CN112708957A - Manufacturing process of antibacterial material for medical protective clothing - Google Patents

Abstract

The invention discloses a manufacturing process of an antibacterial material for medical protective clothing, which comprises the following raw materials in parts by weight: 20-30 parts of antibacterial composite particles, 25-50 parts of antibacterial liquid, 55-80 parts of polyacrylonitrile resin and 10-15 parts of sodium hydroxide solution with the mass fraction of 10%; uniformly mixing polyacrylonitrile resin and antibacterial composite particles, blending, extruding and granulating by using a double-screw extruder to obtain antibacterial master batches, drying the antibacterial master batches, and carrying out melt spinning to obtain antibacterial fibers; soaking the antibacterial fiber in an antibacterial solution, stirring at a constant speed and reacting for 2h in a sodium hydroxide solution after the oscillation is finished, carrying out suction filtration, and washing with deionized water for three times to obtain the antibacterial material for the medical protective clothing; the antibacterial composite particles contain halamine functional groups to endow the particles with excellent antibacterial property, and then the polyacrylonitrile resin and the antibacterial composite particles are subjected to melt spinning to prepare antibacterial fibers, so that the materials prepared by the antibacterial fibers have excellent antibacterial property.

Description

Manufacturing process of antibacterial material for medical protective clothing

Technical Field

The invention belongs to the technical field of antibacterial materials, and particularly relates to a manufacturing process of an antibacterial material for medical protective clothing.

Background

The mainstream antibacterial treatment modes in the market at present comprise two modes: one is a built-in silver ion antibacterial fabric, and an antibacterial agent is directly made into chemical fibers by adopting a spinning-grade antibacterial technology; the other is a post-treatment technology, namely adding the mixture through a subsequent shaping process. The post-treatment process is relatively simple, the cost is easy to control according to the specific requirements of customers, and the post-treatment process is the most applied process in the market. The textile fabric composed of the fibers is favorable for the attachment of microorganisms due to the porous object shape and the chemical structure of the high molecular polymer, and becomes a good parasite for the survival and propagation of the microorganisms. The parasites, besides being harmful to the human body, can also contaminate the fibres and thus cannot meet the requirements of medical protective clothing.

The invention CN111705505A discloses a method for preparing an antibacterial fabric of medical protective clothing, which comprises the following steps: s1, preparing raw materials: absolute ethyl alcohol, triethanolamine, butyl titanate, polyethylene glycol 4000, ZnO, deionized water, CO, silicon dioxide, ammonium bicarbonate silver nitrate solution and fabric; s2, TiO₂Preparing sol; s3, preparing nano ZnO; s4, preparing a silver antibacterial agent; s5, mixing TiO₂Mixing the sol, the nano ZnO and the silver antibacterial agent to obtain a mixture; s6, uniformly coating the mixture on the fabric; s7, drying the fabric to obtain the medical protective clothing antibacterial fabric, and the invention relates to the technical field of medical protective clothing.

Disclosure of Invention

In order to overcome the technical problems, the invention provides a manufacturing process of an antibacterial material for medical protective clothing.

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

the textile fabric composed of the fibers is favorable for the attachment of microorganisms due to the porous object shape and the chemical structure of the high molecular polymer, and becomes a good parasite for the survival and propagation of the microorganisms. The parasites, besides being harmful to the human body, can also contaminate the fibres and thus cannot meet the requirements of medical protective clothing.

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

a manufacturing process of an antibacterial material for medical protective clothing comprises the following steps:

firstly, weighing the following raw materials in parts by weight: 20-30 parts of antibacterial composite particles, 25-50 parts of antibacterial liquid, 55-80 parts of polyacrylonitrile resin and 10-15 parts of sodium hydroxide solution with the mass fraction of 10%.

Secondly, uniformly mixing polyacrylonitrile resin and antibacterial composite particles, blending and extruding the mixture by a double-screw extruder for granulation to prepare antibacterial master batches, drying the antibacterial master batches at the temperature of 110-120 ℃ for 6-10h, feeding the dried antibacterial master batches into a feeder of a spinning machine for melt spinning, and controlling the spinning speed to be 2500m/min and the initial pressure of a spinning assembly to be 8MPa to prepare antibacterial fibers;

and secondly, soaking the antibacterial fiber in the antibacterial liquid, ultrasonically oscillating in a water bath at 10-15 ℃ for 10min, controlling the ultrasonic power to be 50-60W, adding a sodium hydroxide solution with the mass fraction of 10% after oscillation is finished, stirring at a constant speed, reacting for 2h, performing suction filtration, and washing with deionized water for three times to obtain the antibacterial material for the medical protective clothing.

Further, the antibacterial composite particle is prepared by the following method:

step S1, adding acrylic acid into a three-neck flask filled with deionized water, uniformly stirring at a rotating speed of 150-;

step S2, adding the first particles into a reaction kettle filled with toluene, stirring at a constant speed for 10min, adding tert-butylamine and triethylene diamine, heating to 100 ℃ and 110 ℃, stirring at a constant speed at the temperature, reacting for 20h, washing the prepared reaction product with absolute ethyl alcohol and deionized water for three times, centrifuging at a rotating speed of 10000r/min for 3min, and drying the filter cake at 65 ℃ for 2h in vacuum to prepare second particles;

step S3, adding the first particles into deionized water, performing ultrasonic dispersion for 30min, controlling the ultrasonic power to be 60-80W, placing the particles into an ice water bath after the ultrasonic dispersion, dropwise adding a sodium hypochlorite aqueous solution with the mass fraction of 1-3%, controlling the dropwise adding time to be 5-10min, adjusting the pH by dropwise adding 0.1mol/L hydrochloric acid while stirring until the pH is 7-8, stirring the particles in the ice water bath at a constant speed of 180-200r/min for 2h after the dropwise adding is finished, centrifuging and washing the particles until the free chlorine is completely removed, performing vacuum drying at 45-60 ℃ for 2h to obtain the antibacterial composite particles, and controlling the dosage ratio of the first particles, the sodium hypochlorite aqueous solution and the deionized water to be 0.5 g: 20 mL.

In step S1, acrylic acid is mixed with styrene in deionized water, sodium persulfate is added as an initiator to prepare a mixed polymer of polystyrene and polyacrylic acid as first particles, then in step S2, the first particles are added into a solvent toluene, in order to enable N-Cl functional groups on the prepared second particles to be more stable, tert-butylamine with larger steric hindrance is added as an aminating agent, triethylene diamine is added as a catalyst, the tert-butylamine performs amination with the first particles to prepare second particles, then the second particles are mixed with 1-3% of sodium hypochlorite aqueous solution, amide groups generated on the second particles can perform chlorination reaction with the sodium hypochlorite to prepare antibacterial composite particles, and the particles contain halamine functional groups to endow the particles with excellent antibacterial property.

Further, the amount ratio of acrylic acid, styrene and sodium persulfate was controlled to 1 g: 1.2 g: 0.03g in step S1, and the amount ratio of the first particles, toluene, t-butylamine and triethylenediamine was controlled to 1 g: 15 mL: 5 mL: 0.05g in step S2.

Further, the antibacterial liquid is prepared by the following method:

step S11, adding cyanuric chloride and acetone into a three-neck flask, transferring the three-neck flask into an ice water bath after magnetic stirring for 15min, continuing stirring for 15min, then dropwise adding 5% by mass of tetramethylpiperidinol aqueous solution into the three-neck flask, controlling the dropwise adding time to be 10-15min, adding 10% by mass of sodium carbonate solution to adjust the pH value, maintaining the pH value of the system to be 7-8, stirring for 2h at the rotating speed of 150 plus 200r/min after the pH value is stable, performing suction filtration after stirring, washing a filter cake for three times by using absolute ethyl alcohol, then transferring the filter cake into a vacuum drying box at the temperature of 55-60 ℃, controlling the vacuum degree of the vacuum drying box to be-0.10 MPa, and controlling the drying time to be 20h to obtain the antibacterial agent;

and S12, adding the antibacterial agent prepared in the step S11 into deionized water, controlling the weight ratio of the precursor to the deionized water to be 1: 8-10, and stirring at the rotating speed of 100-120r/min for 30min to prepare the antibacterial liquid.

Further, in step S11, the weight ratio of cyanuric chloride, acetone and aqueous tetramethylpiperidinol solution is controlled to 1: 5: 0.8-1.

The method comprises the steps of mixing cyanuric chloride and aqueous solution of tetramethyl piperidinol in acetone in step S11 to enable cyanuric chloride and tetramethyl piperidinol to perform nucleophilic substitution reaction, preparing an antibacterial agent by substituting chlorine on cyanuric chloride molecules, and then mixing a precursor with deionized water in step S12 to prepare the antibacterial liquid.

The invention has the beneficial effects that:

(1) the invention relates to an antibacterial material for medical protective clothing, which takes antibacterial composite particles, antibacterial liquid and the like as raw materials, acrylic acid is mixed with styrene in deionized water in step S1 in the preparation process of the antibacterial composite particles, sodium persulfate is added as an initiator to prepare a mixed polymer of polystyrene and polyacrylic acid as first particles, then the first particles are added into toluene in step S2, tert-butylamine with larger steric hindrance is added as an aminating agent in order to stabilize N-Cl functional groups on the prepared second particles, triethylene diamine is added as a catalyst, the tert-butylamine and the first particles are aminated to prepare second particles, then the second particles are mixed with 1-3% of sodium hypochlorite aqueous solution, amide groups generated on the second particles can be chlorinated with the sodium hypochlorite to prepare the antibacterial composite particles, the particles contain halamine functional groups, so that the particles are endowed with excellent antibacterial property, and then the polyacrylonitrile resin and the antibacterial composite particles are subjected to melt spinning to prepare antibacterial fibers, so that the materials prepared by the antibacterial fibers have excellent antibacterial property;

(2) the invention prepares an antibacterial solution, three chlorine atoms connected with carbon atoms on cyanuric chloride molecules and unsaturated bond carbon-nitrogen bond exist in the preparation process, so that the electron cloud density on the carbon atoms is rapidly reduced, and nucleophilic substitution reaction can be further carried out on most of functional groups such as hydroxyl, amino and the like.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.

Example 1

A manufacturing process of an antibacterial material for medical protective clothing comprises the following steps:

firstly, weighing the following raw materials in parts by weight: 20 parts of antibacterial composite particles, 25 parts of antibacterial liquid, 55 parts of polyacrylonitrile resin and 10 parts of sodium hydroxide solution with the mass fraction of 10%.

Secondly, uniformly mixing polyacrylonitrile resin and antibacterial composite particles, blending, extruding and granulating by using a double-screw extruder to obtain antibacterial master batches, drying the antibacterial master batches at 110 ℃ for 6 hours, feeding the dried antibacterial master batches into a feeder of a spinning machine for melt spinning, and controlling the spinning speed to be 2500m/min and the initial pressure of a spinning assembly to be 8MPa to obtain antibacterial fibers;

and secondly, soaking the antibacterial fiber in the antibacterial liquid, ultrasonically oscillating in a water bath at 10 ℃ for 10min, controlling the ultrasonic power to be 50W, adding a sodium hydroxide solution with the mass fraction of 10% after oscillation is finished, stirring at a constant speed, reacting for 2h, performing suction filtration, and washing with deionized water for three times to obtain the antibacterial material for the medical protective clothing.

The antibacterial composite particle is prepared by the following method:

step S1, adding acrylic acid into a three-neck flask filled with deionized water, uniformly stirring at a rotating speed of 150r/min for 30min, adding styrene, uniformly stirring at a rotating speed of 300r/min for 30min, heating to 65 ℃, adding sodium persulfate, introducing nitrogen to discharge air, continuously stirring for 10h, centrifugally separating the prepared reaction product, washing with the deionized water for three times, transferring to vacuum drying at 65 ℃ for 2h to prepare first particles, and controlling the dosage ratio of the acrylic acid, the styrene and the sodium persulfate to be 1 g: 1.2 g: 0.03 g;

step S2, adding the first particles into a reaction kettle filled with toluene, adding tert-butylamine and triethylene diamine after stirring at a constant speed for 10min, heating to 100 ℃, stirring at a constant speed at the temperature and reacting for 20h, washing the prepared reaction product with absolute ethyl alcohol and deionized water three times, centrifuging at a rotating speed of 10000r/min for 3min, drying a filter cake at 65 ℃ for 2h in vacuum to prepare second particles, and controlling the dosage ratio of the first particles, the toluene, the tert-butylamine and the triethylene diamine to be 1 g: 15 mL: 5 mL: 0.05 g;

step S3, adding the first particles into deionized water, performing ultrasonic dispersion for 30min, controlling the ultrasonic power to be 60W, placing the particles into an ice water bath after the ultrasonic dispersion, dropwise adding a sodium hypochlorite aqueous solution with the mass fraction of 1%, controlling the dropwise adding time to be 5min, dropwise adding hydrochloric acid with the concentration of 0.1mol/L while stirring to adjust the pH value until the pH value is 7, stirring the particles in the ice water bath at a constant speed of 200r/min for 2h after the dropwise addition is finished, centrifuging and washing until free chlorine is completely removed, and then performing vacuum drying at 60 ℃ for 2h to obtain the antibacterial composite particles, wherein the dosage ratio of the first particles, the sodium hypochlorite aqueous solution and the deionized water is controlled to be 0.5 g: 20 mL.

The antibacterial liquid is prepared by the following method:

step S11, adding cyanuric chloride and acetone into a three-neck flask, transferring the three-neck flask into an ice water bath after magnetic stirring for 15min, continuing stirring for 15min, then dropwise adding 5% by mass of tetramethylpiperidinol aqueous solution into the three-neck flask, controlling the dropwise adding time to be 10min, adding 10% by mass of sodium carbonate solution to adjust the pH value, maintaining the pH value of the system to be 7, stirring the three-neck flask at a rotating speed of 150 plus 200r/min for 2h after the pH value is stable, performing suction filtration after stirring, washing a filter cake three times by using absolute ethyl alcohol, transferring the filter cake into a vacuum drying box at 55 ℃, controlling the vacuum degree of the vacuum drying box to be-0.10 MPa and the drying time to be 20h, preparing an antibacterial agent, and controlling the weight ratio of the cyanuric chloride, the acetone and the tetramethylpiperidinol aqueous solution to be 1: 5: 0;

and S12, adding the antibacterial agent prepared in the step S11 into deionized water, controlling the weight ratio of the precursor to the deionized water to be 1: 10, and stirring at the rotating speed of 100r/min for 30min to prepare the antibacterial liquid.

Example 2

A manufacturing process of an antibacterial material for medical protective clothing comprises the following steps:

firstly, weighing the following raw materials in parts by weight: 24 parts of antibacterial composite particles, 35 parts of antibacterial liquid, 65 parts of polyacrylonitrile resin and 12 parts of sodium hydroxide solution with the mass fraction of 10%.

Secondly, uniformly mixing polyacrylonitrile resin and antibacterial composite particles, blending, extruding and granulating by using a double-screw extruder to obtain antibacterial master batches, drying the antibacterial master batches at 110 ℃ for 6 hours, feeding the dried antibacterial master batches into a feeder of a spinning machine for melt spinning, and controlling the spinning speed to be 2500m/min and the initial pressure of a spinning assembly to be 8MPa to obtain antibacterial fibers;

and secondly, soaking the antibacterial fiber in the antibacterial liquid, ultrasonically oscillating in a water bath at 10 ℃ for 10min, controlling the ultrasonic power to be 50W, adding a sodium hydroxide solution with the mass fraction of 10% after oscillation is finished, stirring at a constant speed, reacting for 2h, performing suction filtration, and washing with deionized water for three times to obtain the antibacterial material for the medical protective clothing.

The antibacterial composite particle is prepared by the following method:

step S1, adding acrylic acid into a three-neck flask filled with deionized water, uniformly stirring at a rotating speed of 150r/min for 30min, adding styrene, uniformly stirring at a rotating speed of 300r/min for 30min, heating to 65 ℃, adding sodium persulfate, introducing nitrogen to discharge air, continuously stirring for 10h, centrifugally separating the prepared reaction product, washing with the deionized water for three times, transferring to vacuum drying at 65 ℃ for 2h to prepare first particles, and controlling the dosage ratio of the acrylic acid, the styrene and the sodium persulfate to be 1 g: 1.2 g: 0.03 g;

step S2, adding the first particles into a reaction kettle filled with toluene, adding tert-butylamine and triethylene diamine after stirring at a constant speed for 10min, heating to 100 ℃, stirring at a constant speed at the temperature and reacting for 20h, washing the prepared reaction product with absolute ethyl alcohol and deionized water three times, centrifuging at a rotating speed of 10000r/min for 3min, drying a filter cake at 65 ℃ for 2h in vacuum to prepare second particles, and controlling the dosage ratio of the first particles, the toluene, the tert-butylamine and the triethylene diamine to be 1 g: 15 mL: 5 mL: 0.05 g;

step S3, adding the first particles into deionized water, performing ultrasonic dispersion for 30min, controlling the ultrasonic power to be 60W, placing the particles into an ice water bath after the ultrasonic dispersion, dropwise adding a sodium hypochlorite aqueous solution with the mass fraction of 1%, controlling the dropwise adding time to be 5min, dropwise adding hydrochloric acid with the concentration of 0.1mol/L while stirring to adjust the pH value until the pH value is 7, stirring the particles in the ice water bath at a constant speed of 200r/min for 2h after the dropwise addition is finished, centrifuging and washing until free chlorine is completely removed, and then performing vacuum drying at 60 ℃ for 2h to obtain the antibacterial composite particles, wherein the dosage ratio of the first particles, the sodium hypochlorite aqueous solution and the deionized water is controlled to be 0.5 g: 20 mL.

The antibacterial liquid is prepared by the following method:

step S11, adding cyanuric chloride and acetone into a three-neck flask, transferring the three-neck flask into an ice water bath after magnetic stirring for 15min, continuing stirring for 15min, then dropwise adding 5% by mass of tetramethylpiperidinol aqueous solution into the three-neck flask, controlling the dropwise adding time to be 10min, adding 10% by mass of sodium carbonate solution to adjust the pH value, maintaining the pH value of the system to be 7, stirring the three-neck flask at a rotating speed of 150 plus 200r/min for 2h after the pH value is stable, performing suction filtration after stirring, washing a filter cake three times by using absolute ethyl alcohol, transferring the filter cake into a vacuum drying box at 55 ℃, controlling the vacuum degree of the vacuum drying box to be-0.10 MPa and the drying time to be 20h, preparing an antibacterial agent, and controlling the weight ratio of the cyanuric chloride, the acetone and the tetramethylpiperidinol aqueous solution to be 1: 5: 0;

and S12, adding the antibacterial agent prepared in the step S11 into deionized water, controlling the weight ratio of the precursor to the deionized water to be 1: 10, and stirring at the rotating speed of 100r/min for 30min to prepare the antibacterial liquid.

Example 3

A manufacturing process of an antibacterial material for medical protective clothing comprises the following steps:

firstly, weighing the following raw materials in parts by weight: 28 parts of antibacterial composite particles, 45 parts of antibacterial liquid, 70 parts of polyacrylonitrile resin and 14 parts of sodium hydroxide solution with the mass fraction of 10%.

Secondly, uniformly mixing polyacrylonitrile resin and antibacterial composite particles, blending, extruding and granulating by using a double-screw extruder to obtain antibacterial master batches, drying the antibacterial master batches at 110 ℃ for 6 hours, feeding the dried antibacterial master batches into a feeder of a spinning machine for melt spinning, and controlling the spinning speed to be 2500m/min and the initial pressure of a spinning assembly to be 8MPa to obtain antibacterial fibers;

and secondly, soaking the antibacterial fiber in the antibacterial liquid, ultrasonically oscillating in a water bath at 10 ℃ for 10min, controlling the ultrasonic power to be 50W, adding a sodium hydroxide solution with the mass fraction of 10% after oscillation is finished, stirring at a constant speed, reacting for 2h, performing suction filtration, and washing with deionized water for three times to obtain the antibacterial material for the medical protective clothing.

The antibacterial composite particle is prepared by the following method:

step S1, adding acrylic acid into a three-neck flask filled with deionized water, uniformly stirring at a rotating speed of 150r/min for 30min, adding styrene, uniformly stirring at a rotating speed of 300r/min for 30min, heating to 65 ℃, adding sodium persulfate, introducing nitrogen to discharge air, continuously stirring for 10h, centrifugally separating the prepared reaction product, washing with the deionized water for three times, transferring to vacuum drying at 65 ℃ for 2h to prepare first particles, and controlling the dosage ratio of the acrylic acid, the styrene and the sodium persulfate to be 1 g: 1.2 g: 0.03 g;

step S2, adding the first particles into a reaction kettle filled with toluene, adding tert-butylamine and triethylene diamine after stirring at a constant speed for 10min, heating to 100 ℃, stirring at a constant speed at the temperature and reacting for 20h, washing the prepared reaction product with absolute ethyl alcohol and deionized water three times, centrifuging at a rotating speed of 10000r/min for 3min, drying a filter cake at 65 ℃ for 2h in vacuum to prepare second particles, and controlling the dosage ratio of the first particles, the toluene, the tert-butylamine and the triethylene diamine to be 1 g: 15 mL: 5 mL: 0.05 g;

step S3, adding the first particles into deionized water, performing ultrasonic dispersion for 30min, controlling the ultrasonic power to be 60W, placing the particles into an ice water bath after the ultrasonic dispersion, dropwise adding a sodium hypochlorite aqueous solution with the mass fraction of 1%, controlling the dropwise adding time to be 5min, dropwise adding hydrochloric acid with the concentration of 0.1mol/L while stirring to adjust the pH value until the pH value is 7, stirring the particles in the ice water bath at a constant speed of 200r/min for 2h after the dropwise addition is finished, centrifuging and washing until free chlorine is completely removed, and then performing vacuum drying at 60 ℃ for 2h to obtain the antibacterial composite particles, wherein the dosage ratio of the first particles, the sodium hypochlorite aqueous solution and the deionized water is controlled to be 0.5 g: 20 mL.

The antibacterial liquid is prepared by the following method:

step S11, adding cyanuric chloride and acetone into a three-neck flask, transferring the three-neck flask into an ice water bath after magnetic stirring for 15min, continuing stirring for 15min, then dropwise adding 5% by mass of tetramethylpiperidinol aqueous solution into the three-neck flask, controlling the dropwise adding time to be 10min, adding 10% by mass of sodium carbonate solution to adjust the pH value, maintaining the pH value of the system to be 7, stirring the three-neck flask at a rotating speed of 150 plus 200r/min for 2h after the pH value is stable, performing suction filtration after stirring, washing a filter cake three times by using absolute ethyl alcohol, transferring the filter cake into a vacuum drying box at 55 ℃, controlling the vacuum degree of the vacuum drying box to be-0.10 MPa and the drying time to be 20h, preparing an antibacterial agent, and controlling the weight ratio of the cyanuric chloride, the acetone and the tetramethylpiperidinol aqueous solution to be 1: 5: 0;

and S12, adding the antibacterial agent prepared in the step S11 into deionized water, controlling the weight ratio of the precursor to the deionized water to be 1: 10, and stirring at the rotating speed of 100r/min for 30min to prepare the antibacterial liquid.

Example 4

A manufacturing process of an antibacterial material for medical protective clothing comprises the following steps:

firstly, weighing the following raw materials in parts by weight: 30 parts of antibacterial composite particles, 50 parts of antibacterial liquid, 80 parts of polyacrylonitrile resin and 15 parts of sodium hydroxide solution with the mass fraction of 10%.

Secondly, uniformly mixing polyacrylonitrile resin and antibacterial composite particles, blending, extruding and granulating by using a double-screw extruder to obtain antibacterial master batches, drying the antibacterial master batches at 110 ℃ for 6 hours, feeding the dried antibacterial master batches into a feeder of a spinning machine for melt spinning, and controlling the spinning speed to be 2500m/min and the initial pressure of a spinning assembly to be 8MPa to obtain antibacterial fibers;

and secondly, soaking the antibacterial fiber in the antibacterial liquid, ultrasonically oscillating in a water bath at 10 ℃ for 10min, controlling the ultrasonic power to be 50W, adding a sodium hydroxide solution with the mass fraction of 10% after oscillation is finished, stirring at a constant speed, reacting for 2h, performing suction filtration, and washing with deionized water for three times to obtain the antibacterial material for the medical protective clothing.

The antibacterial composite particle is prepared by the following method:

step S1, adding acrylic acid into a three-neck flask filled with deionized water, uniformly stirring at a rotating speed of 150r/min for 30min, adding styrene, uniformly stirring at a rotating speed of 300r/min for 30min, heating to 65 ℃, adding sodium persulfate, introducing nitrogen to discharge air, continuously stirring for 10h, centrifugally separating the prepared reaction product, washing with the deionized water for three times, transferring to vacuum drying at 65 ℃ for 2h to prepare first particles, and controlling the dosage ratio of the acrylic acid, the styrene and the sodium persulfate to be 1 g: 1.2 g: 0.03 g;

step S2, adding the first particles into a reaction kettle filled with toluene, adding tert-butylamine and triethylene diamine after stirring at a constant speed for 10min, heating to 100 ℃, stirring at a constant speed at the temperature and reacting for 20h, washing the prepared reaction product with absolute ethyl alcohol and deionized water three times, centrifuging at a rotating speed of 10000r/min for 3min, drying a filter cake at 65 ℃ for 2h in vacuum to prepare second particles, and controlling the dosage ratio of the first particles, the toluene, the tert-butylamine and the triethylene diamine to be 1 g: 15 mL: 5 mL: 0.05 g;

step S3, adding the first particles into deionized water, performing ultrasonic dispersion for 30min, controlling the ultrasonic power to be 60W, placing the particles into an ice water bath after the ultrasonic dispersion, dropwise adding a sodium hypochlorite aqueous solution with the mass fraction of 1%, controlling the dropwise adding time to be 5min, dropwise adding hydrochloric acid with the concentration of 0.1mol/L while stirring to adjust the pH value until the pH value is 7, stirring the particles in the ice water bath at a constant speed of 200r/min for 2h after the dropwise addition is finished, centrifuging and washing until free chlorine is completely removed, and then performing vacuum drying at 60 ℃ for 2h to obtain the antibacterial composite particles, wherein the dosage ratio of the first particles, the sodium hypochlorite aqueous solution and the deionized water is controlled to be 0.5 g: 20 mL.

The antibacterial liquid is prepared by the following method:

step S11, adding cyanuric chloride and acetone into a three-neck flask, transferring the three-neck flask into an ice water bath after magnetic stirring for 15min, continuing stirring for 15min, then dropwise adding 5% by mass of tetramethylpiperidinol aqueous solution into the three-neck flask, controlling the dropwise adding time to be 10min, adding 10% by mass of sodium carbonate solution to adjust the pH value, maintaining the pH value of the system to be 7, stirring the three-neck flask at a rotating speed of 150 plus 200r/min for 2h after the pH value is stable, performing suction filtration after stirring, washing a filter cake three times by using absolute ethyl alcohol, transferring the filter cake into a vacuum drying box at 55 ℃, controlling the vacuum degree of the vacuum drying box to be-0.10 MPa and the drying time to be 20h, preparing an antibacterial agent, and controlling the weight ratio of the cyanuric chloride, the acetone and the tetramethylpiperidinol aqueous solution to be 1: 5: 0;

and S12, adding the antibacterial agent prepared in the step S11 into deionized water, controlling the weight ratio of the precursor to the deionized water to be 1: 10, and stirring at the rotating speed of 100r/min for 30min to prepare the antibacterial liquid.

Comparative example 1

Compared with example 1, the preparation method of the comparative example is as follows without adding the antibacterial composite particles:

firstly, weighing the following raw materials in parts by weight: 25 parts of antibacterial liquid, 55 parts of polyacrylonitrile resin and 10 parts of sodium hydroxide solution with the mass fraction of 10%.

Secondly, blending, extruding and granulating polyacrylonitrile resin by a double-screw extruder to obtain master batches, drying the master batches at 110 ℃ for 6 hours, feeding the master batches into a feeder of a spinning machine for melt spinning, and controlling the spinning speed to be 2500m/min and the initial pressure of a spinning assembly to be 8MPa to obtain fibers;

and secondly, soaking the fiber in an antibacterial solution, carrying out ultrasonic oscillation in a water bath at 10 ℃ for 10min, controlling the ultrasonic power to be 50W, adding a sodium hydroxide solution with the mass fraction of 10% after the oscillation is finished, stirring at a constant speed, reacting for 2h, carrying out suction filtration, and washing with deionized water for three times to obtain the antibacterial material for the medical protective clothing.

Comparative example 2

Compared with example 1, the comparative example is not soaked in the antibacterial liquid, and the preparation method is as follows:

firstly, weighing the following raw materials in parts by weight: 20 parts of antibacterial composite particles, 55 parts of polyacrylonitrile resin and 10 parts of sodium hydroxide solution with the mass fraction of 10%.

And secondly, uniformly mixing the polyacrylonitrile resin and the antibacterial composite particles, blending and extruding the mixture by using a double-screw extruder for granulation to prepare antibacterial master batches, drying the antibacterial master batches at 110 ℃ for 6 hours, feeding the dried antibacterial master batches into a feeder of a spinning machine for melt spinning, and controlling the spinning speed to be 2500m/min and the initial pressure of a spinning assembly to be 8MPa to prepare the antibacterial material for the medical protective clothing.

Comparative example 3

The comparative example is an antibacterial material for medical protection in the market.

The antibacterial properties of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in the following table:

as can be seen from the above table, the bacteriostatic ratio of the examples 1-4 to Escherichia coli is 99.3-99.8%, the bacteriostatic ratio to Staphylococcus aureus is 95.8-96.5%, the bacteriostatic ratio of the comparative examples 1-3 to Escherichia coli is 82.5-88.5%, and the bacteriostatic ratio to Staphylococcus aureus is 80.3-85.6%; the method comprises the steps of carrying out amination on tert-butylamine and first particles to prepare second particles, mixing the second particles with 1-3% of sodium hypochlorite aqueous solution, carrying out chlorination reaction on amide groups generated on the second particles and the sodium hypochlorite to prepare antibacterial composite particles, wherein the particles contain halamine functional groups to endow the particles with excellent antibacterial property, and carrying out melt spinning on polyacrylonitrile resin and the antibacterial composite particles to prepare antibacterial fibers to endow the materials prepared by the antibacterial composite particles with excellent antibacterial property.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims (5)

1. A manufacturing process of an antibacterial material for medical protective clothing is characterized by comprising the following steps:

firstly, weighing the following raw materials in parts by weight: 20-30 parts of antibacterial composite particles, 25-50 parts of antibacterial liquid, 55-80 parts of polyacrylonitrile resin and 10-15 parts of sodium hydroxide solution with the mass fraction of 10%;

secondly, uniformly mixing polyacrylonitrile resin and antibacterial composite particles, blending and extruding the mixture by a double-screw extruder for granulation to prepare antibacterial master batches, drying the antibacterial master batches at the temperature of 110-120 ℃ for 6-10h, feeding the dried antibacterial master batches into a feeder of a spinning machine for melt spinning, and controlling the spinning speed to be 2500m/min and the initial pressure of a spinning assembly to be 8MPa to prepare antibacterial fibers;

and secondly, soaking the antibacterial fiber in the antibacterial liquid, ultrasonically oscillating in a water bath at 10-15 ℃ for 10min, controlling the ultrasonic power to be 50-60W, adding a sodium hydroxide solution with the mass fraction of 10% after oscillation is finished, stirring at a constant speed, reacting for 2h, performing suction filtration, and washing with deionized water for three times to obtain the antibacterial material for the medical protective clothing.

2. The process for preparing the antibacterial material for the medical protective clothing according to claim 1, wherein the antibacterial composite particles are prepared by the following method:

step S1, adding acrylic acid into a three-neck flask filled with deionized water, uniformly stirring at a rotating speed of 150-;

step S2, adding the first particles into a reaction kettle filled with toluene, stirring at a constant speed for 10min, adding tert-butylamine and triethylene diamine, heating to 100 ℃ and 110 ℃, stirring at a constant speed at the temperature, reacting for 20h, washing the prepared reaction product with absolute ethyl alcohol and deionized water for three times, centrifuging at a rotating speed of 10000r/min for 3min, and drying the filter cake at 65 ℃ for 2h in vacuum to prepare second particles;

step S3, adding the first particles into deionized water, performing ultrasonic dispersion for 30min, controlling the ultrasonic power to be 60-80W, placing the particles into an ice water bath after the ultrasonic dispersion, dropwise adding a sodium hypochlorite aqueous solution with the mass fraction of 1-3%, controlling the dropwise adding time to be 5-10min, adjusting the pH by dropwise adding 0.1mol/L hydrochloric acid while stirring until the pH is 7-8, stirring the particles in the ice water bath at a constant speed of 180-200r/min for 2h after the dropwise adding is finished, centrifuging and washing the particles until the free chlorine is completely removed, performing vacuum drying at 45-60 ℃ for 2h to obtain the antibacterial composite particles, and controlling the dosage ratio of the first particles, the sodium hypochlorite aqueous solution and the deionized water to be 0.5 g: 20 mL.

3. The process of claim 2, wherein the ratio of the acrylic acid, styrene and sodium persulfate in step S1 is controlled to be 1 g: 1.2 g: 0.03g, and the ratio of the first particles, toluene, tert-butylamine and triethylenediamine in step S2 is controlled to be 1 g: 15 mL: 5 mL: 0.05 g.

4. The process for preparing the antibacterial material for the medical protective clothing according to claim 1, wherein the antibacterial liquid is prepared by the following method:

step S11, adding cyanuric chloride and acetone into a three-neck flask, transferring the three-neck flask into an ice water bath after magnetic stirring for 15min, continuing stirring for 15min, then dropwise adding 5% by mass of tetramethylpiperidinol aqueous solution into the three-neck flask, controlling the dropwise adding time to be 10-15min, adding 10% by mass of sodium carbonate solution to adjust the pH value, maintaining the pH value of the system to be 7-8, stirring for 2h at the rotating speed of 150 plus 200r/min after the pH value is stable, performing suction filtration after stirring, washing a filter cake for three times by using absolute ethyl alcohol, then transferring the filter cake into a vacuum drying box at the temperature of 55-60 ℃, controlling the vacuum degree of the vacuum drying box to be-0.10 MPa, and controlling the drying time to be 20h to obtain the antibacterial agent;

and S12, adding the antibacterial agent prepared in the step S11 into deionized water, controlling the weight ratio of the precursor to the deionized water to be 1: 8-10, and stirring at the rotating speed of 100-120r/min for 30min to prepare the antibacterial liquid.

5. The process for preparing the antibacterial material for medical protective clothing according to claim 4, wherein the weight ratio of cyanuric chloride, acetone and aqueous solution of tetramethyl piperidinol in step S11 is controlled to 1: 5: 0.8-1.