Bacteriostatic medical protective boots and production process thereof

Abstract

The invention discloses a pair of bacteriostatic medical protective boots and a production process thereof, and belongs to the technical field of special boot production. The antibacterial medical protective boot is prepared from the following raw materials in parts by weight: 30 to 80 parts of PVC (Polyvinyl Chloride) resin, 15 to 35 parts of polyacrylate, 5 to 13 parts of plasticizer, 0.5 to 4.5 parts of antioxidant, 1 to 2.5 parts of calcium stearate, 0.5 to 3.5 parts of paraffin and 2.5 to 7 parts of multiple antibacterial agent. Substituted benzoic acid, methanol, hydrazine hydrate and carbon disulfide are gradually reacted to form an intermediate 4; gradually reacting 4-hydroxybutyric acid with diethylenetriamine and chloroacetyl chloride to form an intermediate 7; the intermediate 7 and the intermediate 4 are gradually reacted to obtain a multi-antibacterial agent, the multi-antibacterial agent is efficient in sterilization and wide in sterilization spectrum, and after the multi-antibacterial agent is added into raw materials of the antibacterial medical protective boots, the obtained medical protective boots have excellent sterilization and antibacterial performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of special boot production, and in particular, relates to an antibacterial medical protective boot and a production process thereof. Background Art

[0002] Medical protective boots are safety boots that can protect the wearer's feet and legs from dangerous factors in the workplace. Due to the particularity of the health industry, the protective boots worn by operators are not only comfortable to wear, but also need other protective functions. For example, if the operator wears protective boots for a long time, the sweat on the feet is difficult to dissipate, and the inside of the boots is not exposed to sunlight for many years, which is prone to various molds. From a safety perspective, it is necessary to increase the antibacterial function of safety boots so that the product will not only not produce bacteria, but more importantly, it can kill bacteria and protect the operator's feet and legs from bacterial infection.

[0003] Therefore, the present invention provides an antibacterial medical protective boot and a production process thereof. Summary of the invention

[0004] The purpose of the present invention is to provide an antibacterial medical protective boot and a production process thereof, so as to solve the technical problem that the current medical protective boots have insufficient antibacterial and sterilization effects.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] The invention discloses an antibacterial medical protective boot, comprising the following raw materials in parts by weight: 30-80 parts of PVC resin, 15-35 parts of polyacrylate, 5-13 parts of plasticizer, 0.5-4.5 parts of antioxidant, 1-2.5 parts of calcium stearate, 0.5-3.5 parts of paraffin wax and 2.5-7 parts of multiple antibacterial agents.

[0007] Furthermore, the plasticizer is one of dioctyl phthalate, diethyl phthalate, and dibutyl phthalate, or a mixture of any ratio of the two or more thereof.

[0008] Furthermore, the antioxidant is a mixture of antioxidant 626 and antioxidant 1010 in a mass ratio of 1-3:5-10.

[0009] Furthermore, the multi-antimicrobial agent is prepared by the following steps:

[0010] Step A, add substituted benzoic acid and anhydrous methanol into a three-necked flask with a stirrer and a condenser, add concentrated sulfuric acid under stirring, heat the reaction system to 74°C in a water bath, reflux at constant temperature for 8 hours, add saturated sodium bicarbonate solution until no bubbles are generated, add dichloromethane for separation, take the organic layer, add anhydrous sodium sulfate to dry for 1 hour, filter to obtain intermediate 1, and produce intermediate 1 by esterification reaction of carboxylic acid and alcohol, wherein the amount ratio of substituted benzoic acid, anhydrous methanol and concentrated sulfuric acid is 0.01 mol: 16-60 mL: 2-4 mL, the substituted benzoic acid is monosubstituted benzoic acid, and the substituent is methyl, One of the methoxy groups, the substitution position is one of the meta-position, the ortho-position, and the mass fraction of sulfuric acid in the concentrated sulfuric acid is 98%; the intermediate 1 and ethanol are added to a three-necked flask with a stirrer and a condenser, and hydrazine hydrate with a mass fraction of 80% is slowly added dropwise at room temperature, and the dropping speed is 1 drop / second, and the reaction system is heated to 61°C with a water bath, refluxed for 8 hours, and the ethanol is removed under reduced pressure, cooled, filtered, and ethanol is recrystallized to obtain the intermediate 2, and hydrazide is generated by hydrazinolysis of the ester, wherein the amount ratio of the intermediate 1, ethanol, and hydrazine hydrate is 0.01 mol: 16-60 mL: 0.7-1.5 g; the reaction formula is shown below;

[0011]

[0012] R1 is -CH3 or -OCH3

[0013] Step B, add intermediate 2, potassium hydroxide, and anhydrous ethanol to a three-necked flask with a stirrer and a condenser, stir evenly at room temperature, slowly drop an ethanol solution of carbon disulfide at a rate of 1 drop / second, heat the reaction system to 52°C with a water bath, reflux at a constant temperature for 5 hours, remove ethanol by vacuum rotary evaporation, add deionized water, adjust the pH of the solution to 5 with 10% dilute hydrochloric acid, filter, and dry to constant weight to obtain intermediate 3, and use an acylhydrazide group and carbon disulfide to form a ring under alkaline conditions, wherein the amount ratio of intermediate 2, potassium hydroxide, anhydrous ethanol, and carbon disulfide ethanol solution is 0.07 mol: 3.6-4.6 g. : 100-150mL: 30-50mL, the ethanol solution of carbon disulfide is 3-3.5mmol / mL; the intermediate 3 and anhydrous ethanol are added to a three-necked flask with a stirrer and a condenser, and hydrazine hydrate with a mass fraction of 80% is slowly added dropwise at room temperature, and the dropping speed is 1 drop / second, and the reaction system temperature is heated to 73°C with a water bath, and the reaction is refluxed at a constant temperature for 24 hours, and the ethanol is removed by vacuum rotary evaporation, and the reaction is dried to a constant weight to obtain the intermediate 4, and the triazole ring is generated by the reduction of the diazole ring ether group by hydrazine hydrate, wherein the amount ratio of the intermediate 3, anhydrous ethanol, and hydrazine hydrate is 0.01mol: 30-70mL: 2-3g, and the reaction formula is shown below;

[0014]

[0015] Step C, add 4-hydroxybutyric acid and diethylenetriamine to a three-necked flask equipped with a condensing reflux device and a stirrer, heat the reaction system to 83°C with a heating jacket under stirring, and continue to heat the reaction system to 153°C under circulating water conditions until the reactants are completely melted, start the vacuum pump when gas is released, react for 2.5 hours, and when no gas is released, heat to 200°C and react for 3 hours, and cool to room temperature under vacuum to obtain intermediate 5, and use the cyclization reaction of 4-hydroxybutyric acid and diethylenetriamine, wherein the amount ratio of 4-hydroxybutyric acid to diethylenetriamine is 1m / s. ol: 1.5-2mol; After heating and melting the intermediate 5, benzyl chloride is slowly added dropwise using a constant pressure dropping funnel at a dropping speed of 1 drop / second, the reaction system is heated to 102°C, and the reaction is carried out at a constant temperature for 3.5 hours. When the reaction system is cooled to 35°C, potassium carbonate and dichloromethane are added, and the reaction is carried out at a constant temperature for 4 hours. The reaction is cooled to obtain the intermediate 6, and the alcoholic hydroxyl group in the intermediate 5 is reacted with benzyl chloride to produce benzyl ether, wherein the amount ratio of the intermediate 5, benzyl chloride, potassium carbonate and dichloromethane is 1mol: 1mol: 5-10g: 60-150mL. The reaction formula is shown below;

[0016]

[0017] Step D, adding intermediate 6, potassium carbonate and anhydrous dichloromethane into a three-necked flask with a stirrer, stirring evenly, slowly adding chloroacetyl chloride with a dropping funnel at room temperature, the dropping speed is 1 drop / second, and stirring at room temperature at 350r / min for 20h, removing dichloromethane by vacuum rotary evaporation, washing with ice water 3 times, filtering, drying to constant weight, obtaining intermediate 7, utilizing the reaction of chloroacetyl chloride and amino group, wherein the amount ratio of intermediate 6, potassium carbonate, anhydrous dichloromethane, and chloroacetyl chloride is 0.01mol: 0.013mol: 0.013-0.016mol: 80-200mL, and the reaction formula is shown below;

[0018]

[0019] Step E, add intermediate 7, potassium carbonate and acetone to a three-necked flask with a stirrer, stir evenly, add intermediate 4 under stirring, and control the reaction temperature at 43°C, stir and react for 6 hours, cool and filter, separate through a column to obtain intermediate 8, and use the reaction of chlorine and thiol in intermediate 7 to generate thioether, wherein the amount ratio of intermediate 7, potassium carbonate, acetone and intermediate 4 is 0.01 mol: 0.012 mol: 80-150 mL: 0.011-0.013 mol; add intermediate 8 and pyridine to a three-necked flask with a stirrer In a three-necked flask with a reflux device, high-purity nitrogen is passed for 30 minutes, and then a 10% volume fraction Pd / C catalyst is added, hydrogen is passed, and the reaction is stirred at room temperature for 24 hours under the protection of hydrogen. After the reaction is completed, it is filtered and washed with methanol three times. The filtrate is combined and the filtrate is evaporated under reduced pressure at room temperature to obtain a multiple antibacterial agent. The intermediate 8 is debenzylated under the Pd / C catalyst to generate a multiple antibacterial agent, wherein the amount ratio of intermediate 8, pyridine, and Pd / C catalyst is 0.1mmol:30-80mL:0.1-0.3g, and the reaction formula is shown below.

[0020]

[0021] A production process of antibacterial medical protective boots, comprising the following steps:

[0022] Step S1, adding paraffin wax and calcium stearate into a pulverizer for pulverization, passing through a 200-300 mesh sieve, and mixing to obtain a mixed powder;

[0023] Step S2, preheating the PVC resin, plasticizer, and multiple antibacterial agent at 90° C. and 750 r / min for 5 min with stirring, then adding the polyacrylate, heating to 105° C., stirring at 900 r / min for 5 min, raising the temperature to 115° C., mixing for 15-20 min, finally adding the antioxidant and the mixed powder, raising the temperature to 130° C., mixing for 15-40 min, and obtaining a rubber compound;

[0024] Step S3, injecting the mixed rubber obtained in step S2 into a mold, and compression molding at 140-155° C., and then cooling to obtain an antibacterial medical protective boot.

[0025] Beneficial effects of the present invention:

[0026] 1. The present invention utilizes substituted benzoic acid and methanol to react to generate substituted benzoic acid methyl ester (intermediate 1), then utilizes substituted benzoic acid methyl ester to undergo hydrazine hydrolysis under the action of hydrazine hydrate to generate hydrazide (intermediate 2), then utilizes hydrazide group and carbon disulfide to undergo cyclization reaction under alkaline conditions to form intermediate 3, then utilizes diazole ring ether group to undergo reduction action of hydrazine hydrate to generate triazole ring to form intermediate 4, and intermediate 4 is a triazole ring with bactericidal effect; then utilizes 4-hydroxybutyric acid and diethylenetriamine to undergo cyclization reaction to form intermediate 5, then utilizes benzyl chloride to perform benzyl protection on hydroxyl group in the molecular structure of intermediate 5 to obtain intermediate 6, then utilizes chloroacetyl chloride and intermediate 6 to obtain intermediate 7. The amino group in the molecular structure of intermediate 6 is reacted to obtain intermediate 7, and then the chlorine in intermediate 7 is reacted with the thiol in intermediate 4 to obtain intermediate 8, and intermediate 8 is debenzylated under a Pd / C catalyst to obtain the target product, namely, a multi-antibacterial agent. The multi-antibacterial agent contains a 1,2,4-triazole structure, an imidazoline quaternary ammonium salt structure and a sulfide structure, which have good biological activity against bacteria, and each structure has a different bactericidal and antibacterial mechanism against bacteria, and synergistically exerts a bactericidal effect, and is environmentally friendly, so that the multi-antibacterial agent has high bactericidal efficiency and a wide bactericidal spectrum. Therefore, the multi-antibacterial agent has excellent bactericidal and antibacterial effects;

[0027] 2. The present invention introduces the above-mentioned multiple antibacterial agents into the raw materials of protective boots to solve the problem that the current medical protective boots have insufficient antibacterial and bactericidal effects, so that the medical protective boots provided by the present invention have excellent bactericidal and antibacterial properties. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present invention are described clearly and completely. 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.

[0029] Embodiment 1:

[0030] The multi-antimicrobial agent is prepared by the following steps:

[0031] Step A, 0.01 mol of substituted benzoic acid and 16 mL of anhydrous methanol are added to a three-necked flask with a stirrer and a condenser, 2 mL of concentrated sulfuric acid is added under stirring, and the reaction system is heated to 74°C with a water bath, and refluxed at a constant temperature for 8 hours, saturated sodium bicarbonate solution is added until no bubbles are generated, dichloromethane is added for separation, the organic layer is taken, anhydrous sodium sulfate is added for drying for 1 hour, and filtered to obtain intermediate 1, wherein the substituted benzoic acid is a monosubstituted benzoic acid, and the substituent is one of methyl and methoxy, the substitution position is one of meta, ortho, and para, and the mass fraction of sulfuric acid in the concentrated sulfuric acid is 98%; 0.01 mol of intermediate 1 and 16 mL of ethanol are added to a three-necked flask with a stirrer and a condenser, 0.7 g of hydrazine hydrate with a mass fraction of 80% is slowly added dropwise at room temperature, the dropping speed is 1 drop / second, and the reaction system is heated to 61°C with a water bath, refluxed for 8 hours, ethanol is removed under reduced pressure, cooled, filtered, and ethanol is recrystallized to obtain intermediate 2;

[0032] Step B, add 0.07 mol of intermediate 2, 3.6 g of potassium hydroxide, and 100 mL of anhydrous ethanol into a three-necked flask with a stirrer and a condenser, stir evenly at room temperature, slowly drop 30 mL of carbon disulfide ethanol solution, the drop rate is 1 drop / second, the reaction system temperature is heated to 52 ° C with a water bath, constant temperature reflux reaction for 5 hours, vacuum rotary evaporation to remove ethanol, add deionized water, adjust the pH of the solution to 5 with 10% mass fraction of dilute hydrochloric acid, filter, dry to constant weight, and obtain intermediate Intermediate 3, using the cyclization reaction of hydrazide group and carbon disulfide under alkaline conditions, wherein the ethanol solution of carbon disulfide is 3mmol / mL; 0.01mol of intermediate 3 and 30mL of anhydrous ethanol are added to a three-necked flask with a stirrer and a condenser, 2g of 80% hydrazine hydrate by mass is slowly added dropwise at room temperature at a rate of 1 drop / second, the reaction system is heated to 73°C in a water bath, refluxed at a constant temperature for 24h, ethanol is removed by vacuum rotary evaporation, and dried to constant weight to obtain intermediate 4;

[0033] Step C, add 1 mol 4-hydroxybutyric acid and 1.5 mol diethylenetriamine to a three-necked flask equipped with a condensing reflux device and a stirrer, and heat the reaction system to 83° C. with a heating jacket under stirring. When the reactants are completely melted, continue to heat the reaction system to 153° C. under circulating water conditions, and start the vacuum pump when gas is released, react for 2.5 hours, and when no gas is released, heat to 200° C. and react for 3 hours, and cool to room temperature under vacuum to obtain intermediate 5, and use the cyclization reaction of 4-hydroxybutyric acid and diethylenetriamine; After heating and melting 1 mol of intermediate 5, slowly add 1 mol of benzyl chloride with a constant pressure dropping funnel at a dropping speed of 1 drop / second, heat the reaction system to 102° C., and react at a constant temperature for 3.5 hours. When the reaction system is cooled to 35° C., add 5 g potassium carbonate and 60 mL dichloromethane, react at a constant temperature for 4 hours, and cool to obtain intermediate 6;

[0034] Step D, 0.01 mol of intermediate 6, 0.013 mol of potassium carbonate and 0.013 mol of anhydrous dichloromethane were added to a three-necked flask with a stirrer, and after stirring evenly, 80 mL of chloroacetyl chloride was slowly added dropwise using a dropping funnel at room temperature, and the dropping speed was 1 drop / second, and stirred at room temperature at 350 r / min for 20 h, and dichloromethane was removed by vacuum rotary evaporation, washed with ice water 3 times, filtered, and dried to constant weight to obtain intermediate 7;

[0035] Step E, add 0.01 mol of intermediate 7, 0.012 mol of potassium carbonate and 80 mL of acetone into a three-necked flask with a stirrer, stir evenly, add 0.011 mol of intermediate 4 under stirring, control the reaction temperature at 43°C, stir the reaction for 6 hours, cool and filter, separate through a column, and obtain intermediate 8; add 0.1 mmol of intermediate 8 and 30 mL of pyridine into a three-necked flask with a stirrer and a reflux device, pass high-purity nitrogen for 30 minutes, then add 0.1 g of 10% Pd / C catalyst by volume, pass hydrogen, and react at room temperature under hydrogen protection for 24 hours. After the reaction is completed, filter, wash with methanol 3 times, combine the filtrate, and evaporate the filtrate under reduced pressure at room temperature to obtain a multiple antibacterial agent.

[0036] Embodiment 2:

[0037] The multi-antimicrobial agent is prepared by the following steps:

[0038] Step A, 0.01 mol of substituted benzoic acid and 16 mL of anhydrous methanol are added to a three-necked flask with a stirrer and a condenser, 2 mL of concentrated sulfuric acid is added under stirring, and the reaction system is heated to 74°C with a water bath, and refluxed at a constant temperature for 8 hours, saturated sodium bicarbonate solution is added until no bubbles are generated, dichloromethane is added for separation, the organic layer is taken, anhydrous sodium sulfate is added for drying for 1 hour, and filtered to obtain intermediate 1, wherein the substituted benzoic acid is a monosubstituted benzoic acid, and the substituent is one of methyl and methoxy, the substitution position is one of meta, ortho, and para, and the mass fraction of sulfuric acid in the concentrated sulfuric acid is 98%; 0.01 mol of intermediate 1 and 16 mL of ethanol are added to a three-necked flask with a stirrer and a condenser, 0.7 g of hydrazine hydrate with a mass fraction of 80% is slowly added dropwise at room temperature, the dropping speed is 1 drop / second, and the reaction system is heated to 61°C with a water bath, refluxed for 8 hours, ethanol is removed under reduced pressure, cooled, filtered, and ethanol is recrystallized to obtain intermediate 2;

[0039] Step B, add 0.07 mol of intermediate 2, 3.6 g of potassium hydroxide, and 100 mL of anhydrous ethanol into a three-necked flask with a stirrer and a condenser, stir evenly at room temperature, slowly drop 30 mL of carbon disulfide ethanol solution, the drop rate is 1 drop / second, heat the reaction system temperature to 52 ° C with a water bath, reflux at a constant temperature for 5 hours, remove ethanol by vacuum rotary evaporation, add deionized water, adjust the pH of the solution to 5 with 10% by mass dilute hydrochloric acid, filter, and dry to constant weight to obtain the intermediate The intermediate 3 is prepared by a cyclization reaction of hydrazide group and carbon disulfide under alkaline conditions, wherein the ethanol solution of carbon disulfide is 3 mmol / mL; 0.01 mol of intermediate 3 and 30 mL of anhydrous ethanol are added to a three-necked flask with a stirrer and a condenser, 2-3 g of 80% hydrazine hydrate by mass is slowly added dropwise at room temperature at a rate of 1 drop / second, the reaction system is heated to 73°C in a water bath, refluxed at a constant temperature for 24 hours, ethanol is removed by vacuum rotary evaporation, and dried to constant weight to obtain intermediate 4;

[0040] Step C, add 1 mol 4-hydroxybutyric acid and 1.5 mol diethylenetriamine to a three-necked flask equipped with a condensing reflux device and a stirrer, and heat the reaction system to 83° C. with a heating jacket under stirring. When the reactants are completely melted, continue to heat the reaction system to 153° C. under circulating water conditions, and start the vacuum pump when gas is released, react for 2.5 hours, and when no gas is released, heat to 200° C. and react for 3 hours, and cool to room temperature under vacuum to obtain intermediate 5, and use the cyclization reaction of 4-hydroxybutyric acid and diethylenetriamine; After heating and melting 1 mol of intermediate 5, slowly add 1 mol of benzyl chloride with a constant pressure dropping funnel at a dropping speed of 1 drop / second, heat the reaction system to 102° C., and react at a constant temperature for 3.5 hours. When the reaction system is cooled to 35° C., add 5 g potassium carbonate and 60 mL dichloromethane, react at a constant temperature for 4 hours, and cool to obtain intermediate 6;

[0041] Step D, 0.01 mol of intermediate 6, 0.013 mol of potassium carbonate and 0.013 mol of anhydrous dichloromethane were added to a three-necked flask with a stirrer, and after stirring evenly, 80 mL of chloroacetyl chloride was slowly added dropwise using a dropping funnel at room temperature, and the dropping speed was 1 drop / second, and stirred at room temperature at 350 r / min for 20 h, and dichloromethane was removed by vacuum rotary evaporation, washed with ice water 3 times, filtered, and dried to constant weight to obtain intermediate 7;

[0042] Step E, add 0.01 mol of intermediate 7, 0.012 mol of potassium carbonate and 80 mL of acetone into a three-necked flask with a stirrer, stir evenly, add 0.013 mol of intermediate 4 under stirring, control the reaction temperature at 43°C, stir the reaction for 6 hours, cool and filter, separate through a column to obtain intermediate 8; add 0.1 mmol of intermediate 8 and 30 mL of pyridine into a three-necked flask with a stirrer and a reflux device, pass high-purity nitrogen for 30 minutes, then add 0.1 g of 10% Pd / C catalyst by volume, pass hydrogen, and react at room temperature under hydrogen protection for 24 hours. After the reaction is completed, filter, wash with methanol 3 times, combine the filtrate, and evaporate the filtrate under reduced pressure at room temperature to obtain a multiple antibacterial agent.

[0043] Embodiment 3:

[0044] A kind of antibacterial medical protective boots, comprising the following raw materials in parts by weight: 30 parts of PVC resin, 15 parts of polyacrylate, 5 parts of plasticizer, 0.5 parts of antioxidant, 1 part of calcium stearate, 0.5 parts of paraffin, and 2.5 parts of the multiple antibacterial agent prepared in Example 1; the plasticizer is dioctyl phthalate; the antioxidant is a mixture of antioxidant 626 and antioxidant 1010 mixed in a mass ratio of 1:5.

[0045] The antibacterial medical protective boots are made by the following steps:

[0046] Step S1, adding paraffin wax and calcium stearate into a pulverizer for pulverization, passing through a 200-mesh sieve, and mixing to obtain a mixed powder;

[0047] Step S2, preheating the PVC resin, plasticizer, and multiple antibacterial agent at 90° C. and 750 r / min for 5 min with stirring, then adding the polyacrylate, heating to 105° C., stirring at 900 r / min for 5 min, raising the temperature to 115° C., mixing for 15 min, finally adding the antioxidant and the mixed powder, raising the temperature to 130° C., mixing for 15 min, and obtaining a mixed rubber;

[0048] Step S3, injecting the mixed rubber obtained in step S2 into a mold, compression molding at 140° C., and then cooling to obtain an antibacterial medical protective boot.

[0049] Embodiment 4:

[0050] A kind of antibacterial medical protective boots, comprising the following raw materials in parts by weight: 60 parts of PVC resin, 20 parts of polyacrylate, 7 parts of plasticizer, 2 parts of antioxidant, 1.5 parts of calcium stearate, 2 parts of paraffin, and 4 parts of the multiple antibacterial agent prepared in Example 2; the plasticizer is diethyl phthalate; the antioxidant is a mixture of antioxidant 626 and antioxidant 1010 in a mass ratio of 2:7.

[0051] The antibacterial medical protective boots are made by the following steps:

[0052] Step S1, adding paraffin wax and calcium stearate into a pulverizer for pulverization, passing through a 200-mesh sieve, and mixing to obtain a mixed powder;

[0053] Step S2, preheating the PVC resin, plasticizer, and multiple antibacterial agent at 90° C. and 750 r / min for 5 min with stirring, then adding the polyacrylate, heating to 105° C., stirring at 900 r / min for 5 min, raising the temperature to 115° C., mixing for 18 min, finally adding the antioxidant and the mixed powder, raising the temperature to 130° C., mixing for 20 min, and obtaining a mixed rubber;

[0054] Step S3, injecting the mixed rubber obtained in step S2 into a mold, compression molding at 140° C., and then cooling to obtain an antibacterial medical protective boot.

[0055] Embodiment 5:

[0056] A kind of antibacterial medical protective boots, comprising the following raw materials in parts by weight: 80 parts of PVC resin, 35 parts of polyacrylate, 13 parts of plasticizer, 4.5 parts of antioxidant, 2.5 parts of calcium stearate, 3.5 parts of paraffin, and 7 parts of the multiple antibacterial agent prepared in Example 1; the plasticizer is dibutyl phthalate; the antioxidant is a mixture of antioxidant 626 and antioxidant 1010 mixed in a mass ratio of 3:10.

[0057] The antibacterial medical protective boots are made by the following steps:

[0058] Step S1, adding paraffin wax and calcium stearate into a pulverizer for pulverization, passing through a 300-mesh sieve, and mixing to obtain a mixed powder;

[0059] Step S2, preheating the PVC resin, plasticizer, and multiple antibacterial agent at 90° C. and 750 r / min for 5 min with stirring, then adding polyacrylate, heating to 105° C., stirring at 900 r / min for 5 min, raising the temperature to 115° C., mixing for 20 min, finally adding antioxidant and mixed powder, raising the temperature to 130° C., mixing for 40 min, and obtaining a mixed rubber;

[0060] Step S3, injecting the mixed rubber obtained in step S2 into a mold, compression molding at 155° C., and then cooling to obtain an antibacterial medical protective boot.

[0061] Comparative Example 1:

[0062] A pair of antibacterial medical protective boots, comprising the following raw materials in parts by weight: 30 parts of PVC resin, 15 parts of polyacrylate, 5 parts of plasticizer, 0.5 parts of antioxidant, 1 part of calcium stearate, and 0.5 parts of paraffin; the plasticizer is dioctyl phthalate; the antioxidant is a mixture of antioxidant 626 and antioxidant 1010 in a mass ratio of 1:5.

[0063] The antibacterial medical protective boots are made by the following steps: refer to the steps in Example 3.

[0064] Comparative Example 2:

[0065] A pair of antibacterial medical protective boots, comprising the following raw materials in parts by weight: 60 parts of PVC resin, 20 parts of polyacrylate, 7 parts of plasticizer, 2 parts of antioxidant, 1.5 parts of calcium stearate, 2 parts of paraffin, and 4 parts of commercially available PP antibacterial agent (produced by Foshan Liyuan Chemical Co., Ltd.); the plasticizer is diethyl phthalate; the antioxidant is a mixture of antioxidant 626 and antioxidant 1010 in a mass ratio of 2:7.

[0066] The antibacterial medical protective boots are made by the following steps: refer to the steps in Example 4.

[0067] Comparative Example 3:

[0068] A pair of antibacterial medical protective boots, comprising the following raw materials in parts by weight: 80 parts of PVC resin, 35 parts of polyacrylate, 13 parts of plasticizer, 4.5 parts of antioxidant, 2.5 parts of calcium stearate, 3.5 parts of paraffin, and 7 parts of silicone quaternary ammonium salt antibacterial agent TMSQ (produced by Wuhan Woxuan Technology Co., Ltd.); the plasticizer is dibutyl phthalate; the antioxidant is a mixture of antioxidant 626 and antioxidant 1010 in a mass ratio of 3:10.

[0069] The antibacterial medical protective boots are made by the following steps: refer to the steps in Example 5.

[0070] Embodiment 6:

[0071] The protective boots obtained in Examples 3-5 and Comparative Examples 1-3 were tested for antibacterial properties according to “HG / T 3663-2014 Test Method for Antibacterial Properties of Rubber Shoes”, and the test results are shown in Table 1.

[0072] Table 1

[0073]

[0074] It can be seen from the data in Table 1 that the antibacterial properties of the protective boots obtained in Examples 3-5 are better than the antibacterial properties of the protective boots obtained in Comparative Examples 1-3.

[0075] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0076] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. An antibacterial medical protective boot, characterized in that: The invention comprises the following raw materials in parts by weight: 30-80 parts of PVC resin, 15-35 parts of polyacrylate, 5-13 parts of plasticizer, 0.5-4.5 parts of antioxidant, 1-2.5 parts of calcium stearate, 0.5-3.5 parts of paraffin wax, and 2.5-7 parts of multiple antibacterial agent; The multi-antimicrobial agent is prepared by the following steps: Step A, after mixing substituted benzoic acid and anhydrous methanol, add concentrated sulfuric acid under stirring, reflux at 74°C for 8h, add saturated sodium bicarbonate solution until no bubbles are generated, separate the liquids, take the organic layer, dry, filter, and obtain intermediate 1; after mixing intermediate 1 and ethanol, add dropwise 80% hydrazine hydrate at room temperature, reflux at 61°C for 8h, evaporate under reduced pressure, cool, filter, and recrystallize to obtain intermediate 2; Step B, after mixing intermediate 2, potassium hydroxide and anhydrous ethanol, add dropwise an ethanol solution of carbon disulfide, reflux at 52°C for 5h, perform rotary evaporation under reduced pressure, add deionized water, adjust the pH of the solution to 5 with 10% by mass dilute hydrochloric acid, filter, and dry to obtain intermediate 3; after mixing intermediate 3 and anhydrous ethanol, add dropwise 80% by mass hydrazine hydrate, reflux at 73°C for 24h, perform rotary evaporation under reduced pressure, and dry to obtain intermediate 4; Step C, after heating and melting 4-hydroxybutyric acid and diethylenetriamine and mixing, the reaction system is heated to 153° C. under circulating water conditions, and when gas is released, the reaction is carried out under vacuum for 2.5 hours, and when no gas is released, the temperature is raised to 200° C. and the reaction is carried out for 3 hours, and the reaction is cooled to room temperature under vacuum to obtain intermediate 5; after heating and melting intermediate 5, benzyl chloride is added dropwise, and the reaction is carried out at 102° C. for 3.5 hours, and when the reaction system is cooled to 35° C., potassium carbonate and dichloromethane are added, and the reaction is carried out at a constant temperature for 4 hours, and the reaction is cooled to obtain intermediate 6; Step D, after mixing intermediate 6, potassium carbonate and anhydrous dichloromethane, add chloroacetyl chloride dropwise, react at room temperature for 20 hours, evaporate under reduced pressure, wash, filter and dry to obtain intermediate 7; Step E, after mixing intermediate 7, potassium carbonate and acetone, add intermediate 4, stir and react at 43°C for 6 hours, cool, filter and obtain intermediate 8; after mixing intermediate 8 and pyridine, pass high-purity nitrogen for 30 minutes, then add 10% by volume Pd / C catalyst, stir and react at room temperature for 24 hours under hydrogen protection, filter, wash, combine the filtrate, and evaporate the filtrate under reduced pressure at room temperature to obtain a multiple antibacterial agent.

2. The antibacterial medical protective boots according to claim 1, characterized in that: In step A, the usage ratio of substituted benzoic acid, anhydrous methanol and concentrated sulfuric acid is 0.01 mol: 16-60 mL: 2-4 mL, the substituted benzoic acid is monosubstituted benzoic acid, the substituent is one of methyl and methoxy, and the substitution position is one of meta, ortho and para; the usage ratio of intermediate 1, ethanol and hydrazine hydrate is 0.01 mol: 16-60 mL: 0.7-1.5 g.

3. The antibacterial medical protective boots according to claim 1, characterized in that: In step B, the usage ratio of intermediate 2, potassium hydroxide, anhydrous ethanol, and ethanol solution of carbon disulfide is 0.07 mol: 3.6-4.6 g: 100-150 mL: 30-50 mL; the usage ratio of intermediate 3, anhydrous ethanol, and hydrazine hydrate is 0.01 mol: 30-70 mL: 2-3 g.

4. The antibacterial medical protective boots according to claim 1, characterized in that: In step C, the usage ratio of 4-hydroxybutyric acid and diethylenetriamine is 1 mol: 1.5-2 mol; the usage ratio of intermediate 5, benzyl chloride, potassium carbonate and dichloromethane is 1 mol: 1 mol: 5-10 g: 60-150 mL.

5. The antibacterial medical protective boots according to claim 1, characterized in that: In step D, the usage ratio of intermediate 6, potassium carbonate, anhydrous dichloromethane and chloroacetyl chloride is 0.01 mol: 0.013 mol: 0.013-0.016 mol: 80-200 mL.

6. The antibacterial medical protective boots according to claim 1, characterized in that: In step E, the usage ratio of intermediate 7, potassium carbonate, acetone and intermediate 4 is 0.01 mol: 0.012 mol: 80-150 mL: 0.011-0.013 mol; the usage ratio of intermediate 8, pyridine and Pd / C catalyst is 0.1 mmol: 30-80 mL: 0.1-0.3 g.

7. The production process of the antibacterial medical protective boots according to claim 1, characterized in that: The following steps are involved: Step S1, adding paraffin wax and calcium stearate into a pulverizer for pulverization, sieving, and mixing to obtain a mixed powder; Step S2, preheating the PVC resin, plasticizer, and multiple antibacterial agent at 90° C. and 750 r / min for 5 min with stirring, then adding the polyacrylate, heating to 105° C., stirring at 900 r / min for 5 min, raising the temperature to 115° C., mixing for 15-20 min, finally adding the antioxidant and the mixed powder, raising the temperature to 130° C., mixing for 15-40 min, and obtaining a rubber compound; Step S3, injecting the mixed rubber obtained in step S2 into a mold, and performing compression molding at 140-155° C., cooling, and obtaining an antibacterial medical protective boot.

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