean polyester fiber surface;

[0060] Step 2: Prepare a 1 mg / mL, pH 3, strongly acidic aqueous solution of polyethylene sulfonic acid with a weight average molecular weight of 20 kDa using a 2 M hydrochloric acid solution;

[0061] Step 3: Prepare a 4 mg / mL alkaline aqueous solution of N,N-dibutylheptylamine with a pH of 9.7 using a 0.5 M KOH solution. The chemical formula of the solution is CH3(CH2)6N((CH2)3CH3)2.

[0062] Step 4: mixing the alkaline aqueous solution of N,N-dibutylheptylamine prepared in step 3 with a 1:1 volume ratio of pentanediol to cyclohexane to obtain a mixed solution of N,N-dibutylheptylamine having a mass concentration of 5 mg / mL and an organic mixture / water volume ratio of 1.5;

[0063] Step 5: The strongly acidic aqueous solution of polyethylene sulfonic acid prepared in step 2 is mixed with the mixed solution of N,N-dibutylheptylamine prepared in step 4, and hydrogen bonding is carried out for 7 hours. The mixture is then washed with a mixture of cyclohexane and water at a volume ratio of 3 to obtain a coating solution of a polymer having the chemical structure shown in the following formula (x:y = 7, organic solvent / water volume ratio is 3);

[0064]

[0065] Step 6: Soak the clean polyester fiber surface obtained in step 1 in the polymer coating solution obtained in step 5 at 15° C. for 20 minutes, repeat the soaking 4 times after drying, and obtain a polymer coating with a chemical structure shown in the above formula based on hydrogen bonding after drying.

[0066] Example 5

[0067] Step 1: Treat the polyurethane sheet in an oxygen environment of a plasma cleaning machine for 10 minutes to remove surface impurities and obtain a clean polyurethane surface;

[0068] Step 2: Prepare a 10 mg / mL, pH 3, and strongly acidic aqueous solution of polystyrene sulfonic acid with a weight average molecular weight of 70 kDa using a 1 M sulfuric acid solution;

[0069] Step 3: Prepare a 10 mg / mL, pH 10.5, alkaline aqueous solution of N,N-diethyldodecylamine using 1M LiOH solution. The chemical formula is CH3(CH2) 11 N(CH2CH3)2;

[0070] Step 4: mixing the alkaline aqueous solution of N,N-diethyldodecylamine prepared in step 3 with carbon tetrachloride to obtain a mixed solution of N,N-diethyldodecylamine with a mass concentration of 5 mg / mL and a carbon tetrachloride / water volume ratio of 2;

[0071] Step 5: The strongly acidic aqueous solution of polystyrene sulfonic acid prepared in step 2 is mixed with the mixed solution of N,N-diethyldodecylamine prepared in step 4, and the two are subjected to hydrogen bonding for 2 hours. The mixture is then washed with a mixture of carbon tetrachloride and water at a volume ratio of 5 to obtain a polymer coating solution having the chemical structure shown in the following formula (x:y=7.5, carbon tetrachloride / water volume ratio is 5);

[0072]

[0073] Step 6: Use a desktop coating machine to spin-coat the polymer coating solution obtained in step 5 at 35°C onto the clean polyurethane sheet obtained in step 1 for 10 minutes. After air drying, repeat the spin coating 3 times to obtain a polymer coating having a chemical structure based on hydrogen bonding as shown in the above formula.

[0074] Example 6

[0075] Step 1: Soak the silicon wafer in a hydrogen peroxide / concentrated sulfuric acid mixture (volume ratio of 1:3) at 90°C for 4 hours to remove surface impurities, and then ultrasonically clean the silicon wafer several times with ultrapure water to obtain a clean silicon wafer surface;

[0076] Step 2: Prepare a 2 mg / mL, pH 2, and strongly acidic aqueous solution of sodium polyvinyl sulfonate with a weight average molecular weight of 8 kDa using 1 M hydrochloric acid solution;

[0077] Step 3: Prepare a 2 mg / mL alkaline aqueous solution of N,N-dimethylhexylamine with a pH of 11 using a 1 M NaOH solution. The chemical formula of the solution is CH3(CH2)5N(CH3)2.

[0078] Step 4: mixing the alkaline aqueous solution of N,N-dimethylhexylamine prepared in step 3 with cyclohexane to obtain a mixed solution of N,N-dimethylhexylamine with a mass concentration of 2 mg / mL and a cyclohexane / water volume ratio of 3;

[0079] Step 5: The strongly acidic aqueous solution of sodium polyvinyl sulfonate prepared in step 2 is mixed with the mixed solution of N,N-dimethylhexylamine prepared in step 4, and hydrogen bonding is carried out for 6.5 hours. The mixture is then washed with a mixture of cyclohexane and water at a volume ratio of 3 to obtain a coating solution of a polymer having the chemical structure shown in the following formula (x:y=9, cyclohexane / water volume ratio of 3);

[0080]

[0081] Step 6: Immerse the clean silicon wafer obtained in step 1 in the polymer coating solution prepared in step 5 at room temperature for 30 minutes, dry it, and repeat the immersion 4 times to obtain a polymer coating having a chemical structure based on hydrogen bonding as shown in the above formula.

[0082] Example 7

[0083] Step 1: Treat the polyester sheet in an oxygen environment of a plasma cleaning machine for 10 minutes to remove surface impurities and obtain a clean polyester surface;

[0084] Step 2: Prepare a 4 mg / mL, pH 2.7, strongly acidic aqueous solution of sodium polyvinyl sulfonate with a weight average molecular weight of 20 kDa and potassium polyvinyl sulfate with a weight average molecular weight of 15 kDa (the molar ratio of the two polymers is 4:1) using 3 M hydrochloric acid solution;

[0085] Step 3: Prepare a 6 mg / mL alkaline aqueous solution of N,N-dimethylbutylamine with a pH of 11 using a 1 M NaOH solution. The chemical formula of the solution is CH3(CH2)3N(CH3)2;

[0086] Step 4: mixing the alkaline aqueous solution of N,N-dimethylbutylamine prepared in step 3 with an organic solvent of cyclopentane / n-pentane / pentanediol in a volume ratio of 1:3:3 to obtain a mixed solution of N,N-dimethylbutylamine with a mass concentration of 3 mg / mL and an organic reagent / water volume ratio of 2;

[0087] Step 5: The strongly acidic aqueous solution of sodium polysulfonate-potassium polysulfate prepared in step 2 is mixed with the mixed solution of N,N-dimethylbutylamine prepared in step 4, and the two are subjected to hydrogen bonding for 9 hours. The mixture is then washed with a mixture of cyclopentane and water at a volume ratio of 4.5 to obtain a polymer coating solution having the chemical structure shown in the following formula (x:y=8, organic reagent / water volume ratio is 4.5);

[0088]

[0089] Step 6: Inject the polymer coating solution prepared in step 5 at 37°C into the syringe of the electrospinning device, and electrospin the polymer film on the clean polyester sheet obtained in step 1. The coating time is 25 minutes, and the film is dried at 50°C and then repeated 7 times. After drying, a polymer coating with a chemical structure shown in the above formula formed based on hydrogen bonding is obtained.

[0090] Example 8

[0091] Step 1: Soak the glass slide in a hydrogen peroxide / concentrated sulfuric acid mixed solution (volume ratio of 1:3) at 90° C. for 4 hours to remove surface impurities, and then ultrasonically clean the glass slide with ultrapure water several times to obtain a clean glass slide surface;

[0092] Step 2: Prepare a 4 mg / mL, pH 2.3, strongly acidic aqueous solution of sodium polystyrene sulfonate with a weight average molecular weight of 1000 kDa using a 3 M sulfuric acid solution;

[0093] Step 3: Prepare a 6 mg / mL alkaline aqueous solution of N,N-dipropyldecylamine with a pH of 10.5 using a 2.5 M NaOH solution. The chemical formula of the solution is CH3(CH2)9N((CH2)2CH3)2.

[0094] Step 4: mixing the alkaline aqueous solution of N,N-dipropyldecylamine prepared in step 3 with isopentane to obtain a mixed solution of N,N-dipropyldecylamine with a mass concentration of 3 mg / mL and an isopentane / water volume ratio of 5;

[0095] Step 5: The strongly acidic aqueous solution of sodium polystyrene sulfonate prepared in step 2 is mixed with the mixed solution of N,N-dipropyldecylamine prepared in step 4, and hydrogen bonding is carried out for 3 hours. The mixture is then washed with a mixture of isopentane and water at a volume ratio of 2 to obtain a coating solution of a polymer having the chemical structure shown in the following formula (x:y=6.8, isopentane / water volume ratio is 2);

[0096]

[0097] Step 6: Soak the clean glass sheet obtained in step 1 in the polymer coating solution obtained in step 5 at 15° C. for 10 minutes, and repeat the soaking 5 times after drying. After drying, a polymer coating having a chemical structure based on hydrogen bonding as shown in the above formula is obtained.

[0098] Example 9

[0099] Step 1: Treat the polyethylene tube in an oxygen environment of a plasma cleaning machine for 10 minutes to remove surface impurities and obtain a clean polyethylene surface;

[0100] Step 2: Prepare a 0.8 mg / mL, pH 2.5, strongly acidic aqueous solution of sodium polystyrene sulfonate with a weight average molecular weight of 1000 kDa, sodium polyvinyl sulfonate with a weight average molecular weight of 8 kDa, and lithium polyvinyl sulfate with a weight average molecular weight of 25 kDa (the molar ratio of the three polymers is 1:3:1) using 1 M hydrochloric acid solution;

[0101] Step 3: Prepare a 1 mg / mL, pH 9.5, alkaline aqueous solution of N,N-dibutylundecylamine using 1 M LiOH solution. The chemical formula is CH3(CH2) 10 N((CH2)3CH3)2;

[0102] Step 4: mixing the alkaline aqueous solution of N,N-dibutyl undecylamine prepared in step 3 with an organic solvent of cyclopentane / cyclohexane / petroleum ether in a volume ratio of 2:3:5 to obtain a mixed solution of N,N-dibutyl undecylamine with a mass concentration of 1 mg / mL and an organic solvent / water volume ratio of 5;

[0103] Step 5: The strongly acidic aqueous solution of sodium polystyrene sulfonate-sodium polyvinyl sulfonate-potassium polyvinyl sulfate prepared in step 2 is mixed with the mixed solution of N,N-dibutylundecylamine prepared in step 4, and hydrogen bonding is carried out for 6 hours. The mixture is then washed with a mixture of cyclohexane / petroleum ether / water in a volume ratio of 3:4:1 to obtain a coating solution of three polymers having the chemical structures shown in the following formula (x:y = 4, organic reagent / water volume ratio is 7);

[0104]

[0105] Step 6: Soak the clean polyethylene tube obtained in step 1 in the polymer coating solution obtained in step 5 at 35° C. for 20 minutes, repeat the soaking 7 times after drying, and obtain a polymer coating having a chemical structure shown in the above formula based on hydrogen bonding after drying.

[0106] Example 10

[0107] Step 1: Treat the polytetrafluoroethylene sheet in an oxygen environment of a plasma cleaning machine for 10 minutes to remove surface impurities and obtain a clean polytetrafluoroethylene surface;

[0108] Step 2: Prepare a 4 mg / mL, pH 2.8, strongly acidic aqueous solution of polystyrene sulfonic acid with a weight average molecular weight of 70 kDa and polyethylene sulfonic acid with a weight average molecular weight of 7 kDa (the two polymers are in a molar ratio of 1:2) using 2 M hydrochloric acid solution;

[0109] Step 3: Prepare a 6 mg / mL alkaline aqueous solution of N,N-diethylnonylamine with a pH of 9.8 using a 2M NaOH solution. The chemical formula of the solution is CH3(CH2)8N(CH2CH3)2;

[0110] Step 4: mixing the alkaline aqueous solution of N,N-diethylnonylamine prepared in step 3 with an organic solvent of hexane / cyclohexane / carbon tetrachloride in a volume ratio of 1:1:2 to obtain a mixed solution of N,N-diethylnonylamine with a mass concentration of 4 mg / mL and an organic reagent / water volume ratio of 5;

[0111] Step 5: The strongly acidic aqueous solution of polystyrene sulfonic acid-polyvinyl sulfate prepared in step 2 is mixed with the mixed solution of N,N-diethylnonylamine prepared in step 4, and hydrogen bonding is carried out for 7 hours. The mixture is then washed with a mixture of hexane / carbon tetrachloride / water in a volume ratio of 2:4:1 to obtain a polymer coating solution having the chemical structure shown in the following formula (x:y = 5.3, organic reagent / water volume ratio is 7);

[0112]

[0113] Step 6: Inject the polymer coating solution obtained in step 5 at 15° C. into a spray gun and spray it on the surface of the clean polytetrafluoroethylene sheet obtained in step 1. The coating time is 5 minutes. After drying, the spraying is repeated 4 times. After drying, a polymer coating with a chemical structure shown in the above formula formed based on hydrogen bonding is obtained.

[0114] Example 11

[0115] Step 1: Treat the silk in an oxygen environment of a plasma cleaning machine for 10 minutes to remove surface impurities and obtain a clean silk surface;

[0116] Step 2: Prepare a 6 mg / mL, pH 3, strongly acidic aqueous solution of polystyrene sulfonic acid with a weight average molecular weight of 500 kDa, polyvinyl sulfate with a weight average molecular weight of 12 kDa, and polyvinyl sulfonic acid with a weight average molecular weight of 8 kDa (the three polymers are in a molar ratio of 3::1:1) using 3M hydrochloric acid solution;

[0117] Step 3: Prepare a 4.5 mg / mL alkaline aqueous solution of N,N-diethylhexylamine with a pH of 9.9 using a 2.5 M KOH solution. The chemical formula of the solution is CH3(CH2)5N(CH2CH3)2;

[0118] Step 4: mixing the alkaline aqueous solution of N,N-diethylhexylamine prepared in step 3 with an organic solvent of isopentane / cyclopentane / carbon tetrachloride in a volume ratio of 2:1:3 to obtain a mixed solution of N,N-diethylhexylamine with a mass concentration of 0.5 mg / mL and an organic solvent / water volume ratio of 3;

[0119] Step 5: The strongly acidic aqueous solution of polystyrene sulfonic acid-polyvinyl sulfuric acid-polyvinyl sulfonic acid prepared in step 2 is mixed with the mixed solution of N,N-diethylhexylamine prepared in step 4, and hydrogen bonding is carried out for 5 hours. The mixture is then washed with a mixture of cyclopentane / carbon tetrachloride / water in a volume ratio of 1:1:1 to obtain a polymer coating solution having the chemical structure shown in the following formula (x:y=6.5, organic reagent / water volume ratio is 2);

[0120]

[0121] Step 6: Inject the polymer coating solution prepared in step 5 at room temperature into an inkjet printer and print on the clean silk surface obtained in step 1. The coating time is 45 minutes. After drying, repeat the printing twice to obtain a polymer coating having a chemical structure based on hydrogen bonding as shown in the above formula.

[0122] Example 12

[0123] Step 1: Treat the cotton cloth in an oxygen environment of a plasma cleaning machine for 10 minutes to remove surface impurities and obtain a clean cotton cloth surface;

[0124] Step 2: Prepare a 2 mg / mL, pH 3, strongly acidic aqueous solution of sodium polystyrene sulfonate with a weight average molecular weight of 70 kDa and polyethylene sulfonic acid with a weight average molecular weight of 8 kDa (the molar ratio of the two polymers is 1:2) using 3 M sulfuric acid;

[0125] Step 3: Prepare a 4 mg / mL, pH 10.5, alkaline aqueous solution of N,N-dipropylhexadecylamine using 3M NaOH solution. The chemical formula is CH3(CH2): 15 N((CH2)2CH3)2;

[0126] Step 4: mixing the alkaline aqueous solution of N,N-dipropylhexadecylamine prepared in step 3 with an organic solvent of isopentane / carbon tetrachloride in a volume ratio of 1:2 to obtain a mixed solution of N,N-dipropylhexadecylamine with a mass concentration of 3 mg / mL and an organic reagent / water volume ratio of 6;

[0127] Step 5: The strongly acidic aqueous solution of sodium polystyrene sulfonate-polyethylene sulfonic acid prepared in step 2 is mixed with the mixed solution of N,N-dipropylhexadecylamine prepared in step 4, and hydrogen bonding is carried out for 8 hours. The mixture is then washed with a mixture of isopentane / carbon tetrachloride / water in a volume ratio of 2:3:1 to obtain a polymer coating solution having the chemical structure shown in the following formula (x:y=9, organic reagent / water volume ratio is 5);

[0128]

[0129] Step 6: Using a tabletop spin coater, spin-coat the polymer coating solution obtained in Step 5 at 32°C onto the clean cotton cloth obtained in Step 1 for 20 minutes. After drying, repeat the spin coating twice. After drying, a polymer coating with the chemical structure shown above, formed by hydrogen bonding, is obtained.

[0130] Example 13

[0131] Step 1: Treat the polypropylene sheet in an oxygen environment of a plasma cleaning machine for 10 minutes to remove surface impurities and obtain a clean polypropylene surface;

[0132] Step 2: Prepare a 10 mg / mL, pH 2.8, strongly acidic aqueous solution of polystyrene sulfonic acid (1000 kDa weight average molecular weight) and polyvinyl sulfate (12 kDa weight average molecular weight) (the two polymers are in a molar ratio of 3:1) using a 2.5 M sulfuric acid solution;

[0133] Step 3: Prepare a 10 mg / mL alkaline aqueous solution of N,N-dimethyloctylamine with a pH of 9.2 using a 2M KOH solution. The chemical formula of the solution is CH3(CH2)7N(CH3)2;

[0134] Step 4: mixing the alkaline aqueous solution of N,N-dimethyloctylamine prepared in step 3 with a petroleum ether / cyclopentane organic solvent in a volume ratio of 1:3 to obtain a mixed solution of N,N-dimethyloctylamine with a mass concentration of 3 mg / mL and an organic reagent / water volume ratio of 5;

[0135] Step 5: The strongly acidic aqueous solution of polystyrene sulfonic acid-polyvinyl sulfate prepared in step 2 is mixed with the mixed solution of N,N-dimethyloctylamine prepared in step 4, and hydrogen bonding is carried out for 2 hours. The mixture is then washed with a mixture of petroleum ether / cyclopentane / water in a volume ratio of 1:3:1 to obtain a polymer coating solution having the chemical structure shown in the following formula (x:y=5, organic reagent / water volume ratio is 4);

[0136]

[0137] Step 5: mixing the polymer aqueous solution obtained in step 4 with a chloroform / cyclopentane organic solvent in a volume ratio of 1:3 to obtain a polymer coating solution with an organic solvent / water volume ratio of 4 and a polymer concentration of 0.8 mg / mL;

[0138] Step 6: Inject the polymer coating solution prepared in step 5 at 27°C into the syringe of the electrospinning device, and electrospin the polymer film on the clean polypropylene sheet obtained in step 1. The coating time is 10 minutes, and the film is dried at 50°C and repeated 6 times. After drying, a polymer coating with a chemical structure shown in the above formula formed based on hydrogen bonding is obtained.

[0139] In order to demonstrate the beneficial effects of the present invention, the inventors verified the self-cleaning effect of a polymer coating with multifunctional self-cleaning function formed based on hydrogen bonding. The specific experiments are as follows:

[0140] Test 1

[0141] The anti-soybean oil contamination effect of the sample was verified according to the following steps.

[0142] Step 1: dropping edible soybean oil onto the sample obtained in Example 2 and the unmodified solid surface as a control sample in air as an oil contaminant;

[0143] Step 2: After a uniform oil film is formed on the soybean oil-contaminated surface obtained in step 1, the surface is placed in water to observe the cleaning effect of the soybean oil contaminants under the action of water.

[0144] The results of the anti-soybean oil pollution test on the samples are as follows: Figure 1 As shown: After the sample of Example 2 was contaminated with oil and placed in water for a few seconds, the oil film shrank into oil droplets and completely floated off from the surface; while the oil contaminants on the surface of the blank comparative example could not be detached from the surface in water.

[0145] The anti-oil pollution effect of the polymer coating with multifunctional self-cleaning function formed based on hydrogen bonding was verified.

[0146] Test 2

[0147] Follow the steps below to verify the anti-oil pollution effect of the sample.

[0148] The anti-oil contamination process was inhibited according to the standards described in Test 1, except that [engine oil] was tested. The anti-engine oil contamination effect of the sample obtained in Example 3 was verified, and the cleaning effect of the engine oil contaminants on Example 3 and the corresponding blank control sample under the action of water was analyzed.

[0149] The results of the verification of the anti-engine oil pollution effect of the samples showed that after the sample of Example 3 was contaminated with oil and placed in water within 10 seconds, the oil film shrank into oil droplets and completely floated off from the surface; while the oil pollutants on the surface of the blank control example could not be detached from the surface in water.

[0150] The anti-oil pollution effect of the polymer coating with multifunctional self-cleaning function formed based on hydrogen bonding was verified.

[0151] Test 3

[0152] Follow the steps below to verify the anti-fog effect of the sample.

[0153] Step 1: Select two culture dishes, fill them with 1 / 2 of water and heat them to 80°C;

[0154] Step 2: Place the sample obtained in Example 8 and an unmodified solid surface as a control sample on a culture dish, and observe the adhesion behavior of water vapor on the two surfaces.

[0155] The results of the anti-fog effect verification of the samples show that the water vapor on the sample of Example 8 can be spread into small droplets within 5 seconds and disappear from the field of view; while the water vapor on the surface of the blank control example will condense into droplets on the surface, and then gather into large droplets, which continue to appear in the field of view.

[0156] The anti-fog effect of the polymer coating with multifunctional self-cleaning function formed based on hydrogen bonding was verified.

[0157] Test 4

[0158] Follow the steps below to verify the anti-icing adhesion effect of the sample.

[0159] Step 1: Dropping room temperature water in air onto the sample obtained in Example 6 and an unmodified solid surface as a control sample;

[0160] Step 2: Immediately place the two solid surfaces soaked in water obtained in step 1 in a freezer at -20°C for 24 hours to allow a layer of ice to form on the surfaces;

[0161] Step 3: Take the two objects adhered to ice obtained in Step 2 out of the freezer, place them vertically at room temperature, and observe the detachment behavior of the ice layer on the sample obtained in Example 6 and the unmodified solid surface as a control sample.

[0162] The anti-icing adhesion effect on the samples showed that the ice layer attached to Example 6 began to slide off the surface after being placed at room temperature for 10 seconds, and the entire ice layer fell off completely; while the ice layer on the surface of the blank comparative example began to melt into water droplets after being placed at room temperature for 5 minutes, and gradually dripped until it was completely melted.

[0163] The anti-icing adhesion effect of the polymer coating with multifunctional self-cleaning function formed based on hydrogen bonding was verified.

[0164] In summary, the results of the above embodiments and test examples show that the present invention has achieved the following technical effects:

[0165] 1. The method for preparing the polymer coating and the method for coating the surface of a substance of the present invention are simple and easy to implement;

[0166] 2. The present invention can make the surface of the coated object exhibit excellent hydrophilicity. Without the help of detergent, various oily stains on the coating can be simply and effectively washed away with clean water alone. It also has good anti-fog and anti-icing adhesion properties.

[0167] Those skilled in the art will readily appreciate other embodiments of the present disclosure after considering the specification and practicing the disclosure disclosed herein. This application is intended to cover any variations, uses, or adaptations of the present disclosure that follow the general principles of the present disclosure and include common knowledge or customary techniques in the art not disclosed herein. The description and examples are to be considered merely as exemplary, and the true scope and spirit of the present disclosure are indicated by the claims of this application.

Claims

1. A polymer coating with multifunctional self-cleaning function, characterized in that: Contains a polymer component having a chemical structure shown in Formula 1: Formula 1 Where R1 is a strong acid group: sulfonic acid group -SO3, sulfuric acid group -OSO3 or benzenesulfonic acid group ; R2 is C n H 2n group, n is an integer greater than or equal to 1; R3 is methyl, ethyl, propyl or butyl; M is Li + 、Na + or K + metal cation; x, y are degrees of polymerization, each selected from an integer ranging from 30 to 2000 and the ratio of x:y is in the range of 1.5 to 10.

2. A method for coating the surface of an object using the polymer coating according to claim 1, characterized in that the steps include: Step 1: Clean the solid surface to be coated to obtain a clean solid surface; Step 2: preparing a strongly acidic aqueous solution of a strong electrolyte anion polymer with a pH of 1.6 to 3, wherein the strong electrolyte anion polymer comprises any one of polyvinyl sulfonic acid or a salt thereof, polyvinyl sulfate or a salt thereof, and polystyrene sulfonic acid or a salt thereof; Step 3: Prepare a mixed solution of an alkaline aqueous solution with a pH of 9 to 11 and an organic solvent of a tertiary amine compound, wherein the chemical structural formula of the tertiary amine compound is CH3(CH2): n N(R3)2, n is an integer greater than or equal to 1, and R3 is one of methyl, ethyl, propyl, or butyl; Step 4: mixing the strongly acidic aqueous solution of the strong electrolyte anionic polymer prepared in step 2 with the mixed solution containing the tertiary amine compound prepared in step 3, and hydrogen bonding the two to obtain a coating solution containing a polymer component having a chemical structure as shown in Formula 1 above after washing; Step 5: coating the polymer coating solution prepared in step 4 on the clean solid surface obtained in step 1 to obtain a coating having a polymer component having a chemical structure as shown in Formula 1 formed based on hydrogen bonding.

3. The method according to claim 2, characterized in that In step 1, the material of the solid to be coated includes: inorganic non-metallic materials, metal products, artificial synthetic or natural polymer materials.

4. The method according to claim 2, characterized in that In step 2, the weight average molecular weight of the strong electrolyte anion polymer is in the range of 5 to 1000 kDa, and the mass concentration of the strongly acidic aqueous solution of the strong electrolyte anion polymer is in the range of 0.2 to 20 mg / mL.

5. The method according to claim 2, characterized in that In step 2, the pH value of the strongly acidic aqueous solution is adjusted to 1.6 to 3 by using a hydrochloric acid solution or a sulfuric acid solution.

6. The method according to claim 2, characterized in that In step 3, the alkaline aqueous solution with a pH of 9 to 11 is obtained by adjusting the pH value with sodium hydroxide, potassium hydroxide or lithium hydroxide; The organic solvent includes one or more of isopentane, n-pentane, petroleum ether, hexane, cyclohexane, cyclopentane, carbon tetrachloride, pentanediol or tetrahydrofuran; The mass concentration of the tertiary amine compound in the mixed solution is 0.2 to 20 mg / mL.

7. The method according to claim 2, characterized in that In step 4, the volume ratio of the organic solvent to the aqueous solution in the polymer coating solution is in the range of 2 to 9.

8. The method according to claim 2, characterized in that In step 5, the coating method of the polymer coating solution includes: dipping, spin coating, spraying, electrostatic spinning or inkjet printing.

9. The method according to claim 8, characterized in that The coating time is 10 seconds to 80 minutes, the coating temperature is 10 to 50° C., and the coating times are more than 1 time.

10. Use of a method for coating an object surface using the polymer coating according to claim 1 or the polymer coating according to any one of claims 2 to 9 in the field of self-cleaning of object surfaces, wherein the self-cleaning field includes anti-oil, anti-fog or anti-icing adhesion.

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