A method for preparing a functional coating based on self-polymerization of aminomalonic nitrile

Abstract

The present application relates to the field of coating, disclose a kind of preparation method of functional coating based on aminomalonic nitrile self-polymerization, comprising: S1: modifying hyaluronic acid to introduce aldehyde group, obtain aldehyde group hyaluronic acid;S2: amino malonic nitrile p-toluenesulfonic acid salt is dissolved together with aldehyde group hyaluronic acid in tris-hydroxymethyl aminomethane hydrochloride buffer solution and mixed, obtain functional coating solution;S3: substrate is immersed in functional coating solution, after oscillation incubation, remove, clean, dry, obtain the substrate that surface is uniformly coated with functional coating.The present application first carries out aldehyde group modification to hyaluronic acid to give its copolymerization ability with amino malonic nitrile p-toluenesulfonic acid salt, then it is mixed with amino malonic nitrile p-toluenesulfonic acid salt under alkaline condition, and is deposited on substrate surface by oscillation reaction, and the coating with anti-inflammatory function is prepared.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating, in particular to a preparation method of functional coating based on amino malononitrile self-polymerization. BACKGROUND

[0002] Surface modification technology of materials is widely used and plays an important role in the fields of medical devices, automotive industry, aerospace, electronics, nanotechnology, etc. By modifying the surface of materials, the corrosion resistance, friction and wear resistance, biocompatibility, optical performance, etc. of the materials can be improved, and special functions such as antibacterial property, antifouling property, photocatalytic property, etc. can also be realized.

[0003] Currently available surface modification methods include dip coating, electroplating, layer-by-layer assembly, hydrolysis, plasma treatment, electron beam irradiation, organosilane chemistry, graft polymerization and interfacial polymerization, etc. Generally, these methods have time-consuming and complex processes and cannot be extended to a wider range of material surfaces, which are largely limited by the characteristics of the substrate surface. Therefore, there is an urgent need for a simple, efficient and universal strategy to improve the surface of materials.

[0004] In recent years, a surface modification strategy based on amino malononitrile p-toluenesulfonate self-polymerization technology has been developed. Under alkaline conditions, amino malononitrile can be rapidly deposited on a wide range of material surfaces. Compared with other technologies, this surface modification strategy has multiple advantages in deposition processing under mild conditions and can be applied to various surfaces and a wide range of applications. The coating preparation has the advantages of simple operation, rapid efficiency, stability and uniformity, etc.

[0005] However, the coating constructed based on the amino malononitrile surface modification technology currently has relatively single functionality and is not rich enough. The amino malononitrile surface coating modification is mainly used to improve the hydrophilic property and biocompatibility of the material surface, which is not rich enough.

[0006] Therefore, how to give the coating more functionality (such as anti-inflammatory, antibacterial, etc.) based on the amino malononitrile surface modification technology is a subject that needs to be further studied. SUMMARY

[0007] In order to solve the above technical problems, the present application provides a preparation method of functional coating based on amino malononitrile self-polymerization. The present application first modifies hyaluronic acid with aldehyde group to give it the ability to copolymerize with amino malononitrile p-toluenesulfonate, then mixes it with amino malononitrile p-toluenesulfonate under alkaline conditions and deposits on the substrate surface by oscillation reaction to prepare a functional coating with anti-inflammatory function, which greatly expands the application field. And compared with the conventional surface modification method, the method of the present application is simple, fast and mild in process.

[0008] The specific technical scheme of the present application is: a preparation method of a functional coating based on amino malonitrile self-polymerization, comprising the following steps:

[0009] S1: modifying hyaluronic acid to introduce aldehyde groups to obtain aldehyde group-containing hyaluronic acid; S2: dissolving amino malonitrile p-toluenesulfonate and aldehyde group-containing hyaluronic acid in a tris-hydroxymethyl aminomethane hydrochloride buffer solution with pH = 8.0-9.5, and adjusting the pH of the system to 8-9 with a base to obtain a functional coating solution.

[0010] In the functional coating solution, the concentration of amino malonitrile p-toluenesulfonate is 0.02-0.1 g / mL, and the concentration of aldehyde group-containing hyaluronic acid is 0.3-0.8 mg / mL.

[0011] S3: immersing a substrate in the functional coating solution, taking it out after oscillation incubation, washing to remove residual un-polymerized precipitates or derivatives on the surface of the substrate, and drying to obtain a substrate with a uniform functional coating on the surface.

[0012] Hyaluronic acid has excellent anti-inflammatory efficacy, so if it is introduced into a coating based on amino malonitrile self-polymerization, the coating can be endowed with anti-inflammatory efficacy. However, the molecules of hyaluronic acid do not have groups that can polymerize with amino malonitrile. Therefore, in S1, the present application first modifies hyaluronic acid by aldehyde modification. After the modification of hyaluronic acid by the present application, the hyaluronic acid not only has the ability to copolymerize with amino malonitrile p-toluenesulfonate, but also the functional active structure of the hyaluronic acid is not damaged during the modification process, so the original activity can almost be maintained.

[0013] In S2, aldehyde group-containing hyaluronic acid is mixed with amino malonitrile p-toluenesulfonate under alkaline conditions to obtain a functional coating solution; in S3, a method of immersion + oscillation incubation is used for surface copolymerization reaction on the substrate to construct a functional coating with anti-inflammatory function.

[0014] Preferably, in S1, the aldehyde modification method of the hyaluronic acid is: dissolving 2-6 g of sodium hyaluronate and 1-3 g of sodium periodate in a phosphate buffered saline with pH = 4.5-5.5, and stirring at 20-30℃ in the dark for 2-6 h; finally, adding ethylene glycol to terminate the reaction; dialyzing and freeze-drying to obtain aldehyde group-containing hyaluronic acid.

[0015] The principle of the above modification is: by sodium periodate, part of the hydroxyl groups on the hyaluronic acid are oxidized into aldehyde groups, which can be introduced into the main chain of the hyaluronic acid. Thus, in the formation process of the functional coating, Schiff base reaction occurs between the amino groups on the amino malonitrile p-toluenesulfonate and the aldehyde groups on the modified hyaluronic acid.

[0016] Preferably, in S3, the temperature of the oscillation incubation is 15-45℃, and the time is 8-24 h.

[0017] Preferably, S4 is further included: the substrate with the surface coated with the functional coating obtained in S3 is immersed in an antibacterial modification solution containing copper chloride and / or silver nitrate, and a secondary oscillation reaction is performed, and then the substrate is ultrasonically cleaned and dried to obtain a secondary modified functional coating; the number of amino groups in the amino malononitrile p-toluenesulfonate is in excess compared to the aldehyde groups in the aldehyde-modified hyaluronic acid.

[0018] In order to further endow the functional coating with antibacterial function, an antibacterial element (the amino group in the amino malononitrile p-toluenesulfonate can be chelated with metals through coordination) can be introduced into the functional coating by the method of immersion + oscillation reaction. In addition, in order to make there still be excess active groups in the functional coating that can react with copper chloride and / or silver nitrate, the number of amino groups in the amino malononitrile p-toluenesulfonate needs to be controlled to be in excess compared to the aldehyde groups in the functional molecule, and the preferred molar ratio of amino groups to aldehyde groups is (30-200): 1.

[0019] Further preferably, the temperature of the secondary oscillation reaction is 20-40℃, and the time is 12-24h.

[0020] Further preferably, the total concentration of copper chloride and / or silver nitrate in the antibacterial modification solution is 10-60mg / mL.

[0021] Preferably, in S3, the substrate is a planar substrate.

[0022] Further preferably, the planar substrate is an aluminum sheet, a zinc sheet, a copper sheet, a nickel sheet, a titanium sheet, an iron sheet, a stainless steel substrate, a polytetrafluoroethylene plate, a polyvinyl chloride plate, a polypropylene plate, a terylene fabric, a silicon wafer, an acetate fabric, or a glass sheet.

[0023] Preferably, in S3, the cleaning is ultrasonic cleaning: deionized water is used for ultrasonic cleaning for at least 30min, the ultrasonic frequency is 25-40kHz, and the power is 150-200W. This step is used to remove polymers with weak surface bonding strength.

[0024] Compared with the prior art, the present application has the following beneficial effects:

[0025] (1) The present application first modifies hyaluronic acid by aldehyde modification to endow it with the ability to copolymerize with amino malononitrile p-toluenesulfonate, then mixes it with amino malononitrile p-toluenesulfonate under alkaline conditions, and deposits it on the surface of a substrate through an oscillation reaction to prepare a functional coating with anti-inflammatory function, which can greatly expand the application field.

[0026] (2) The present application further combines antibacterial metal elements on the surface of the functional coating, which can further endow the functional coating with antibacterial properties.

[0027] (3) The method of the present application is compared with the conventional surface modification method, the material is safe and easy to obtain, the environment is friendly, the process is simple, fast, and the conditions are mild, which is suitable for industrialization. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 Digital photos of the deposition of coatings on various organic and inorganic substrate surfaces in Example 1;

[0029] Figure 2 Scanning electron microscope pictures of the polyester fiber fabric;

[0030] Figure 3 Scanning electron microscope pictures of the anti-inflammatory coating of the polyester fiber fabric in Example 2;

[0031] Figure 4 Anti-inflammatory function test photos of the polyester fiber fabric.

[0032] Figure 5 Bacteriostatic circle photos of the polyester fiber fabric; DETAILED DESCRIPTION

[0033] The present application will be further described below in conjunction with examples. In view of the fact that the existing functional coating preparation method is complex and cumbersome, the modification process of the functional molecules is complex and cumbersome, and the reaction conditions are harsh, the present application proposes a functional coating based on amino malonitrile self-polymerization and a preparation method and application thereof

[0034] Example 1

[0035] A method for preparing a polyamino malonitrile coating on a planar substrate, comprising the steps of:

[0036] Step 1: Preparation of buffer: prepare a tris-hydroxymethyl aminomethane buffer with pH = 8.5 and concentration of 0.1 M.

[0037] Step 2: Substrate pretreatment: prepare aluminum sheet, zinc sheet, copper sheet, nickel sheet, titanium sheet, iron sheet, stainless steel sheet, polytetrafluoroethylene plate (PTFE), polyvinyl chloride plate (PVC), polypropylene plate (PP), polyester fiber fabric (PET), acetate fabric and silicon wafer in turn with acetone, anhydrous ethanol, ultrasonic treatment for 3 times, 30 min each time; then use deionized water ultrasonic cleaning for 3 times, 30 min each time; the ultrasonic frequency is 40 kHz and the power is 200 W; the temperature of the mixed solution is maintained at 25℃ by ice water bath during the treatment process. Finally, the substrate is placed in a normal pressure ventilation condition and dried at 65℃ for 4h.

[0038] Step 3: Preparation of polyaminomalonitrile coating: 1 g of aminomalonitrile p-toluene sulfonate was added to a Tris buffer solution (50 ml, pH = 8.5) to prepare an AMN solution with a concentration of 0.02 g / mL; after complete dissolution, the pH of the aminomalonitrile solution was adjusted to 8.5 using 2 M sodium hydroxide; the cleaned substrate was immersed in the aminomalonitrile solution and placed in a water bath constant temperature shaker for 10 h of deposition; after the deposition was completed, it was removed and ultrasonically cleaned with deionized water for 60 min (ultrasonic frequency was 40 kHz and power was 200 W), and then dried for standby use.

[0039] Figure 1 Digital photos of the coating deposited on various organic and inorganic substrates.

[0040] Example 2

[0041] Step 1: Preparation of buffer solution: a Tris buffer solution was prepared with a pH of 8.5 and a concentration of 0.1 M.

[0042] Step 2: Substrate pretreatment: the prepared polyester fabric (PET) was sequentially treated with acetone, anhydrous ethanol, and ultrasonic treatment for 3 times, 30 min each time; then it was ultrasonically cleaned with deionized water for 3 times, 30 min each time; the ultrasonic frequency was 40 kHz and the power was 200 W; the temperature of the mixed solution was maintained at 25°C by ice water bath during the treatment process. Finally, the substrate was dried at 65°C under normal pressure and ventilation conditions for 4 h.

[0043] Step 3: Preparation of aldehyde hyaluronic acid: 4 g of sodium hyaluronate and 2 g of sodium periodate (SP) were dissolved in 200 mL of phosphate buffered saline (PBS, pH = 5.0) and stirred at 25°C in the dark for 4 hours. Finally, 3 ml of ethylene glycol was added to terminate the reaction. Finally, the reaction mixture was dialyzed and lyophilized to obtain the dialdehyde-modified hyaluronic acid.

[0044] Step 4: Preparation of anti-inflammatory coating: 1 g of aminomalonitrile p-toluene sulfonate and 25 mg of aldehyde hyaluronic acid were added to a Tris buffer solution (50 mL, pH = 8.5) to prepare a solution with a final concentration of 20 mg / mL and 0.5 mg / mL, respectively; after mixing, the pH was adjusted to 8.5 using 2 M sodium hydroxide. Then the cleaned polyester fabric was immersed in the immersion solution and placed in a 25°C water bath constant temperature shaker for 10 h of reaction; after ultrasonic cleaning with deionized water for 60 min (ultrasonic frequency was 40 kHz and power was 200 W), it was removed and dried for standby use.

[0045] Example 3

[0046] Step 1: Preparation of buffer solution: a Tris buffer solution was prepared with a pH of 8.5 and a concentration of 0.1 M.

[0047] Step 2: Pretreatment of the substrate: The prepared PET fabric was sequentially treated with acetone, anhydrous ethanol, and ultrasonic treatment for 3 times, 30 min each time; then washed with deionized water for 3 times, 30 min each time; the ultrasonic frequency was 40 kHz, and the power was 200 W; the temperature of the mixture was maintained at 25 °C by ice water bath during the treatment process. Finally, the substrate was dried at 65 °C under normal pressure and ventilation conditions for 4 h.

[0048] Step 3: Preparation of aldehyde hyaluronic acid: 4 g of sodium hyaluronate and 2 g of sodium periodate (SP) were dissolved in 200 mL of phosphate buffered saline (PBS, pH = 5.0), and stirred at 25 °C in the dark for 4 hours. Finally, 3 ml of ethylene glycol was added to terminate the reaction. Finally, the reaction mixture was dialyzed and lyophilized to obtain the dialdehyde-modified hyaluronic acid.

[0049] Step 4: Preparation of anti-inflammatory coating: 1 g of aminomalonitrile p-toluenesulfonate and 25 mg of aldehyde hyaluronic acid were added to a Tris buffer solution (50 mL, pH = 8.5), and the final concentrations of aminomalonitrile p-toluenesulfonate and aldehyde hyaluronic acid were 0.02 g / mL and 0.5 mg / mL, respectively. After mixing, the pH was adjusted to 8.5 using 2M sodium hydroxide. Then the cleaned PET fabric was immersed in the immersion solution and placed in a 25 °C water bath constant temperature oscillator for 10 h. After ultrasonic washing with deionized water for 60 min (ultrasonic frequency was 40 kHz, power was 200 W), it was taken out and dried for standby.

[0050] Step 5: Preparation of antibacterial and anti-inflammatory coating: First, a silver nitrate solution with a concentration of 40 mg / mL was prepared under dark conditions, then the PET fabric with anti-inflammatory coating was immersed in silver nitrate for 24 h to obtain the antibacterial and anti-inflammatory coating, and then washed and dried with deionized water for standby.

[0051] Example 4

[0052] Step 1: Preparation of buffer: Tris buffer solution with pH = 8.5 was prepared, and the concentration was 0.1 M.

[0053] Step 2: Pretreatment of the substrate: The prepared PET fabric was sequentially treated with acetone, anhydrous ethanol, and ultrasonic treatment for 3 times, 30 min each time; then washed with deionized water for 3 times, 30 min each time; the ultrasonic frequency was 40 kHz, and the power was 200 W; the temperature of the mixture was maintained at 25 °C by ice water bath during the treatment process. Finally, the substrate was dried at 65 °C under normal pressure and ventilation conditions for 4 h.

[0054] Step 3: Preparation of aldehyde hyaluronic acid: 4 g of sodium hyaluronate and 2 g of sodium periodate (SP) were dissolved in 200 mL of phosphate buffered saline (PBS, pH = 5.0) and stirred at 25 °C in the dark for 4 hours. Finally, 3 ml of ethylene glycol was added to terminate the reaction. Finally, the reaction mixture was dialyzed and lyophilized to obtain the dialdehyde-modified hyaluronic acid.

[0055] Step 4: Preparation of anti-inflammatory coating: 1 g of aminomalonitrile p-toluenesulfonate and 15 mg of aldehyde hyaluronic acid were added to a Tris buffer solution (50 mL, pH = 8.5), and the final concentrations of aminomalonitrile p-toluenesulfonate and aldehyde hyaluronic acid were 0.02 g / mL and 0.3 mg / mL, respectively. After mixing, the pH was adjusted to 8.5 using 2M sodium hydroxide. Then the cleaned polyester fabric was immersed in the immersion solution and placed in a 25 °C water bath constant temperature shaker for 10 h. After ultrasonic cleaning with deionized water for 60 min (ultrasonic frequency of 40 kHz, power of 200 W), it was taken out and dried for standby.

[0056] Step 5: Preparation of bactericidal anti-inflammatory coating: First, a silver nitrate solution with a concentration of 40 mg / mL was prepared in the dark, and then the polyester fabric with an anti-inflammatory coating was immersed in the silver nitrate solution and incubated for 24 h to obtain the bactericidal anti-inflammatory coating. After ultrasonic cleaning with deionized water and drying, it was ready for use.

[0057] Example 5

[0058] Step 1: Preparation of buffer: Tris buffer solution with pH = 8.5, concentration of 0.1 M.

[0059] Step 2: Pretreatment of the substrate: The prepared polyester fabric (PET) was sequentially treated with acetone, anhydrous ethanol, and ultrasonic treatment for 3 times, 30 min each time; then ultrasonic cleaning with deionized water for 3 times, 30 min each time; ultrasonic frequency of 40 kHz, power of 200 W; the temperature of the mixed solution was maintained at 25 °C by ice water bath during the treatment. Finally, the substrate was dried at 65 °C under normal pressure and ventilation conditions for 4 h.

[0060] Step 3: Preparation of aldehyde hyaluronic acid: 4 g of sodium hyaluronate and 2 g of sodium periodate (SP) were dissolved in 200 mL of phosphate buffered saline (PBS, pH = 5.0) and stirred at 25 °C in the dark for 4 hours. Finally, 3 ml of ethylene glycol was added to terminate the reaction. Finally, the reaction mixture was dialyzed and lyophilized to obtain the dialdehyde-modified hyaluronic acid.

[0061] Step 4: Preparation of anti-inflammatory coating: 1 g of aminomalononitrile p-toluensulfonate and 40 mg of aldehyde hyaluronic acid were added to a Tris buffer solution (50 mL, pH = 8.5) to give a final concentration of 0.02 g / mL and 0.8 mg / mL, respectively. The mixture was stirred at 25 °C in the dark for 10 h. The cleaned PET fabric was then immersed in the solution and placed in a water bath shaker at 25 °C for 10 h. The fabric was then washed with deionized water for 60 min (ultrasonic frequency of 40 kHz and power of 200 W) and dried for use.

[0062] Step 5: Preparation of anti-inflammatory and antibacterial coating: First, a silver nitrate solution with a concentration of 40 mg / mL was prepared in the dark. Then, the PET fabric with the anti-inflammatory coating was immersed in the silver nitrate solution and incubated for 24 h to obtain the anti-inflammatory and antibacterial coating. The fabric was then washed with deionized water and dried for use.

[0063] Example 6

[0064] Step 1: Preparation of buffer: A Tris buffer solution with a pH of 8.5 was prepared with a concentration of 0.1 M.

[0065] Step 2: Pretreatment of the substrate: The prepared PET fabric was sequentially treated with acetone, anhydrous ethanol, and ultrasonic treatment for 3 times, each for 30 min. Then, the fabric was washed with deionized water for 3 times, each for 30 min. The ultrasonic frequency was 40 kHz and the power was 200 W. The temperature of the mixture was maintained at 25 °C during the treatment process. Finally, the substrate was dried at 65 °C under normal pressure and ventilation conditions for 4 h.

[0066] Step 3: Preparation of aldehyde hyaluronic acid: 4 g of sodium hyaluronate and 2 g of sodium periodate (SP) were dissolved in 200 mL of phosphate buffered saline (PBS, pH = 5.0) and stirred at 25 °C in the dark for 4 h. Finally, 3 ml of ethylene glycol was added to terminate the reaction. The reaction mixture was then dialyzed and freeze-dried to obtain the dialdehyde-modified hyaluronic acid.

[0067] Step 4: Preparation of anti-inflammatory coating: 1 g of aminomalononitrile p-toluensulfonate and 40 mg of aldehyde hyaluronic acid were added to a Tris buffer solution (50 mL, pH = 8.5) to give a final concentration of 0.02 g / mL and 0.8 mg / mL, respectively. The mixture was stirred at 25 °C in the dark for 10 h. The cleaned PET fabric was then immersed in the solution and placed in a water bath shaker at 25 °C for 10 h. The fabric was then washed with deionized water for 60 min (ultrasonic frequency of 40 kHz and power of 200 W) and dried for use.

[0068] Step 5: Preparation of the bactericidal anti-inflammatory coating: First, prepare a silver nitrate solution with a concentration of 40 mg / mL under dark conditions, then immerse the polyester fabric with the deposited anti-inflammatory coating in the silver nitrate solution for 24 h to obtain the bactericidal anti-inflammatory coating, and then ultrasonically clean and dry with deionized water for standby.

[0069] Example 7

[0070] Step 1: Preparation of buffer: Prepare a tris buffer with a pH of 8.5 and a concentration of 0.1 M.

[0071] Step 2: Pretreatment of the substrate: The prepared polyester fabric (PET) is sequentially treated with acetone, anhydrous ethanol, and ultrasonic treatment for 3 times, 30 min each time; then ultrasonically cleaned with deionized water for 3 times, 30 min each time; the ultrasonic frequency is 40 kHz and the power is 200 W; the temperature of the mixed solution is maintained at 25°C during the treatment process by ice water bath. Finally, the substrate is dried at 65°C under normal pressure and ventilation conditions for 4 h.

[0072] Step 3: Preparation of aldehyde hyaluronic acid: Dissolve 4 g of sodium hyaluronate and 2 g of sodium periodate (SP) in 200 mL of phosphate buffered saline (PBS, pH = 5.0) and stir at 25°C in the dark for 4 hours. Finally, add 3 ml of ethylene glycol to terminate the reaction. Finally, dialyze and lyophilize the reaction mixture to obtain the dialdehyde-modified hyaluronic acid.

[0073] Step 4: Preparation of anti-inflammatory coating: Add 5 g of aminomalonitrile p-toluenesulfonate and 40 mg of aldehyde hyaluronic acid to the Tris buffer solution (50 mL, pH = 8.5), the final concentration of aminomalonitrile p-toluenesulfonate and aldehyde hyaluronic acid is 0.1 g / mL and 0.8 mg / mL respectively, after mixing evenly, adjust the pH to 8.5 using 2M sodium hydroxide. Then immerse the cleaned polyester fabric into the immersion solution, place it in a 25°C water bath constant temperature shaker for 10 h, then ultrasonically clean with deionized water for 60 min (ultrasonic frequency is 40 kHz and power is 200 W), take out and dry for standby.

[0074] Step 5: Preparation of the bactericidal anti-inflammatory coating: First, prepare a silver nitrate solution with a concentration of 60 mg / mL under dark conditions, then immerse the polyester fabric with the deposited anti-inflammatory coating in the silver nitrate solution for 24 h to obtain the bactericidal anti-inflammatory coating, and then ultrasonically clean and dry with deionized water for standby.

[0075] Performance test

[0076] (1) Morphology observation: Figure 2 、 3 are the scanning electron microscope pictures of the polyester fabric and the polyester fabric with functional coating deposited on the surface in Example 2 respectively.

[0077] (4) Anti-inflammatory function test: PET-AMN (Example 1), PET-AMN-HA (Example 2), PET-AMN-HA-Ag (Example 3) samples were placed in phosphate buffered saline (pH = 7.3) containing 0.4M NaCl, 0.5% bovine serum albumin (BSA), 0.05% Tween 20 and protease inhibitors for 12h. Then the solution was centrifuged at 14000rpm for 30min. The concentration of interleukin-1β (IL-1β) tumor necrosis factor α (TNF-α) was detected using a commercially available enzyme-linked immunosorbent assay kit.

[0078] Figure 4 Figure for anti-inflammatory function test of the resulting polyester fiber fabric in Example 1, Example 2 and Example 3; TNF-α and IL-1β are inflammatory factors that can cause excessive infiltration of inflammatory cells on the wound surface to hinder wound repair. As shown in Figure 4 , the expression of TNF-α and IL-1β in PET-AMN-HA and PET-AMN-HA-Ag coatings is reduced.

[0079] (5) Bacteriostatic circle test: polyester fiber fabric (PET), PET-AMN-HA (Example 2), PET-AMN-HA-Ag (Example 3) were cut and ready for use. The polyester fiber fabric was respectively pasted in the culture dish coated with E. coli (10 7 CFU / mL) and S. aureus (10 7 CFU / mL), 3 parallel samples in each group, then placed in a 37℃, 95% humidity incubator for 24h. After the end of the experiment, the samples were taken out and the diameter of the bacteriostatic circle was measured with a vernier caliper and photographed. As shown in Figure 5 , the PET-AMN-HA-Ag (Example 3) coating material prepared in the application has excellent antibacterial effect.

[0080] The raw materials and equipment used in the application, if not specifically stated, are commonly used raw materials and equipment in the art; the methods used in the application, if not specifically stated, are conventional methods in the art.

[0081] The above is only the preferred embodiment of the present application, not any limitation on the present application, any simple modification, change and equivalent transformation of the above embodiment according to the technical essence of the present application are still within the protection scope of the technical solution of the present application.

Claims

1. A process for the preparation of a functional coating based on self-polymerization of aminomalonitrile, characterized in that The method comprises the following steps: S1: modifying hyaluronic acid to introduce aldehyde groups to obtain hyaluronic acid with aldehyde groups; S2: dissolving aminomalonitrile p-toluenesulfonate and hyaluronic acid with aldehyde groups in a tris-hydroxymethyl aminomethane hydrochloride buffer solution with a pH of 8.0-9.5, adjusting the pH of the system to 8-9 with a base to obtain a functional coating solution; The concentration of aminomalonitrile p-toluenesulfonate in the functional coating solution is 0.02-0.1 g / mL, and the concentration of hyaluronic acid with aldehyde groups is 0.3-0.8 mg / mL; S3: immersing the substrate in the functional coating solution, taking it out after oscillation incubation, washing to remove residual unaggregated precipitates or derivatives on the surface of the substrate, and drying to obtain a substrate with a uniform functional coating on the surface; S4: immersing the substrate with a uniform functional coating on the surface obtained in S3 in an antibacterial modification solution containing copper chloride and / or silver nitrate, performing secondary oscillation reaction, ultrasonic cleaning, and drying to obtain a secondary modified functional coating; the number of aminos in the aminomalonitrile p-toluenesulfonate is in excess of the number of aldehyde groups in the hyaluronic acid with aldehyde groups.

2. The method of claim 1, wherein: In S1, the aldehyde group modification method of the hyaluronic acid is as follows: dissolving 2-6 g of sodium hyaluronate and 1-3 g of sodium periodate in a phosphate buffered saline with a pH of 4.5-5.5, and stirring at 20-30 ℃ in the dark for 2-6 h; finally, adding ethylene glycol to terminate the reaction; dialyzing, freeze-drying to obtain hyaluronic acid with aldehyde groups.

3. The method of claim 1, wherein: In S3, the temperature of the oscillation incubation is 15-45 ℃, and the time is 8-24 h.

4. The method of claim 1, wherein: The temperature of the secondary oscillation reaction is 20-40 ℃, and the time is 12-24 h.

5. The method of claim 1, wherein: The total concentration of copper chloride and / or silver nitrate in the antibacterial modification solution is 10-60 mg / mL.

6. The method of claim 1, wherein: In S3, the substrate is a planar substrate.

7. The method of claim 6, wherein: The planar substrate is an aluminum sheet, a zinc sheet, a copper sheet, a nickel sheet, a titanium sheet, an iron sheet, a stainless steel substrate, a polytetrafluoroethylene plate, a polyvinyl chloride plate, a polypropylene plate, a polyester fabric, a silicon wafer, a acetate fabric, or a glass sheet.

8. The production method according to claim 6 or 7, characterized in that: In S3, the washing is ultrasonic cleaning: using deionized water for ultrasonic cleaning for at least 30 min, with an ultrasonic frequency of 25-40 kHz and a power of 150-200 W.

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