CN113699787B - Antibacterial anti-static fiber coating and preparation method thereof - Google Patents
Antibacterial anti-static fiber coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antibacterial anti-static fiber coating and a preparation method thereof. The method comprises the steps of firstly reacting carboxymethyl chitosan with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to prepare carboxymethyl chitosan, then reacting with potassium borohydride, adding lactose to prepare modified carboxymethyl chitosan quaternary ammonium salt, then reacting with triethylene tetramine and graphene oxide to prepare modified graphene oxide, then carrying out ultrasonic treatment and mixing on the modified carboxymethyl chitosan quaternary ammonium salt and the modified graphene, finally reacting with a resin mixed solution, cooling, and drying to obtain the antibacterial and antistatic fiber coating. The antibacterial and antistatic fiber coating prepared by the invention has excellent antibacterial property and antistatic capability.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to an antibacterial and antistatic fiber coating and a preparation method thereof.
Background
The coating is the most important of textile industry, along with the development of society, the science and technology of the coating are changed day by day, in order to adapt to the needs of various high-tech and people's life, the development of functional coatings with various special properties has extremely important significance to the development of society and the improvement of people's living standard.
The microorganisms in the environment are widely distributed, and although the microorganisms are the smallest organic substances, the microorganisms can damage our bodies in different ways and cause various infectious diseases. Controlling the growth of microorganisms on clothing is vital to create a healthy, hygienic, fresh environment. Conventional fabrics must be chemically treated to limit the growth of microorganisms. The growth rate of bacteria in the textile is high, and the bacteria directly contact the skin of people, so that the safety of the textile becomes very important. The new antibacterial coating is one of the special coatings developed specifically for this purpose. It can effectively kill microorganisms and control bacterial growth by antibacterial treatment of textile fibers.
The traditional antibacterial coating is an additive antibacterial coating, and is prepared by adding an antibacterial agent which has an antibacterial function and can stably exist in the coating and processing the antibacterial agent by a certain process, and the coating with the antibacterial function is mainly divided into an inorganic antibacterial coating, a natural antibacterial coating, an organic antibacterial coating and a composite antibacterial coating.
Meanwhile, with the development of high and new technologies and the wide application of polymer materials, the electrostatic problem is more and more regarded in various aspects. When rubbing occurs against the fabric, the two rubbed skins become two opposing charges. As the friction continues, the textile surface develops an electric current and the strength continues to increase until the surface touches or comes into proximity with another conductor, such as a metal heater, or a metal door handle, at which point the static charge disappears. Sparks may be generated therebetween and the wearer may also feel an electric shock, which is uncomfortable. Static electricity also causes the cloth to stick to the human body. Another problem with static electricity is that the charged textiles will collect or carry particles of dust, ash, leaving an imperceptible spot on the surface of the garment.
At present, common antistatic coatings are classified into conductive inorganic antistatic coatings and surfactant antistatic coatings. The conductive inorganic substance coating is formed by adding various inorganic conductive materials such as copper, aluminum, alloy fibers, stainless steel fibers and the like into a high polymer material, and although the cost is low, the addition amount is large, the inorganic conductive material is easy to oxidize, the mechanical property and the stability of the material are influenced, and the coloring and the appearance are difficult to influence; the antistatic coating of the surfactant has better antistatic capability and more stability, but the antistatic coating depends on the humidity of the environment seriously, and the formation of a water sliding layer is influenced if the humidity is too low, so that the antistatic performance is influenced, and even the antistatic effect disappears too early. Therefore, a permanent antistatic coating which is independent of environment, strong in antistatic ability and good in stability needs to be prepared.
Disclosure of Invention
The invention aims to provide an antibacterial and antistatic fiber coating and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the antibacterial and antistatic fiber coating is characterized by mainly comprising 1-2 parts by weight of modified carboxymethyl chitosan quaternary ammonium salt and 4-16 parts by weight of aminated modified graphene.
Further, the antibacterial and antistatic fiber coating is characterized in that the modified carboxymethyl chitosan is prepared from carboxymethyl chitosan, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, potassium borohydride and lactose.
Furthermore, the antibacterial and antistatic fiber coating is characterized in that the aminated modified graphene is prepared from graphite oxide and triethylene tetramine.
Further, the antibacterial and antistatic fiber coating is characterized by comprising the following raw material components in parts by weight: 2 parts of modified carboxymethyl chitosan quaternary ammonium salt and 16 parts of aminated modified graphene.
Further, the preparation method of the antibacterial and antistatic fiber coating is characterized by mainly comprising the following preparation steps:
(1) adding carboxymethyl chitosan into a stirring reflux device, taking isopropanol and sodium hydroxide aqueous solution, stirring, alkalizing, dropwise adding 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, washing, and drying to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) putting potassium borocyanide into a sodium hydroxide aqueous solution, and stirring and dissolving to obtain a potassium borocyanide saturated solution;
(3) dissolving the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1) in water, adding lactose while stirring, adding the potassium borocyanide saturated solution obtained in the step (2), washing, and drying to obtain a modified carboxymethyl chitosan quaternary ammonium salt;
(4) carrying out ultrasonic treatment on graphite oxide to obtain a suspension, and adding triethylene tetramine and dicyclohexylcarbodiimide to prepare modified graphene oxide;
(5) mixing the modified graphene oxide obtained in the step (4) with the modified carboxymethyl chitosan quaternary ammonium salt obtained in the step (3), performing ultrasonic dispersion in ice bath, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, and stirring for reaction to obtain the modified graphene oxide-carboxymethyl chitosan quaternary ammonium salt;
(6) and (3) uniformly stirring the modified graphene oxide-carboxymethyl chitosan quaternary ammonium salt obtained in the step (5) with methyl methacrylate, butyl acrylate and solvent n-butyl alcohol, adding an initiator, cooling and discharging to obtain the antibacterial antistatic fiber coating.
Further, the preparation method of the antibacterial and antistatic fiber coating is characterized by mainly comprising the following preparation steps:
(1) adding carboxymethyl chitosan into a three-necked bottle with a stirring and refluxing device, adding isopropanol 7 times the mass of the carboxymethyl chitosan and a 40% sodium hydroxide aqueous solution 1 time the mass of the carboxymethyl chitosan, stirring, heating in a water bath to raise the temperature of the materials to 45.0 ℃, and continuously stirring and alkalizing for 1h to obtain a mixed solution; then slowly dripping a 40 mass percent 3-chloro-2 hydroxypropyl trimethyl ammonium chloride solution into the mixed solution at a speed of 15 drops/min, and controlling the titration time to be 1-2 h; after reacting for 8 hours, adjusting the pH value to 7.0 by using 0.5mol/L hydrochloric acid, and filtering to obtain filter residue; soaking filter residues in 85% methanol aqueous solution, wherein the mass ratio of the filter residues to the methanol aqueous solution is 1:1, washing the filter residues for 5-6 times by using the 85% methanol aqueous solution, carrying out suction filtration, washing the filter residues by using absolute ethyl alcohol with the mass being 5 times that of carboxymethyl chitosan, soaking the filter residues, and carrying out suction filtration to obtain a solid material; finally, the solid material is placed in a dryer and dried for 1h at the temperature of 80 ℃ to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) grinding the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1), adding distilled water with the mass being 20 times that of the carboxymethyl chitosan quaternary ammonium salt, stirring until the distilled water is dissolved, adding absolute ethyl alcohol with the mass being 48 times that of the carboxymethyl chitosan quaternary ammonium salt, precipitating, filtering, washing for 2-3 times by using the absolute ethyl alcohol, and drying for 1h at the temperature of 80 ℃ to obtain the refined carboxymethyl chitosan quaternary ammonium salt;
(3) mixing potassium borocyanide with 10% sodium hydroxide which is 0.5 times of the weight of the potassium borocyanide, stirring until the potassium borocyanide is not dissolved, and filtering to obtain a saturated potassium borocyanide solution;
(4) dissolving the refined carboxymethyl chitosan quaternary ammonium salt obtained in the step (2) in water 29 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt, adding lactose 2.5 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt while stirring, reacting at room temperature for 2 hours, then adding the saturated potassium borocyanide solution obtained in the step (3) at a rate of 1mL/min, controlling the time to be 0.5-1 hour, reacting for 24 hours, precipitating a product by using an acetone solution 73 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt, washing the precipitate for 5-6 times by using 70% ethanol, and drying at 80 ℃ for 1 hour to obtain the modified carboxymethyl chitosan quaternary ammonium salt;
(5) adding graphite oxide into dimethylformamide with the mass being 944 times that of the graphite oxide, carrying out ultrasonic treatment for 2.5 hours under the condition of 22kHz to obtain a graphene oxide suspension, then adding triethylene tetramine with the mass being 150 times that of the graphite oxide and dicyclohexyl carbodiimide with the mass being 25 times that of the graphite oxide, carrying out ultrasonic treatment for 5 minutes under the condition of 22kHz, carrying out reaction for 48 hours at 120 ℃, adding absolute ethyl alcohol with the mass being 237 times that of the graphite oxide, standing for 12 hours, removing supernatant, filtering lower-layer precipitate with a polytetrafluoroethylene film, washing for 7-8 times with ethanol and deionized water, and drying at 70 ℃ to obtain modified graphene;
(6) mixing the modified graphene obtained in the step (5) with the modified carboxymethyl chitosan quaternary ammonium salt obtained in the step (4), adding the mixture into deionized water 120 times the mass of the modified graphene, fully mixing, then performing ultrasonic dispersion for 3 hours in a water bath at 0-3 ℃ under the condition of 25kHz to obtain the modified graphene-carboxymethyl chitosan quaternary ammonium salt, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride 0.1 times the mass of the modified graphene-carboxymethyl chitosan quaternary ammonium salt and N-hydroxysuccinimide 0.06 times the mass of the modified graphene-carboxymethyl chitosan quaternary ammonium salt, stirring and reacting for 48 hours at room temperature, performing ultrasonic treatment for 30 minutes on the mixture under the condition of 22kHz when the reaction is performed for 24 hours, after the reaction is finished, placing the mixture into deionized water for dialysis for three days, wherein the molecular weight cutoff is 12-14 kDa, then freeze-drying to obtain dark gray modified graphene-carboxymethyl chitosan quaternary ammonium salt powder;
(7) stirring n-butanol and the modified graphene-carboxymethyl chitosan quaternary ammonium salt powder obtained in the step (6) and the resin mixture uniformly according to the mass ratio of 1.5:1:1 to obtain a mixed solution, adding the mixed solution of 1/3 into a three-neck flask, magnetically stirring, heating to 95 ℃, and keeping the temperature for 0.5 h; dissolving an initiator azodiisobutyronitrile with the mass 1 time that of the modified graphene-carboxymethyl chitosan quaternary ammonium salt into an acetone solution with the mass 50 times that of the modified graphene-carboxymethyl chitosan quaternary ammonium salt, then pouring the solution into a constant-pressure dropping funnel, adding the other 2/3 mixed solution into the other constant-pressure funnel, simultaneously dropping the rest 2/3 mixed solution and the initiator benzoyl peroxide by 20 drops/min, and controlling the dropping within 1 hour; after finishing dripping, reacting for 1h at 95 ℃, cooling and discharging, coating the mixture on the surface of the fiber for 0.01-0.03 mm, and drying for 2h at 100-120 ℃ to obtain the antibacterial and antistatic fiber coating.
Further, the preparation method of the antibacterial and antistatic fiber coating is characterized in that the dropping speed in the step (1) is 15 drops/min; the material temperature is controlled at 50-60 ℃.
Further, the preparation method of the antibacterial antistatic fiber coating is characterized in that the mass ratio of the modified graphene to the modified carboxymethyl chitosan quaternary ammonium salt in the step (6) is 1: 4-1: 8.
Further, the preparation method of the antibacterial and antistatic fiber coating is characterized in that the resin mixed solution in the step (7) is prepared by mixing methyl methacrylate, butyl methacrylate and butyl acrylate according to the mass ratio of 2:1: 1; the drying temperature is kept at 140-150 ℃.
Compared with the prior art, the invention has the following beneficial effects:
when the antibacterial antistatic fiber coating is prepared, modified graphene and modified carboxymethyl chitosan quaternary ammonium salt are used as raw materials. Firstly, the modified graphene is subjected to amidation reaction with graphene oxide by taking triethylene tetramine as a raw material to prepare aminated modified graphene, wherein the triethylene tetramine has nucleophilicity and can react with carboxyl in the graphene oxide, carbonyl forms an imine structure and has a strong-tension epoxy group to perform substitution reaction to form an open-loop product, so that the average size of modified graphene microcrystals is reduced, the lamella is more compact and smoother, the van der Waals force and pi-pi action are weakened, stable chemical bond combination can be formed with an organic solvent and a polymer, the interface binding force with the polymer is improved, and the compatibility with an antibacterial antistatic polymer is enhanced.
Secondly, the modified graphene and the modified carboxymethyl chitosan quaternary ammonium salt react to prepare the modified graphene-quaternary ammonium salt, positive charges in the quaternary ammonium salt group interact with carboxyl groups with negative charges on the surface of the modified graphene through electrostatic interaction, so that the modified graphene is combined to the surface of the modified graphene or inserted between the modified graphene layers, the interaction force between the modified graphene layers is weakened, the stacking number of the modified graphene-carboxymethyl chitosan quaternary ammonium salt nano composite layers is reduced, the size distribution of the layers is more uniform, the compound is more stable and can exist even at high temperature, therefore, the antibacterial performance of the modified graphene-carboxymethyl chitosan quaternary ammonium salt not only comes from the simple stacking sterilization effect of the modified graphene and the modified carboxymethyl chitosan quaternary ammonium salt, but also comes from the synergistic effect of the two substances and can destroy bacterial cell membranes more quickly, thereby having wider antibacterial range and stronger antibacterial ability;
moreover, the quaternary ammonium salt structure is provided with positive ions, a physical electric field generated by the quaternary ammonium salt structure adsorbs charges with negative charges, so that the static charges are quickly leaked, double bonds in the quaternary ammonium salt molecular structure are polymerized with methyl methacrylate, butyl methacrylate and butyl acrylate free radicals, the antibacterial and antistatic quaternary ammonium salt group is connected to the high polymer resin, so that the antistatic capability of the coating is shown, and meanwhile, lactose containing a plurality of hydroxyl functional groups is introduced in the process of preparing the modified quaternary ammonium salt, so that the polarity of the hydrophilic group of the modified graphene-carboxymethyl chitosan is increased, the moisture of the environment is more easily absorbed, a thin layer of continuous water phase is generated on the coating, the release of the charges on the surface of the coating is facilitated, and the antistatic capability of the modified graphene-carboxymethyl chitosan quaternary ammonium salt is improved.
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.
In order to more clearly illustrate the method provided by the present invention, the following examples are provided to illustrate the method of the present invention, and the method for testing each index of the antibacterial and antistatic fiber coating prepared in the following examples is as follows:
the sterilization rate is as follows: the antibacterial rate of the antibacterial and antistatic fiber coating obtained in each example and the antibacterial rate of the comparative product are tested by adopting an agar diffusion experiment and a plate counting method.
Resistivity: and (3) measuring the resistivities of the antibacterial and antistatic fiber coatings obtained in the examples and the comparative products by using a surface resistance tester.
Example 1
An antibacterial antistatic fiber coating and a preparation method thereof, which mainly comprise the following components in parts by weight: 2 parts of modified carboxymethyl chitosan quaternary ammonium salt and 16 parts of aminated modified graphene.
A preparation method of an antibacterial anti-static fiber coating mainly comprises the following preparation steps:
(1) adding carboxymethyl chitosan into a three-necked bottle with a stirring and refluxing device, adding isopropanol 7 times the mass of the carboxymethyl chitosan and a 40% sodium hydroxide aqueous solution 1 time the mass of the carboxymethyl chitosan, stirring, heating in a water bath to raise the temperature of the materials to 45.0 ℃, and continuously stirring and alkalizing for 1h to obtain a mixed solution; then slowly dripping a 40 percent solution of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the mixed solution at 15 drops/min, and controlling the titration time to be 1 h; after reacting for 8 hours, adjusting the pH value to 7.0 by using 0.5mol/L hydrochloric acid, and filtering to obtain filter residue; soaking filter residue in 85% methanol water solution with the mass of 1:1, washing with 85% methanol water solution for 5 times, vacuum filtering, washing with anhydrous ethanol 5 times of carboxymethyl chitosan, soaking, and vacuum filtering to obtain solid material; finally, the solid material is placed in a dryer and dried for 1h at the temperature of 80 ℃ to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) grinding the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1), adding distilled water with the mass being 20 times that of the carboxymethyl chitosan quaternary ammonium salt, stirring until the carboxymethyl chitosan quaternary ammonium salt is dissolved, adding absolute ethyl alcohol with the mass being 48 times that of the carboxymethyl chitosan quaternary ammonium salt, precipitating, filtering, washing for 2 times by using the absolute ethyl alcohol, and drying for 1h at the temperature of 80 ℃ to obtain the refined carboxymethyl chitosan quaternary ammonium salt;
(3) mixing potassium borocyanide with 10% sodium hydroxide which is 0.5 times of the weight of the potassium borocyanide, stirring until the potassium borocyanide is not dissolved, and filtering to obtain a saturated potassium borocyanide solution;
(4) dissolving the refined carboxymethyl chitosan quaternary ammonium salt obtained in the step (2) in water 29 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt, adding lactose 2.5 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt while stirring, reacting at room temperature for 2 hours, then adding the saturated potassium borocyanide solution obtained in the step (3) at a rate of 1mL/min, controlling the time to be 1 hour, reacting for 24 hours, precipitating a product by using an acetone solution 73 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt, washing the precipitate for 6 times by using 70% ethanol, and drying at 80 ℃ for 1 hour to obtain the modified carboxymethyl chitosan quaternary ammonium salt;
(5) adding graphite oxide into dimethylformamide with the mass being 944 times that of the graphite oxide, carrying out ultrasonic treatment for 2.5 hours under the condition of 22kHz to obtain a graphene oxide suspension, then adding triethylene tetramine with the mass being 150 times that of the graphite oxide and dicyclohexyl carbodiimide with the mass being 25 times that of the graphite oxide, carrying out ultrasonic treatment for 5 minutes under the condition of 22kHz, reacting for 48 hours at 120 ℃, adding absolute ethyl alcohol with the mass being 237 times that of the graphite oxide, standing for 12 hours, removing supernatant, filtering lower-layer precipitate with a polytetrafluoroethylene film, washing for 7 times with ethanol and deionized water, and drying at 70 ℃ to obtain modified graphene;
(6) mixing the modified graphene obtained in the step (5) with the modified carboxymethyl chitosan quaternary ammonium salt obtained in the step (4), adding deionized water with the mass being 120 times that of the modified graphene, fully mixing, then ultrasonically dispersing for 3 hours in water bath at the temperature of 0 ℃ under the condition of 25kHz to prepare modified graphene-modified carboxymethyl chitosan quaternary ammonium salt, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride which is 0.1 time of the mass of the modified graphene-modified carboxymethyl chitosan quaternary ammonium salt and N-hydroxysuccinimide which is 0.06 time of the mass of the modified graphene-modified carboxymethyl chitosan quaternary ammonium salt, stirring and reacting for 48 hours at room temperature, when the reaction time is 24 hours, the mixture is treated by ultrasonic treatment for 30 minutes under the condition of 22kHz, after the reaction is finished, the mixture is placed in deionized water for dialysis for three days, then freeze-drying to obtain dark gray modified graphene-modified carboxymethyl chitosan quaternary ammonium salt powder;
(7) stirring n-butanol and the modified graphene-modified carboxymethyl chitosan quaternary ammonium salt powder obtained in the step (6) and the resin mixture uniformly according to the mass ratio of 1.5:1:1 to obtain a mixed solution, adding the mixed solution of 1/3 into a three-neck flask, magnetically stirring, heating to 95 ℃, and keeping the temperature for 0.5 h; dissolving an initiator azobisisobutyronitrile with the mass of 1 time of that of the modified graphene-carboxymethyl chitosan quaternary ammonium salt into an acetone solution with the mass of 50 times of that of the modified graphene-carboxymethyl chitosan quaternary ammonium salt, then pouring the solution into a constant-pressure dropping funnel, adding the other 2/3 mixed solution into the other constant-pressure funnel, simultaneously dropping the rest 2/3 mixed solution and the initiator benzoyl peroxide at 20 drops/min, and controlling the dropping within 1 hour; after dripping, reacting for 1h at 95 ℃, cooling and discharging, coating the fiber surface for 0.01mm, and drying for 2h at 100-120 ℃ to obtain the antibacterial and antistatic fiber coating.
Further, the preparation method of the antibacterial and antistatic fiber coating is characterized in that the dropping speed in the step (1) is 15 drops/min; the temperature of the material was controlled at 50 ℃.
Further, the preparation method of the antibacterial antistatic fiber coating is characterized in that the mass ratio of the modified graphene to the modified carboxymethyl chitosan quaternary ammonium salt in the step (6) is 1: 8.
Further, the preparation method of the antibacterial antistatic fiber coating is characterized in that the resin mixed solution in the step (7) is prepared by mixing methyl methacrylate, butyl methacrylate and butyl acrylate according to the mass ratio of 2:1: 1; the drying temperature was maintained at 140 ℃.
Example 2
An antibacterial antistatic fiber coating and a preparation method thereof, which mainly comprise the following components in parts by weight: 2 parts of carboxymethyl chitosan quaternary ammonium salt and 16 parts of aminated modified graphene.
A preparation method of an antibacterial and antistatic fiber coating mainly comprises the following preparation steps:
(1) adding carboxymethyl chitosan into a three-necked bottle with a stirring and refluxing device, adding isopropanol 7 times the mass of the carboxymethyl chitosan and a 40% sodium hydroxide aqueous solution 1 time the mass of the carboxymethyl chitosan, stirring, heating in a water bath to raise the temperature of the materials to 45.0 ℃, and continuously stirring and alkalizing for 1h to obtain a mixed solution; then slowly dripping a 40 percent solution of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the mixed solution at 15 drops/min, and controlling the titration time to be 1 h; after reacting for 8 hours, adjusting the pH value to 7.0 by using 0.5mol/L hydrochloric acid, and filtering to obtain filter residue; soaking filter residue in 85% methanol water solution with the mass of 1:1, washing with 85% methanol water solution for 5 times, vacuum filtering, washing with anhydrous ethanol 5 times of carboxymethyl chitosan, soaking, and vacuum filtering to obtain solid material; finally, the solid material is placed in a dryer and dried for 1h at the temperature of 80 ℃ to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) grinding the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1), adding distilled water with the mass being 20 times that of the carboxymethyl chitosan quaternary ammonium salt, stirring until the carboxymethyl chitosan quaternary ammonium salt is dissolved, adding absolute ethyl alcohol with the mass being 48 times that of the carboxymethyl chitosan quaternary ammonium salt, precipitating, filtering, washing for 2 times by using the absolute ethyl alcohol, and drying for 1h at the temperature of 80 ℃ to obtain the refined carboxymethyl chitosan quaternary ammonium salt;
(3) adding graphite oxide into dimethylformamide with the mass being 944 times that of the graphite oxide, carrying out ultrasonic treatment for 2.5 hours under the condition of 22kHz to obtain a graphene oxide suspension, then adding triethylene tetramine with the mass being 150 times that of the graphite oxide and dicyclohexyl carbodiimide with the mass being 25 times that of the graphite oxide, carrying out ultrasonic treatment for 5 minutes under the condition of 22kHz, reacting for 48 hours at 120 ℃, adding absolute ethyl alcohol with the mass being 237 times that of the graphite oxide, standing for 12 hours, removing supernatant, filtering lower-layer precipitate with a polytetrafluoroethylene film, washing for 7 times with ethanol and deionized water, and drying at 70 ℃ to obtain modified graphene;
(4) mixing the modified graphene obtained in the step (3) with the refined carboxymethyl chitosan quaternary ammonium salt obtained in the step (2), adding deionized water 120 times of the mass of the modified graphene, fully mixing, then ultrasonically dispersing for 3 hours in a water bath at the temperature of 0 ℃ under the condition of 25kHz to prepare modified graphene-carboxymethyl chitosan quaternary ammonium salt, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride which is 0.1 time of the mass of the modified graphene-carboxymethyl chitosan quaternary ammonium salt and N-hydroxysuccinimide which is 0.06 time of the mass of the modified graphene-carboxymethyl chitosan quaternary ammonium salt, stirring and reacting for 48 hours at room temperature, when the reaction time is 24 hours, the mixture is treated by ultrasonic treatment for 30min under the condition of 22kHz, after the reaction is finished, the mixture is placed in deionized water for dialysis for three days, then freeze-drying to obtain dark gray modified graphene-carboxymethyl chitosan quaternary ammonium salt powder;
(5) stirring n-butanol and the modified graphene-carboxymethyl chitosan quaternary ammonium salt powder obtained in the step (4) and the resin mixture uniformly according to the mass ratio of 1.5:1:1 to obtain a mixed solution, adding the mixed solution of 1/3 into a three-neck flask, magnetically stirring, heating to 95 ℃, and keeping the temperature for 0.5 h; dissolving an initiator azobisisobutyronitrile with the mass of 1 time of that of the modified graphene-carboxymethyl chitosan quaternary ammonium salt into an acetone solution with the mass of 50 times of that of the modified graphene-carboxymethyl chitosan quaternary ammonium salt, then pouring the solution into a constant-pressure dropping funnel, adding the other 2/3 mixed solution into the other constant-pressure funnel, simultaneously dropping the rest 2/3 mixed solution and the initiator benzoyl peroxide at 20 drops/min, and controlling the dropping within 1 hour; after dripping, reacting for 1h at 95 ℃, cooling and discharging, coating on the surface of the fiber for 0.01mm, and drying for 2h at 100 ℃ to obtain the antibacterial and antistatic fiber coating.
Further, the preparation method of the antibacterial and antistatic fiber coating is characterized in that the dropping speed in the step (1) is 15 drops/min; the temperature of the material was controlled at 50 ℃.
Further, the preparation method of the antibacterial antistatic fiber coating is characterized in that the mass ratio of the modified graphene to the carboxymethyl chitosan quaternary ammonium salt in the step (4) is 1: 8.
Further, the preparation method of the antibacterial and antistatic fiber coating is characterized in that the resin mixed solution in the step (5) is prepared by mixing methyl methacrylate, butyl methacrylate and butyl acrylate according to the mass ratio of 2:1: 1; the drying temperature was maintained at 140 ℃.
Example 3
An antibacterial antistatic fiber coating and a preparation method thereof, which mainly comprise the following components in parts by weight: 2 parts of modified carboxymethyl chitosan quaternary ammonium salt and 16 parts of graphene oxide.
A preparation method of an antibacterial anti-static fiber coating mainly comprises the following preparation steps:
(1) adding carboxymethyl chitosan into a three-necked bottle with a stirring and refluxing device, adding isopropanol which is 7 times the mass of the carboxymethyl chitosan and a 40% sodium hydroxide aqueous solution which is 1 time the mass of the carboxymethyl chitosan, stirring, heating in a water bath to raise the temperature of the materials to 45.0 ℃, and continuously stirring and alkalizing for 1 hour to prepare a mixed solution; then slowly dripping a 40 percent solution of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the mixed solution at 15 drops/min, and controlling the titration time to be 1 h; after reacting for 8 hours, adjusting the pH value to 7.0 by using 0.5mol/L hydrochloric acid, and filtering to obtain filter residue; soaking filter residue in 85% methanol water solution with the mass ratio of 1:1, washing with 85% methanol water solution for 5 times, vacuum filtering, washing with 5 times of anhydrous ethanol of carboxymethyl chitosan, soaking, and vacuum filtering to obtain solid material; finally, the solid material is placed in a dryer and dried for 1h at the temperature of 80 ℃ to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) grinding the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1), adding distilled water with the mass being 20 times that of the carboxymethyl chitosan quaternary ammonium salt, stirring until the carboxymethyl chitosan quaternary ammonium salt is dissolved, adding absolute ethyl alcohol with the mass being 48 times that of the carboxymethyl chitosan quaternary ammonium salt, precipitating, filtering, washing for 2 times by using the absolute ethyl alcohol, and drying for 1h at the temperature of 80 ℃ to obtain the refined carboxymethyl chitosan quaternary ammonium salt;
(3) mixing potassium borocyanide with 10% sodium hydroxide which is 0.5 times of the weight of the potassium borocyanide, stirring until the potassium borocyanide is not dissolved, and filtering to obtain a saturated potassium borocyanide solution;
(4) dissolving the refined carboxymethyl chitosan quaternary ammonium salt obtained in the step (2) in water 29 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt, adding lactose 2.5 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt while stirring, reacting at room temperature for 2 hours, then adding the saturated potassium borocyanide solution obtained in the step (3) at a rate of 1mL/min, controlling the time to be 0.5 hour, reacting for 24 hours, precipitating a product by using an acetone solution 73 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt, washing the precipitate for 5 times by using 70% ethanol, and drying at 80 ℃ for 1 hour to obtain the modified carboxymethyl chitosan quaternary ammonium salt;
(5) mixing graphene oxide with the modified carboxymethyl chitosan quaternary ammonium salt obtained in the step (4), adding deionized water with the mass of 120 times that of the graphene oxide, fully mixing, then ultrasonically dispersing for 3 hours in a water bath at the temperature of 0 ℃ under the condition of 25kHz to prepare the oxidized graphene-modified carboxymethyl chitosan quaternary ammonium salt, adding 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide which are respectively 0.1 time of the mass of the oxidized graphene-modified carboxymethyl chitosan quaternary ammonium salt and 0.06 time of the mass of the oxidized graphene-modified carboxymethyl chitosan quaternary ammonium salt, stirring and reacting for 48 hours at room temperature, when the reaction time is 24 hours, the mixture is treated by ultrasonic treatment for 30min under the condition of 22kHz, after the reaction is finished, the mixture is placed in deionized water for dialysis for three days, then freeze-drying to obtain graphene oxide-modified carboxymethyl chitosan quaternary ammonium salt powder;
(6) stirring n-butanol and the graphene oxide-modified carboxymethyl chitosan quaternary ammonium salt powder obtained in the step (5) and the resin mixture uniformly according to the mass ratio of 1.5:1:1 to obtain a mixed solution, adding the mixed solution of 1/3 into a three-neck flask, magnetically stirring, heating to 95 ℃, and keeping the temperature for 0.5 h; dissolving azodiisobutyronitrile serving as an initiator 1 time the mass of the graphene oxide-modified carboxymethyl chitosan quaternary ammonium salt into an acetone solution 50 times the mass of the graphene oxide-modified carboxymethyl chitosan quaternary ammonium salt, pouring the solution into a constant-pressure dropping funnel, adding the other 2/3 mixed solution into the other constant-pressure funnel, dropwise adding the rest 2/3 mixed solution and benzoyl peroxide serving as the initiator at the same time by 20 drops/min, and controlling the completion of dropwise adding within 1 hour; after dripping, reacting for 1h at 95 ℃, cooling and discharging, coating on the surface of the fiber for 0.01mm, and drying for 2h at 100 ℃ to obtain the antibacterial and antistatic fiber coating.
Further, the preparation method of the antibacterial and antistatic fiber coating is characterized in that the dropping speed in the step (1) is 15 drops/min; the temperature of the material was controlled at 50 ℃.
Further, the preparation method of the antibacterial antistatic fiber coating is characterized in that the mass ratio of the graphene oxide to the modified carboxymethyl chitosan quaternary ammonium salt in the step (5) is 1: 8.
Further, the preparation method of the antibacterial antistatic fiber coating is characterized in that the resin mixed solution in the step (6) is prepared by mixing methyl methacrylate, butyl methacrylate and butyl acrylate according to the mass ratio of 2:1: 1; the drying temperature was maintained at 140 ℃.
Comparative example
An antibacterial antistatic fiber coating and a preparation method thereof, which mainly comprise the following components in parts by weight: 2 parts of carboxymethyl chitosan quaternary ammonium salt.
The preparation method of the antibacterial antistatic fiber coating mainly comprises the following preparation steps:
(1) adding carboxymethyl chitosan into a three-necked bottle with a stirring and refluxing device, adding isopropanol 7 times the mass of the carboxymethyl chitosan and a 40% sodium hydroxide aqueous solution 1 time the mass of the carboxymethyl chitosan, stirring, heating in a water bath to raise the temperature of the materials to 45.0 ℃, and continuously stirring and alkalizing for 1h to obtain a mixed solution; then slowly dripping a 40 percent solution of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the mixed solution at 15 drops/min, and controlling the titration time to be 1 h; after reacting for 8 hours, adjusting the pH value to 7.0 by using 0.5mol/L hydrochloric acid, and filtering to obtain filter residue; soaking filter residue in 85% methanol water solution with the mass of 1:1, washing with 85% methanol water solution for 5 times, vacuum filtering, washing with anhydrous ethanol 5 times of carboxymethyl chitosan, soaking, and vacuum filtering to obtain solid material; finally, the solid material is placed in a dryer and dried for 1h at the temperature of 80 ℃ to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) grinding the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1), adding distilled water with the mass 20 times that of the carboxymethyl chitosan quaternary ammonium salt, stirring until the carboxymethyl chitosan quaternary ammonium salt is dissolved, adding absolute ethyl alcohol with the mass 48 times that of the carboxymethyl chitosan quaternary ammonium salt for precipitation, performing suction filtration, washing for 2 times by using the absolute ethyl alcohol, and drying for 1h at the temperature of 80 ℃ to obtain the refined carboxymethyl chitosan quaternary ammonium salt;
(3) stirring n-butanol, the graphene oxide-carboxymethyl chitosan quaternary ammonium salt powder obtained in the step (2) and the resin mixture uniformly according to the mass ratio of 1.5:1:1 to obtain a mixed solution, adding the mixed solution of 1/3 into a three-neck flask, magnetically stirring, heating to 95 ℃, and keeping the temperature for 0.5 h; dissolving an initiator azodiisobutyronitrile with the mass of 1 time of that of the carboxymethyl chitosan quaternary ammonium salt in an acetone solution with the mass of 50 times of that of the carboxymethyl chitosan quaternary ammonium salt, pouring the solution into a constant-pressure dropping funnel, adding another 2/3 mixed solution into another constant-pressure funnel, simultaneously dropping the rest 2/3 mixed solution and the initiator benzoyl peroxide at the rate of 20 drops/min, and controlling the dropping within 1 hour; after dripping, reacting for 1h at 95 ℃, cooling and discharging, coating on the surface of the fiber for 0.01mm, and drying for 2h at 100 ℃ to obtain the antibacterial and antistatic fiber coating.
Further, the preparation method of the antibacterial and antistatic fiber coating is characterized in that the dropping speed in the step (1) is 15 drops/min; the temperature of the material was controlled at 50 ℃.
Further, the preparation method of the antibacterial and antistatic fiber coating is characterized in that the resin mixed solution in the step (3) is prepared by mixing methyl methacrylate, butyl methacrylate and butyl acrylate according to the mass ratio of 2:1: 1; the drying temperature was maintained at 140 ℃.
Effects of the invention
The following table 1 shows the results of performance analysis of the antibacterial and antistatic fiber coating using examples 1 to 3 of the present invention and comparative example.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Sterilizing rate (%) | 93.2 | 90.8 | 58.3 | 55.1 |
| Resistivity (omega) | 105 | 108 | 1010 | 1011 |
Compared with experimental data of a comparative example, the experiment data of example 1 shows that the sterilization rate of example 1 is higher and the resistivity is lower, which indicates that in the process of preparing raw materials, modified carboxymethyl chitosan quaternary ammonium salt is grafted on the surface of modified graphene, so that the modified carboxymethyl chitosan quaternary ammonium salt can perform synergistic action to quickly sterilize and has a wide antibacterial range, and simultaneously, lactose-modified graphene oxide is added, so that continuous formation can be realized on the surface of a fiber coating, the charge release on the surface of the coating is promoted, and the antibacterial and antistatic capabilities of the fiber coating are improved; compared with the experimental data of example 1 and example 2, the resistivity of example 1 is lower, which indicates that a thin continuous aqueous phase cannot be formed on the coating layer due to modification without lactose in the raw material preparation process, the moisture in the environment is difficult to absorb, and the release of the surface charge of the coating layer is hindered, and the antistatic ability is weak only due to the fact that the quaternary ammonium salt positive ions are used for conducting and adsorbing the charge; from the comparison of the experimental data of the example 1 and the example 3, it can be seen that the bactericidal rate of the example 1 is higher, and the resistivity is lower, which indicates that in the process of preparing the fiber coating, if graphene oxide is not chemically modified, the graphene oxide is easy to agglomerate in the solution, the graphene oxide is difficult to polymerize with the modified carboxymethyl chitosan quaternary ammonium salt, only a small amount of quaternary ammonium salt is bonded to the surface of the modified graphene oxide, the grafting rate is low, so that the reaction with the resin mixed solution is incomplete, and the antibacterial and antistatic effects are poor.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (3)
1. The preparation method of the antibacterial anti-static fiber coating is characterized by mainly comprising the following preparation steps:
(1) adding carboxymethyl chitosan into a three-necked bottle with a stirring and refluxing device, adding isopropanol 7 times the mass of the carboxymethyl chitosan and a 40% sodium hydroxide aqueous solution 1 time the mass of the carboxymethyl chitosan, stirring, heating in a water bath to raise the temperature of the materials to 45.0 ℃, and continuously stirring and alkalizing for 1h to obtain a mixed solution; then slowly dripping a 40 mass percent 3-chloro-2 hydroxypropyl trimethyl ammonium chloride solution into the mixed solution at a speed of 15 drops/min, and controlling the titration time to be 1-2 h; after reacting for 8 hours, adjusting the pH value to 7.0 by using 0.5mol/L hydrochloric acid, and filtering to obtain filter residue; soaking filter residues in 85% methanol water solution, wherein the mass ratio of the filter residues to the methanol water solution is 1:1, washing the filter residues for 5-6 times by using the 85% methanol water solution, performing suction filtration, washing the filter residues for soaking by using absolute ethyl alcohol with the mass 5 times that of carboxymethyl chitosan, and performing suction filtration to obtain a solid material; finally, the solid material is placed in a dryer and dried for 1h at the temperature of 80 ℃ to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) grinding the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1), adding distilled water with the mass being 20 times that of the carboxymethyl chitosan quaternary ammonium salt, stirring until the distilled water is dissolved, adding absolute ethyl alcohol with the mass being 48 times that of the carboxymethyl chitosan quaternary ammonium salt, precipitating, filtering, washing for 2-3 times by using the absolute ethyl alcohol, and drying for 1h at the temperature of 80 ℃ to obtain the refined carboxymethyl chitosan quaternary ammonium salt;
(3) mixing potassium borohydride with 10% sodium hydroxide which is 0.5 times of the mass of the potassium borohydride, stirring until the potassium borohydride is not dissolved, and filtering to obtain a saturated solution of the potassium borohydride;
(4) dissolving the refined carboxymethyl chitosan quaternary ammonium salt obtained in the step (2) in water 29 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt, adding lactose 2.5 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt while stirring, reacting at room temperature for 2 hours, then adding the saturated solution of potassium borohydride in the step (3) at a rate of 1mL/min, controlling the time to be 0.5-1 hour, reacting for 24 hours, precipitating the product by using an acetone solution 73 times the mass of the refined carboxymethyl chitosan quaternary ammonium salt, washing the precipitate by using 70% ethanol for 5-6 times, and drying at 80 ℃ for 1 hour to obtain the modified carboxymethyl chitosan quaternary ammonium salt;
(5) adding graphite oxide into dimethylformamide with the mass being 944 times that of the graphite oxide, carrying out ultrasonic treatment for 2.5 hours under the condition of 22kHz to obtain a graphene oxide suspension, then adding triethylene tetramine with the mass being 150 times that of the graphite oxide and dicyclohexyl carbodiimide with the mass being 25 times that of the graphite oxide, carrying out ultrasonic treatment for 5 minutes under the condition of 22kHz, reacting for 48 hours at 120 ℃, adding absolute ethyl alcohol with the mass being 237 times that of the graphite oxide, standing for 12 hours, removing supernatant, filtering lower-layer precipitate with a polytetrafluoroethylene film, washing for 7-8 times with ethanol and deionized water, and drying at 70 ℃ to obtain aminated modified graphene;
(6) mixing the aminated modified graphene obtained in the step (5) with the modified carboxymethyl chitosan quaternary ammonium salt obtained in the step (4), adding deionized water 120 times the mass of the aminated modified graphene, fully mixing, then performing ultrasonic dispersion for 3 hours under the condition of 25kHz in a water bath at the temperature of 0-3 ℃ to prepare aminated modified graphene-modified carboxymethyl chitosan quaternary ammonium salt, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride 0.1 times the mass of the aminated modified graphene-modified carboxymethyl chitosan quaternary ammonium salt and N-hydroxysuccinimide 0.06 times the mass of the aminated modified graphene-modified carboxymethyl chitosan quaternary ammonium salt, stirring and reacting for 48 hours at room temperature, performing ultrasonic treatment for 30 minutes under the condition of 22kHz when the mixture reacts for 24 hours, and after the reaction is finished, dialyzing in deionized water for three days, wherein the molecular weight cutoff is 12-14 kDa, and then freeze-drying to obtain dark gray aminated modified graphene-modified carboxymethyl chitosan quaternary ammonium salt powder;
(7) mixing methyl methacrylate, butyl methacrylate and butyl acrylate according to the mass ratio of 2:1:1 to prepare a resin monomer mixture; stirring n-butanol and the amination modified graphene-modified carboxymethyl chitosan quaternary ammonium salt powder obtained in the step (6) and a resin monomer mixture uniformly according to the mass ratio of 1.5:1:1 to obtain a mixed solution, adding the mixed solution of 1/3 into a three-neck flask, magnetically stirring, heating to 95 ℃, and keeping the temperature for 0.5 h; dissolving azodiisobutyronitrile serving as an initiator 1 time the mass of the aminated modified graphene-modified carboxymethyl chitosan quaternary ammonium salt into an acetone solution 50 times the mass of the aminated modified graphene-modified carboxymethyl chitosan quaternary ammonium salt, pouring the solution into a constant-pressure dropping funnel, adding the other 2/3 mixed solution into the other constant-pressure funnel, simultaneously dropping the rest 2/3 mixed solution and benzoyl peroxide serving as the initiator at a rate of 20 drops/min, and controlling the dropping within 1 hour; after dripping, reacting for 1h at 95 ℃, cooling and discharging, coating on the surface of the fiber for 0.01-0.03 mm, and drying for 2h at 100-120 ℃ to obtain the antibacterial and antistatic fiber coating.
2. The preparation method of the antibacterial and antistatic fiber coating according to claim 1, characterized in that when the 3-chloro-2-hydroxypropyltrimethylammonium chloride solution is dropwise added in the step (1), the temperature of the material is controlled to be 50-60 ℃.
3. The preparation method of the antibacterial and antistatic fiber coating according to claim 1, wherein the mass ratio of the aminated modified graphene to the modified carboxymethyl chitosan quaternary ammonium salt in the step (6) is 1: 4-1: 8.
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