Preparation process of composite peracetic acid endoscope disinfectant

Abstract

The invention provides a preparation process of a composite peracetic acid endoscope disinfectant, and belongs to the technical field of disinfectants. Comprising the following steps: preparing a peracetic acid solution; preparing a stabilizer; preparing a modified corrosion inhibitor; and preparing the composite peracetic acid endoscope disinfectant. The preparation method comprises the following steps: firstly, adding microcrystalline cellulose into a sodium periodate solution to react to prepare aldehyde cellulose, then aminating the aldehyde cellulose by using an ethylenediamine solution, and finally, functionally modifying the aminated aldehyde cellulose by using asparagine as a modifier to prepare the stabilizer. After the stabilizer is added into the peracetic acid disinfectant, the stabilizer and metal ions can form a stable complex, and the catalytic action of the metal ions on decomposition of peracetic acid is reduced, so that the stability of the peracetic acid is effectively improved, and the validity period of the composite peracetic acid endoscope disinfectant can be prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of disinfectants and bactericides, and in particular to a preparation process of a composite peracetic acid endoscope disinfectant. Background Art

[0002] With the development of medical technology, endoscopy has become one of the important means of diagnosing and treating digestive system diseases. Endoscopes will come into contact with the patient's body fluids and tissues during use, so disinfection and sterilization of endoscopes are crucial. Effective disinfection can not only prevent cross infection, but also protect the patient's life safety.

[0003] Traditional disinfectants mainly include glutaraldehyde, quaternary ammonium salt disinfectants and chlorine-containing disinfectants. Among them, glutaraldehyde has a broad-spectrum bactericidal effect, but has certain toxicity to the human body, and requires a long soaking time during use; quaternary ammonium salt disinfectants have a fast sterilization speed, but are prone to drug resistance and have certain irritation to the human body; chlorine-containing disinfectants are low in cost and have good sterilization effects, but have certain corrosiveness to endoscopic materials, and the residue treatment is relatively complicated. And peracetic acid, as a new type of disinfectant, has spectrum bactericidal properties, can effectively kill various microorganisms such as bacteria, viruses, fungi, and has less residues and little impact on the environment. It can achieve sterilization and disinfection in a short time at low concentrations, and is very suitable for endoscope disinfection, but low-concentration peracetic acid has poor stability, is easily decomposed during storage and use, affects its disinfection effect, and has certain corrosiveness to metals, and long-term use can damage endoscope equipment.

[0004] Therefore, it is necessary to propose a preparation process of a composite peracetic acid endoscope disinfectant with good stability and low corrosivity to extend its shelf life. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide a preparation process of a composite peracetic acid endoscope disinfectant.

[0006] A preparation process of a composite peracetic acid endoscope disinfectant comprises the following steps:

[0007] S1: Preparation of peracetic acid solution

[0008] Dilute hydrogen peroxide with water, then add glacial acetic acid and concentrated sulfuric acid to react to obtain a peracetic acid solution;

[0009] S2: Preparation of stabilizer

[0010] Adding microcrystalline cellulose to a sodium periodate solution for reaction to prepare aldehyde cellulose, dispersing the aldehyde cellulose in an ethylenediamine aqueous solution for reaction to prepare aminated cellulose for later use, dissolving asparagine in distilled water, and adding the aminated cellulose for reaction to obtain a stabilizer;

[0011] S3: Preparation of modified corrosion inhibitor

[0012] Dissolving 3,3'-diaminobenzidine in acetonitrile, adding toluene diisocyanate to react and preparing a corrosion inhibitor, then mixing the corrosion inhibitor, diphenylmethane diisocyanate and dimethyl sulfoxide and heating to react, and finally adding polyethylene glycol to continue the heat-keeping reaction to obtain a modified corrosion inhibitor;

[0013] S4: Preparation of compound peracetic acid endoscope disinfectant

[0014] The peracetic acid solution, polyhexamethylene biguanide, the stabilizer, the modified corrosion inhibitor, folic acid, methionine and water are fully mixed to obtain a composite peracetic acid endoscope disinfectant.

[0015] Furthermore, S1 specifically includes the following steps:

[0016] S1.1: Add distilled water to 30% hydrogen peroxide in a volume ratio of (2-4):1 to dilute the solution;

[0017] S1.2: Add glacial acetic acid to the above diluted solution, stir well to mix, then add concentrated sulfuric acid, stir and react for 10-12 hours to obtain a peracetic acid solution.

[0018] Furthermore, S2 specifically includes the following steps:

[0019] S2.1: Add sodium periodate into deionized water at a solid-liquid ratio of 1 g: (20-30) mL, stir thoroughly to dissolve, and then add hydrochloric acid to adjust the pH to 3-4 to obtain a sodium periodate solution;

[0020] S2.2: Add microcrystalline cellulose to the sodium periodate solution, heat and stir at 40-50°C for 2-3h, transfer to a dialysis bag, dialyze for 40-48h, and then freeze-dry to obtain aldehyde cellulose;

[0021] S2.3: dispersing the aldehyde cellulose in an aqueous solution of ethylenediamine, heating and stirring at 70-80° C. for 4-5 hours to obtain a suspension;

[0022] S2.4: The suspension is transferred to a dialysis bag, dialyzed to remove ethylenediamine, and then freeze-dried to obtain aminated cellulose;

[0023] S2.5: Add asparagine into distilled water at a solid-liquid ratio of 1g: (30-40)mL, stir thoroughly to dissolve, then add the above-mentioned aminated cellulose, heat to 160-180℃ for reaction for 1-2h, then transfer to a dialysis bag, dialyze to remove unreacted asparagine, and obtain a stabilizer after freeze-drying.

[0024] Furthermore, S3 specifically includes the following steps:

[0025] S3.1: Add 3,3'-diaminobenzidine to acetonitrile at a solid-liquid ratio of 1 g: (25-35) mL, heat and stir at 60-70°C to dissolve, and obtain a 3,3'-diaminobenzidine mixed solution;

[0026] S3.2: Keeping the temperature constant, add toluene diisocyanate to the above 3,3'-diaminobenzidine mixed solution while stirring, continue stirring and reacting for 4-6 hours, filter, wash and dry to obtain a corrosion inhibitor;

[0027] S3.3: Add the above corrosion inhibitor to dimethyl sulfoxide, then add diphenylmethane diisocyanate, heat and stir at 60-70°C for 2-3h to obtain an intermediate solution;

[0028] S3.4: Add polyethylene glycol to the intermediate solution, continue to keep the reaction warm for 4-5 hours, cool naturally to room temperature, filter, wash and dry to obtain a modified corrosion inhibitor.

[0029] Furthermore, the mass ratio of glacial acetic acid to the dilution solution is 1:(8-10).

[0030] Furthermore, the volume ratio of concentrated sulfuric acid to the dilute solution is 1:(1800-2000).

[0031] Furthermore, the mass ratio of microcrystalline cellulose to sodium periodate is (2-3):1, the molar ratio of aldehyde cellulose to ethylenediamine is 1:(1.3-1.5), and the molar ratio of aminated cellulose to asparagine is 1:(2.2-2.8).

[0032] Furthermore, the solid-liquid ratio of the mixed solution of toluene diisocyanate and 3,3'-diaminobenzidine is 1 g: (20-30) mL.

[0033] Furthermore, the solid-liquid ratio of the corrosion inhibitor, diphenylmethane diisocyanate and dimethyl sulfoxide is 1 g: (1.5-2.5) g: (30-40) mL, and the mass ratio of the corrosion inhibitor to polyethylene glycol is (2-3):1.

[0034] Furthermore, the composite peracetic acid endoscope disinfectant comprises, by mass percentage, 12-16% peracetic acid solution, 1-3% polyhexamethylene biguanide, 3-5% stabilizer, 4-6% modified corrosion inhibitor, 1-2% folic acid, 0.8-1.4% methionine, and the remainder is water.

[0035] Compared with the prior art, the present invention has at least the following beneficial effects:

[0036] 1. The present invention prepares aldehyde cellulose by first adding microcrystalline cellulose to a sodium periodate solution for reaction, then uses an ethylenediamine solution to aminize the aldehyde cellulose, and finally uses asparagine as a modifier to functionalize the aminated aldehyde cellulose to obtain a stabilizer. After the stabilizer is added to a peracetic acid disinfectant, it can form a stable complex with metal ions, reducing the catalytic effect of metal ions on the decomposition of peracetic acid, thereby effectively improving the stability of peracetic acid and helping to extend the shelf life of the composite peracetic acid endoscope disinfectant.

[0037] 2. The present invention dissolves 3,3'-diaminobenzidine in acetonitrile, adds toluene diisocyanate to react, prepares a corrosion inhibitor, then adds the corrosion inhibitor into dimethyl sulfoxide, adds diphenylmethane diisocyanate to react, and finally adds polyethylene glycol to carry out a grafting modification reaction to modify the corrosion inhibitor so as to improve the water solubility of the corrosion inhibitor. After the modified corrosion inhibitor is added into a peracetic acid disinfectant, it can form a protective film on the metal surface to isolate the direct contact between the peracetic acid and the metal surface, thereby reducing the occurrence of corrosion reactions and achieving the effect of inhibiting the corrosion of the endoscope by the peracetic acid.

[0038] 3. After adding folic acid and methionine to the peracetic acid solution, the methylated groups provided by folic acid and methionine can enhance the coordination ability of the stabilizer to metal ions, thereby strengthening the effect of the stabilizer, further improving the stability of peracetic acid, and achieving the effect of further extending the effective period of the composite peracetic acid endoscope disinfectant.

[0039] 4. The present invention adds polyhexamethylene biguanide to a peracetic acid solution and fully mixes and compounds. Since polyhexamethylene biguanide has a broad-spectrum antibacterial property, it can effectively kill a variety of bacteria, fungi and viruses. When polyhexamethylene biguanide and peracetic acid are used in combination, a synergistic bactericidal effect can be produced, and they act together on different parts of pathogenic microorganisms, thereby enhancing the bactericidal effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The accompanying drawings, which are incorporated herein and constitute a part of the specification, illustrate embodiments of the present disclosure and, together with the description, further serve to explain the principles of the present disclosure and to enable those skilled in the relevant art to make and use the present disclosure.

[0041] Figure 1 The present invention is a flow chart of the preparation process of the composite peracetic acid endoscope disinfectant used in the embodiments of the present invention.

[0042] Figure 2 This is a summary table of the stability test results of Examples 1-3 of the present invention.

[0043] Figure 3 This is a summary table of metal corrosion test results of Examples 1-3 of the present invention.

[0044] Figure 4 This is a summary table of the bactericidal effect simulation test results of Examples 1-3 of the present invention. DETAILED DESCRIPTION

[0045] The preparation process of a composite peracetic acid endoscope disinfectant provided by the present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0046] Example 1

[0047] A preparation process of a composite peracetic acid endoscope disinfectant, such as Figure 1 As shown, the following steps are included:

[0048] S1: Preparation of magnetic composite materials

[0049] S1.1: Add distilled water to 30% hydrogen peroxide in a volume ratio of 2:1 to dilute the solution;

[0050] S1.2: Add glacial acetic acid to the above diluted solution, stir and mix thoroughly, then add concentrated sulfuric acid, stir and react for 10 hours to obtain a peracetic acid solution, wherein the mass ratio of glacial acetic acid to the diluted solution is 1:8, and the volume ratio of concentrated sulfuric acid to the diluted solution is 1:1800;

[0051] S2: Modification of magnetic composites

[0052] S2.1: Add sodium periodate into deionized water at a solid-liquid ratio of 1 g:20 mL, stir thoroughly to dissolve, and then add hydrochloric acid to adjust the pH to 3 to obtain a sodium periodate solution;

[0053] S2.2: Add microcrystalline cellulose to the sodium periodate solution, heat and stir at 40°C for 2 hours, transfer to a dialysis bag, dialyze for 40 hours, and then freeze-dry to obtain aldehyde cellulose, wherein the mass ratio of microcrystalline cellulose to sodium periodate is 2:1;

[0054] S2.3: dispersing the aldehyde cellulose in an aqueous solution of ethylenediamine, heating and stirring at 70°C for 4-5 hours to obtain a suspension, wherein the molar ratio of the aldehyde cellulose to the ethylenediamine is 1:1.3;

[0055] S2.4: The suspension is transferred to a dialysis bag, dialyzed to remove ethylenediamine, and then freeze-dried to obtain aminated cellulose;

[0056] S2.5: Add asparagine to distilled water at a solid-liquid ratio of 1g:30mL, stir thoroughly to dissolve, then add the above-mentioned aminated cellulose, heat to 160°C for reaction for 1h, then transfer to a dialysis bag, dialyze to remove unreacted asparagine, and freeze-dry to obtain a stabilizer, wherein the molar ratio of aminated cellulose to asparagine is 1:2.2;

[0057] S3: Preparation of polyacids

[0058] S3.1: Add 3,3'-diaminobenzidine to acetonitrile at a solid-liquid ratio of 1 g:25 mL, heat and stir at 60°C to dissolve, and obtain a 3,3'-diaminobenzidine mixed solution;

[0059] S3.2: Keeping the temperature constant, add toluene diisocyanate to the above 3,3'-diaminobenzidine mixed solution while stirring, continue stirring and reacting for 4 hours, filter, wash and dry to obtain a corrosion inhibitor, wherein the solid-liquid ratio of toluene diisocyanate to 3,3'-diaminobenzidine mixed solution is 1g:20mL;

[0060] S3.3: Add the above corrosion inhibitor to dimethyl sulfoxide, then add diphenylmethane diisocyanate, heat and stir at 60°C for 2h to obtain an intermediate solution, wherein the solid-liquid ratio of the corrosion inhibitor, diphenylmethane diisocyanate and dimethyl sulfoxide is 1g:1.5g:30mL;

[0061] S3.4: Add polyethylene glycol to the intermediate solution, continue to keep the temperature for 4 hours, cool naturally to room temperature, filter, wash and dry to obtain a modified corrosion inhibitor, wherein the mass ratio of the corrosion inhibitor to the polyethylene glycol is 2:1;

[0062] S4: Preparation of composite catalyst

[0063] The peracetic acid solution, polyhexamethylene biguanide, the stabilizer, the modified corrosion inhibitor, folic acid, methionine and water are fully mixed to obtain a composite peracetic acid endoscope disinfectant, wherein the composite peracetic acid endoscope disinfectant comprises, by mass percentage, 12% peracetic acid solution, 1% polyhexamethylene biguanide, 3% stabilizer, 4% modified corrosion inhibitor, 1% folic acid, 0.8% methionine, and the remainder is water.

[0064] Example 2

[0065] A preparation process of a composite peracetic acid endoscope disinfectant, such as Figure 1 As shown, the following steps are included:

[0066] S1: Preparation of magnetic composite materials

[0067] S1.1: Add distilled water to 30% hydrogen peroxide in a volume ratio of 3:1 to dilute the solution;

[0068] S1.2: Add glacial acetic acid to the above diluted solution, stir and mix thoroughly, then add concentrated sulfuric acid, stir and react for 11 hours to obtain a peracetic acid solution, wherein the mass ratio of glacial acetic acid to the diluted solution is 1:9, and the volume ratio of concentrated sulfuric acid to the diluted solution is 1:1900;

[0069] S2: Modification of magnetic composites

[0070] S2.1: Add sodium periodate into deionized water at a solid-liquid ratio of 1 g:25 mL, stir thoroughly to dissolve, and then add hydrochloric acid to adjust the pH to 3.5 to obtain a sodium periodate solution;

[0071] S2.2: Add microcrystalline cellulose to the sodium periodate solution, heat and stir at 45°C for 2.5 hours, transfer to a dialysis bag, dialyze for 44 hours, and then freeze-dry to obtain aldehyde cellulose, wherein the mass ratio of microcrystalline cellulose to sodium periodate is 2.5:1;

[0072] S2.3: dispersing the aldehyde cellulose in an aqueous solution of ethylenediamine, heating and stirring at 75° C. for 4.5 hours to obtain a suspension, wherein the molar ratio of the aldehyde cellulose to the ethylenediamine is 1:1.4;

[0073] S2.4: The suspension is transferred to a dialysis bag, dialyzed to remove ethylenediamine, and then freeze-dried to obtain aminated cellulose;

[0074] S2.5: Add asparagine to distilled water at a solid-liquid ratio of 1g:35mL, stir thoroughly to dissolve, then add the above-mentioned aminated cellulose, heat to 170°C for reaction for 1.5h, then transfer to a dialysis bag, dialyze to remove unreacted asparagine, and freeze-dry to obtain a stabilizer, wherein the molar ratio of aminated cellulose to asparagine is 1:2.5;

[0075] S3: Preparation of polyacids

[0076] S3.1: Add 3,3'-diaminobenzidine to acetonitrile at a solid-liquid ratio of 1 g:30 mL, heat and stir at 65°C to dissolve, and obtain a 3,3'-diaminobenzidine mixed solution;

[0077] S3.2: Keeping the temperature constant, add toluene diisocyanate to the above 3,3'-diaminobenzidine mixed solution while stirring, continue stirring and reacting for 5 hours, filter, wash and dry to obtain a corrosion inhibitor, wherein the solid-liquid ratio of toluene diisocyanate to 3,3'-diaminobenzidine mixed solution is 1g:25mL;

[0078] S3.3: Add the above corrosion inhibitor to dimethyl sulfoxide, then add diphenylmethane diisocyanate, heat and stir at 65°C for 2.5h to obtain an intermediate solution, wherein the solid-liquid ratio of the corrosion inhibitor, diphenylmethane diisocyanate and dimethyl sulfoxide is 1g:2g:35mL;

[0079] S3.4: Add polyethylene glycol to the intermediate solution, continue to keep the temperature for 4.5 hours, cool naturally to room temperature, filter, wash and dry to obtain a modified corrosion inhibitor, wherein the mass ratio of the corrosion inhibitor to the polyethylene glycol is 2.5:1;

[0080] S4: Preparation of composite catalyst

[0081] The peracetic acid solution, polyhexamethylene biguanide, the stabilizer, the modified corrosion inhibitor, folic acid, methionine and water are fully mixed to obtain a composite peracetic acid endoscope disinfectant, wherein the composite peracetic acid endoscope disinfectant comprises, by mass percentage, 14% peracetic acid solution, 2% polyhexamethylene biguanide, 4% stabilizer, 5% modified corrosion inhibitor, 1.5% folic acid, 1.1% methionine, and the remainder is water.

[0082] Example 3

[0083] A preparation process of a composite peracetic acid endoscope disinfectant, such as Figure 1 As shown, the following steps are included:

[0084] S1: Preparation of magnetic composite materials

[0085] S1.1: Add distilled water to 30% hydrogen peroxide in a volume ratio of 4:1 to dilute the solution;

[0086] S1.2: Add glacial acetic acid to the above diluted solution, stir and mix thoroughly, then add concentrated sulfuric acid, stir and react for 12 hours to obtain a peracetic acid solution, wherein the mass ratio of glacial acetic acid to the diluted solution is 1:10, and the volume ratio of concentrated sulfuric acid to the diluted solution is 1:2000;

[0087] S2: Modification of magnetic composites

[0088] S2.1: Add sodium periodate into deionized water at a solid-liquid ratio of 1 g:30 mL, stir thoroughly to dissolve, and then add hydrochloric acid to adjust the pH to 4 to obtain a sodium periodate solution;

[0089] S2.2: Add microcrystalline cellulose to the sodium periodate solution, heat and stir at 50°C for 3 hours, transfer to a dialysis bag, dialyze for 48 hours, and then freeze-dry to obtain aldehyde cellulose, wherein the mass ratio of microcrystalline cellulose to sodium periodate is 3:1;

[0090] S2.3: dispersing the aldehyde cellulose in an aqueous solution of ethylenediamine, heating and stirring at 80° C. for 5 h to obtain a suspension, wherein the molar ratio of the aldehyde cellulose to the ethylenediamine is 1:1.5;

[0091] S2.4: The suspension is transferred to a dialysis bag, dialyzed to remove ethylenediamine, and then freeze-dried to obtain aminated cellulose;

[0092] S2.5: Add asparagine to distilled water at a solid-liquid ratio of 1g:40mL, stir thoroughly to dissolve, then add the above-mentioned aminated cellulose, heat at 180°C for 2h, transfer to a dialysis bag, dialyze to remove unreacted asparagine, and freeze-dry to obtain a stabilizer, wherein the molar ratio of aminated cellulose to asparagine is 1:2.8;

[0093] S3: Preparation of polyacids

[0094] S3.1: Add 3,3'-diaminobenzidine to acetonitrile at a solid-liquid ratio of 1 g:35 mL, heat and stir at 70°C to dissolve, and obtain a 3,3'-diaminobenzidine mixed solution;

[0095] S3.2: Keeping the temperature constant, add toluene diisocyanate to the above 3,3'-diaminobenzidine mixed solution while stirring, continue stirring and reacting for 6 hours, filter, wash and dry to obtain a corrosion inhibitor, wherein the solid-liquid ratio of toluene diisocyanate to 3,3'-diaminobenzidine mixed solution is 1g:30mL;

[0096] S3.3: Add the above corrosion inhibitor to dimethyl sulfoxide, then add diphenylmethane diisocyanate, heat and stir at 70°C for 3 hours to obtain an intermediate solution, wherein the solid-liquid ratio of the corrosion inhibitor, diphenylmethane diisocyanate and dimethyl sulfoxide is 1g:2.5g:40mL;

[0097] S3.4: Add polyethylene glycol to the intermediate solution, continue to keep the temperature for reaction for 5 hours, cool naturally to room temperature, filter, wash and dry to obtain a modified corrosion inhibitor, wherein the mass ratio of the corrosion inhibitor to the polyethylene glycol is 3:1;

[0098] S4: Preparation of composite catalyst

[0099] The peracetic acid solution, polyhexamethylene biguanide, the stabilizer, the modified corrosion inhibitor, folic acid, methionine and water are fully mixed to obtain a composite peracetic acid endoscope disinfectant, wherein the composite peracetic acid endoscope disinfectant comprises, by mass percentage, 16% peracetic acid solution, 3% polyhexamethylene biguanide, 5% stabilizer, 6% modified corrosion inhibitor, 2% folic acid, 0.8-1.4% methionine, and the remainder is water.

[0100] Performance testing:

[0101] 1. Stability test.

[0102] Storage conditions: The composite peracetic acid endoscope disinfectant prepared in Examples 1-3 was placed in a 54°C water-tight constant temperature incubator for 14 days, and then the initial concentration, the peracetic acid content on the 2nd day, 4th day, 6th day, 8th day, 10th day, 12th day and 14th day were tested according to the following test method, and the rate of decrease of the peracetic acid content was calculated. The results are as follows: Figure 2 shown.

[0103] Test method: First, add 5 mL of 2mol / L sulfuric acid and 3 drops of 100g / L manganese sulfate solution to a 100mL iodine volumetric flask, and accurately add 5.0 mL of the composite peracetic acid endoscope disinfectant prepared in Example 1-3, shake well, and titrate with 0.01mol / L potassium permanganate solution until the solution is pink, then add 10mL of 100g / L potassium iodide solution and 3 drops of 30g / L ammonium molybdate, shake well and titrate with 0.05mol / L sodium thiosulfate titrant (loaded in a 25mL burette) to light yellow, then add 3 drops of 5g / L starch solution (the solution immediately turns blue), continue to titrate with sodium thiosulfate until the blue disappears, and obtain the composite peracetic acid disinfectant stock solution. Record the total amount of sodium thiosulfate titrant, repeat the measurement twice, and take the average of the two times for calculation.

[0104] 2. Metal corrosion test.

[0105] Soak the metal (carbon steel, copper, aluminum, stainless steel) sheet in a surfactant-containing detergent for 10 minutes to fully remove the oil, wash it, then use sandpaper to grind off the oxide layer on the surface of the metal sheet, rinse it with tap water, then degrease it with anhydrous ethanol, dry it in a 50°C electric constant temperature drying oven for 1 hour and weigh it, then hang it and soak it in a wide-mouth reagent bottle containing the composite peracetic acid endoscope disinfectant prepared in Examples 1-3. After soaking for 72 hours, take out the metal sheet, rinse it with tap water, remove the corrosion products with a brush and wash it, absorb the water with coarse filter paper, dry it in a 50°C electric constant temperature drying oven for 1 hour, and weigh it. At the same time, set up a blank control of stainless steel soaked in distilled water. Soak 3 pieces of the same metal sheet in the test liquid for each 600mL sample, with each piece separated by more than 1cm. Each piece of sandpaper only grinds one metal material, and observe the changes in the appearance of the metal sample. The results are as follows Figure 3 shown.

[0106] 3. Sterilization effect simulation test.

[0107] Testing basis: Item 2.1.1.7.5 of "Technical Specifications for Disinfection" (2002 edition) and GB / T38497-2020 "Method for Evaluation of Endoscope Disinfection Effect" 6.2.

[0108] Preparation of bacterial contamination carrier: take a suspension of Staphylococcus aureus and drip it on the inner wall of the polytetrafluoroethylene tube carrier, dry it, make a bacterial contamination carrier, and connect the bacterial contamination carrier to the simulated endoscope at 50mm.

[0109] Experimental method: Add the composite peracetic acid endoscope disinfectant prepared in Examples 1-3 into the endoscope cleaning and disinfection machine respectively and connect it to it, then place the prepared bacteria-stained simulated endoscope in the specified position of the cleaning and disinfection machine, start the machine cleaning and disinfection program, and after the end, remove the bacteria-stained carriers by aseptic operation, and transfer them into TSB test tubes containing 10mL of neutralizer respectively as test group samples. Transfer the 3 bacteria-stained carriers into TSB test tubes containing 10mL of neutralizer as positive controls. Inoculate the culture medium in each group and culture in a 37°C incubator for 7 days. Take another 2 bacteria-stained carriers for live bacterial culture counting as bacterial count controls. The results are as follows: Figure 4 shown.

[0110] Comparative Example 1

[0111] The difference between this comparative example 1 and Example 1 is that step S2 is removed, and the stabilizer in step S4 is removed, and then the performance test of the prepared composite peracetic acid endoscope disinfectant is carried out according to the test method in Example 1, and the results are shown in Table 1.

[0112] Table 1: Comparative Example 1 and Example 1 Stability Test Comparison Table

[0113]

[0114] As can be seen from Table 1, after the stabilizer in the composite peracetic acid endoscope disinfectant in Comparative Example 1 is removed, the obtained composite peracetic acid disinfectant is stored at 54° C. for 14 days, and the rate of decrease of the peroxide content increases day by day, until the rate of decrease of the peroxide content reaches 59.43% on the 14th day, while the composite peracetic acid disinfectant to which the stabilizer is added in Example 1 is stored at 54° C. for 14 days, and the rate of decrease of the peroxide content is only 6.39%, which is much less than that in Comparative Example 1. It can be seen that aldehyde cellulose is prepared by first adding microcrystalline cellulose to a sodium periodate solution, and then aminating the aldehyde cellulose with an ethylenediamine solution, and finally using asparagine as a modifier to functionalize the aminated aldehyde cellulose to obtain a stabilizer, and after the stabilizer is added to the peracetic acid disinfectant, a stable complex can be formed with metal ions, thereby reducing the catalytic effect of metal ions on the decomposition of peracetic acid, thereby effectively improving the stability of peracetic acid, and helping to extend the shelf life of the composite peracetic acid endoscope disinfectant.

[0115] Comparative Example 2

[0116] The difference between this comparative example 2 and example 1 is that step S3 is removed, and the modified corrosion inhibitor in step S4 is removed, and then the performance test method in example 1 is used for testing, and the results are shown in Table 1.

[0117] Table 2: Comparison of metal corrosion tests between Comparative Example 2 and Example 1

[0118]

[0119] As can be seen from Table 2, after the modified corrosion inhibitor in the composite peracetic acid endoscope disinfectant is removed in Comparative Example 2, the prepared composite peracetic acid endoscope disinfectant has severe corrosiveness to carbon steel sheet and copper sheet, and moderate corrosiveness to aluminum sheet after soaking carbon steel sheet, copper sheet, aluminum sheet and stainless steel sheet for 72 hours, while the composite peracetic acid endoscope disinfectant after adding the modified corrosion inhibitor in Example 1 has mild corrosiveness to copper sheet and aluminum sheet, and is basically non-corrosive to carbon steel and stainless steel. It can be seen that by first dissolving 3,3'-diaminobenzidine in the In acetonitrile, toluene diisocyanate is added to react to prepare a corrosion inhibitor, then the corrosion inhibitor is added to dimethyl sulfoxide, and diphenylmethane diisocyanate is added to react, and finally polyethylene glycol is added to carry out a grafting modification reaction to modify the corrosion inhibitor to improve the water solubility of the corrosion inhibitor. After the modified corrosion inhibitor is added to peracetic acid disinfectant, it can form a protective film on the metal surface to isolate the direct contact between peracetic acid and the metal surface, thereby reducing the occurrence of corrosion reactions and achieving the effect of inhibiting peracetic acid corrosion of endoscopes.

[0120] Comparative Example 3

[0121] The difference between this comparative example 3 and example 1 is that folic acid and methionine in step S4 are removed, and then the prepared composite peracetic acid endoscope disinfectant is tested according to the stability test method in example 1. The results are shown in Table 3.

[0122] Comparative Example 4

[0123] The difference between this comparative example 4 and Example 1 is that the folic acid in step S4 is replaced by an equal amount of methionine, and then the prepared composite peracetic acid endoscope disinfectant is tested according to the stability test method in Example 1. The results are shown in Table 3.

[0124] Comparative Example 5

[0125] The difference between this comparative example 3 and example 1 is that the methionine in step S4 is replaced with an equal amount of folic acid, and then the prepared composite peracetic acid endoscope disinfectant is tested according to the stability test method in example 1. The results are shown in Table 3.

[0126] Table 3: Comparison of stability test results of Comparative Examples 3-5 and Example 1

[0127]

[0128] As can be seen from Table 3, the composite peracetic acid endoscope disinfectant prepared without adding folic acid and methionine in Comparative Example 3 was stored at 54° C. for 14 days, and the peroxide radical content decreased by 8.97%, which was higher than that of the composite peracetic acid endoscope disinfectant to which folic acid and methionine were added in Example 1. It can be seen that after adding folic acid and methionine to the peracetic acid solution, the methylated groups provided by folic acid and methionine can enhance the coordination ability of the stabilizer to metal ions, thereby strengthening the effect of the stabilizer, further improving the stability of peracetic acid, and achieving the effect of further extending the effective period of the composite peracetic acid endoscope disinfectant;

[0129] After storage at 54°C for 14 days, the decrease rates of peroxide content in the composite Woyang acetic acid endoscope disinfectant prepared by adding single methionine and single folic acid in Comparative Examples 4 and 5 were 7.73% and 7.59%, respectively. Although they were lower than the composite peracetic acid endoscope disinfectant prepared in Comparative Example 3, they were higher than the composite peracetic acid endoscope disinfectant prepared in Example 1. It can be seen that folic acid and methionine have a synergistic effect, and the two can synergistically enhance the stabilizing effect of the stabilizer.

[0130] Comparative Example 6

[0131] The difference between this comparative example 6 and example 1 is that the polyhexamethylene biguanide in step S4 is removed, and then the test is performed according to the bactericidal effect simulation test method in example 1. The results are shown in Table 4.

[0132] Table 4: Comparison of the results of the bactericidal effect simulation test of Comparative Example 6 and Example 1

[0133] Bacterial growth Example 1 － Example 2 － Example 3 － Comparative Example 6 ＋

[0134] Note: “-” represents sterile growth; “+” represents bacterial growth.

[0135] As can be seen from Table 4, the bactericidal effect of the composite peracetic acid endoscope disinfectant prepared without adding polyhexamethylene biguanide in Comparative Example 6 is weaker than that of the composite peracetic acid endoscope disinfectant prepared by adding polyhexamethylene biguanide in Example 1-3. It can be seen that by adding polyhexamethylene biguanide to the peracetic acid solution and fully mixing and compounding, since polyhexamethylene biguanide has a broad-spectrum antibacterial property, it can effectively kill a variety of bacteria, fungi and viruses. When polyhexamethylene biguanide is compounded with peracetic acid, a synergistic bactericidal effect can be produced, and they act together on different parts of pathogenic microorganisms, thereby enhancing the bactericidal effect.

[0136] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A preparation process of a composite peracetic acid endoscope disinfectant, characterized in that: The steps include: S1: Preparation of peracetic acid solution Dilute hydrogen peroxide with water, then add glacial acetic acid and concentrated sulfuric acid to react to obtain a peracetic acid solution; S2: Preparation of stabilizer Adding microcrystalline cellulose to a sodium periodate solution for reaction to prepare aldehyde cellulose, dispersing the aldehyde cellulose in an ethylenediamine aqueous solution for reaction to prepare aminated cellulose for later use, dissolving asparagine in distilled water, and adding the aminated cellulose for reaction to obtain a stabilizer; S3: Preparation of modified corrosion inhibitor Dissolving 3,3'-diaminobenzidine in acetonitrile, adding toluene diisocyanate to react and preparing a corrosion inhibitor, then mixing the corrosion inhibitor, diphenylmethane diisocyanate and dimethyl sulfoxide and heating to react, and finally adding polyethylene glycol to continue the heat-keeping reaction to obtain a modified corrosion inhibitor; S4: Preparation of compound peracetic acid endoscope disinfectant The peracetic acid solution, polyhexamethylene biguanide, the stabilizer, the modified corrosion inhibitor, folic acid, methionine and water are fully mixed to obtain a composite peracetic acid endoscope disinfectant.

2. The preparation process of a composite peracetic acid endoscope disinfectant according to claim 1, characterized in that: S1 specifically includes the following steps: S1.1: Add distilled water to 30% hydrogen peroxide in a volume ratio of (2-4):1 to dilute the solution; S1.2: Add glacial acetic acid to the above diluted solution, stir well to mix, then add concentrated sulfuric acid, stir and react for 10-12 hours to obtain a peracetic acid solution.

3. The preparation process of a composite peracetic acid endoscope disinfectant according to claim 2, characterized in that: S2 specifically includes the following steps: S2.1: Add sodium periodate into deionized water at a solid-liquid ratio of 1 g: (20-30) mL, stir thoroughly to dissolve, and then add hydrochloric acid to adjust the pH to 3-4 to obtain a sodium periodate solution; S2.2: Add microcrystalline cellulose to the sodium periodate solution, heat and stir at 40-50°C for 2-3h, transfer to a dialysis bag, dialyze for 40-48h, and then freeze-dry to obtain aldehyde cellulose; S2.3: dispersing the aldehyde cellulose in an aqueous solution of ethylenediamine, heating and stirring at 70-80° C. for 4-5 hours to obtain a suspension; S2.4: The suspension is transferred to a dialysis bag, dialyzed to remove ethylenediamine, and then freeze-dried to obtain aminated cellulose; S2.5: Add asparagine into distilled water at a solid-liquid ratio of 1g: (30-40)mL, stir thoroughly to dissolve, then add the above-mentioned aminated cellulose, heat to 160-180℃ for reaction for 1-2h, then transfer to a dialysis bag, dialyze to remove unreacted asparagine, and obtain a stabilizer after freeze-drying.

4. The preparation process of a composite peracetic acid endoscope disinfectant according to claim 3, characterized in that: S3 specifically includes the following steps: S3.1: Add 3,3'-diaminobenzidine to acetonitrile at a solid-liquid ratio of 1 g: (25-35) mL, heat and stir at 60-70°C to dissolve, and obtain a 3,3'-diaminobenzidine mixed solution; S3.2: Keeping the temperature constant, add toluene diisocyanate to the above 3,3'-diaminobenzidine mixed solution while stirring, continue stirring and reacting for 4-6 hours, filter, wash and dry to obtain a corrosion inhibitor; S3.3: Add the above corrosion inhibitor to dimethyl sulfoxide, then add diphenylmethane diisocyanate, heat and stir at 60-70°C for 2-3h to obtain an intermediate solution; S3.4: Add polyethylene glycol to the intermediate solution, continue to keep the reaction warm for 4-5 hours, cool naturally to room temperature, filter, wash and dry to obtain a modified corrosion inhibitor.

5. The preparation process of a composite peracetic acid endoscope disinfectant according to claim 2, characterized in that: The mass ratio of glacial acetic acid to dilution solution is 1:(8-10).

6. The preparation process of a composite peracetic acid endoscope disinfectant according to claim 2, characterized in that: The volume ratio of concentrated sulfuric acid to dilute solution is 1:(1800-2000).

7. The preparation process of a composite peracetic acid endoscope disinfectant according to claim 3, characterized in that: The mass ratio of microcrystalline cellulose to sodium periodate is (2-3):1, the molar ratio of aldehyde cellulose to ethylenediamine is 1:(1.3-1.5), and the molar ratio of aminated cellulose to asparagine is 1:(2.2-2.8).

8. The preparation process of a composite peracetic acid endoscope disinfectant according to claim 4, characterized in that: The solid-liquid ratio of the mixed solution of toluene diisocyanate and 3,3'-diaminobenzidine is 1g: (20-30)mL.

9. The preparation process of a composite peracetic acid endoscope disinfectant according to claim 4, characterized in that: The solid-liquid ratio of the corrosion inhibitor, diphenylmethane diisocyanate and dimethyl sulfoxide is 1g: (1.5-2.5)g: (30-40)mL, and the mass ratio of the corrosion inhibitor to polyethylene glycol is (2-3):

1.

10. The preparation process of a composite peracetic acid endoscope disinfectant according to claim 4, characterized in that: Calculated by mass percentage, the composite peracetic acid endoscope disinfectant includes: 12-16% peracetic acid solution, 1-3% polyhexamethylene biguanide, 3-5% stabilizer, 4-6% modified corrosion inhibitor, 1-2% folic acid, 0.8-1.4% methionine, and the balance is water.

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