阅读说明：本技术 一种抗菌石墨烯浆液的制作方法 (Preparation method of antibacterial graphene slurry ) 是由 任礼新 于 2020-07-23 设计创作，主要内容包括：本发明公开了一种抗菌石墨烯浆液的制作方法,涉及纺织品加工技术领域,本发明通过对氧化石墨烯的两步化学改性处理制得不仅具有抗菌性能而且对阴离子染料吸附性好的抗菌石墨烯浆液,在该抗菌石墨烯浆液中加入阴离子染料后即可对纤维素纤维织物进行高效染色,从而显著提高染料的利用率和赋予纤维素纤维织物优良的抗菌性能。(The invention discloses a preparation method of antibacterial graphene slurry, and relates to the technical field of textile processing.)

1. The preparation method of the antibacterial graphene slurry is characterized by comprising the following steps: the method comprises the following manufacturing steps:

(1) adding graphene oxide into water, and performing ultrasonic dispersion to obtain a graphene oxide solution;

(2) adding 3-amino-1-cyclopropyl pyrazole and a catalyst into the graphene oxide solution, carrying out ultrasonic dissolution, then heating for reaction, filtering, washing filter residues with water, and drying to obtain modified graphene oxide;

(3) adding modified graphene oxide into water, performing ultrasonic dispersion, adding nano-zinc oxide, heating for reaction, dropwise adding concentrated sulfuric acid in the reaction process, filtering after the reaction is finished, washing filter residues with water, and drying to obtain nano-zinc oxide/modified graphene oxide;

(4) and adding nano zinc oxide/modified graphene oxide into water, and performing ultrasonic dispersion to obtain the antibacterial graphene slurry.

2. The method for producing an antibacterial graphene slurry according to claim 1, characterized in that: the mass ratio of the graphene oxide to the 3-amino-1-cyclopropyl pyrazole to the nano zinc oxide is 50:30-50: 10-20.

3. The method for producing an antibacterial graphene slurry according to claim 1, characterized in that: the molar ratio of the 3-amino-1-cyclopropyl pyrazole to the catalyst is 1: 1.1-1.2.

4. The method for producing an antibacterial graphene slurry according to claim 1, characterized in that: the catalyst consists of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) in a molar ratio of 2: 1.

5. The method for producing an antibacterial graphene slurry according to claim 1, characterized in that: the dosage of the concentrated sulfuric acid is 3-8% of that of the nano zinc oxide.

6. The method for producing an antibacterial graphene slurry according to claim 1, characterized in that: the concentration of the antibacterial graphene slurry is 10-30g/L, and is calculated by nano zinc oxide/modified graphene oxide.

7. Use of an antimicrobial graphene slurry prepared according to any one of claims 1 to 6 in the dyeing of cellulosic fibre fabrics.

The technical field is as follows:

the invention relates to the technical field of textile processing, in particular to a preparation method of antibacterial graphene slurry.

Background art:

graphene is a new star carbon-based material that has been developed in recent years. Graphene is a polymer made of carbon atoms in sp²The hybrid tracks form hexagonal honeycomb lattice planar films with only one carbon atom thick of two-dimensional material. Due to sp²Due to the existence of the hybrid orbit, the graphene can adsorb aromatic substances through pi-pi stacking, so that the graphene can be used for removing organic dyes with aromatic ring structures.

Graphene oxide is an oxide of graphene, has a large number of carboxyl groups, hydroxyl groups and epoxy groups on the surface, and is electronegative. Patent CN 102995394a discloses a graphene oxide-based dyeing and antibacterial finishing agent, which is a chitosan/graphene oxide/dye composite material, wherein the dye is one or more of a reactive dye, an acid dye and a direct dye with a conjugated system. Firstly, acylating and chlorinating the graphene oxide by utilizing the reactivity of carboxyl groups rich on the surface of the graphene oxide, and then covalently grafting the natural antibacterial material chitosan onto the graphene oxide by utilizing the reactivity among acyl chloride, active amino and hydroxyl; and adsorbing the dye on a graphene oxide plane by utilizing the pi-pi interaction between the graphene oxide and the water-soluble dye.

Acid dyes are also known as anionic dyes, which contain acid groups in the dye molecule. Since graphene oxide is electronegative, it has poor adsorption to anionic dyes that are also electronegative. Although patent CN 102995394a discloses that the dye contains anionic dye, and theoretically states that van der waals force, hydrogen bond and ionic bond can be generated between the dye and chitosan, the adsorption capacity of the prepared chitosan/graphene oxide composite material to the anionic dye is not tested, and thus the effect of dyeing textiles by the anionic dye cannot be objectively reflected by the fact that the chitosan/graphene oxide composite material can be significantly improved.

Although chitosan belongs to a natural antibacterial agent, the grafting rate of chitosan on graphene oxide is limited due to the large molecular structure of chitosan. In addition, in order to improve the grafting ratio and further ensure the antibacterial property of the finishing agent, the chitosan needs to be greatly excessive compared with the graphene oxide when the chitosan/graphene oxide composite material is prepared, so that a great amount of chitosan is wasted. In addition, the water solubility of chitosan is poor, and the patent CN 102995394A adopts dimethylformamide as a solvent, and the dimethylformamide has certain toxicity, so that the preparation method of the chitosan is poor in environmental protection and is not suitable for the current green production concept.

The invention content is as follows:

the invention aims to provide a preparation method of antibacterial graphene slurry, which is prepared by modifying graphene oxide to obtain the antibacterial graphene slurry with antibacterial performance and good adsorption to anionic dye, and the fabric can be efficiently dyed after the anionic dye is added into the antibacterial graphene slurry, so that the utilization rate of the dye is obviously improved, and the fabric is endowed with excellent antibacterial performance.

The technical problem to be solved by the invention is realized by adopting the following technical scheme:

a preparation method of antibacterial graphene slurry comprises the following preparation steps:

(1) adding graphene oxide into water, and performing ultrasonic dispersion to obtain a graphene oxide solution;

(2) adding 3-amino-1-cyclopropyl pyrazole and a catalyst into the graphene oxide solution, carrying out ultrasonic dissolution, then heating for reaction, filtering, washing filter residues with water, and drying to obtain modified graphene oxide;

(3) adding modified graphene oxide into water, performing ultrasonic dispersion, adding nano-zinc oxide, heating for reaction, dropwise adding concentrated sulfuric acid in the reaction process, filtering after the reaction is finished, washing filter residues with water, and drying to obtain nano-zinc oxide/modified graphene oxide;

(4) and adding nano zinc oxide/modified graphene oxide into water, and performing ultrasonic dispersion to obtain the antibacterial graphene slurry.

The mass ratio of the graphene oxide to the 3-amino-1-cyclopropyl pyrazole to the nano zinc oxide is 50:30-50: 10-20.

The molar ratio of the 3-amino-1-cyclopropyl pyrazole to the catalyst is 1: 1.1-1.2.

The catalyst consists of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) in a molar ratio of 2: 1.

The dosage of the concentrated sulfuric acid is 3-8% of that of the nano zinc oxide.

The concentration of the antibacterial graphene slurry is 10-30g/L, and is calculated by nano zinc oxide/modified graphene oxide.

Graphene oxide has a high specific surface area, contains a large number of oxygen-containing groups such as carboxyl and hydroxyl on the surface, is electronegative, and has electrostatic interaction besides pi-pi stacking effect when adsorbing polycyclic aromatic hydrocarbon substances, so that the graphene oxide has poor adsorption on anionic dyes which are also electronegative.

According to the invention, part of carboxyl on the surface of graphene oxide and amino in a 3-amino-1-cyclopropyl pyrazole molecular structure are subjected to amide condensation reaction, so that charges on the surface of the graphene oxide are changed through graft modification of the 3-amino-1-cyclopropyl pyrazole on the graphene oxide, and the adsorption capacity of the graphene oxide on anionic dye is enhanced.

The nano zinc oxide has the particle size of 1-100nm, has high safety such as heat resistance, durability, no toxicity, no odor, no stimulation to skin and the like, and has excellent antibacterial effect. The antibacterial mechanism mainly comprises a photocatalytic antibacterial mechanism and a contact type sterilization mechanism. The photocatalytic antibacterial mechanism is as follows: the nano zinc oxide has strong photocatalysis capability, electrons in a valence band of the nano zinc oxide irradiated by ultraviolet rays can be excited to a conduction band to form freely moving negatively charged electrons and positively charged holes, the holes react with oxygen, hydroxyl, water and the like adsorbed on the surface of a material to generate hydroxyl radicals and active oxygen examples with reduction effects such as hydroxyl, oxygen anions, hydrogen peroxide and the like, the oxygen in air and water can be excited to be changed into active oxygen, and the active oxygen has strong oxidation activity and can react with organic matters in various microorganisms to destroy the multiplication capability of bacterial cells and inhibit or kill bacteria. The contact sterilization mechanism is as follows: due to the surface effect of the nano particles, the nano particles can easily generate affinity with contacted bacteria and have sterilization capability. The nanometer zinc oxide slowly releases zinc ions in an aqueous medium, the zinc ions are gradually dissociated, and due to the oxidation-reduction property of the zinc ions, when the zinc ions are combined with bacterial cell membranes, the zinc ions react with organic matters in the bacterial cell membranes, so that the structure of membrane proteins is damaged, the activity of the membrane proteins is lost, and the aim of sterilization is fulfilled. When the bacteria are killed, zinc ions are dissociated from the bacteria and then contacted with other bacteria to continuously sterilize, so that the zinc ions show strong bactericidal activity. Meanwhile, holes on the surface of the nano zinc oxide can generate electrons to directly participate in the reaction, more holes can generate more electrons, and the sterilizing capability of the nano zinc oxide is stronger.

In view of the antibacterial activity of the nano-zinc oxide and the characteristic that the surface of the nano-zinc oxide has hydroxyl groups, the invention utilizes partial carboxyl groups on the surface of the graphene oxide and the hydroxyl groups on the surface of the nano-zinc oxide to perform esterification reaction under the action of concentrated sulfuric acid, so as to graft the nano-zinc oxide onto the graphene oxide, and further endow the graphene oxide with excellent antibacterial performance.

The technical problem to be solved by the invention is also to provide a dyeing method of a cellulose fiber fabric, aiming at improving the dye uptake of an anionic dye to the cellulose fiber fabric, and mainly by means of the antibacterial graphene slurry prepared by the technical scheme.

When the cellulose fiber fabric is contacted with the aqueous solution, the surface of the fabric is negatively charged due to the ionization of certain groups in cellulose macromolecules, and the anionic dye is also negatively charged in the aqueous solution, so that large electrostatic repulsion force exists between the dye and the fiber during dyeing, and the dye uptake rate of the dye is reduced. At present, a large amount of neutral electrolyte is added in the dyeing process to reduce the electric point positions on the surface of the fiber, and the electrostatic repulsion between the dye and the fiber is reduced, so that the dye uptake is improved. However, the addition of the electrolyte increases the dyeing cost, and simultaneously increases the concentration of the electrolyte in the dyeing wastewater, thus increasing the difficulty of wastewater treatment.

The antibacterial graphene slurry prepared by the technical scheme is applied to dyeing of cellulose fiber fabrics.

A method of dyeing a cellulosic fibre fabric comprising the steps of:

(1) adding antibacterial graphene slurry, an anionic dye and a leveling agent into water, performing ultrasonic dispersion to obtain a dye solution, and adding a pH regulator to adjust the pH value of the dye solution;

(2) soaking the cellulose fiber fabric in a dye solution, heating for dyeing, taking out, drying, fixing color, washing, soaping, washing again and drying.

The concentration of the nano zinc oxide/modified graphene oxide in the dye solution is 5-10g/L, the concentration of the anionic dye is 10-20g/L, and the concentration of the leveling agent is 1-5 g/L.

The pH regulator is citric acid, and the pH value is 4-5.

According to the invention, the addition of the antibacterial graphene slurry into the dye solution is used for improving the dye-uptake of the cellulose fiber fabric and endowing the cellulose fiber fabric with excellent antibacterial property, and the addition of the leveling agent into the dye solution is used for ensuring the uniform dyeing of the cellulose fiber fabric, so that defects such as color stripes and color spots are avoided.

The leveling agent is hexanediol histidine ester, and the structural formula is as follows:

the invention adopts a novel compound of the structural formula, namely hexanediol histidine ester as a leveling agent, wherein hydroxyl in the hexanediol histidine molecular structure can form a hydrogen bond with hydroxyl in the cellulose fiber molecular structure, and the surface charge of the cellulose fiber molecules is changed by utilizing the molecular structure of the hexanediol histidine ester, so that the negative charge on the surface of a cellulose fiber fabric is reduced, and the leveling effect is improved.

The bath ratio of the dyeing is 1: 10-30.

The invention has the beneficial effects that: according to the invention, the antibacterial graphene slurry with antibacterial performance and good adsorption to anionic dye is prepared by two-step chemical modification treatment of graphene oxide, and the cellulose fiber fabric can be efficiently dyed after the anionic dye is added into the antibacterial graphene slurry, so that the utilization rate of the dye is remarkably improved, and the cellulose fiber fabric is endowed with excellent antibacterial performance.

The specific implementation mode is as follows:

in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.

Graphene oxide is purchased from Beijing Deke island gold science and technology Limited, has a purity of more than 99 wt%, a thickness of 0.55-1.2nm and a diameter of 0.5-3 μm.

The nanometer zinc oxide is obtained from textile nanometer zinc oxide of Ishikaki technologies of Beijing Deke, pH of 7-9, and average particle diameter of 50 nm.

Congo red was purchased from carbofuran technologies ltd.

The soaping agent was purchased from soaping agent Y-32 of the chemical and industrial technologies of Xian Yuesheng.