A platinum alloy neutralization ring for hydrogen peroxide care solution and preparation method thereof

Abstract

The present invention relates to the field of contact lens care and catalytic technology, and specifically to a platinum alloy neutralization ring for hydrogen peroxide care solution and a preparation method thereof. The present invention solves the problem of poor cyclic catalytic performance and insufficient antibacterial and bactericidal performance of the platinum alloy neutralization ring in the prior art. The present invention performs swelling treatment on a plastic substrate by adding an organic solvent and a silver nitrate solution, and silver ions are plated on the surface to obtain a silver-plated substrate by reduction. A metal complexing agent is used to complex with a platinum salt, and a platinum nanolayer is formed on the surface of the silver-plated substrate by sodium nitrite activation to obtain a platinum alloy neutralization ring; the type of metal complexing agent is adjusted to improve the stability of the plating solution A; the temperature and time of chemical plating are controlled to improve the catalytic rate of the neutralization ring; the dosage composition ratio of the metal complexing agent is controlled to improve the catalytic ability of the neutralization ring; the dosage of the organic solvent is changed to improve the cyclic catalytic performance of the neutralization ring; the dosage of each component of the organic solvent and the dosage of silver nitrate are adjusted to improve the antibacterial performance of the platinum neutralization ring.

Description

Technical Field

[0001] The invention relates to the fields of contact lens care and catalysis technology, and in particular to a platinum alloy neutralization ring for hydrogen peroxide care solution and a preparation method thereof. Background Art

[0002] The platinum neutralization ring is the core component of the hydrogen peroxide neutralization cup and is the key technology that determines the performance of hydrogen peroxide care products. Hydrogen peroxide, also known as hydrogen peroxide, is a functional component of contact lens care solution. Due to its strong oxidizing property, it can clean, sterilize and disinfect lenses. Contact lens care solution with hydrogen peroxide as a functional component is usually called hydrogen peroxide care solution. It is currently widely used for cleaning and care of contact lenses. However, in daily use, due to the strong oxidizing property of hydrogen peroxide, if the operation is wrong or it is used improperly, hydrogen peroxide may cause conjunctival and corneal damage after entering the eyes. In severe cases, it may also cause vision loss. Therefore, when caring for contact lenses, reducing the concentration of hydrogen peroxide to a safe concentration is the most important process for contact lens cleaning. Although hydrogen peroxide will decompose into water and oxygen during the use of hydrogen peroxide care solution, the decomposition rate of hydrogen peroxide is extremely slow. Therefore, a corresponding catalyst can be added to the contact lens care solution so that the hydrogen peroxide in the hydrogen peroxide care solution maintains a sufficiently high concentration within a predetermined time from the start of lens disinfection. At the same time, after completing the cleaning and sterilization process, it can be quickly catalyzed to achieve a sufficiently low hydrogen peroxide concentration.

[0003] The existing contact lens hydrogen peroxide care solution catalytic products on the market include neutralization tablets and neutralization rings, but neutralization tablets are inconvenient to operate and easy to forget to add. Directly removing the lens can easily cause eye damage, which causes many inconveniences during use. Compared with neutralization tablets, hydrogen peroxide care solution neutralization rings have a higher safety factor and are more convenient to operate. The existing neutralization ring catalytic components are all platinum materials, and the preparation and production processes are different. There are mainly two categories of neutralization ring products. One is a product coated with platinum black nanoparticles. This type of product has excellent catalytic performance, but the platinum black particles are easy to peel off. During use, there is a risk of poor cyclic catalytic performance and low safety factor; the other type is a product coated with a complete platinum coating. However, in this type of product, the platinum coating has limited bonding with the substrate, and after multiple cycles of use, the platinum coating is easy to fall off, reducing the catalytic rate. Patent CN116212859B reports a platinum alloy neutralization ring for hydrogen peroxide care solution and a preparation method thereof. The platinum alloy neutralization ring is prepared by using a plastic substrate and a first platinum alloy layer and a second platinum alloy layer. The platinum alloy is directly plated on the surface of the substrate, and the bonding ability is not high. At the same time, the neutralization ring has poor antibacterial and bactericidal properties, and the cyclic catalytic performance needs to be further improved.

[0004] In summary, platinum neutralization rings have been reported in the prior art, but the problems of poor cyclic catalytic performance and insufficient antibacterial and bactericidal performance of platinum alloy neutralization rings have not been solved.

[0005] Therefore, a platinum alloy neutralization ring for hydrogen peroxide care solution and a preparation method thereof are proposed. Summary of the invention

[0006] The invention aims to provide a platinum alloy neutralization ring for hydrogen peroxide care solution and a preparation method thereof. The invention comprises the following steps: swelling a plastic substrate by adding an organic solvent and a silver nitrate solution, coating the surface with silver ions, reducing the plastic substrate with glucose, complexing a metal complexing agent with a platinum salt, activating the platinum salt with sodium nitrite, and chemically plating the platinum nanolayer on the surface of the silver-plated substrate to prepare the platinum alloy neutralization ring; improving the stability of a plating solution A by adjusting the type of the metal complexing agent; improving the catalytic rate of the neutralization ring by controlling the temperature and time of the chemical plating and adjusting the amount of sodium nitrite in the plating solution B; improving the catalytic ability of the neutralization ring to hydrogen peroxide by controlling the amount composition ratio of the metal complexing agent; improving the cyclic catalytic performance of the platinum alloy neutralization ring by changing the amount of the organic solvent; and improving the antibacterial performance of the platinum neutralization ring by adjusting the amount of each component of the organic solvent and adjusting the amount of silver nitrate.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] The present invention provides a method for preparing a platinum alloy neutralization ring for a hydrogen peroxide care solution. The preparation of the platinum alloy neutralization ring for a hydrogen peroxide care solution comprises the following steps:

[0009] The plastic substrate is immersed in a concentrated sulfuric acid solution to obtain a treated substrate; 5-15 parts of silver nitrate are added to an organic solvent, and mixed evenly to obtain a mixed solution; the treated substrate is added to the mixed solution, immersed to obtain an impregnated substrate, and the impregnated substrate is placed in a vacuum drying oven to obtain a dry substrate; glucose and tartaric acid are added to deionized water, mixed, added to the dry substrate, and taken out after 30 minutes to obtain a silver-plated substrate; a metal complexing agent, 4-8 parts of a platinum salt, and 3.6 parts of an acid-base regulator are added to deionized water, the pH is maintained at 8-10, and a complex reaction is performed at 30-80°C to obtain a plating solution A; sodium nitrite and 10% hydrochloric acid are dissolved in deionized water, stirred and mixed at room temperature, and constant volume is obtained to obtain a plating solution B; the plating solution B is slowly added to the plating solution A, stirred at 100-300rpm for 30 minutes, and mixed evenly to obtain a platinum-plating solution; the silver-plated substrate is immersed in the platinum-plating solution, and the platinum alloy neutralization ring is obtained by chemical plating;

[0010] The mass ratio of the organic solvent to the silver nitrate is 8-10:1;

[0011] The mass fraction ratio of the metal complexing agent to the platinum salt is 1:3-6;

[0012] The mass ratio of the glucose to the tartaric acid is 5-18:1;

[0013] The mass ratio of the sodium nitrite to the platinum salt is 1-1.8:1;

[0014] The chemical plating temperature is 20-90°C; the chemical plating time is 30-100min;

[0015] The plastic substrate is selected from ABS engineering plastics.

[0016] Preferably, the organic solvent is selected from one or two of dichloromethane, ethanol, acetone and ether.

[0017] Preferably, the organic solvent is a mixture of the dichloromethane and the ethanol; wherein the amount of the dichloromethane is 3-20 parts; and the amount of the ethanol is 70-87 parts.

[0018] Preferably, the metal complexing agent is selected from one or two of hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, and ethylenediaminetetraacetic acid.

[0019] Preferably, the metal complexing agent is a mixture of the hydroxyethylethylenediaminetriacetic acid and the dihydroxyethylglycine; wherein the amount of the hydroxyethylethylenediaminetriacetic acid is 5-25 parts; and the amount of the dihydroxyethylglycine is 5-25 parts.

[0020] Preferably, the platinum salt is selected from one of chloroplatinic acid, platinum nitrate and potassium chloroplatinate.

[0021] Preferably, the acid-base regulator is selected from one of sodium hydroxide, ammonia water and triethylamine.

[0022] Preferably, the complexation reaction temperature is 30-60°C.

[0023] Preferably, the chemical plating temperature is 30-80° C.; and the chemical plating time is 30-90 min.

[0024] The invention also provides a platinum alloy neutralization ring for hydrogen peroxide care solution. The platinum alloy neutralization ring comprises a plastic substrate, an inner silver-plated layer and an outer platinum-plated layer.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The present invention uses hydroxyethylethylenediaminetriacetic acid and dihydroxyethylglycine as metal complexing agents, reacts with potassium chloroplatinate under the action of sodium hydroxide, and utilizes the metal complexing agent to react with platinum metal, so that the platinum ions in the system form a stable crystalline phase structure, thereby increasing the stability of the plating solution A. The prepared plating solution A has no stratification phenomenon when placed at 30°C for 5 hours, is not turbid when placed at 50°C for 5 hours, and has no precipitation.

[0027] 2. The present invention obtains a platinum plating solution by stirring and dissolving the prepared plating solution A and sodium nitrite under acidic conditions, and then forms a platinum nanolayer on the surface of the silver-plated substrate by chemical plating. The formed microscopic honeycomb structure is used to increase the catalytic area of ​​the platinum alloy neutralization ring and the catalytic rate. By controlling the time and temperature of the chemical plating and adjusting the mass ratio of potassium chloroplatinate to sodium nitrite, the hydrogen peroxide residual content of the prepared platinum alloy neutralization ring after 360 minutes is 26 ppm, which meets the standard.

[0028] 3. The present invention uses hydroxyethylethylenediaminetriacetic acid and dihydroxyethylglycine in combination, adjusts the amount of potassium chloroplatinate, and uses a complexing agent to make the platinum element in the plating solution appear in a stable crystal form. During the chemical plating process, a microscopic honeycomb structure can be formed. At the same time, the complexing temperature is adjusted. The prepared platinum alloy neutralizing ring has a residual hydrogen peroxide content of 8 ppm after being placed in a 3.66% hydrogen peroxide disinfectant at a constant temperature of 25° C. for 6 hours, and a residual hydrogen peroxide content of 6 ppm after being placed in a 3.78% hydrogen peroxide disinfectant at a constant temperature of 25° C. for 6 hours, thereby improving the catalytic ability of the neutralizing ring to hydrogen peroxide.

[0029] 4. The present invention utilizes the plastic substrate to retain silver ions on the plastic surface through solvent swelling, and the infiltrated part is embedded in the plastic surface like a rivet, so that the inner layer structure is dense and the coating strength is high; the outer layer is formed into a platinum nanolayer by chemical platinum plating; the type and mass fraction of the organic solvent in the silver plating process are changed, and the type of platinum salt and the mixing speed in the platinum plating process are adjusted. The residual hydrogen peroxide in the obtained platinum alloy after 45 cycles is 9ppm, and the cyclic catalytic performance is excellent.

[0030] 5. The present invention controls the mass fractions of dichloromethane and ethanol in the organic solvent, adjusts the amount of silver nitrate, and utilizes the swelling effect to embed silver ions into the plastic surface like rivets. The introduction of elemental silver increases the antibacterial property of the platinum alloy neutralization ring. The prepared platinum alloy neutralization ring is immersed in a Staphylococcus aureus culture solution for 30 minutes, and the average reduction value of the number of restored growing bacteria per milliliter reaches 99.9%, and the antibacterial and bactericidal property is good. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a graph showing the change in hydrogen peroxide content over time catalyzed by the platinum alloy neutralization ring prepared in Example 11 of the present invention;

[0032] Figure 2 This is a graph showing the change in the residual amount of hydrogen peroxide in the neutralization ring obtained in Example 40 of the present invention and Comparative Example 4 as the number of cycles increases;

[0033] Figure 3 This is a micrograph of the catalytic hydrogen peroxide reaction of Example 11 of the present invention;

[0034] Figure 4The front view and side view of the platinum alloy neutralization ring prepared in Example 11 of the present invention. DETAILED DESCRIPTION

[0035] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] See also Figures 1 to 4 The present invention provides a platinum alloy neutralization ring for hydrogen peroxide care solution and a preparation method thereof, and the technical scheme is as follows:

[0037] Example 1 30 parts of hydroxyethylethylenediaminetriacetic acid, 3.6 parts of sodium hydroxide and 6 parts of potassium chloroplatinate were added to 1000 parts of deionized water under stirring at 50° C., the pH was adjusted to 9, and a plating solution A was obtained by reaction.

[0038] Embodiment 2-9

[0039] The preparation method and parameter conditions of Example 1 are referred to, and the differences are shown in Table 1.

[0040] Table 1 Preparation parameters of Examples 1-9

[0041]

[0042] Comparative Example 1 The preparation method and parameter conditions are the same as those of Example 1, except that no metal complexing agent is added.

[0043] Example 10 Plating solution stability test

[0044] The plating solutions prepared in Examples 1-9 and Comparative Example 1 were placed at 30°C for 5 hours, and the liquid state was observed. The plating solutions were placed in a constant temperature box and kept at 50°C for 5 hours, and the plating solutions were observed to see if they were turbid or precipitated. The results are shown in Table 2.

[0045] Table 2 Plating solution stability test of Examples 1-9 and Comparative Example 1

[0046]

[0047] From the results in Table 1, it can be seen that in Comparative Example 1, no metal complexing agent is added to the platinum atoms in potassium chloroplatinate for complexing treatment. The prepared plating solution A has stratification under 30°C conditions. The plating solution becomes turbid and precipitates after being placed at 50°C for two hours, showing significantly reduced stability compared to Example 10. From the results of Examples 1-5, it can be seen that the plating solution prepared using a single metal complexing agent has poor stability. The plating solution becomes turbid after being placed at 50°C for 2 hours. The solubility of potassium chloroplatinate decreases under high temperature conditions, resulting in decreased stability. Since the metal complexing agent can react with the platinum metal, the platinum ions in the system form a stable crystalline structure and are stably dispersed in deionized water to avoid high temperature. The crystal form changes and the solubility is reduced; the use of metal complexes improves the complexing ability of the complexing agent and the platinum metal, thereby improving the stability of the plating solution; the results of Examples 5 and 7-8 show that with the increase in the amount of potassium chloroplatinate, the stability of the plating solution gradually increases; the results of Examples 5 and 6-9 show that with the change in the type of acid-base regulator, the adjusted pH value of the plating solution gradually changes, the addition of ammonia water maintains the pH value of the plating solution at about 8, and then the high temperature causes the decomposition of ammonia water to further reduce the stability of the plating solution; the addition of the organic base triethylamine reduces the overall compatibility of the system, and there is a stratification phenomenon under room temperature conditions, which affects the later use of the plating solution, and the plating solution A When the pH value is 9, the solution is very stable and can be stored for a long time without turbidity and precipitation. From the results in Table 2, it can be seen that by controlling the type of metal complexing agent, changing the dosage ratio of the metal complexing agent to potassium aluminate, and adjusting the pH of the plating solution, the prepared plating solution A has no stratification phenomenon when placed at 30°C for 5 hours, and is not turbid or precipitated when placed at 50°C for 5 hours, which improves the stability of the plating solution A, reduces the preparation cost of the platinum alloy neutralization ring, and improves the production efficiency.

[0048] Embodiment 11

[0049] The plastic substrate is placed in a concentrated sulfuric acid solution, kept at 45°C, and soaked for 10 minutes to obtain a treated substrate; 10 parts of silver nitrate are added to a mixed solution of 8 parts of dichloromethane and 82 parts of anhydrous ethanol, and mixed evenly to obtain a mixed solution; the treated substrate is added to the mixed solution, soaked at 30°C for 30 minutes to obtain an impregnated substrate, and the impregnated substrate is placed in a vacuum drying oven at 60°C for 2 hours to obtain the dry substrate; 45 parts of glucose, 4 parts of tartaric acid, and 1000 ml of deionized water are mixed evenly, added to the dry substrate, and taken out after 30 minutes to obtain a silver-plated substrate; hydroxyethylethylenediamine triethylamine is added to the mixed solution, and the treated substrate is added to the mixed solution, and the treated substrate is soaked at 30°C for 30 minutes to obtain an impregnated substrate; the impregnated substrate is placed in a vacuum drying oven at 60°C for 2 hours to obtain a dry substrate; 45 parts of glucose, 4 parts of tartaric acid, and 1000 ml of deionized water are mixed evenly, added to the dry substrate, and taken out after 30 minutes to obtain a silver-plated substrate; 15 parts of acid, 15 parts of dihydroxyethylglycine, 3.6 parts of sodium hydroxide and 6 parts of potassium chloroplatinate are added to 1000 parts of deionized water under stirring at 50°C, the pH is adjusted to 9, and the plating solution A is obtained; 7.5 parts of sodium nitrite and 2 ml of 10% hydrochloric acid are dissolved in 50 ml of deionized water, stirred and mixed at room temperature, and the deionized water is fixed to 1000 ml to obtain a plating solution B; the plating solution B is slowly added to the plating solution A, stirred at 100 rpm for 30 minutes, and mixed evenly to obtain a platinum plating solution; the silver-plated substrate is immersed in the platinum plating solution, and chemically plated at 50°C for 60 minutes to obtain a platinum alloy neutralization ring.

[0050] The front and side surfaces of the platinum alloy neutralization ring prepared in Example 11 are as follows Figure 4 shown.

[0051] Examples 12-21 The preparation methods and parameter conditions of Example 11 are referred to, with the differences shown in Table 3.

[0052] Comparative Example 2 The preparation method and parameter conditions are the same as those of Example 11, except that no silver plating is performed.

[0053] Example 22 Platinum alloy neutralization ring catalytic rate test

[0054] The platinum alloy neutralization rings prepared in Examples 11-21 and Comparative Example 2 were added to a hydrogen peroxide disinfectant to perform a catalytic rate test. The catalytic time was set at 2 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 60 min, 180 min, and 360 min. The residual amount of hydrogen peroxide in the solution was detected by titration. The initial hydrogen peroxide content of the solution was about 3.5% (35000 ppm). The residual amount of hydrogen peroxide after 360 min is shown in Table 3. The residual amount of hydrogen peroxide in Example 11 changes with time as shown in Table 3. Figure 1 As shown; the micrograph of the catalytic hydrogen peroxide reaction of Example 11 of the present invention is as shown Figure 3 shown.

[0055] Table 3 Residual amount of hydrogen peroxide in Examples 11-21 and Comparative Example 2

[0056]

[0057] The results in Table 3 show that the 360-min hydrogen peroxide residual amount of the platinum alloy neutralization ring obtained without silver plating in Comparative Example 2 is significantly increased compared with Examples 11-21. By using step-by-step electrochemical plating, the plastic substrate is swollen by the solvent, leaving silver ions on the plastic surface, and the infiltrated part is embedded in the plastic surface like a rivet, so that the inner layer structure is dense and the plating strength is improved. The outer layer is chemically plated to form a platinum nanolayer to improve the catalytic activity. The multi-layer structure improves the adhesion and bonding force, forms a microscopic honeycomb structure, and increases the specific surface area. The catalytic sites of the platinum alloy neutralization ring are increased, and the catalytic rate is increased over time; Figure 1 The results show that the residual amount of hydrogen peroxide decreases with the increase of catalytic time, and the reaction catalytic rate gradually slows down with time. The catalytic rate reaches the maximum in 0-5min, and the catalytic rate gradually decreases in 5-25min. The catalytic efficiency tends to be flat after 60min. The content of hydrogen peroxide in the solution after 6h of catalysis is less than 30ppm. With the change of the embodiment, the catalytic rate of the platinum alloy neutralization ring shows the same catalytic curve, and then due to the change of the preparation parameters, the catalytic ability of the platinum alloy neutralization ring shows obvious differences; from the results of Examples 11-15, it can be seen that with the increase of the chemical plating temperature, the 360min residual amount of hydrogen peroxide of the platinum alloy neutralization ring shows a trend of first decreasing and then increasing. The increase in chemical plating temperature gradually increases the thickness of the platinum nanolayer, which reduces the specific surface area of ​​the plastic substrate surface and the contact area with the hydrogen peroxide solution, affecting the catalytic ability of hydrogen peroxide. The results of Example 11 and Examples 16-18 show that with the extension of chemical plating time, the 360-min hydrogen peroxide residue of the platinum alloy neutralization ring gradually decreases and tends to be constant. The results of Examples 11 and Examples 19-21 show that with the gradual increase in the dosage ratio of sodium nitrite to potassium chloroplatinate, the binding ability of plating solution B and plating solution A increases. In the process of chemical plating, the honeycomb structure formed by the platinum nanolayer formed on the outer layer can increase the adhesion with the inner silver-plated layer, thereby improving the catalytic rate. Comprehensive Table 3, Figure 1 The results show that the prepared platinum alloy neutralization ring shows a significantly improved catalytic rate. By controlling the chemical plating temperature and time and changing the amount of sodium nitrite, the residual hydrogen peroxide in the prepared platinum alloy neutralization ring is 26ppm after 360 minutes, which can meet the limit requirements for residual hydrogen peroxide in Part 2 Basic Requirements for Ophthalmic Optical Contact Lenses of YY0719.2-2022.

[0058] Embodiment 23

[0059] The plastic substrate is placed in a concentrated sulfuric acid solution, kept at 45°C, and soaked for 10 minutes to obtain a treated substrate; 10 parts of silver nitrate are added to a mixed solution of 8 parts of dichloromethane and 82 parts of anhydrous ethanol, and mixed evenly to obtain a mixed solution; the treated substrate is added to the mixed solution, soaked at 30°C for 30 minutes to obtain an impregnated substrate, and the impregnated substrate is placed in a vacuum drying oven at 60°C for 2 hours to obtain the dry substrate; 45 parts of glucose, 4 parts of tartaric acid, and 1000 ml of deionized water are mixed evenly, added to the dry substrate, and taken out after 30 minutes to obtain a silver-plated substrate; hydroxyethylethylenediamine triethylamine is added to the mixed solution, and the treated substrate is added to the mixed solution, and the treated substrate is soaked at 30°C for 30 minutes to obtain an impregnated substrate; the impregnated substrate is placed in a vacuum drying oven at 60°C for 2 hours to obtain a dry substrate; 45 parts of glucose, 4 parts of tartaric acid, and 1000 ml of deionized water are mixed evenly, added to the dry substrate, and taken out after 30 minutes to obtain a silver-plated substrate; 15 parts of acid, 15 parts of dihydroxyethylglycine, 3.6 parts of sodium hydroxide and 6 parts of potassium chloroplatinate are added to 1000 parts of deionized water under stirring at 50°C, the pH is adjusted to 9, and the plating solution A is obtained; 7.5 parts of sodium nitrite and 2 ml of 10% hydrochloric acid are dissolved in 50 ml of deionized water, stirred and mixed at room temperature, and the deionized water is fixed to 1000 ml to obtain a plating solution B; the plating solution B is slowly added to the plating solution A, stirred at 100 rpm for 30 minutes, and mixed evenly to obtain a platinum plating solution; the silver-plated substrate is immersed in the platinum plating solution, and chemically plated at 50°C for 60 minutes to obtain a platinum alloy neutralization ring.

[0060] Examples 24-34 Refer to the preparation method and parameter conditions of Example 22, with the differences as shown in Table 4.

[0061] Example 35 Determination of hydrogen peroxide limit

[0062] The platinum alloy neutralization rings prepared in Examples 23-34 were added to hydrogen peroxide disinfectants with hydrogen peroxide contents of 3.66% and 3.78%, and placed at a constant temperature of 25° C. for 6 hours. The residual amount of hydrogen peroxide in the solution was detected by titration. The test results are shown in Table 4.

[0063] Table 4 Variation of preparation parameters of Examples 23-34

[0064]

[0065] Example 35 Determination of hydrogen peroxide limit

[0066] The platinum alloy neutralization rings prepared in Examples 23-34 were added to hydrogen peroxide disinfectants with hydrogen peroxide contents of 3.66% and 3.78%, respectively, and placed at a constant temperature of 25° C. for 6 hours. The residual amount of hydrogen peroxide in the solution was detected by titration. The test results are shown in Table 5.

[0067] Table 5 Determination of residual hydrogen peroxide in Examples 23-34

[0068]

[0069] The results in Table 5 show that the residual amount of hydrogen peroxide in the platinum alloy neutralization ring prepared in Examples 23-34 and placed at a constant temperature of 25°C for 6 hours is less than 30 ppm, showing a significant improvement in the catalytic performance of hydrogen peroxide; the results in Examples 23-28 show that changing the amount of each component of the complexing agent has a significant effect on the complexation of the platinum metal, keeping the mass fraction of hydroxyethylethylenediaminetriacetic acid at 8-10 parts and the mass fraction of dihydroxyethylglycine at 20-22 parts, in 3.66% hydrogen peroxide disinfectant and 3.78% hydrogen peroxide disinfectant, the residual amount of hydrogen peroxide in the platinum alloy neutralization ring placed at a constant temperature of 25°C for 6 hours is less than 10 ppm, compared with hydroxyethylethylenediaminetriacetic acid. Ethylethylenediaminetriacetic acid and dihydroxyethylglycine were added in a mass ratio of 1:1, showing a significantly improved hydrogen peroxide catalytic ability. The compound use of the complexing agent significantly improved the stability of the plating solution A, improved the production efficiency of the platinum alloy neutralization ring, and reduced the production cost. At the same time, the complexing agent used in combination made the platinum element in the plating solution appear in a stable crystalline form. During the chemical plating process, a microscopic honeycomb structure can be formed. The platinum nanolayer with a significantly increased specific surface area further improves the hydrogen peroxide catalytic performance of the platinum alloy neutralization ring; the results of Examples 25 and 29-31 show that with the increase in the amount of potassium chloroplatinate, the residual hydrogen peroxide shows a gradual decrease. The trend of decreasing is that due to the increase in the amount of metal platinum, the thickness of the platinum nanolayer formed in the outer layer increases, and the specific surface area further increases. The honeycomb structure provides a binding site for the hydrogen peroxide reaction, thereby increasing the catalytic rate. However, the introduction of excessive platinum will cause the outer layer of nano-platinum to agglomerate, which is not conducive to the cyclic catalytic performance of the platinum alloy neutralization ring. As the number of uses increases, the catalytic performance of the neutralization ring is lost to a certain extent. The results of Examples 25 and 32-34 show that as the complexing temperature increases, the residual hydrogen peroxide content of the platinum alloy neutralization ring shows a trend of first decreasing and then increasing. The increase in temperature makes the complexing reaction of the platinum salt and the complexing agent more sufficient. , while improving the stability of the plating solution, the bonding ability of plating solution A and plating solution B is improved, which is beneficial to the formation of a platinum nanolayer during chemical plating; It can be seen from the results in Table 5 that by changing the mass fractions of each component of the complexing agent, adjusting the mass fraction of potassium chloroplatinate, and changing the complexing temperature, the prepared platinum alloy middle ring has a hydrogen peroxide residue of 8 ppm after being placed in a 3.66% hydrogen peroxide disinfectant at a constant temperature of 25°C for 6 hours, and a hydrogen peroxide residue of 6 ppm after being placed in a 3.78% hydrogen peroxide disinfectant at a constant temperature of 25°C for 6 hours, which can meet the limit requirements for hydrogen peroxide residues in Part 2 Basic Requirements for Ophthalmic Optical Contact Lenses of YY0719.2-2022.

[0070] Embodiment 36

[0071] The plastic substrate is placed in a concentrated sulfuric acid solution, kept warm at 45°C, and soaked for 10 minutes to obtain a treated substrate; 10 parts of silver nitrate are added to an organic solvent of 8 parts of dichloromethane and 82 parts of anhydrous ethanol, and mixed evenly to obtain a mixed solution; the treated substrate is added to the mixed solution, soaked at 30°C for 30 minutes to obtain an impregnated substrate, and the impregnated substrate is placed in a vacuum drying oven at 60°C for 2 hours to obtain the dry substrate; 45 parts of glucose, 4 parts of tartaric acid, and 1000 ml of deionized water are mixed evenly, added to the dry substrate, and taken out after 30 minutes to obtain a silver-plated substrate; hydroxyethylethylenediaminetriacetic acid is added to the dry substrate; 15 parts of sodium nitrite, 15 parts of dihydroxyethylglycine, 3.6 parts of sodium hydroxide, and 6 parts of potassium chloroplatinate are added to 1000 parts of deionized water under stirring at 50°C, the pH is adjusted to 9, and the plating solution A is obtained; 7.5 parts of sodium nitrite and 2 ml of 10% hydrochloric acid are dissolved in 50 ml of deionized water, stirred and mixed at room temperature, and the deionized water is fixed to 1000 ml to obtain a plating solution B; the plating solution B is slowly added to the plating solution A, and the mixture is stirred at 200 rpm for 30 minutes, and the mixture is uniformly mixed to obtain a platinum plating solution; the silver-plated substrate is immersed in the platinum plating solution, and chemically plated at 50°C for 60 minutes to obtain a platinum alloy neutralization ring.

[0072] Examples 37-48 The preparation methods and parameter conditions of Example 36 are referred to, with the differences shown in Table 6.

[0073] Table 6 Parameter changes of Examples 36-48

[0074]

[0075] Comparative Example 3 Refer to Example 36, except that chemical platinum plating is performed first and then silver plating is performed.

[0076] Comparative Example 4: The neutralizing ring product of Alcon was selected.

[0077] Example 49 Cyclic Catalytic Performance Test

[0078] The platinum alloy neutralization rings prepared in Examples 36-48 and Comparative Examples 3-4 were added to a hydrogen peroxide disinfectant with a hydrogen peroxide content of 3.66%, and the temperature was kept at 25°C. The residual amount of hydrogen peroxide in the catalytic solution was detected by recycling, and whether the catalytic performance was long-term stable was determined. The residual amount of hydrogen peroxide was recorded for 1-45 cycles. The residual amount of hydrogen peroxide after 1, 15, 30, and 45 cycles is shown in Table 7. The changes in the residual amount of hydrogen peroxide in Example 40 of the present invention and Comparative Example 4 with the number of cycles are shown in Table 8. Figure 2 shown.

[0079] Table 7 Cyclic stability test of Examples 36-48 and Comparative Examples 3-4

[0080]

[0081] pass Figure 2 The results show that, compared with the commercially available product in Comparative Example 4, the platinum alloy neutralization ring prepared in Example 40 of the present invention has a residual amount of hydrogen peroxide below 10 ppm after 45 cycles of use, which can meet the limit requirements for residual hydrogen peroxide in Part 2 Basic Requirements for Ophthalmic Optical Contact Lenses of YY0719.2-2022; The results of Comparative Example 3 show that by changing the order of chemical silver plating and chemical platinum plating, the residual amount of hydrogen peroxide in the prepared platinum alloy ring after 45 cycles is significantly increased compared with Examples 36-48. Since the plastic substrate is swollen by the solvent, the silver ions are retained on the plastic surface, and the infiltrated part is like a rivet. The silver ions are embedded in the plastic surface like nails, making the inner layer structure dense and improving the strength of the coating. The outer layer is chemically platinum-plated to form a platinum nanolayer, which improves the cyclic catalytic activity and changes the order of chemical plating. The binding ability of the platinum nanolayer with the plastic substrate is reduced, and the solvent swelling effect cannot effectively retain the silver ions on the plastic surface. The binding ability of the platinum alloy with the substrate as a whole is reduced, and it falls off during the cyclic use process, affecting the catalytic performance of the neutralization ring. The results of Examples 36-41 show that with the change of the type of organic solvent, the cyclic catalytic performance changes significantly. The use of dichloromethane and ethanol in combination improves the swelling effect on the surface of the plastic substrate. The organic solvent The plastic surface is swollen by solvation to improve the bonding strength of the silver-plated layer. At the same time, the introduction of the silver-plated layer increases the bonding ability of the platinum-plated layer and the plastic substrate, thereby preventing the platinum-plated layer from detaching during the recycling process. The results of Examples 40 and 42-43 show that changing the mass fraction ratio of the organic solvent to silver nitrate has little effect on the cycle stability. However, excessive organic solvent is prone to reduce the silver particles loaded on the surface of the plastic substrate, affecting the cycle performance of the neutralization ring. The results of Examples 40 and 44-45 show that the use of potassium chloroplatinate has significantly improved cycle stability compared to the use of chloroplatinic acid and platinum nitrate. The addition of the metal complexing agent is beneficial to the complexation between platinum ions and the metal complexing agent, promotes the growth of the crystal form, promotes the formation of the outer platinum nanolayer, and improves the cycle stability; the results of Examples 40 and 46-48 show that with the increase of the mixing and stirring speed, the residual amount of hydrogen peroxide in the platinum alloy after 45 cycles shows a trend of first increasing and then decreasing; the results of Table 7 show that by changing the type and mass fraction of the organic solvent in the silver plating process, adjusting the type of platinum salt and the mixing and stirring speed in the platinum plating process, the residual amount of hydrogen peroxide in the platinum alloy after 45 cycles is 9ppm, and a relatively high hydrogen peroxide catalytic performance is still maintained.

[0082] Examples 50-61 The preparation methods and parameter conditions of Example 40 are referred to, with the differences shown in Table 8.

[0083] Table 8 Parameter changes of Examples 50-61

[0084]

[0085] Comparative Example 4: Alcon neutralizing ring product was selected.

[0086] Comparative Example 5: Shenzhen Zhonghehuan products were selected.

[0087] Example 62 Antibacterial and Bactericidal Performance Test

[0088] The platinum alloy neutralization rings prepared in Examples 50-61 and Comparative Examples 4-5 were tested for bactericidal performance. The initial inoculated bacteria concentration was 1.0×10 5 CFU / mL-1.0×10 6 CFU / mL range, the inoculated bacteria are Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, and Candida albicans, the prepared neutralization ring is immersed in a bacterial culture dish, the growth of the inoculated bacteria is stagnant during the immersion time, and the average reduction value of the number of bacteria per milliliter that recovers growth at 6 min, 15 min, 30 min, and 60 min is recorded respectively, wherein the test result of Staphylococcus aureus is shown in Table 9, the neutralization ring prepared in Example 50 of the present invention is immersed in the culture solution of Pseudomonas aeruginosa, Escherichia coli, and Candida albicans for 30 min, and the average reduction value of the number of bacteria per milliliter that recovers growth is greater than 99%, which meets the requirements.

[0089] Table 9 Antibacterial performance test of Examples 50-61 and Comparative Examples 4-5

[0090]

[0091] The results in Table 9 show that the neutralization ring prepared by the present invention has an average reduction value of more than 99.9% in the number of bacteria per milliliter of Staphylococcus aureus that resumes growth within 60 minutes of immersion, which is significantly better than the commercially available products of Comparative Examples 4 and 5; the results of Examples 50-54 show that the change in the amount of organic solvent used has a significant effect on the antibacterial properties of the neutralization ring. The use of non-polar solvents enhances the swelling effect on the surface of the plastic substrate, causing the plastic surface to swell, and the silver ions in the solvent penetrate better into the plastic surface layer. After the low-boiling point solvent evaporates, the silver ions remain on the plastic surface, and the penetrated part is embedded in the plastic surface like a rivet, and then the elemental silver is plated on the surface of the plastic substrate by reduction. The rivet-like structure increases the bonding strength with the plastic, and the introduction of the silver-plated layer reduces the difficulty of chemical platinum plating. The increase in compatibility forms a platinum nanolayer on the outer layer, which improves the catalytic activity. Improve the antibacterial properties of the plastic substrate and improve the performance of the neutralization ring; from the results of Examples 50 and 55-57, it can be seen that the increase in the mass fraction of silver nitrate is beneficial to the overall antibacterial and bactericidal properties of the neutralization ring. However, the introduction of excessive elemental silver will increase the agglomeration ability between metals and further reduce the cyclic stability of the neutralization ring; from the results of Examples 50 and 58-61, it can be seen that with the increase in the amount of reducing agent glucose, the antibacterial and bactericidal properties of the platinum alloy neutralization ring are gradually enhanced, and the average reduction value of the number of Staphylococcus aureus recovering growth per milliliter after 30 minutes is greater than 99.9%; from the results of Table 9, it can be seen that by changing the mass fraction of the organic solvent and the amount of silver nitrate, the platinum alloy neutralization ring prepared is immersed in the Staphylococcus aureus culture solution for 30 minutes, and the average reduction value of the number of recovering growth per milliliter reaches 99.9%, which has significantly improved antibacterial and bactericidal properties.

[0092] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a platinum alloy neutralization ring for hydrogen peroxide care solution, characterized in that: The preparation of the platinum alloy neutralization ring for hydrogen peroxide care solution comprises the following steps: The plastic substrate is immersed in a concentrated sulfuric acid solution to obtain a treated substrate; 5-15 parts of silver nitrate are added to an organic solvent, and mixed evenly to obtain a mixed solution; the treated substrate is added to the mixed solution, immersed to obtain an impregnated substrate, and the impregnated substrate is placed in a vacuum drying oven to obtain a dry substrate; glucose and tartaric acid are added to deionized water, mixed, added to the dry substrate, and taken out after 30 minutes to obtain a silver-plated substrate; a metal complexing agent, 4-8 parts of a platinum salt, and 3.6 parts of an acid-base regulator are added to deionized water, the pH is maintained at 8-10, and a complex reaction is performed at 30-80°C to obtain a plating solution A; sodium nitrite and 10% hydrochloric acid are dissolved in deionized water, stirred and mixed at room temperature, and constant volume is obtained to obtain a plating solution B; the plating solution B is slowly added to the plating solution A, stirred at 100-300rpm for 30 minutes, and mixed evenly to obtain a platinum-plating solution; the silver-plated substrate is immersed in the platinum-plating solution, and the platinum alloy neutralization ring is obtained by chemical plating; The mass ratio of the organic solvent to the silver nitrate is 8-10:1; The mass ratio of the metal complexing agent to the platinum salt is 1:3-6; The mass ratio of the glucose to the tartaric acid is 5-18:1; The mass ratio of the sodium nitrite to the platinum salt is 1-1.8:1; The chemical plating temperature is 20-90°C; the chemical plating time is 30-100min; The plastic substrate is selected from ABS engineering plastics.

2. The method for preparing a platinum alloy neutralization ring for hydrogen peroxide care solution according to claim 1, characterized in that: The organic solvent is selected from one or two of dichloromethane, ethanol, acetone and ether.

3. The method for preparing a platinum alloy neutralization ring for hydrogen peroxide care solution according to claim 2, characterized in that: The organic solvent is a mixture of the dichloromethane and the ethanol; wherein the amount of the dichloromethane is 3-20 parts; and the amount of the ethanol is 70-87 parts.

4. The method for preparing a platinum alloy neutralization ring for hydrogen peroxide care solution according to claim 1, characterized in that: The metal complexing agent is selected from one or two of hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, and ethylenediaminetetraacetic acid.

5. The method for preparing a platinum alloy neutralization ring for hydrogen peroxide care solution according to claim 4, characterized in that: The metal complexing agent is a mixed system of the hydroxyethylethylenediaminetriacetic acid and the dihydroxyethylglycine; wherein the amount of the hydroxyethylethylenediaminetriacetic acid is 5-25 parts; and the amount of the dihydroxyethylglycine is 5-25 parts.

6. The method for preparing a platinum alloy neutralization ring for hydrogen peroxide care solution according to claim 1, characterized in that: The platinum salt is selected from one of chloroplatinic acid, platinum nitrate and potassium chloroplatinate.

7. The method for preparing a platinum alloy neutralization ring for hydrogen peroxide care solution according to claim 1, characterized in that: The acid-base regulator is selected from one of sodium hydroxide, ammonia water and triethylamine.

8. The method for preparing a platinum alloy neutralization ring for hydrogen peroxide care solution according to claim 1, characterized in that: The complexation reaction is carried out at a temperature of 30-60°C.

9. The method for preparing a platinum alloy neutralization ring for hydrogen peroxide care solution according to claim 1, characterized in that: The chemical plating temperature is 30-80° C.; the chemical plating time is 30-90 min.

10. A platinum alloy neutralization ring for hydrogen peroxide care solution prepared by the method of claim 1, characterized in that: The platinum alloy neutralization ring comprises a plastic substrate, an inner silver-plated layer and an outer platinum-plated layer.

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