A polymer coating containing strong acid groups with bactericidal function, preparation method and application thereof

Abstract

A polymer coating containing strong acid groups with a bactericidal function has a chemical structure as follows: the polymer coating solution is coated on a clean solid surface to obtain an object with the polymer coating coated on its surface; the polymer coating containing acidic groups on the surface of the object can inactivate bacteria such as Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Helicobacter pylori, and fungi such as Candida, thereby achieving the effects of inhibiting microbial growth and killing bacteria.

Description

Technical Field

[0001] The invention belongs to the field of organic chemistry for preventing and treating bacterial infection of crops, and particularly relates to a polymer coating containing strong acid groups with a bactericidal function, a preparation method and an application thereof. Background Art

[0002] Microorganisms such as bacteria and fungi are ubiquitous in the natural environment and the human body, and pathogenic bacteria pose a significant threat to public health. Bacterial contamination of food sources, leading to foodborne illnesses, urinary tract infections, tuberculosis, and other bacterial-derived diseases, has become a major public health concern. Furthermore, bacterial adhesion and proliferation have been long-standing issues in the biomedical field. Tissue infections and device failures caused by bacterial adhesion and proliferation are the main causes of implant failure in medical materials, imposing a significant economic burden on patients and society, while also posing a serious threat to human life and health, posing a significant challenge to global healthcare.

[0003] The bacterial resistance crisis has led researchers to avoid the use of antibiotics in material modification. However, bacteria adhering to the surface of the equipment require higher concentrations of fungicides and longer sterilization times to inhibit bacterial growth on the surface. Conventional sterilization surfaces require the use of some natural or synthetic organic compounds or heavy metal fungicides. These fungicides are not only expensive but also have the problem of drug residues caused by incomplete cleaning, which has irreversible effects on both the body and the biological environment. Organic acids have long played an important role in food preservation. Benzoic acid, sorbic acid, etc. are often added to food as preservatives. Acetic acid, lactic acid, fumaric acid, etc. can prevent or delay the growth of pathogenic bacteria or spoilage bacteria. The use of hydrogen ions as antimicrobial fungicides has the advantages of strong, widespread and reusable antimicrobial function, as well as low production cost, showing great application potential.

[0004] Therefore, preparing a polymer coating containing strong acid groups that can be coated on the surface of any object and can effectively kill bacteria is of great significance for preventing and treating bacterial infections and protecting human health and safety. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, the present invention provides a polymer coating containing strong acid groups that can be formed on the surface of an object through electrostatic interaction and has a bactericidal effect. This polymer coating containing strong acid groups is coated on any surface by introducing quaternary ammonium groups with a certain carbon chain, utilizing hydrophobic forces. This polymer coating containing strong acid groups can release hydrogen ions in the presence of microorganisms, inactivating bacteria such as Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Helicobacter pylori, as well as fungi such as Candida, thereby inhibiting microbial growth and achieving a bactericidal effect.

[0006] Specifically, the first aspect of the present invention is to provide a polymer coating containing strong acid groups with a bactericidal function, which has 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 a methyl group or a hydrogen atom; x and y are degrees of polymerization, each selected from an integer of 30 to 2000, and the ratio of x::y is in the range of 0.1 to 0.95.

[0009] The second aspect of the present invention is to provide a method for preparing the polymer coating according to the first aspect of the present invention and a method for coating a surface of a material using the coating, 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 is 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 solution is 0.5 to 1.5;

[0012] Step 3, prepare a strongly acidic aqueous solution of a quaternary ammonium salt compound, the chemical structural formula of which is CH3(CH2) n N(R3)3·X, wherein R3 is a methyl group or a hydrogen atom, n is an integer greater than or equal to 1, and X is Cl - Br - , I - Any one of the above, the solution pH range is 0.5 to 1.5;

[0013] Step 4: mixing the strongly acidic aqueous solution of the strong electrolyte anion polymer prepared in step 2 with the strongly acidic aqueous solution of the quaternary ammonium salt compound prepared in step 3, and subjecting the two to electrostatic action to obtain an aqueous solution of a polymer having a chemical structure as shown in Formula 1; or directly mixing the quaternary ammonium salt compound powder described in step 3 with the strongly acidic aqueous solution of the strong electrolyte anion polymer prepared in step 2, and subjecting the two to electrostatic action to obtain an aqueous solution of a polymer having a chemical structure as shown in Formula 1;

[0014] Step 5: mixing the polymer solution obtained in step 4 with an organic solvent to obtain a polymer coating solution containing an organic solvent;

[0015] Step 6: coating the polymer coating solution prepared in step 5 on the clean solid surface obtained in step 1 to obtain a polymer coating containing strong acid groups having a chemical structure as shown in Formula 1.

[0016] In the present invention, the solid materials to be coated include inorganic non-metallic materials, metal products, wood materials, and synthetic or natural polymer materials. Specifically, these 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.

[0017] 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 acidic aqueous solution of the strong electrolyte anion polymer is in the range of 0.2 to 20 mg / mL.

[0018] In the present invention, the mass concentration of the quaternary ammonium salt compound in the strongly acidic aqueous solution is 0.2-20 mg / mL or the mass concentration of the quaternary ammonium salt compound in the strongly acidic aqueous solution of the strong electrolyte anion polymer is 0.1-20 mg / mL.

[0019] Preferably, the strong acidic aqueous solution with a pH of 0.5 to 1.5 is obtained by adjusting the pH value of a hydrochloric acid solution or a sulfuric acid solution.

[0020] In the present invention, the organic solvent mixed with the polymer aqueous solution having a chemical structure as shown in Formula 1 includes one or more of methanol, ethanol, isopropanol, propanol, ethylene glycol, dimethyl sulfoxide, dimethylformamide, acetonitrile, acetone, chloroform or ethyl acetate.

[0021] Preferably, the volume ratio of the organic solvent to the aqueous solution in the polymer coating solution is in the range of 0.1 to 0.5.

[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 anion polymer or the strongly acidic aqueous solution of the quaternary ammonium salt compound is 1 to 1.5.

[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 strongly acidic aqueous solution of the quaternary ammonium salt compound is 0.5 to 10 mg / mL, or the mass concentration of the quaternary ammonium salt compound in the strongly acidic aqueous solution of the strong electrolyte anion polymer is 0.5 to 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 the use of 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 using the coating to coat the surface of a substance in inhibiting the growth of microorganisms on the surface of an object. Preferably, the microorganisms include Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Helicobacter pylori bacteria or Candida albicans.

[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 inactive, such as Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Helicobacter pylori and Candida albicans, thereby inhibiting the growth of microorganisms and killing bacteria. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The figure is a comparison of the inhibitory effect of the solid surface containing the polymer coating containing strong acid groups of the present invention and the solid surface without the modified coating on the growth of Escherichia coli.

[0033] Figure 2 The figure is a comparison of the fungal growth inhibition effects of the solid surface containing the polymer coating containing strong acid groups of the present invention and the solid surface without the modified coating on Candida.

[0034] Figure 3 The figure is a comparison of the bactericidal effects of the solid surface containing the polymer coating containing strong acid groups of the present invention and the solid surface without the modified coating on Staphylococcus aureus.

[0035] Figure 4 The figure is a comparison of the bactericidal effects of the solid surface containing the polymer coating containing strong acid groups of the present invention and the solid surface without the modified coating on Candida. DETAILED DESCRIPTION

[0036] In order to further understand the present invention, the preferred technical solutions of the present invention are described in detail below with specific examples and test 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.

[0037] Example 1

[0038] 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;

[0039] Step 2: Prepare a 2 mg / mL, pH=1, strongly acidic aqueous solution of sodium polyvinyl sulfonate with a weight average molecular weight of 8 kDa using 1 M hydrochloric acid solution;

[0040] Step 3: Prepare a 2 mg / mL, pH 1, strongly acidic aqueous solution of hexyltrimethylammonium bromide using a 1 M hydrochloric acid solution. The chemical formula of the solution is CH3(CH2)5N(Br)(CH3)3.

[0041] Step 4: The strongly acidic aqueous solution of sodium polyvinyl sulfonate prepared in Step 2 is mixed with the strongly acidic aqueous solution of hexyltrimethylammonium bromide prepared in Step 3, and the two are subjected to electrostatic action for 6 hours. After washing with a saturated aqueous sulfur dioxide solution, an aqueous solution of a polymer having the chemical structure shown in the following formula (x:y=0.1) is obtained;

[0042]

[0043] Step 5: mixing the polymer aqueous solution obtained in step 4 with ethanol to obtain a polymer coating solution with an ethanol / water volume ratio of 0.3 and a polymer concentration of 10 mg / mL;

[0044] Step 6: Soak the clean silicon wafer obtained in step 1 in the polymer coating solution prepared in step 5 for 30 minutes at room temperature. Repeat the soaking twice after drying to obtain a polymer coating containing strong acid groups having a chemical structure shown in the above formula formed based on electrostatic interaction.

[0045] Example 2

[0046] 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;

[0047] Step 2: Prepare a 2 mg / mL, pH 1.3, 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;

[0048] Step 3: Prepare a 2 mg / mL, pH 1.2, strongly acidic aqueous solution of amyltrimethylammonium chloride using 1 M hydrochloric acid solution. The chemical formula of the solution is CH3(CH2)4N(Cl)(CH3)3.

[0049] Step 4: Mix the strongly acidic aqueous solution of potassium polyvinyl sulfate prepared in step 2 and the strongly acidic aqueous solution of amyltrimethylammonium chloride prepared in step 3, subject the two to electrostatic action for 8 hours, and wash with a saturated aqueous sulfur dioxide solution to obtain an aqueous solution of a polymer having a chemical structure shown in the following formula;

[0050]

[0051] Step 5: mixing the polymer aqueous solution obtained in step 4 with ethylene glycol to obtain a polymer coating solution with an ethylene glycol / water volume ratio of 0.4 and a polymer concentration of 5 mg / mL;

[0052] 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 4 times after drying, and obtain a polymer coating containing strong acid groups having a chemical structure shown in the above formula formed based on electrostatic action after drying.

[0053] Example 3

[0054] 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;

[0055] Step 2: Prepare a 10 mg / mL, pH=1, strongly acidic aqueous solution of polystyrene sulfonic acid with a weight average molecular weight of 70 kDa using a 1 M sulfuric acid solution;

[0056] Step 3: directly mixing the powder of decyltrimethylammonium bromide compound having the chemical formula CH3(CH2)9N(Br)(CH3)3 with the strongly acidic aqueous solution of polystyrene sulfonic acid prepared in Step 2, subjecting the two to electrostatic action for 3 hours, and washing with a saturated aqueous sulfur dioxide solution to obtain an aqueous solution of a polymer having the chemical structure shown in the following formula;

[0057]

[0058] Step 4: mixing the polymer aqueous solution obtained in step 3 with propanol to obtain a polymer coating solution with a propanol / water volume ratio of 0.2 and a polymer concentration of 10 mg / mL;

[0059] Step 5: Use a desktop coating machine to spin-coat the polymer coating solution obtained in step 4 at 35°C onto the clean polyurethane sheet obtained in step 1 for 10 minutes. After air drying, repeat the spin coating once. After drying, a polymer coating containing strong acid groups having a chemical structure shown in the above formula formed based on electrostatic action is obtained.

[0060] Example 4

[0061] 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;

[0062] Step 2: Prepare a 1 mg / mL, pH 1.2, strongly acidic aqueous solution of polyethylene sulfonic acid with a weight average molecular weight of 20 kDa using a 2 M hydrochloric acid solution;

[0063] Step 3: Prepare a 4 mg / mL, pH 1.1, strongly acidic aqueous solution of octadecyltrimethylammonium chloride using 0.5 M sulfuric acid solution. The chemical formula is CH3(CH2): 17 N(Cl)(CH3)3;

[0064] Step 4: The strongly acidic aqueous solution of polyethylene sulfonic acid prepared in step 2 is mixed with the strongly acidic aqueous solution of octadecyltrimethylammonium chloride prepared in step 3, and the two are subjected to electrostatic action for 12 hours. After washing with a saturated aqueous sulfur dioxide solution, an aqueous solution of a polymer having the chemical structure shown in the following formula (x:y=0.2) is obtained;

[0065]

[0066] Step 5: mixing the polymer aqueous solution obtained in step 4 with an ethanol / propanol mixture at a volume ratio of 1:1 to obtain a polymer coating solution with a polymer concentration of 1 mg / mL and an organic mixture / water volume ratio of 0.15;

[0067] 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 three times after drying, and obtain a polymer coating containing strong acid groups having a chemical structure shown in the above formula formed based on electrostatic action after drying.

[0068] Example 5

[0069] 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;

[0070] Step 2: Prepare a 4 mg / mL, pH 1.5, strongly acidic aqueous solution of sodium polystyrene sulfonate with a weight average molecular weight of 1000 kDa using a 3 M sulfuric acid solution;

[0071] Step 3: directly mixing a powder of a butyltrimethylammonium bromide compound having the chemical formula CH3(CH2)3N(Br)(CH3)3 with the strongly acidic aqueous solution of sodium polystyrene sulfonate prepared in Step 2, subjecting the mixture to electrostatic action for 1 hour, and washing with a saturated aqueous sulfur dioxide solution to obtain an aqueous solution of a polymer having the chemical structure shown in the following formula (x:y = 0.95);

[0072] Step 4: mixing the polymer aqueous solution obtained in step 3 with methanol to obtain a polymer coating solution with a methanol / water volume ratio of 0.5 and a polymer concentration of 7.5 mg / mL;

[0073]

[0074] Step 5: Immerse the surface of the clean glass sheet obtained in step 1 in the polymer coating solution obtained in step 4 at 10° C. for 10 minutes, repeat the immersion 5 times after drying, and obtain a polymer coating containing strong acid groups having a chemical structure shown in the above formula formed based on electrostatic action after drying.

[0075] Example 6

[0076] 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;

[0077] Step 2: Prepare a 0.5 mg / mL, pH=1, 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;

[0078] Step 3: Prepare a 5 mg / mL, pH 1, strongly acidic aqueous solution of octadecyltrimethylammonium bromide using 1 M sulfuric acid solution. The chemical formula is CH3(CH2): 17 N(Br)(CH3)3;

[0079] Step 4: The strongly acidic aqueous solution of potassium polyvinyl sulfate prepared in step 2 is mixed with the strongly acidic aqueous solution of octadecyltrimethylammonium bromide prepared in step 3, and the two are subjected to electrostatic action for 18 hours. After washing with a saturated aqueous sulfur dioxide solution, an aqueous solution of a polymer having the chemical structure shown in the following formula (x:y=0.05) is obtained;

[0080]

[0081] Step 5: mixing the polymer aqueous solution obtained in step 4 with ethyl acetate to obtain a polymer coating solution with an ethyl acetate / water volume ratio of 0.3 and a polymer concentration of 3 mg / mL;

[0082] Step 6: Inject the polymer coating solution obtained in step 5 at 20° 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, the spraying is repeated 4 times. After drying, a polymer coating containing strong acid groups having a chemical structure shown in the above formula formed based on electrostatic action is obtained.

[0083] Example 7

[0084] 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;

[0085] Step 2: Prepare a 2 mg / mL, pH=1, 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;

[0086] Step 3: Prepare a 2.5 mg / mL, pH 1.05, strongly acidic aqueous solution of dodecyltrimethylammonium bromide using a 3M sulfuric acid solution. The chemical formula is CH3(CH2): 11 N(Br)(CH3)3;

[0087] Step 4: Mixing the strongly acidic aqueous solution of sodium polystyrene sulfonate-polyethylene sulfonic acid prepared in Step 2 with the strongly acidic aqueous solution of dodecyltrimethylammonium bromide prepared in Step 3, subjecting the two to electrostatic action for 1 hour, and washing with a saturated aqueous sulfur dioxide solution to obtain an aqueous solution of two polymers having the chemical structure shown in the following formula (x:y = 0.17);

[0088]

[0089] Step 5: mixing the polymer aqueous solution obtained in step 4 with an ethanol / ethylene glycol organic solvent in a volume ratio of 1:2 to obtain a polymer coating solution with an organic solvent / water volume ratio of 0.5 and a polymer concentration of 6 mg / mL;

[0090] Step 6: Use a desktop coating machine to spin-coat the polymer coating solution obtained in step 5 at 17°C onto the clean cotton cloth obtained in step 1 for 20 minutes. After drying, repeat the spin coating twice to obtain a polymer coating containing strong acid groups whose chemical structure is shown in the above formula and is formed based on electrostatic action.

[0091] Example 8

[0092] 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;

[0093] Step 2: Prepare a 10 mg / mL, pH=1, 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;

[0094] Step 3: Prepare a 5 mg / mL, pH 1.2, strongly acidic aqueous solution of octyltrimethylammonium chloride using 1 M hydrochloric acid solution. The chemical formula of the solution is CH3(CH2)7N(Cl)(CH3)3.

[0095] Step 4: The strongly acidic aqueous solution of lithium polyvinyl sulfonate-sodium polyvinyl sulfate prepared in Step 2 is mixed with the strongly acidic aqueous solution of octyltrimethylammonium chloride prepared in Step 3, and the two are subjected to electrostatic action for 10 hours. After washing with a saturated aqueous sulfur dioxide solution, an aqueous solution of two polymers having the chemical structure shown in the following formula (x:y=0.2) is obtained;

[0096]

[0097] Step 5: mixing the polymer aqueous solution obtained in step 4 with a dimethyl sulfoxide / propanol organic solvent in a volume ratio of 1:3 to obtain a polymer coating solution with an organic solvent / water volume ratio of 0.26 and a polymer concentration of 1 mg / mL;

[0098] Step 6: Inject the polymer coating solution prepared in step 5 at 30° 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 containing strong acid groups having a chemical structure shown in the above formula formed based on electrostatic action is obtained.

[0099] Example 9

[0100] 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;

[0101] Step 2: Prepare a 10 mg / mL, pH 1.5, strongly acidic aqueous solution of polystyrene sulfonic acid (1000 kDa weight average molecular weight) and polyvinyl sulfate (12 kDa weight average molecular weight) (the molar ratio of the two polymers is 3:1) using a 2.5 M sulfuric acid solution;

[0102] Step 3: Prepare a 10 mg / mL, pH 1, strong acidic aqueous solution of undecyltrimethylammonium chloride using 2M hydrochloric acid solution. Its chemical formula is CH3(CH2): 10 N(Cl)(CH3)3;

[0103] Step 4: The strongly acidic aqueous solution of polystyrene sulfonic acid-polyvinyl sulfate prepared in Step 2 is mixed with the strongly acidic aqueous solution of undecyltrimethylammonium chloride prepared in Step 3, and the two are subjected to electrostatic action for 2 hours. After washing with a saturated aqueous sulfur dioxide solution, an aqueous solution of two polymers having the chemical structure shown in the following formula (x:y = 0.35) is obtained;

[0104]

[0105] Step 5: mixing the polymer aqueous solution obtained in step 4 with a chloroform / ethylene glycol organic solvent in a volume ratio of 1:3 to obtain a polymer coating solution with an organic solvent / water volume ratio of 0.4 and a polymer concentration of 0.8 mg / mL;

[0106] 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. The coating is repeated 3 times. After drying, a polymer coating containing strong acid groups having the chemical structure shown in the above formula formed based on electrostatic action is obtained.

[0107] Example 10

[0108] 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;

[0109] Step 2: Prepare a 4 mg / mL, pH 1.1, 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 molar ratio of the two polymers is 1:2) using 2 M hydrochloric acid solution;

[0110] Step 3: Prepare a 3 mg / mL, pH 1.3, strongly acidic aqueous solution of tetradecyltrimethylammonium bromide using a 2M sulfuric acid solution. The chemical formula is CH3(CH2): 13 N(Br)(CH3)3;

[0111] Step 4: The strongly acidic aqueous solution of polystyrene sulfonic acid-polyethylene sulfonic acid prepared in Step 2 is mixed with the strongly acidic aqueous solution of tetradecyltrimethylammonium bromide prepared in Step 3, and the two are subjected to electrostatic action for 3 hours. After washing with a saturated aqueous sulfur dioxide solution, an aqueous solution of two polymers having the chemical structure shown in the following formula (x:y = 0.45) is obtained;

[0112]

[0113] Step 5: mixing the polymer aqueous solution obtained in step 4 with a dimethyl sulfoxide / ethanol / isopropanol organic solvent in a volume ratio of 1:1:2 to obtain a polymer coating solution with an organic solvent / water volume ratio of 0.17 and a polymer concentration of 5 mg / mL;

[0114] 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 containing strong acid groups having a chemical structure shown in the above formula formed based on electrostatic action is obtained.

[0115] Example 11

[0116] 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;

[0117] Step 2: Prepare a 6 mg / mL, pH 1.2, 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 3 M hydrochloric acid solution;

[0118] Step 3: Prepare a 0.5 mg / mL, pH 1.5, strongly acidic aqueous solution of octadecylamine hydrochloride using 2.5 M hydrochloric acid solution. Its chemical formula is CH3(CH2): 17 NH3·Cl;

[0119] Step 4: The strongly acidic aqueous solution of polystyrene sulfonic acid-polyvinyl sulfuric acid-polyvinyl sulfonic acid prepared in Step 2 is mixed with the strongly acidic aqueous solution of octadecylamine hydrochloride prepared in Step 3, and the two are subjected to electrostatic action for 7 hours. After washing with a saturated aqueous sulfur dioxide solution, an aqueous solution of three polymers having the chemical structure shown in the following formula (x:y=0.5) is obtained;

[0120]

[0121] Step 5: mixing the polymer aqueous solution obtained in step 4 with an organic solvent of acetone / acetonitrile / isopropanol in a volume ratio of 2:1:3 to obtain a polymer coating solution with an organic solvent / water volume ratio of 0.2 and a polymer concentration of 10 mg / mL;

[0122] 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, the printing is repeated twice. After drying, a polymer coating containing strong acid groups having a chemical structure shown in the above formula formed based on electrostatic action is obtained.

[0123] Example 12

[0124] 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;

[0125] Step 2: Prepare a 4 mg / mL, pH 1.3, 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;

[0126] Step 3: Prepare a 6 mg / mL, pH 1.3, strongly acidic aqueous solution of dodecylamine hydrochloride using 1 M sulfuric acid solution. Its chemical formula is CH3(CH2): 11 NH3·Cl;

[0127] Step 4: Mix the strongly acidic aqueous solution of sodium polyvinyl sulfonate-potassium polyvinyl sulfate prepared in Step 2 with the strongly acidic aqueous solution of dodecylamine hydrochloride prepared in Step 3, subject the two to electrostatic action for 9 hours, and wash with a saturated aqueous sulfur dioxide solution to obtain an aqueous solution of two polymers having the chemical structure shown in the following formula (x:y=0.6);

[0128]

[0129] Step 5: mixing the polymer aqueous solution obtained in step 4 with an organic solvent of dimethylformamide / acetonitrile / ethylene glycol in a volume ratio of 1:3:1 to obtain a polymer coating solution with an organic solvent / water volume ratio of 0.35 and a polymer concentration of 3 mg / mL;

[0130] Step 6: Inject the polymer coating solution prepared in step 5 at 23°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 containing strong acid groups with the chemical structure shown in the above formula formed based on electrostatic action is obtained.

[0131] Example 13

[0132] 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;

[0133] Step 2: Prepare a 0.8 mg / mL, pH=1, 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;

[0134] Step 3: Prepare a 0.7 mg / mL, pH 1.4, strongly acidic aqueous solution of octylamine hydrochloride using 1 M hydrochloric acid solution. The chemical formula of the solution is CH3(CH2)7NH3·Cl.

[0135] Step 4: The strongly acidic aqueous solution of sodium polystyrene sulfonate-sodium polyethylene sulfonate-lithium polyethylene sulfate prepared in Step 2 is mixed with the strongly acidic aqueous solution of octylamine hydrochloride prepared in Step 3, and the two are subjected to electrostatic action for 5 hours. After washing with a saturated aqueous sulfur dioxide solution, an aqueous solution of three polymers having the chemical structure shown in the following formula (x:y=0.4) is obtained;

[0136]

[0137] Step 5: mixing the polymer aqueous solution obtained in step 4 with a dimethyl sulfoxide / acetone / ethanol organic solvent in a volume ratio of 2:3:5 to obtain a polymer coating solution with an organic solvent / water volume ratio of 0.2 and a polymer concentration of 0.5 mg / mL;

[0138] 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 6 times after drying, and obtain a polymer coating containing strong acid groups having a chemical structure shown in the above formula formed based on electrostatic action after drying.

[0139] In order to demonstrate the beneficial effects of the present invention, the present invention verifies the growth inhibition and sterilization effect of a polymer coating containing strong acid groups with a sterilization function formed based on electrostatic action on bacteria (including fungi). The specific test is as follows:

[0140] The present invention uses bacteria such as Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Helicobacter pylori, and fungi such as Candida to conduct verification tests.

[0141] Test 1

[0142] The inhibitory effect of the samples on the growth of E. coli was verified according to the following steps.

[0143] Step 1: Prepare bacterial culture lysate broth (LB) solution: Dissolve 25g LB powder in 1000ml water and stir thoroughly to dissolve. Sterilize the prepared culture solution in a high-temperature sterilizer.

[0144] Step 2: Prepare E. coli bacterial culture solution: dissolve 10 μL of bacterial culture in 10 mL of LB solution sterilized in step 1;

[0145] Step 3: Place the bacterial liquid treated in step 2 in a shaker at a temperature of 37°C and a shaking speed of 250 rpm and culture for 24 hours;

[0146] Step 4: centrifuge the bacterial solution cultured in step 3 at a speed of 3000 rpm for 10 min;

[0147] Step 5: The bacteria centrifuged in step 4 were quantitatively diluted with the LB solution sterilized in step 1, so that the absorption value at OD=600nm under ultraviolet absorption test was 0.008-0.01, corresponding to a bacterial concentration of 10 8 CFU / mL, and then the bacterial concentration was 10 8 The bacterial solution was further diluted with LB solution to a bacterial concentration of 10 CFU / mL. 4 CFU / mL bacterial solution is used for subsequent experimental operations;

[0148] Step 6: Place the sample obtained in Example 1 and the unmodified solid surface as a control sample on the solid surface with a bacterial concentration of 10 4 CFU / mL of bacterial solution was cultured at 37°C, the shaker speed was 200 rpm, and the OD value was measured every 2 hours. The culture time was 18 hours.

[0149] Step 7: Analyze the bacterial growth process of the cultured samples of Example 1 and the blank control sample placed separately in step 6.

[0150] The results of the verification of the inhibition of E. coli growth on the samples are as follows Figure 1 As shown, the sample from Example 1 released hydrogen ions, which inhibited the normal growth of bacteria in the bacterial solution it was immersed in (the OD value was close to 0.5 after 18 hours of bacterial culture). In contrast, the OD value of the bacterial solution immersed in the blank sample after 18 hours of culture was greater than 1.2. The number of bacteria in the bacterial solution immersed in the sample from Example 1 was far lower than that in the blank sample, showing a difference of orders of magnitude.

[0151] The inhibitory effect of the polymer coating containing strong acid groups with bactericidal function formed based on electrostatic interaction on the growth of Escherichia coli was verified.

[0152] Test 2

[0153] The inhibitory effect of the sample on the growth of Staphylococcus aureus was verified according to the following steps.

[0154] The bacterial growth inhibition process was performed according to the standards described in Experiment 1, except that the Staphylococcus aureus seed solution was prepared. The effectiveness of Example 6 in inhibiting the growth of Staphylococcus aureus was verified, and the bacterial growth process of the sample of Example 6 and the corresponding blank control sample were analyzed by placing them separately.

[0155] Verification of the samples' effectiveness at inhibiting Staphylococcus aureus growth showed that the large amount of hydrogen ions adsorbed by the Example 6 sample inhibited normal bacterial growth in the bacterial solution it was immersed in (after 18 hours of incubation, the OD value was below 0.5). In contrast, the OD value of the blank control sample, after 18 hours of incubation, was close to 1.5. The number of bacteria in the bacterial solution immersed in the Example 6 sample was significantly lower than that in the blank control sample, representing an order of magnitude difference in bacterial counts.

[0156] The inhibitory effect of the polymer coating containing strong acid groups with bactericidal function formed based on electrostatic interaction on the growth of Staphylococcus aureus was verified.

[0157] Test 3

[0158] The inhibitory effect of the samples on the growth of Pseudomonas aeruginosa was verified according to the following steps.

[0159] The bacterial growth process was inhibited according to the standards described in Experiment 1, except that the Pseudomonas aeruginosa seed solution was prepared for the experiment. The effect of Example 7 on inhibiting the growth of Pseudomonas aeruginosa was verified, and the bacterial growth process of the sample of Example 7 and the corresponding blank control sample were cultured separately and analyzed.

[0160] Results from the samples' effectiveness at inhibiting Pseudomonas aeruginosa growth showed that the high hydrogen ion content of the Example 7 sample inhibited normal bacterial growth in the bacterial solution it was immersed in (after 18 hours of incubation, the OD value was less than 0.4). In contrast, the OD value of the blank control sample's bacterial solution after 18 hours of incubation was close to 1.3. The number of bacteria in the bacterial solution immersed in the Example 7 sample was significantly lower than that in the blank control sample, representing an order of magnitude difference in bacterial counts.

[0161] The inhibitory effect of the polymer coating containing strong acid groups with bactericidal function formed based on electrostatic interaction on the growth of Pseudomonas aeruginosa was verified.

[0162] Test 4

[0163] The inhibition effect of the samples on the growth of Candida species was verified according to the following steps.

[0164] The bacterial growth inhibition process was carried out according to the standards described in Experiment 1, except that the Candida seed solution was prepared. The effect of Example 2 on inhibiting Candida growth was verified by analyzing the fungal growth process of the sample of Example 2 and the corresponding blank control sample cultured separately.

[0165] The results of the verification of the inhibition effect of the sample on the growth of Candida albicans are as follows: Figure 2As shown, the large amount of hydrogen ions adsorbed by the Example 2 sample inhibited normal fungal growth in the fungal solution it was immersed in (the OD value was less than 0.4 after 18 hours of fungal culture). In contrast, the OD value of the fungal solution immersed in the blank control sample approached 1.4 after 18 hours of culture. The number of fungi in the fungal solution immersed in the Example 2 sample was far lower than the number of bacteria in the blank control sample, showing an order of magnitude difference in the number of fungi.

[0166] The inhibitory effect of the polymer coating containing strong acid groups with bactericidal function formed based on electrostatic interaction on the growth of Candida albicans was verified.

[0167] Test 5

[0168] Follow the steps below to verify the bactericidal effect of the sample.

[0169] Step 1: Cultivate the bacterial solution according to steps 1-4 described in Experiment 1, except that the Staphylococcus aureus seed solution is prepared;

[0170] Step 2: The bacterial solution centrifuged in step 1 was quantitatively diluted with phosphate buffered saline (PBS) so that the absorption value at OD=600nm under ultraviolet absorption test was 0.008-0.01, corresponding to a bacterial concentration of 10 8 CFU / mL, and then the bacterial concentration was 10 8 The bacterial solution was further diluted with PBS to a bacterial concentration of 10 CFU / mL. 7 CFU / mL bacterial solution is used for subsequent experimental operations;

[0171] Step 3: The samples in Example 3 and the corresponding blank control samples were respectively mixed with the bacterial concentration of 10 7 The bacterial solution with CFU / mL was spread on the agar plate by a spreader;

[0172] Step 4: Place the agar plate coated in step 3 in a constant temperature box at 37° C. and humidity RH=10% for 24 hours, and observe the bactericidal effects of the sample of Example 3 and the corresponding blank control sample.

[0173] The results of the sterilization effect verification of the samples are as follows Figure 3 As shown in the figure: the agar plate coated with the blank control sample is full of bacterial colonies, while the agar plate coated with the sample of Example 3 has obvious inhibition rings due to the release of a large amount of hydrogen ions carried by it.

[0174] The bactericidal effect of the polymer coating containing strong acid groups with bactericidal function formed based on electrostatic interaction on Staphylococcus aureus was verified.

[0175] Test 6

[0176] Follow the steps below to verify the bactericidal effect of the sample.

[0177] The bactericidal effect of Example 8 on Helicobacter pylori was verified by following the standard sterilization process described in Experiment 5, except that the Helicobacter pylori seed solution was prepared. The bactericidal effect of the Example 8 sample and the corresponding blank control sample were analyzed based on the separation.

[0178] The results of the bactericidal effect verification of the samples showed that the agar plate coated with the blank control sample was full of bacterial colonies, while the agar plate coated with the sample of Example 8 had obvious antibacterial rings due to the release of a large amount of hydrogen ions carried by it.

[0179] The bactericidal effect of the polymer coating containing strong acid groups with bactericidal function formed based on electrostatic interaction on Helicobacter pylori was verified.

[0180] Test 7

[0181] Follow the steps below to verify the bactericidal effect of the sample.

[0182] The bactericidal effect of Example 9 on Pseudomonas aeruginosa was verified by following the standard sterilization process described in Experiment 5, except that the Pseudomonas aeruginosa seed solution was prepared. The bactericidal effect of Example 9 and the corresponding blank control sample were analyzed based on the sterilization effect of the sample of Example 9 and the corresponding blank control sample placed separately.

[0183] The results of the bactericidal effect verification of the samples showed that the agar plate coated with the blank control sample was full of bacterial colonies, while the agar plate coated with the sample of Example 9 had obvious inhibition rings due to the release of a large amount of hydrogen ions carried by it.

[0184] The bactericidal effect of the polymer coating containing strong acid groups with bactericidal function formed based on electrostatic interaction on Pseudomonas aeruginosa was verified.

[0185] Test 8

[0186] Follow the steps below to verify the bactericidal (fungicide) effect of the sample.

[0187] The bactericidal activity of Example 4 against Candida was verified by following the standard sterilization process described in Experiment 5, except that the Candida seed solution was prepared. The bactericidal effect of the Example 4 sample and the corresponding blank control sample were analyzed separately.

[0188] The results of the sterilization effect verification of the samples are as follows Figure 4 As shown, the agar plate coated with the blank control sample is full of fungal colonies, while the agar plate coated with the sample of Example 4 has obvious inhibition rings due to the release of a large amount of hydrogen ions carried by it.

[0189] The bactericidal effect of the polymer coating containing strong acid groups with bactericidal function formed based on electrostatic interaction on Candida albicans was verified.

[0190] In summary, the results of the above embodiments and test examples show that the present invention has achieved the following technical effects:

[0191] 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;

[0192] 2. The present invention can make the surface of the coated object inactive, such as Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Helicobacter pylori and Candida albicans, thereby inhibiting the growth of microorganisms and killing bacteria.

[0193] 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 containing strong acid groups with bactericidal 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 a methyl group or a hydrogen atom; x and y are degrees of polymerization, each selected from an integer between 30 and 2000, and the ratio of x:y is in the range of 0.1 to 0.

95.

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, wherein the strong electrolyte anion polymer is 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 solution is 0.5 to 1.5; Step 3, prepare a strongly acidic aqueous solution of a quaternary ammonium salt compound, the chemical structural formula of which is CH3(CH2) n N(R3)3·X, wherein R3 is a methyl group or a hydrogen atom, n is an integer greater than or equal to 1, and X is Cl - Br - or I - , the solution pH range is 0.5 ~ 1.5; Step 4: mixing the strongly acidic aqueous solution of the strong electrolyte anion polymer prepared in step 2 with the strongly acidic aqueous solution of the quaternary ammonium salt compound prepared in step 3, or directly mixing the quaternary ammonium salt compound powder described in step 3 with the strongly acidic aqueous solution of the strong electrolyte anion polymer prepared in step 2, and obtaining an aqueous solution of a polymer having a chemical structure as shown in Formula 1 through electrostatic interaction between the two; Step 5: mixing the polymer aqueous solution obtained in step 4 with an organic solvent to obtain a polymer coating solution containing an organic solvent; Step 6: coating the polymer coating solution prepared in step 5 on the clean solid surface obtained in step 1, so that a coating having a polymer component containing a strong acid group and a chemical structure as shown in Formula 1 is formed on the surface of the object.

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 3, the mass concentration of the strongly acidic aqueous solution of the quaternary ammonium salt compound is 0.2 to 20 mg / mL, or in step 4, the mass concentration of the quaternary ammonium salt compound in the strongly acidic aqueous solution of the strong electrolyte anion polymer is 0.1 to 20 mg / mL.

6. The method according to claim 2, characterized in that In steps 2 and 3, the strongly acidic aqueous solution is obtained by adjusting the pH of the solution to 0.5 to 1.5 using a hydrochloric acid solution or a sulfuric acid solution.

7. The method according to claim 2, characterized in that In step 5, the organic solvent is one or more of methanol, ethanol, isopropanol, propanol, ethylene glycol, dimethyl sulfoxide, dimethylformamide, acetonitrile, acetone, chloroform or ethyl acetate; The volume ratio of the organic solvent to the aqueous solution in the polymer coating solution is in the range of 0.1 to 0.

5.

8. The method according to claim 2, characterized in that In step 6, 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 number is more than one time.

10. Use of a method for coating an object surface with the polymer coating according to claim 1 or the polymer coating according to any one of claims 2 to 9 for inhibiting the growth of microorganisms on the object surface, wherein the microorganisms include Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Helicobacter pylori bacteria, or Candida fungi.

Images