阅读说明：本技术 一种用于纤维纱线以及布料的抗菌整理剂及其制备方法 (Antibacterial finishing agent for fiber yarns and cloth and preparation method thereof ) 是由 高宏业 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种用于纤维纱线以及布料的抗菌整理剂及其制备方法,所述抗菌整理剂按照重量份计算,由以下成分组成：改性电气石纳米粉1～10份、聚二烯丙基二甲基氯化铵0.2～2份、羟乙基纤维素0.5～5份、去离子水100份。本发明制备的抗菌整理剂对人体安全无毒副作用,且电气石能够散发氧负离子以及发射红外线,对人体的健康起到有益的作用；且本发明的抗菌整理剂具有较强的重复使用性,能够起到长久强力抗菌的作用。(The invention discloses an antibacterial finishing agent for fiber yarns and fabrics and a preparation method thereof, wherein the antibacterial finishing agent comprises the following components in parts by weight: 1-10 parts of modified tourmaline nano powder, 0.2-2 parts of poly diallyl dimethyl ammonium chloride, 0.5-5 parts of hydroxyethyl cellulose and 100 parts of deionized water. The antibacterial finishing agent prepared by the invention is safe to human bodies and has no toxic or side effect, and the tourmaline can emit oxygen anions and infrared rays and has beneficial effects on the health of human bodies; the antibacterial finishing agent has strong reusability and can play a role in long-term strong antibiosis.)

1. The antibacterial finishing agent for fiber yarns and cloth is characterized by comprising the following components in parts by weight:

1-10 parts of modified tourmaline nano powder, 0.2-2 parts of poly diallyl dimethyl ammonium chloride, 0.5-5 parts of hydroxyethyl cellulose and 100 parts of deionized water.

2. The antibacterial finishing agent for fiber yarns and cloth according to claim 1, wherein the preparation method of the modified tourmaline nano powder comprises the following steps:

step 1, reacting nitrofurantoin with 1-octadecylamine hydrochloride to obtain a solid product B grafted with an alkylamino group;

step 2, carrying out bromine end group treatment on the solid product B prepared in the step 1, and then reacting the solid product B with hinokitiol to obtain an antibacterial compound containing a plurality of amide groups;

step 3, carrying out surface treatment on the tourmaline nano powder to obtain a tourmaline nano powder surface treatment substance;

and 4, carrying out graft modification on the tourmaline nano powder surface treatment substance prepared in the step 3 by using the antibacterial compound prepared in the step 2 to obtain modified tourmaline nano powder.

3. The antibacterial finishing agent for fiber yarns and cloth according to claim 2, wherein the tourmaline nano powder has a particle size of 10 to 100 nm.

4. The antibacterial finishing agent for fiber yarns and cloth according to claim 2, wherein the step 1 is specifically as follows:

s1, weighing nitrofurantoin, adding the nitrofurantoin into N-methylpyrrolidone, stirring until the nitrofurantoin is completely dissolved, introducing nitrogen as protective gas, adding potassium tert-butoxide while stirring until the pH value of the solution reaches 13.0-14.0, then adding 1-octadecylamine hydrochloride, stirring uniformly, heating to 90-120 ℃, and continuously reacting for 8-12 hours to obtain a mixed reaction liquid A;

wherein the mass ratio of the nitrofurantoin, the 1-octadecylamine hydrochloride and the N-methylpyrrolidone is 1: 0.8-1.3: 8-15;

s2, adding deionized water into the mixed reaction liquid A while stirring, gradually precipitating in the adding process, stirring until the precipitate does not increase continuously after the adding is finished, performing suction filtration and collecting the precipitate, washing the precipitate for 5-8 times by using purified water, and drying the washed precipitate in a drying oven to constant weight to obtain a solid product B;

wherein the mass ratio of the mixed reaction liquid A to the deionized water is 1: 2-5.

5. The antibacterial finishing agent for fiber yarns and fabrics according to claim 2, wherein the step 2 is specifically as follows:

x1., adding the solid product B into N-methyl pyrrolidone, stirring until the solid product B is completely dissolved, adding triethylamine, then placing the mixed solution into an ice-water bath condition, stirring for 0.2-0.5 h, introducing nitrogen as a protective gas, dropwise adding 2-bromobutyryl bromide at a speed of 1-3 seconds/drop, after completely dropwise adding, stirring and reacting for 1-2 h under the ice-water bath condition, then heating to room temperature, and stirring and reacting for 3-8 h under the room temperature condition to obtain a mixed reaction solution C;

wherein the mass ratio of the solid product B, triethylamine, 2-bromobutyryl bromide to N-methylpyrrolidone is 1: 0.02-0.05: 0.32-0.65: 8-15;

x2. adding hinokitiol into the mixed reaction solution C, heating to 90-120 ℃, carrying out condensation reflux reaction for 5-12 h, cooling to room temperature, carrying out rotary evaporation on the reaction solution to remove a solvent, collecting a solid, washing the collected solid for 3-5 times by using absolute ethyl alcohol, and then placing in a drying oven to dry to constant weight to obtain an antibacterial compound;

wherein the mass ratio of the hinokitiol to the mixed reaction solution C is 1: 6-12.

6. The antibacterial finishing agent for fiber yarns and fabrics according to claim 2, wherein the step 3 is specifically:

weighing tourmaline nano powder, adding the tourmaline nano powder into deionized water, ultrasonically dispersing until the tourmaline nano powder is uniform, adding a titanate coupling agent, stirring for 2-6 h under the condition of water bath at 40-60 ℃, filtering and collecting solid nano powder, washing the collected solid nano powder with purified water for 3-5 times, and then putting the solid nano powder into a drying oven to be dried to constant weight;

wherein the mass ratio of the tourmaline nano powder to the titanate coupling agent to the deionized water is 1: 0.02-0.05: 10-15.

7. The antibacterial finishing agent for fiber yarns and fabrics according to claim 2, wherein the step 4 is specifically:

weighing an antibacterial compound, adding the antibacterial compound into N, N-dimethylformamide, stirring until the antibacterial compound is completely dissolved, adding a tourmaline nano powder surface treatment substance, carrying out ultrasonic dispersion until the surface treatment substance is uniform, pouring a dispersion liquid into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, treating at 160-200 ℃ for 8-15 hours, cooling to room temperature, carrying out suction filtration on liquid in the reaction kettle, collecting solids, washing the collected solids with acetonitrile for 3-5 times, and drying under reduced pressure to constant weight to finally obtain modified tourmaline nano powder;

wherein the mass ratio of the antibacterial compound, the tourmaline nano powder surface treatment substance and the N, N-dimethylformamide is 1: 4-8: 15-30.

8. A preparation method of an antibacterial finishing agent for fiber yarns and cloth is characterized in that the preparation method is used for preparing the antibacterial finishing agent for fiber yarns and cloth according to any one of claims 1 to 7, and comprises the following steps:

(1) respectively weighing the polydiallyldimethyl chloride and the hydroxyethyl cellulose according to the weight, adding the polydiallyldimethyl chloride and the hydroxyethyl cellulose into the deionized water weighed according to the weight, and stirring and mixing the mixture uniformly to obtain a first mixed solution;

(2) adding the modified tourmaline nano powder weighed according to the amount into the first mixed solution prepared in the step (1), and stirring for 0.1-1 h to prepare a second mixed solution;

(3) and (3) heating the second mixed liquid prepared in the step (2) to 40-70 ℃, stirring for 0.1-0.5 h, and cooling to room temperature to obtain the antibacterial finishing agent.

Technical Field

The invention relates to the field of fiber yarn antibacterial finishing agents, in particular to an antibacterial finishing agent for fiber yarns and fabrics and a preparation method thereof.

Background

With the social development and the improvement of living standard of people, the comfort and the functionality of the fabric are more and more valued by people. As the cloth for close-fitting wearing, the cloth has higher requirement on comfort, not only has super-soft hand feeling, but also has higher requirements on antibacterial performance and skin-friendly performance.

However, the antibacterial finishing agent for fiber yarns and cloth at present has many defects, the function is especially single, the requirement of modern people is difficult to meet, and the following defects are often existed:

1) most of the existing antibacterial finishing agents for clothing fabrics have toxicity, teratogenicity, variability and carcinogenicity with different degrees, and although the antibacterial finishing agent also has a certain antibacterial effect, the antibacterial finishing agent is easy to generate certain side effects on fabrics and human health after treatment;

2) at present, many antibacterial finishing agents have poor durability and reusability, and the antibacterial finishing agent of the clothing fabric cannot be subjected to a finishing process repeated for many times; secondly, the antibacterial effect of the finished clothing fabric is difficult to maintain for a long time and is easy to lose efficacy.

Disclosure of Invention

In order to solve the problems, the invention provides an antibacterial finishing agent for fiber yarns and fabrics and a preparation method thereof.

In order to achieve the purpose, the invention adopts the technical scheme that:

in a first aspect, the invention provides an antibacterial finishing agent for fiber yarns and fabrics, which comprises the following components in parts by weight:

1-10 parts of modified tourmaline nano powder, 0.2-2 parts of poly diallyl dimethyl ammonium chloride, 0.5-5 parts of hydroxyethyl cellulose and 100 parts of deionized water.

Preferably, the preparation method of the modified tourmaline nano powder comprises the following steps:

step 1, reacting nitrofurantoin with 1-octadecylamine hydrochloride to obtain a solid product B grafted with an alkylamino group;

step 2, carrying out bromine end group treatment on the solid product B prepared in the step 1, and then reacting the solid product B with hinokitiol to obtain an antibacterial compound containing a plurality of amide groups;

step 3, carrying out surface treatment on the tourmaline nano powder to obtain a tourmaline nano powder surface treatment substance;

and 4, carrying out graft modification on the tourmaline nano powder surface treatment substance prepared in the step 3 by using the antibacterial compound prepared in the step 2 to obtain modified tourmaline nano powder.

Preferably, the particle size of the tourmaline nano powder is 10-100 nm.

Preferably, the step 1 specifically comprises:

s1, weighing nitrofurantoin, adding the nitrofurantoin into N-methylpyrrolidone, stirring until the nitrofurantoin is completely dissolved, introducing nitrogen as protective gas, adding potassium tert-butoxide while stirring until the pH value of the solution reaches 13.0-14.0, then adding 1-octadecylamine hydrochloride, stirring uniformly, heating to 90-120 ℃, and continuously reacting for 8-12 hours to obtain a mixed reaction liquid A;

wherein the mass ratio of the nitrofurantoin, the 1-octadecylamine hydrochloride and the N-methylpyrrolidone is 1: 0.8-1.3: 8-15;

s2, adding deionized water into the mixed reaction liquid A while stirring, gradually precipitating in the adding process, stirring until the precipitate does not increase continuously after the adding is finished, performing suction filtration and collecting the precipitate, washing the precipitate for 5-8 times by using purified water, and drying the washed precipitate in a drying oven to constant weight to obtain a solid product B;

wherein the mass ratio of the mixed reaction liquid A to the deionized water is 1: 2-5.

Preferably, the step 2 specifically comprises:

x1., adding the solid product B into N-methyl pyrrolidone, stirring until the solid product B is completely dissolved, adding triethylamine, then placing the mixed solution into an ice-water bath condition, stirring for 0.2-0.5 h, introducing nitrogen as a protective gas, dropwise adding 2-bromobutyryl bromide at a speed of 1-3 seconds/drop, after completely dropwise adding, stirring and reacting for 1-2 h under the ice-water bath condition, then heating to room temperature, and stirring and reacting for 3-8 h under the room temperature condition to obtain a mixed reaction solution C;

wherein the mass ratio of the solid product B, triethylamine, 2-bromobutyryl bromide to N-methylpyrrolidone is 1: 0.02-0.05: 0.32-0.65: 8-15;

x2. adding hinokitiol into the mixed reaction solution C, heating to 90-120 ℃, carrying out condensation reflux reaction for 5-12 h, cooling to room temperature, carrying out rotary evaporation on the reaction solution to remove a solvent, collecting a solid, washing the collected solid for 3-5 times by using absolute ethyl alcohol, and then placing in a drying oven to dry to constant weight to obtain an antibacterial compound;

wherein the mass ratio of the hinokitiol to the mixed reaction solution C is 1: 6-12.

Preferably, the step 3 specifically comprises:

weighing tourmaline nano powder, adding the tourmaline nano powder into deionized water, ultrasonically dispersing until the tourmaline nano powder is uniform, adding a titanate coupling agent, stirring for 2-6 h under the condition of water bath at 40-60 ℃, filtering and collecting solid nano powder, washing the collected solid nano powder with purified water for 3-5 times, and then putting the solid nano powder into a drying oven to be dried to constant weight;

wherein the mass ratio of the tourmaline nano powder to the titanate coupling agent to the deionized water is 1: 0.02-0.05: 10-15.

Preferably, the step 4 specifically includes:

weighing an antibacterial compound, adding the antibacterial compound into N, N-dimethylformamide, stirring until the antibacterial compound is completely dissolved, adding a tourmaline nano powder surface treatment substance, carrying out ultrasonic dispersion until the surface treatment substance is uniform, pouring a dispersion liquid into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, treating at 160-200 ℃ for 8-15 hours, cooling to room temperature, carrying out suction filtration on liquid in the reaction kettle, collecting solids, washing the collected solids with acetonitrile for 3-5 times, and drying under reduced pressure to constant weight to finally obtain modified tourmaline nano powder;

wherein the mass ratio of the antibacterial compound, the tourmaline nano powder surface treatment substance and the N, N-dimethylformamide is 1: 4-8: 15-30.

In a second aspect, the present invention provides a method for preparing an antibacterial finishing agent for fiber yarns and fabrics, comprising the following steps:

(1) respectively weighing polydiallyldimethyl chloride and hydroxyethyl cellulose according to the weight, adding the polydiallyldimethyl chloride and the hydroxyethyl cellulose into the deionized water weighed according to the weight, and stirring and mixing the mixture uniformly to obtain a first mixed solution;

(2) adding the modified tourmaline nano powder weighed according to the amount into the first mixed solution prepared in the step (1), and stirring for 0.1-1 h to prepare a second mixed solution;

(3) and (3) heating the second mixed liquid prepared in the step (2) to 40-70 ℃, stirring for 0.1-0.5 h, and cooling to room temperature to obtain the antibacterial finishing agent.

The invention has the beneficial effects that:

1. tourmaline is a polar silicate crystal with a special structure, has certain antibacterial performance, is mild, and is not enough to effectively kill bacteria in a short contact time. After the antibacterial material is combined with the organic antibacterial agent, the antibacterial material and the organic antibacterial agent can play a role in synergistic sterilization, so that the antibacterial performance of the material is improved. According to the invention, tourmaline is used as a base material, and an antibacterial compound containing a plurality of amide groups is grafted to the surface of the tourmaline in a covalent bond mode according to the principle that the tourmaline can generate negative oxygen ions for a long time, so that the surface of the finally formed modified tourmaline nano powder is coated with and grafted with a large amount of antibacterial compounds. The antibacterial finishing agent prepared by the invention is safe to human bodies and has no toxic or side effect, and the tourmaline can emit oxygen anions and infrared rays and has beneficial effects on the health of human bodies; the antibacterial finishing agent has strong reusability and can play a role in long-term strong antibiosis.

2. The antibacterial action of the modified tourmaline nano powder prepared by the invention is jointly formed by the following three aspects: the air purifier can generate a large amount of negative oxygen ions under the action of water molecules in the air for a long time, and the negative oxygen ions can inhibit the growth of bacteria and germs; the antibacterial organic matter grafted and wrapped on the surface of the tourmaline has an antibacterial effect and can play a stronger antibacterial role; ③ the strong electric field generated by the tourmaline can directly act on the antibacterial organic matters on the surface of the tourmaline and decompose the antibacterial organic matters to generate the nitrofurantoin or the hinokitiol, thereby playing the role of long-term antibiosis.

3. The method for removing tourmaline, nitrofurantoin and hinokitiol used in the modified tourmaline nano powder belongs to the method that polydiallyldimethylammonium chloride and hydroxyethyl cellulose are added into the antibacterial finishing agent, the polydiallyldimethylammonium chloride has the advantages of safety, no toxicity, water solubility, nonflammability, strong cohesive force, good hydrolytic stability, no gel formation, insensitivity to pH value change, chlorine resistance and the like, and can more firmly adsorb the modified tourmaline nano powder on the surface of fiber yarns or cloth; the hydroxyethyl cellulose is tasteless and nontoxic, has the characteristics of good thickening, suspension, dispersion, emulsification, adhesion, film formation, protection and the like, can uniformly disperse the modified tourmaline nano powder more easily and form a film more easily, and can wrap the surface of the modified tourmaline nano powder to form a protection effect.

4. The antibacterial compound prepared by the invention takes natural antibacterial active substance nitrofurantoin as a base material, and then 1-octadecylamine hydrochloride and hinokitiol which also belongs to a natural antibacterial substance are sequentially used for carrying out grafting reaction on the nitrofurantoin, so that the stronger antibacterial compound with a plurality of amide groups is finally obtained. Wherein, the 1-octadecylamine hydrochloride can replace hydrogen bonds on an N-H group in the nitrofurantion and is grafted on a nitrofurantion molecular structure to obtain the nitrofurantion containing grafted alkylamine groups; then carrying out bromine endcapping on amino on the furadantin grafted with the alkylamino group by using 2-bromobutyryl bromide, then reacting and grafting active bromine end groups with hydroxyl in hinokitiol to form an amide structure, and finally obtaining the antibacterial compound with a plurality of amide groups in the molecule, wherein the plurality of amide groups provide strong antibacterial property for the molecule and have more lasting antibacterial effect compared with the furadantin and the hinokitiol.

5. The antibacterial compound prepared by the invention is combined with natural antibacterial material tourmaline and is finally grafted on the surface of the tourmaline to obtain the modified tourmaline nano powder. The antibacterial compound prepared by the invention not only improves the defect of insufficient antibacterial property of the tourmaline, but also strengthens the lasting antibacterial effect of the tourmaline, and the antibacterial compound is basically prepared by using substances with low toxicity or natural antibacterial materials and is safer to human bodies. Therefore, the modified tourmaline nano powder finally prepared by the invention has the advantages of no toxicity, safety, strong effect and durable antibacterial property.

Detailed Description

The invention is further described with reference to the following examples.

Example 1

An antibacterial finishing agent for fiber yarns and fabrics comprises the following components in parts by weight:

8 parts of modified tourmaline nano powder, 1 part of polydiallyl dimethyl ammonium chloride, 3 parts of hydroxyethyl cellulose and 100 parts of deionized water.

The preparation method of the modified tourmaline nano powder comprises the following steps:

step 1, reacting nitrofurantoin with 1-octadecylamine hydrochloride to obtain a solid product B grafted with an alkylamino group;

step 2, carrying out bromine end group treatment on the solid product B prepared in the step 1, and then reacting the solid product B with hinokitiol to obtain an antibacterial compound containing a plurality of amide groups;

step 3, carrying out surface treatment on the tourmaline nano powder to obtain a tourmaline nano powder surface treatment substance;

and 4, carrying out graft modification on the tourmaline nano powder surface treatment substance prepared in the step 3 by using the antibacterial compound prepared in the step 2 to obtain modified tourmaline nano powder.

The particle size of the tourmaline nano powder is 10-100 nm.

The step 1 specifically comprises the following steps:

s1, weighing nitrofurantoin, adding the nitrofurantoin into N-methylpyrrolidone, stirring until the nitrofurantoin is completely dissolved, introducing nitrogen as protective gas, adding potassium tert-butoxide while stirring until the pH value of the solution reaches 13.0-14.0, then adding 1-octadecylamine hydrochloride, stirring uniformly, heating to 90-120 ℃, and continuously reacting for 8-12 hours to obtain a mixed reaction liquid A;

wherein the mass ratio of the nitrofurantoin, the 1-octadecylamine hydrochloride and the N-methylpyrrolidone is 1: 0.8-1.3: 8-15;

s2, adding deionized water into the mixed reaction liquid A while stirring, gradually precipitating in the adding process, stirring until the precipitate does not increase continuously after the adding is finished, performing suction filtration and collecting the precipitate, washing the precipitate for 5-8 times by using purified water, and drying the washed precipitate in a drying oven to constant weight to obtain a solid product B;

wherein the mass ratio of the mixed reaction liquid A to the deionized water is 1: 2-5.

The step 2 specifically comprises the following steps:

x1., adding the solid product B into N-methyl pyrrolidone, stirring until the solid product B is completely dissolved, adding triethylamine, then placing the mixed solution into an ice-water bath condition, stirring for 0.2-0.5 h, introducing nitrogen as a protective gas, dropwise adding 2-bromobutyryl bromide at a speed of 1-3 seconds/drop, after completely dropwise adding, stirring and reacting for 1-2 h under the ice-water bath condition, then heating to room temperature, and stirring and reacting for 3-8 h under the room temperature condition to obtain a mixed reaction solution C;

wherein the mass ratio of the solid product B, triethylamine, 2-bromobutyryl bromide to N-methylpyrrolidone is 1: 0.02-0.05: 0.32-0.65: 8-15;

x2. adding hinokitiol into the mixed reaction solution C, heating to 90-120 ℃, carrying out condensation reflux reaction for 5-12 h, cooling to room temperature, carrying out rotary evaporation on the reaction solution to remove a solvent, collecting a solid, washing the collected solid for 3-5 times by using absolute ethyl alcohol, and then placing in a drying oven to dry to constant weight to obtain an antibacterial compound;

wherein the mass ratio of the hinokitiol to the mixed reaction solution C is 1: 6-12.

The step 3 specifically comprises the following steps:

weighing tourmaline nano powder, adding the tourmaline nano powder into deionized water, ultrasonically dispersing until the tourmaline nano powder is uniform, adding a titanate coupling agent, stirring for 2-6 h under the condition of water bath at 40-60 ℃, filtering and collecting solid nano powder, washing the collected solid nano powder with purified water for 3-5 times, and then putting the solid nano powder into a drying oven to be dried to constant weight;

wherein the mass ratio of the tourmaline nano powder to the titanate coupling agent to the deionized water is 1: 0.02-0.05: 10-15.

The step 4 specifically comprises the following steps:

weighing an antibacterial compound, adding the antibacterial compound into N, N-dimethylformamide, stirring until the antibacterial compound is completely dissolved, adding a tourmaline nano powder surface treatment substance, carrying out ultrasonic dispersion until the surface treatment substance is uniform, pouring a dispersion liquid into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, treating at 160-200 ℃ for 8-15 hours, cooling to room temperature, carrying out suction filtration on liquid in the reaction kettle, collecting solids, washing the collected solids with acetonitrile for 3-5 times, and drying under reduced pressure to constant weight to finally obtain modified tourmaline nano powder;

wherein the mass ratio of the antibacterial compound, the tourmaline nano powder surface treatment substance and the N, N-dimethylformamide is 1: 4-8: 15-30.

The preparation method of the antibacterial finishing agent for the fiber yarns and the cloth comprises the following steps:

(1) respectively weighing polydiallyldimethyl chloride and hydroxyethyl cellulose according to the weight, adding the polydiallyldimethyl chloride and the hydroxyethyl cellulose into the deionized water weighed according to the weight, and stirring and mixing the mixture uniformly to obtain a first mixed solution;

(2) adding the modified tourmaline nano powder weighed according to the amount into the first mixed solution prepared in the step (1), and stirring for 0.1-1 h to prepare a second mixed solution;

(3) and (3) heating the second mixed liquid prepared in the step (2) to 40-70 ℃, stirring for 0.1-0.5 h, and cooling to room temperature to obtain the antibacterial finishing agent.

Example 2

An antibacterial finishing agent for fiber yarns and fabrics comprises the following components in parts by weight:

1 part of modified tourmaline nano powder, 0.2 part of poly diallyl dimethyl ammonium chloride, 0.5 part of hydroxyethyl cellulose and 100 parts of deionized water.

The preparation method of the modified tourmaline nano powder comprises the following steps:

step 1, reacting nitrofurantoin with 1-octadecylamine hydrochloride to obtain a solid product B grafted with an alkylamino group;

step 2, carrying out bromine end group treatment on the solid product B prepared in the step 1, and then reacting the solid product B with hinokitiol to obtain an antibacterial compound containing a plurality of amide groups;

step 3, carrying out surface treatment on the tourmaline nano powder to obtain a tourmaline nano powder surface treatment substance;

and 4, carrying out graft modification on the tourmaline nano powder surface treatment substance prepared in the step 3 by using the antibacterial compound prepared in the step 2 to obtain modified tourmaline nano powder.

The particle size of the tourmaline nano powder is 10-100 nm.

The step 1 specifically comprises the following steps:

s1, weighing nitrofurantoin, adding the nitrofurantoin into N-methylpyrrolidone, stirring until the nitrofurantoin is completely dissolved, introducing nitrogen as protective gas, adding potassium tert-butoxide while stirring until the pH value of the solution reaches 13.0-14.0, then adding 1-octadecylamine hydrochloride, stirring uniformly, heating to 90-120 ℃, and continuously reacting for 8-12 hours to obtain a mixed reaction liquid A;

wherein the mass ratio of the nitrofurantoin, the 1-octadecylamine hydrochloride and the N-methylpyrrolidone is 1: 0.8-1.3: 8-15;

s2, adding deionized water into the mixed reaction liquid A while stirring, gradually precipitating in the adding process, stirring until the precipitate does not increase continuously after the adding is finished, performing suction filtration and collecting the precipitate, washing the precipitate for 5-8 times by using purified water, and drying the washed precipitate in a drying oven to constant weight to obtain a solid product B;

wherein the mass ratio of the mixed reaction liquid A to the deionized water is 1: 2-5.

The step 2 specifically comprises the following steps:

x1., adding the solid product B into N-methyl pyrrolidone, stirring until the solid product B is completely dissolved, adding triethylamine, then placing the mixed solution into an ice-water bath condition, stirring for 0.2-0.5 h, introducing nitrogen as a protective gas, dropwise adding 2-bromobutyryl bromide at a speed of 1-3 seconds/drop, after completely dropwise adding, stirring and reacting for 1-2 h under the ice-water bath condition, then heating to room temperature, and stirring and reacting for 3-8 h under the room temperature condition to obtain a mixed reaction solution C;

wherein the mass ratio of the solid product B, triethylamine, 2-bromobutyryl bromide to N-methylpyrrolidone is 1: 0.02-0.05: 0.32-0.65: 8-15;

x2. adding hinokitiol into the mixed reaction solution C, heating to 90-120 ℃, carrying out condensation reflux reaction for 5-12 h, cooling to room temperature, carrying out rotary evaporation on the reaction solution to remove a solvent, collecting a solid, washing the collected solid for 3-5 times by using absolute ethyl alcohol, and then placing in a drying oven to dry to constant weight to obtain an antibacterial compound;

wherein the mass ratio of the hinokitiol to the mixed reaction solution C is 1: 6-12.

The step 3 specifically comprises the following steps:

weighing tourmaline nano powder, adding the tourmaline nano powder into deionized water, ultrasonically dispersing until the tourmaline nano powder is uniform, adding a titanate coupling agent, stirring for 2-6 h under the condition of water bath at 40-60 ℃, filtering and collecting solid nano powder, washing the collected solid nano powder with purified water for 3-5 times, and then putting the solid nano powder into a drying oven to be dried to constant weight;

wherein the mass ratio of the tourmaline nano powder to the titanate coupling agent to the deionized water is 1: 0.02-0.05: 10-15.

The step 4 specifically comprises the following steps:

weighing an antibacterial compound, adding the antibacterial compound into N, N-dimethylformamide, stirring until the antibacterial compound is completely dissolved, adding a tourmaline nano powder surface treatment substance, carrying out ultrasonic dispersion until the surface treatment substance is uniform, pouring a dispersion liquid into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, treating at 160-200 ℃ for 8-15 hours, cooling to room temperature, carrying out suction filtration on liquid in the reaction kettle, collecting solids, washing the collected solids with acetonitrile for 3-5 times, and drying under reduced pressure to constant weight to finally obtain modified tourmaline nano powder;

wherein the mass ratio of the antibacterial compound, the tourmaline nano powder surface treatment substance and the N, N-dimethylformamide is 1: 4-8: 15-30.

The preparation method of the antibacterial finishing agent for the fiber yarns and the cloth comprises the following steps:

(1) respectively weighing polydiallyldimethyl chloride and hydroxyethyl cellulose according to the weight, adding the polydiallyldimethyl chloride and the hydroxyethyl cellulose into the deionized water weighed according to the weight, and stirring and mixing the mixture uniformly to obtain a first mixed solution;

(2) adding the modified tourmaline nano powder weighed according to the amount into the first mixed solution prepared in the step (1), and stirring for 0.1-1 h to prepare a second mixed solution;

(3) and (3) heating the second mixed liquid prepared in the step (2) to 40-70 ℃, stirring for 0.1-0.5 h, and cooling to room temperature to obtain the antibacterial finishing agent.

Example 3

An antibacterial finishing agent for fiber yarns and fabrics comprises the following components in parts by weight:

10 parts of modified tourmaline nano powder, 2 parts of poly diallyl dimethyl ammonium chloride, 5 parts of hydroxyethyl cellulose and 100 parts of deionized water.

The preparation method of the modified tourmaline nano powder comprises the following steps:

step 1, reacting nitrofurantoin with 1-octadecylamine hydrochloride to obtain a solid product B grafted with an alkylamino group;

step 2, carrying out bromine end group treatment on the solid product B prepared in the step 1, and then reacting the solid product B with hinokitiol to obtain an antibacterial compound containing a plurality of amide groups;

step 3, carrying out surface treatment on the tourmaline nano powder to obtain a tourmaline nano powder surface treatment substance;

and 4, carrying out graft modification on the tourmaline nano powder surface treatment substance prepared in the step 3 by using the antibacterial compound prepared in the step 2 to obtain modified tourmaline nano powder.

The particle size of the tourmaline nano powder is 10-100 nm.

The step 1 specifically comprises the following steps:

s1, weighing nitrofurantoin, adding the nitrofurantoin into N-methylpyrrolidone, stirring until the nitrofurantoin is completely dissolved, introducing nitrogen as protective gas, adding potassium tert-butoxide while stirring until the pH value of the solution reaches 13.0-14.0, then adding 1-octadecylamine hydrochloride, stirring uniformly, heating to 90-120 ℃, and continuously reacting for 8-12 hours to obtain a mixed reaction liquid A;

wherein the mass ratio of the nitrofurantoin, the 1-octadecylamine hydrochloride and the N-methylpyrrolidone is 1: 0.8-1.3: 8-15;

s2, adding deionized water into the mixed reaction liquid A while stirring, gradually precipitating in the adding process, stirring until the precipitate does not increase continuously after the adding is finished, performing suction filtration and collecting the precipitate, washing the precipitate for 5-8 times by using purified water, and drying the washed precipitate in a drying oven to constant weight to obtain a solid product B;

wherein the mass ratio of the mixed reaction liquid A to the deionized water is 1: 2-5.

The step 2 specifically comprises the following steps:

x1., adding the solid product B into N-methyl pyrrolidone, stirring until the solid product B is completely dissolved, adding triethylamine, then placing the mixed solution into an ice-water bath condition, stirring for 0.2-0.5 h, introducing nitrogen as a protective gas, dropwise adding 2-bromobutyryl bromide at a speed of 1-3 seconds/drop, after completely dropwise adding, stirring and reacting for 1-2 h under the ice-water bath condition, then heating to room temperature, and stirring and reacting for 3-8 h under the room temperature condition to obtain a mixed reaction solution C;

wherein the mass ratio of the solid product B, triethylamine, 2-bromobutyryl bromide to N-methylpyrrolidone is 1: 0.02-0.05: 0.32-0.65: 8-15;

x2. adding hinokitiol into the mixed reaction solution C, heating to 90-120 ℃, carrying out condensation reflux reaction for 5-12 h, cooling to room temperature, carrying out rotary evaporation on the reaction solution to remove a solvent, collecting a solid, washing the collected solid for 3-5 times by using absolute ethyl alcohol, and then placing in a drying oven to dry to constant weight to obtain an antibacterial compound;

wherein the mass ratio of the hinokitiol to the mixed reaction solution C is 1: 6-12.

The step 3 specifically comprises the following steps:

weighing tourmaline nano powder, adding the tourmaline nano powder into deionized water, ultrasonically dispersing until the tourmaline nano powder is uniform, adding a titanate coupling agent, stirring for 2-6 h under the condition of water bath at 40-60 ℃, filtering and collecting solid nano powder, washing the collected solid nano powder with purified water for 3-5 times, and then putting the solid nano powder into a drying oven to be dried to constant weight;

wherein the mass ratio of the tourmaline nano powder to the titanate coupling agent to the deionized water is 1: 0.02-0.05: 10-15.

The step 4 specifically comprises the following steps:

weighing an antibacterial compound, adding the antibacterial compound into N, N-dimethylformamide, stirring until the antibacterial compound is completely dissolved, adding a tourmaline nano powder surface treatment substance, carrying out ultrasonic dispersion until the surface treatment substance is uniform, pouring a dispersion liquid into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, treating at 160-200 ℃ for 8-15 hours, cooling to room temperature, carrying out suction filtration on liquid in the reaction kettle, collecting solids, washing the collected solids with acetonitrile for 3-5 times, and drying under reduced pressure to constant weight to finally obtain modified tourmaline nano powder;

wherein the mass ratio of the antibacterial compound, the tourmaline nano powder surface treatment substance and the N, N-dimethylformamide is 1: 4-8: 15-30.

The preparation method of the antibacterial finishing agent for the fiber yarns and the cloth comprises the following steps:

(1) respectively weighing polydiallyldimethyl chloride and hydroxyethyl cellulose according to the weight, adding the polydiallyldimethyl chloride and the hydroxyethyl cellulose into the deionized water weighed according to the weight, and stirring and mixing the mixture uniformly to obtain a first mixed solution;

(2) adding the modified tourmaline nano powder weighed according to the amount into the first mixed solution prepared in the step (1), and stirring for 0.1-1 h to prepare a second mixed solution;

(3) and (3) heating the second mixed liquid prepared in the step (2) to 40-70 ℃, stirring for 0.1-0.5 h, and cooling to room temperature to obtain the antibacterial finishing agent.

Comparative example

An antibacterial finishing agent for fiber yarns and fabrics comprises the following components in parts by weight:

8 parts of tourmaline nano powder, 1 part of polydiallyl dimethyl ammonium chloride, 3 parts of hydroxyethyl cellulose and 100 parts of deionized water.

The particle size of the tourmaline nano powder is 10-100 nm.

The preparation method of the antibacterial finishing agent for the fiber yarns and the cloth comprises the following steps:

(1) respectively weighing polydiallyldimethyl chloride and hydroxyethyl cellulose according to the weight, adding the polydiallyldimethyl chloride and the hydroxyethyl cellulose into the deionized water weighed according to the weight, and stirring and mixing the mixture uniformly to obtain a first mixed solution;

(2) adding the tourmaline nano powder weighed according to the amount into the first mixed solution prepared in the step (1), and stirring for 0.1-1 h to prepare a second mixed solution;

(3) and (3) heating the second mixed liquid prepared in the step (2) to 40-70 ℃, stirring for 0.1-0.5 h, and cooling to room temperature to obtain the antibacterial finishing agent.

For a clearer illustration of the present invention, the antibacterial finishing agents prepared in examples 1 to 3 of the present invention and comparative examples were tested for their performance. Will be provided withThe antibacterial finishing agents prepared in examples 1 to 3 and the comparative example were respectively prepared into 100g/L antibacterial solution with deionized water, and 4 pieces of the same 105g/m antibacterial solution were taken²The pure cotton knitted fabrics (each block is 100g) are respectively immersed into the antibacterial liquid prepared in the embodiments 1-3 for padding, the rolling residual rate is 95%, and 4 different pieces of antibacterial cloth are obtained after drying and sizing.

According to the regulation of national standard GB8629-2001, household washing and drying procedures adopted in textile tests, a B-type stirring washing machine and a washing procedure 8B are selected, four pieces of antibacterial cloth and untreated pure cotton knitted fabrics (blank example) are respectively washed for 10 times, 20 times and 50 times, and then the antibacterial performance of the washed sample is measured.

The antibacterial performance of the washed sample is measured according to the test method of the antibacterial performance of the product of the national standard GB1759-2002 sanitary Standard for Disposable sanitary articles, and the test bacterial liquid is as follows: the bacterial liquid concentration of staphylococcus aureus ATCC 6538 is 1.5 x 10⁵The bacterial liquid concentration of CFU/mL and Escherichia coli ATCC 29214 was 2.0X 10⁵CFU/mL. The test results are shown in table 1:

TABLE 1 antibacterial Properties of various antibacterial finishing Agents after finishing of the cloth

As can be seen from table 1, the antibacterial finishing agent prepared in the embodiment of the present invention has excellent resistance to staphylococcus aureus and escherichia coli, is highly reusable, and can still reach more than 99% after being washed 50 times.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.