阅读说明：本技术 一种防滑抗菌防护靴及其制备方法 (Anti-skid antibacterial protective boot and preparation method thereof ) 是由 黄振 申乾成 申辉 高森森 于 2020-05-25 设计创作，主要内容包括：本发明公开了一种防滑抗菌防护靴及其制备方法,该防护靴由如下重量份原料制成：热塑性丁苯橡胶100～120份、抗菌剂2～3份、抗氧化剂1～2份、增塑剂2～3份、石蜡1～5份、硬脂酸1～5份；在制备防护靴的过程中制备抗菌剂和抗氧化剂,该抗菌剂分子上含有多个硅氧键,硅氧键的键能高,破坏时需要的能量大,进而使得抗菌的耐热性增加,该抗氧化剂分子中含有酚羟基,在橡胶被氧化时能够通过质子给予作用,从而破坏自由基自动氧化链反应,且该抗氧化剂分子中含有易发生断裂的氮氢键,能够很好的捕获自由基,两种基团的配合使得橡胶的抗氧化性增加,进而增加了防滑抗菌防护靴的使用寿命。(The invention discloses an anti-skid antibacterial protective boot and a preparation method thereof, wherein the protective boot is prepared from the following raw materials in parts by weight: 100-120 parts of thermoplastic styrene-butadiene rubber, 2-3 parts of an antibacterial agent, 1-2 parts of an antioxidant, 2-3 parts of a plasticizer, 1-5 parts of paraffin and 1-5 parts of stearic acid; the antibacterial agent and the antioxidant are prepared in the process of preparing the protective boots, the molecules of the antibacterial agent contain a plurality of silicon-oxygen bonds, the bond energy of the silicon-oxygen bonds is high, the energy required in the process of damage is large, the antibacterial heat resistance is increased, the molecules of the antioxidant contain phenolic hydroxyl, the rubber can act through proton when being oxidized, the automatic oxidation chain reaction of free radicals is damaged, the molecules of the antioxidant contain nitrogen-hydrogen bonds which are easy to break, the free radicals can be well captured, the oxidation resistance of the rubber is increased through the matching of the two groups, and the service life of the anti-skidding antibacterial protective boots is prolonged.)

1. The utility model provides an antibiotic protective boots of antiskid which characterized in that: the feed is prepared from the following raw materials in parts by weight: 100-120 parts of thermoplastic styrene-butadiene rubber, 2-3 parts of an antibacterial agent, 1-2 parts of an antioxidant, 2-3 parts of a plasticizer, 1-5 parts of paraffin and 1-5 parts of stearic acid;

the protective boot is prepared by the following steps:

step S1: heating thermoplastic styrene-butadiene rubber at the temperature of 85-100 ℃, and cutting the thermoplastic styrene-butadiene rubber into blocks;

step S2: adding paraffin and stearic acid into a grinder for grinding, and mixing after passing through a screen with 200-300 meshes to obtain mixed powder;

step S3: mixing the blocky thermoplastic styrene-butadiene rubber prepared in the step S1 and the mixed powder for 30-40 min at the temperature of 150-160 ℃, adding an antibacterial agent, an antioxidant and a plasticizer, and continuously mixing for 1-1.5 h to prepare a rubber material;

step S4: and (4) adding the rubber material prepared in the step (S3) into a mold at the temperature of 150-160 ℃, performing compression molding, and cooling to obtain the anti-skid antibacterial protective boot.

2. The anti-slip antibacterial protective boot according to claim 1, characterized in that: the plasticizer is one or a mixture of more of dioctyl phthalate, diethyl phthalate and dibutyl phthalate in any proportion.

3. The anti-slip antibacterial protective boot according to claim 1, characterized in that: the antibacterial agent is prepared by the following steps:

step A1: adding diphenylamine, liquid bromine and ferric bromide into a reaction kettle, reacting for 20-30min to obtain an intermediate E1, adding an intermediate E1 and ethanol into the reaction kettle, stirring until the intermediate E1 is completely dissolved, adding tetramethoxysilane and dropwise adding n-butyllithium at the temperature of-80 to-90 ℃ under the conditions of no water and no oxygen, and reacting for 2-3 h to obtain an intermediate E2;

step A2: adding the intermediate E2 prepared in the step A1 and ethanol into a reaction kettle, stirring until the intermediate E2 is completely dissolved, adding sulfur powder and aluminum chloride, introducing nitrogen for protection, and reacting for 1-1.5 hours at the temperature of 205-210 ℃ to prepare an intermediate E3;

step A3: adding tetrahydrofuran, magnesium powder and bromoethane into a reaction kettle, reacting for 20-30min at the rotating speed of 200-300 r/min, adding the intermediate E3 prepared in the step A2 and benzene, uniformly mixing, and performing reflux reaction for 30-50 min at the temperature of 85-90 ℃ to prepare an intermediate E4;

step A4: uniformly mixing the intermediate E4 prepared in the step A3, 1-chloro-2-dimethylaminopropane and benzene, and carrying out reflux reaction for 2-3 hours at the temperature of 85-90 ℃ to prepare an intermediate E5;

step A5: adding zinc chloride, paraformaldehyde and concentrated hydrochloric acid into a reaction kettle, stirring for 5-10 min at the rotation speed of 300-500 r/min and at the temperature of 60-70 ℃, adding the intermediate E5 prepared in the step A4, introducing hydrogen chloride gas to fill the reaction kettle, reacting for 6-8 h to prepare an intermediate E6, adding the intermediate E6 and ethanol into the reaction kettle, stirring until the intermediate E6 is completely dissolved, adding zinc phosphate, performing reflux reaction for 10-12 h at the temperature of 125-135 ℃, adding a sodium hydroxide solution, and continuing to react for 8-10 h to prepare the antibacterial agent.

4. The anti-slip and anti-bacterial protective boot according to claim 3, wherein: the dosage ratio of diphenylamine, liquid bromine and ferric bromide in the step A1 is 5 g: 1 ml: 0.1g, the dosage ratio of the intermediate E1 to the ethanol is 5 g: 1mL, wherein the molar ratio of the intermediate E1, tetramethoxysilane and n-butyllithium is 1: 2: 1.1, the intermediate E2, the ethanol, the sulfur powder and the zinc chloride in the step A2 are used in an amount of 10: 8: 5: 0.2, wherein the dosage ratio of the tetrahydrofuran, the magnesium powder, the bromoethane, the intermediate E3 and the benzene in the step A3 is 20 g: 1 g: 5 g: 5 g: 100mL of the intermediate E4, 1-chloro-2-dimethylaminopropane and benzene in the step A4 are used in a ratio of 1 g: 1 g: 2mL, wherein the mass ratio of the zinc chloride, the paraformaldehyde, the concentrated hydrochloric acid and the intermediate E5 in the step A5 is 2: 1: 3: 1, the concentration of concentrated hydrochloric acid is 12mol/L, the dosage ratio of the intermediate E6, ethanol, zinc phosphate and sodium hydroxide solution is 10 g: 20mL of: 0.25 g: 5mL, and the mass fraction of the sodium hydroxide solution is 70-80%.

5. The anti-slip antibacterial protective boot according to claim 1, characterized in that: the antioxidant is prepared by the following steps:

step B1: adding p-methylphenol into a reaction kettle, introducing chlorine until the reaction kettle is filled with the chlorine, and reacting for 30-40 min under the illumination condition to obtain an intermediate F1;

step B2: adding the intermediate F1 prepared in the step B1, aluminum powder and triphenoxy aluminum into a reaction kettle, stirring for 3-3.5 hours at the rotation speed of 300-500 r/min and the temperature of 150-160 ℃, introducing isobutene, and reacting for 3-5 hours at the temperature of 130-135 ℃ to prepare an intermediate F2;

step B3: adding the intermediate F2 prepared in the step B2 and a sodium carbonate solution into a reaction kettle, reacting for 6-8 hours at the temperature of 100-110 ℃ to prepare an intermediate F3, adding the intermediate F3 and potassium permanganate into the reaction kettle, reacting for 1-2 hours at the rotation speed of 200-300 r/min and the temperature of 25-30 ℃, adding magnesium oxide and copper oxide, introducing oxygen, and reacting for 8-10 hours at the temperature of 190-210 ℃ to prepare an intermediate F4;

step B4: and B3, adding the intermediate F4, aniline and phosphoric acid into a reaction kettle, and reacting for 5-8 hours under the conditions that the pressure is 9-16 MPa and the temperature is 300-450 ℃ to obtain the antioxidant.

6. The anti-slip and anti-bacterial protective boot according to claim 5, wherein: the intermediate F1, the aluminum powder, the triphenoxy aluminum and the isobutene in the step B2 are used in an amount and mass ratio of 20: 0.2: 0.1: 40, the dosage ratio of the intermediate F2 and the sodium carbonate solution in the step B3 is 1 g: 3mL, wherein the mass fraction of the sodium carbonate solution is 15-20%, and the mass ratio of the intermediate F3 to the potassium permanganate, the magnesium oxide, the copper oxide and the oxygen is 100: 3: 0.2: 0.3: 50, the mass ratio of the intermediate F4, the aniline and the phosphoric acid in the step B4 is 1: 2: 0.1.

7. the method for preparing the anti-slip antibacterial protective boots according to claim 1, wherein the method comprises the following steps:

the method comprises the following specific steps:

step S1: heating thermoplastic styrene-butadiene rubber at the temperature of 85-100 ℃, and cutting the thermoplastic styrene-butadiene rubber into blocks;

step S2: adding paraffin and stearic acid into a grinder for grinding, and mixing after passing through a screen with 200-300 meshes to obtain mixed powder;

step S3: mixing the blocky thermoplastic styrene-butadiene rubber prepared in the step S1 and the mixed powder for 30-40 min at the temperature of 150-160 ℃, adding an antibacterial agent, an antioxidant and a plasticizer, and continuously mixing for 1-1.5 h to prepare a rubber material;

step S4: and (4) adding the rubber material prepared in the step (S3) into a mold at the temperature of 150-160 ℃, performing compression molding, and cooling to obtain the anti-skid antibacterial protective boot.

Technical Field

The invention belongs to the technical field of protective boot production, and particularly relates to an anti-skidding and antibacterial protective boot and a preparation method thereof.

Background

The protective boots are special boots with protective functions, can protect workers from being injured by various dangerous factors in the production process, mainly protect the possible injuries of the instep, toes and sole and other injuries, and can be divided into the following parts according to the functions: safety shoes for protecting toes, anti-puncture shoes, anti-static shoes, conductive shoes, electrical insulation shoes, oil-proof protective boots and heat-proof boots.

Although traditional protection boots have multiple functions but antiskid effect is general, and use the back when long-time, protection shoes's inside and surface can breed a large amount of bacteriums, the appearance of bacterium can cause the influence to user's healthy, use a period back at protection boots, because the long-time contact of oxygen in protection boots and the air, take place oxidation reaction, make the performance reduction of protection boots, the surface and the sole of protection boots appear the crack, and then make the protective nature greatly reduced of protection boots, the phenomenon of sole and vamp separation appears even, greatly reduced protection boots's life.

Disclosure of Invention

The invention aims to provide an anti-skidding and antibacterial protective boot and a preparation method thereof.

The technical problems to be solved by the invention are as follows:

traditional protection boots antiskid effect is general, and use the back when long-time, a large amount of bacteriums can breed on the inside and the surface of protection shoes, the appearance of bacterium can cause the influence to user's healthy, use a period back at protection boots, because the long-time contact of oxygen in protection boots and the air, take place oxidation reaction, make the performance reduction of protection boots, the crack appears in the surface and the sole of protection boots, make the protective nature greatly reduced of protection boots, the phenomenon that sole and vamp separated appears even, greatly reduced the life of protection boots.

The purpose of the invention can be realized by the following technical scheme:

the anti-skid antibacterial protective boot is prepared from the following raw materials in parts by weight: 100-120 parts of thermoplastic styrene-butadiene rubber, 2-3 parts of an antibacterial agent, 1-2 parts of an antioxidant, 2-3 parts of a plasticizer, 1-5 parts of paraffin and 1-5 parts of stearic acid;

the protective boot is prepared by the following steps:

step S1: heating thermoplastic styrene-butadiene rubber at the temperature of 85-100 ℃, and cutting the thermoplastic styrene-butadiene rubber into blocks;

step S2: adding paraffin and stearic acid into a grinder for grinding, and mixing after passing through a screen with 200-300 meshes to obtain mixed powder;

step S3: mixing the blocky thermoplastic styrene-butadiene rubber prepared in the step S1 and the mixed powder for 30-40 min at the temperature of 150-160 ℃, adding an antibacterial agent, an antioxidant and a plasticizer, and continuously mixing for 1-1.5 h to prepare a rubber material;

step S4: and (4) adding the rubber material prepared in the step (S3) into a mold at the temperature of 150-160 ℃, performing compression molding, and cooling to obtain the anti-skid antibacterial protective boot.

Further, the plasticizer is one or a mixture of more of dioctyl phthalate, diethyl phthalate and dibutyl phthalate in any proportion.

Further, the antibacterial agent is prepared by the following steps:

step A1: adding diphenylamine, liquid bromine and ferric bromide into a reaction kettle, reacting for 20-30min to obtain an intermediate E1, adding an intermediate E1 and ethanol into the reaction kettle, stirring until the intermediate E1 is completely dissolved, adding tetramethoxysilane and dropwise adding n-butyllithium at the temperature of-80 to-90 ℃ under the conditions of no water and no oxygen, and reacting for 2-3 h to obtain an intermediate E2;

the reaction process is as follows:

step A2: adding the intermediate E2 prepared in the step A1 and ethanol into a reaction kettle, stirring until the intermediate E2 is completely dissolved, adding sulfur powder and aluminum chloride, introducing nitrogen for protection, and reacting for 1-1.5 hours at the temperature of 205-210 ℃ to prepare an intermediate E3;

the reaction process is as follows:

step A3: adding tetrahydrofuran, magnesium powder and bromoethane into a reaction kettle, reacting for 20-30min at the rotating speed of 200-300 r/min, adding the intermediate E3 prepared in the step A2 and benzene, uniformly mixing, and performing reflux reaction for 30-50 min at the temperature of 85-90 ℃ to prepare an intermediate E4;

the reaction process is as follows:

step A4: uniformly mixing the intermediate E4 prepared in the step A3, 1-chloro-2-dimethylaminopropane and benzene, and carrying out reflux reaction for 2-3 hours at the temperature of 85-90 ℃ to prepare an intermediate E5;

the reaction process is as follows:

step A5: adding zinc chloride, paraformaldehyde and concentrated hydrochloric acid into a reaction kettle, stirring for 5-10 min at the rotation speed of 300-500 r/min and at the temperature of 60-70 ℃, adding the intermediate E5 prepared in the step A4, introducing hydrogen chloride gas to fill the reaction kettle, reacting for 6-8 h to prepare an intermediate E6, adding the intermediate E6 and ethanol into the reaction kettle, stirring until the intermediate E6 is completely dissolved, adding zinc phosphate, performing reflux reaction for 10-12 h at the temperature of 125-135 ℃, adding a sodium hydroxide solution, and continuing to react for 8-10 h to prepare the antibacterial agent.

The reaction process is as follows:

further, the dosage ratio of diphenylamine, liquid bromine and ferric bromide in the step A1 is 5 g: 1 ml: 0.1g, the dosage ratio of the intermediate E1 to the ethanol is 5 g: 1mL, wherein the molar ratio of the intermediate E1, tetramethoxysilane and n-butyllithium is 1: 2: 1.1, the intermediate E2, the ethanol, the sulfur powder and the zinc chloride in the step A2 are used in an amount of 10: 8: 5: 0.2, wherein the dosage ratio of the tetrahydrofuran, the magnesium powder, the bromoethane, the intermediate E3 and the benzene in the step A3 is 20 g: 1 g: 5 g: 5 g: 100mL of the intermediate E4, 1-chloro-2-dimethylaminopropane and benzene in the step A4 are used in a ratio of 1 g: 1 g: 2mL, wherein the mass ratio of the zinc chloride, the paraformaldehyde, the concentrated hydrochloric acid and the intermediate E5 in the step A5 is 2: 1: 3: 1, the concentration of concentrated hydrochloric acid is 12mol/L, the dosage ratio of the intermediate E6, ethanol, zinc phosphate and sodium hydroxide solution is 10 g: 20mL of: 0.25 g: 5mL, and the mass fraction of the sodium hydroxide solution is 70-80%.

Further, the antioxidant is prepared by the following steps:

step B1: adding p-methylphenol into a reaction kettle, introducing chlorine until the reaction kettle is filled with the chlorine, and reacting for 30-40 min under the illumination condition to obtain an intermediate F1;

the reaction process is as follows:

step B2: adding the intermediate F1 prepared in the step B1, aluminum powder and triphenoxy aluminum into a reaction kettle, stirring for 3-3.5 hours at the rotation speed of 300-500 r/min and the temperature of 150-160 ℃, introducing isobutene, and reacting for 3-5 hours at the temperature of 130-135 ℃ to prepare an intermediate F2;

the reaction process is as follows:

step B3: adding the intermediate F2 prepared in the step B2 and a sodium carbonate solution into a reaction kettle, reacting for 6-8 hours at the temperature of 100-110 ℃ to prepare an intermediate F3, adding the intermediate F3 and potassium permanganate into the reaction kettle, reacting for 1-2 hours at the rotation speed of 200-300 r/min and the temperature of 25-30 ℃, adding magnesium oxide and copper oxide, introducing oxygen, and reacting for 8-10 hours at the temperature of 190-210 ℃ to prepare an intermediate F4;

the reaction process is as follows:

step B4: and B3, adding the intermediate F4, aniline and phosphoric acid into a reaction kettle, and reacting for 5-8 hours under the conditions that the pressure is 9-16 MPa and the temperature is 300-450 ℃ to obtain the antioxidant.

The reaction process is as follows:

further, the intermediate F1, the aluminum powder, the triphenoxy aluminum and the isobutene in the step B2 are used in an amount and mass ratio of 20: 0.2: 0.1: 40, the dosage ratio of the intermediate F2 and the sodium carbonate solution in the step B3 is 1 g: 3mL, wherein the mass fraction of the sodium carbonate solution is 15-20%, and the mass ratio of the intermediate F3 to the potassium permanganate, the magnesium oxide, the copper oxide and the oxygen is 100: 3: 0.2: 0.3: 50, the mass ratio of the intermediate F4, the aniline and the phosphoric acid in the step B4 is 1: 2: 0.1.

further, a preparation method of the anti-skid antibacterial protective boots comprises the following specific steps:

step S1: heating thermoplastic styrene-butadiene rubber at the temperature of 85-100 ℃, and cutting the thermoplastic styrene-butadiene rubber into blocks;

step S2: adding paraffin and stearic acid into a grinder for grinding, and mixing after passing through a screen with 200-300 meshes to obtain mixed powder;

step S3: mixing the blocky thermoplastic styrene-butadiene rubber prepared in the step S1 and the mixed powder for 30-40 min at the temperature of 150-160 ℃, adding an antibacterial agent, an antioxidant and a plasticizer, and continuously mixing for 1-1.5 h to prepare a rubber material;

step S4: and (4) adding the rubber material prepared in the step (S3) into a mold at the temperature of 150-160 ℃, and cooling to obtain the anti-skid antibacterial protective boot.

The invention has the beneficial effects that: the invention prepares an antibacterial agent in the process of preparing an anti-skid antibacterial protective boot, the antibacterial agent belongs to one of organic antibacterial agents, the antibacterial agent molecule contains a plurality of silicon-oxygen bonds, the bond energy of the silicon-oxygen bonds is high, the energy required in the process of damage is larger, the antibacterial heat resistance is further increased, the antibacterial agent is prevented from decomposing due to overhigh temperature in the preparation process of the protective boot, the antibacterial agent molecule contains two aldehyde groups, the oxygen on the aldehyde groups has negative charges, the carbon has positive charges, the positively charged carbon and the amino and sulfur groups of bacterial protein have addition reaction, thereby the bacterial protein is damaged, the bacterial protein is caused to die, and the antibacterial agent molecule can act on the genetic material of bacteria, further the bacteria is killed, the invention also prepares an antioxidant, the antioxidant molecule contains phenolic hydroxyl, the rubber can be acted by protons when being oxidized, thereby destroy the free radical autoxidation chain reaction, it is stable to produce the aryl oxygen free radical, and has the ability of catching active free radical, and contain the cracked nitrogen hydrogen bond of easy emergence in this antioxidant molecule, the capture free radical that can be fine, the cooperation of two kinds of groups makes the oxidation resistance of rubber increase, and then has increased the life of anti-skidding antibiotic protection boots, and butadiene styrene rubber has fine wear-resisting anti-skidding effect.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.