CN111979765B

CN111979765B - Preparation method of hydroxyl fiber with antibacterial function

Info

Publication number: CN111979765B
Application number: CN201910432580.4A
Authority: CN
Inventors: 王威; 鄢军; 景晓辉; 郭丁丁
Original assignee: Suzhou Hexiang Textile Technology Co ltd
Current assignee: Suzhou Hexiang Textile Technology Co ltd
Priority date: 2019-05-23
Filing date: 2019-05-23
Publication date: 2022-10-25
Anticipated expiration: 2039-05-23
Also published as: CN111979765A

Abstract

The fiber product with antibacterial and bactericidal functions and the preparation method thereof have strong antibacterial action adaptability and wide application range, and the key point is that a core organic molecule is selected, one end of the core organic molecule can be combined with active hydroxyl on the surface of the fiber, and the other end of the core organic molecule is chemically bonded with the antibacterial and bactericidal body, so that the fiber or the fiber product is firmly connected with the antibacterial and bactericidal body, and the defect that the body in the prior art is easy to fall off or can not be durably attached to the surface of the fiber or the fiber product is overcome. The preparation method mainly comprises three steps of core organic molecule reaction liquid preparation, fiber or fiber products soaking in the reaction liquid and antibacterial sterilization body and core organic molecule bonding reaction, and the preparation method is simple and has good repeatability.

Description

Preparation method of hydroxyl fiber with antibacterial function

Technical Field

The invention relates to a fiber with an antibacterial effect, in particular to a fiber synthesized by chemical reaction and a method for preparing a fiber product, belonging to the field of fiber synthesis.

Background

The fiber is closely related to human life, and is mainly used for clothes, ornaments, kitchen washing appliances and the like used in daily life and industries needing to relate to fiber spinning or fiber products in the field of industrial production. Conventional fibers or fiber products can be broadly classified into two broad categories, namely natural fibers and man-made fibers. Wherein the natural fiber is mainly derived from plants, such as various chemical pulp and semi-chemical pulp prepared from needle-leaved wood, broad-leaved wood, hemp, bamboo, straw, bagasse, reed and the like used in the paper industry as raw materials; whereas, the manmade fiber mainly uses natural cellulose fiber as raw material to prepare such as Viscose fiber (Viscose), modal fiber (Modal), lyocell fiber (Lyocell), cuprammonium fiber (Cupro), polynosic fiber, etc.; and fibers prepared by biological methods, such as those utilizing Bacterial cellulose (Bacterial cellulose): cellulose fibers synthesized under certain conditions by microorganisms belonging to the genera Acetobacter, agrobacterium, rhizobium, and Sarcina.

The fiber or textile is subjected to a post-finishing process, which means that the prepared fiber or fiber product is subjected to subsequent industrial process treatment to form a fiber or fiber product derivative product, and the fiber or fiber product derivative product is further used for other purposes. The most common method is to endow fibers and textiles with some physical and chemical functions through a post-finishing process, wherein the antibacterial function is a topic which is popular in recent years, and especially under the concept of healthy life, researchers can be guided to put in intelligence in the direction.

The prior art antibacterial after-finishing process is divided into four categories: the first type is that the fiber or textile is immersed in a solution containing an antibacterial agent, and after the processes of extrusion, pressing, drying and the like, the antibacterial agent is left on the surface of the fiber or textile, so that the fiber or textile has an antibacterial function. However, the disadvantage is that if the bacteria have no or a weak negative charge, the antibacterial effect of such antibacterial agents is greatly reduced; the second type is diphenyl ether finishing agent, however, the antibacterial agent has no electric charge, has poor binding force to fiber and is easy to fall off from the surface of fiber and textile; the third category is metal antimicrobials that coordinate to the fiber, with major disadvantages: firstly, sulfonate groups and other groups which have complexation with metal ions with antibacterial functions such as silver ions and the like are required on the fiber; secondly, the complexing action strength is low, and the complexed silver ions and the like are easy to fall off from the surface of the fiber; the fourth category is the antimicrobial method of chemically synthesized fibers. Mainly, the inorganic antibacterial agent is used as a carrier and metal ions are loaded as the antibacterial agent, and the spinning process is not suitable for the fiber containing active hydroxyl groups in the invention. Rayon is an inexpensive alternative to natural fiber. The surface of the material generally contains abundant active hydroxyl groups. The invention overcomes the defects of the prior art by utilizing the characteristics of surface hydroxyl, so that the antibacterial body is firmly fixed on the surface of the fiber.

Disclosure of Invention

The invention utilizes the hydroxyl on the surface of the artificial fiber to prepare the fiber and the fiber product with stable antibacterial new energy and wide applicability. The fiber and the fiber product can enable the antibacterial body to be firmly attached to the fiber with the surface containing active hydroxyl, so that chemical bond combination is formed between the antibacterial body and the fiber, and firm loading is realized. As used herein, "fiber" includes, but is not limited to, natural and man-made fibers, and "fibrous products" includes, but is not limited to, two-dimensional fibrous products. The preference refers to a test parameter that is more reproducible than non-preferred. The preparation method comprises the following steps:

s1: a reaction solution was prepared. The main composition of the reaction solution:

a solvent, the solvent comprising: a mixture of alcohol and water; a core reactant (or referred to as a core organic molecule) comprising a molecular structure: one end of the fiber contains a group capable of reacting with active hydroxyl on the fiber; the other end contains a group which can be combined with the inorganic nano antibacterial agent and a pH reagent of the reaction solution.

Wherein the alcohol is selected from: methanol, ethanol, propanol, isopropanol, butanol, 2-methylpropanol, 2-methyl-tert-propanol, ethylene glycol, and the like. Preferably ethanol; the volume ratio of alcohol to water is "alcohol to water = 80-0", preferably 95-100.

The core material comprises: gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltriethoxysilane, gamma- (2, 3-glycidoxy) propylmethyldimethoxysilane, gamma- (2, 3-glycidoxy) propyldimethylmethoxysilane, gamma- (2, 3-glycidoxy) propylmethyldiethoxysilane, gamma- (2, 3-glycidoxy) propyldimethylethoxysilane, gamma- (2, 3-glycidoxy) propylphenyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma- (2, 3-epoxypropyl) methylenetrimethoxysilane, gamma- (2, 3-epoxypropyl) methylenetriethoxysilane, or a thiol substitution of one of the foregoing molecules with a silicon thiol, and the like.

The pH reagent of the reaction solution is used for adjusting the pH range of the reaction solution to 9.5-13, preferably 12-13 by using strong base NaOH, KOH or weak base such as strong ammonia water.

The preparation process comprises the following steps: and adding the core reactant into the solvent, uniformly mixing, and adjusting to the required pH value to obtain a reaction solution.

S2: soaking fibers containing active hydroxyl groups or two-dimensional plane materials such as paper, fabrics and the like woven by using the active hydroxyl fibers in the reaction liquid obtained in the step S1; then, heating the mixed system to 35-70 ℃, preferably 45-60 ℃ by using heating equipment under the condition of gently shaking or stirring;

or, the reaction liquid is heated to 35-70 ℃, preferably 45-60 ℃, and then the fiber of the active hydroxyl or the fiber of the active hydroxyl is woven to obtain a two-dimensional plane material, and the two-dimensional plane material is soaked in the heated reaction liquid.

In the two soaking and heating processes, the active hydroxyl on the fiber is further activated in the alkaline environment in the reaction liquid, and the reaction activity is enhanced; meanwhile, under the action of strong alkalinity and temperature, after the ring opening of the epoxy group of the core reactant, the epoxy group and the active hydroxyl group on the fiber are subjected to chemical reaction, so that the core reactant is connected to the fiber in a chemical bond mode. In this process, the silane group at the other end of the core reactant undergoes hydrolysis to produce a reactive silanol.

The fiber containing active hydroxyl or the two-dimensional plane material woven by the active hydroxyl fiber is subjected to chemical reaction with the core reactant in the reaction solution for 30min-15h. After the reaction is finished, the active hydroxyl fibers or the active hydroxyl fibers are woven to obtain a two-dimensional planar material, the two-dimensional planar material is taken out, the two-dimensional planar material is washed for 3 times by absolute ethyl alcohol, and the core reactant which is remained on the surface of the fibers and does not chemically react with the hydroxyl groups is thoroughly washed clean, so that the fiber or the two-dimensional planar material of the composite core reactant is obtained.

S3: selecting nanometer zinc oxide and nanometer titanium dioxide as nanometer antibacterial substances, wherein the particle size range of the nanometer zinc oxide and the nanometer titanium dioxide is 8-300nm. The preparation method of the dispersion liquid of the nano zinc oxide and the nano titanium dioxide comprises the following steps: preparing an ethanol aqueous solution, wherein the volume ratio of ethanol to water is controlled from "ethanol to water = 80.

Adding the dried nano zinc oxide and nano titanium dioxide with constant weight into an aqueous solution of ethanol, and controlling the mass concentration of the nano zinc oxide and the nano titanium dioxide to be 0.1-2%. Adding the nano zinc oxide and the nano titanium dioxide into an ethanol water solution, and then dispersing in a dispersing device such as an ultrasonic wall breaking machine, an ultrasonic cleaning machine, a high-pressure homogenizer and the like, so that the particles of the nano zinc oxide and the nano titanium dioxide are dispersed into a suspension of single particles without flocculation among the particles.

S4: and (3) adding the fiber or the two-dimensional plane material of the composite core reactant obtained in the step (S2) into the suspension of the nano zinc oxide and the nano titanium dioxide dispersed in the step (S3), and slowly shaking or stirring for 1-24h. In the process, the other end of the core reactant which chemically reacts with active hydroxyl on the fiber is in a silanol structure, and silanol chemically reacts with hydroxyl on the surfaces of nano zinc oxide and nano titanium dioxide, so that nano particles of the nano zinc oxide and the nano titanium dioxide are firmly combined on the surface of the fiber, and the obtained product is the hydroxyl fiber or fiber product with the antibacterial function. If the core reactant is gamma- (2, 3-glycidoxy) propyltrimethoxysilane, the structure of the "fiber-core reactant-nanoparticle" is schematically shown in FIG. 1.

Or alternatively, the core reactant is hydrosulfide, nano gold or nano silver dispersion liquid is prepared, the fiber is soaked in the dispersion liquid and lightly vibrated, and the fiber with the surface combined with nano gold or nano silver through gold-sulfur bonds or silver-sulfur bonds is obtained and also has the antibacterial effect.

The invention has the beneficial effects that: the purposeful selection of the core reactant can generate chemical reaction with active hydroxyl on the surface of the fiber, and the other end of the core reactant can generate chemical reaction with hydroxyl on the surface of the nano particles, so that the core reactant molecules are used as a bridge to enable the fiber and the antibacterial body to be firmly combined by utilizing the hydroxyl on the surface of the fiber, and the defects of falling off of the antibacterial body or poor combination strength in the prior art are overcome; secondly, the conditions of the reaction of the core reactant with the active hydroxyl of the fiber and the hydroxyl on the surface of the nano particle are strictly controlled, and the preparation process with good repeatability is obtained.

Drawings

Fig. 1 is a schematic diagram showing the molecular structure of the "hydroxyl fiber-core reactant-nanoparticle" connection of the fiber and the fiber product according to the present invention.

Fig. 2 is a Scanning Electron Microscope (SEM) image of cotton fibers with nano zinc oxide bonded to the surface thereof, showing fibers and fiber products according to the present invention.

Fig. 3 is a Scanning Electron Microscope (SEM) image showing Lyocell fibers with nano-titania bonded to the surface to which the present invention relates.

Fig. 4 is a Scanning Electron Microscope (SEM) image showing softwood chemical pulp fibers with surface-bound nano-titania according to the present invention.

Detailed Description

The hydroxyl fiber product with antibacterial function and the preparation method thereof according to the present invention will be further described in detail with reference to the following embodiments.

Fig. 1 is a schematic molecular structure diagram showing the "hydroxyl fiber-core reactant-nanoparticle" linkage of the fiber and fiber product according to the present invention.

As shown in FIG. 1, the rightmost side is a nanoparticle, the silicon-oxygen bond of the core reactant is combined with the nanoparticle, and a bond position of-CH 2-at the leftmost end of the core organic molecule as the core reactant is connected with one bond position of the hydroxyl fiber through-O-bond, so that a molecular structure of 'hydroxyl fiber-core reactant-nanoparticle' connection is formed, and the fiber product of the invention are formed. Specifically, the active hydroxyl groups on the fiber are further activated in an alkaline environment in the reaction solution, and the epoxy groups of the core reactant are opened and then chemically reacted with the active hydroxyl groups on the fiber, so that the core reactant is chemically bonded to the fiber.

Example 1: ethanol in the reaction solution, water =95, and the core reactants are: gamma- (2, 3-glycidoxy) propyltrimethoxysilane, and the pH of the reaction solution was adjusted to 12.07 with concentrated aqueous ammonia. Adding cotton fiber into the reaction solution, heating to 50 ℃, and gently shaking to react for 4 hours in total. The cotton fibers were then removed and rinsed 3 times with absolute ethanol. Preparing a dispersion liquid of nano zinc oxide, wherein the mass concentration of the nano zinc oxide is 0.1%, ultrasonically dispersing the nano zinc oxide for 40min by an ultrasonic cleaner, soaking the cotton fiber which is washed by absolute ethyl alcohol for 3 times, and lightly shaking the cotton fiber for 4h to obtain the cotton fiber of which the surface is combined with the nano zinc oxide by chemical bonds. The SEM image is shown in FIG. 2.

Example 2: the ratio of ethanol to water =100 in the reaction solution, and the core reactants are: γ - (2, 3-glycidoxy) propyltriethoxysilane, and the reaction solution pH =12.82 was adjusted with a 1% NaOH solution. Adding Lyocell fiber into the reaction solution, heating to 60 ℃, and gently shaking to react for 12 hours in total. The Lyocell fibers were then removed and rinsed 3 times with absolute ethanol. Preparing a dispersion liquid of nano titanium dioxide, wherein the mass concentration of nano zinc oxide is 0.8%, ultrasonically dispersing for 40min by an ultrasonic cleaner, soaking the Lyocell fiber washed by absolute ethyl alcohol for 3 times, and lightly shaking for 8h to obtain the Lyocell fiber with the surface combined with the nano titanium dioxide by a chemical bond. The SEM image is shown in FIG. 3.

Example 3: water =97, core reactants: γ - (2, 3-glycidoxy) propyltriethoxysilane, and a 1% KOH solution was used to adjust the reaction solution pH =12.40. Adding chemical pulp fiber prepared from softwood into the reaction solution, heating to 55 ℃, and gently shaking to react for 8 hours in total. The softwood chemical pulp fibers were then removed and rinsed 3 times with absolute ethanol. Preparing a dispersion liquid of nano titanium dioxide, wherein the mass concentration of nano zinc oxide is 0.4%, ultrasonically dispersing for 40min by an ultrasonic cleaner, soaking the needle wood chemical pulp fiber which is washed by absolute ethyl alcohol for 3 times, and lightly shaking for 5h to obtain the needle wood chemical pulp fiber of which the surface is combined with the nano titanium dioxide by chemical bonds. The SEM image is shown in FIG. 4.

The nano zinc oxide and the nano titanium dioxide obtained by the preparation method are combined on the surface of the fiber, so that the antibacterial function of the fiber can be fully exerted. In processes such as melt spinning, electrostatic spinning, and dry spinning (solution method) of a chemical synthetic fiber, a large part of nanoparticles are embedded in a fiber structure, and the antibacterial function of the part of nanoparticles cannot be exerted. In the invention, the nano zinc oxide and the nano titanium dioxide are combined on the surface of the fiber in a chemical bond form through a core reactant. The chemical bond is firmest, the nano zinc oxide and nano titanium dioxide particles can not fall off from the surface of the fiber, and the stability is good.

In view of the above, the present invention has been described in detail with reference to the specific embodiments, however, the description is exemplary, and it will be apparent to those skilled in the art that various modifications and variations can be made thereto without departing from the spirit and scope of the invention defined in the appended claims.

Claims

1. A preparation method of hydroxyl fiber with antibacterial function is characterized by comprising the following steps:

s1: preparing a reaction solution, wherein the reaction solution comprises a solvent, a core reactant and a pH reagent, and the preparation process of the reaction solution comprises the following steps: adding the core reactant into the solvent, uniformly mixing, and adjusting the pH value to be alkaline to obtain a reaction solution, wherein the solvent comprises a mixture of alcohol and water; the core reactant comprises a molecular structure: one end of the fiber contains a group which can react with active hydroxyl on the hydroxyl fiber; the other end contains a group which can be combined with the inorganic nano antibacterial agent;

s2: soaking the hydroxyl fibers or a two-dimensional plane material obtained by weaving the hydroxyl fibers in the reaction solution prepared in the step S1; then, heating the mixed system to 35-70 ℃ by using heating equipment under the condition of slight vibration or stirring; or heating the reaction solution to 35-70 ℃, then soaking the hydroxyl fiber or a two-dimensional planar material woven by the hydroxyl fiber in the reaction solution for 30min-15h, taking out the hydroxyl fiber or the two-dimensional planar material woven by the hydroxyl fiber from the reaction solution after the reaction is finished, and washing the two-dimensional planar material for 3 times by absolute ethyl alcohol;

s3: selecting a nano antibacterial substance, and preparing an antibacterial substance dispersion liquid: preparing an alcohol aqueous solution, wherein the volume ratio of alcohol to water is alcohol: water = 80;

s4: adding the fiber or the two-dimensional plane material of the composite core reactant obtained in the step S2 into the antibacterial substance dispersion liquid dispersed in the step S3, and slowly shaking or stirring for 1-24 hours; the nano antibacterial substance is any one of nano zinc oxide, nano titanium dioxide, nano gold and nano silver particles;

when particles of nano zinc oxide or nano titanium dioxide are selected, the core reactant is selected from: gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltriethoxysilane, gamma- (2, 3-glycidoxy) propylmethyldimethoxysilane, gamma- (2, 3-glycidoxy) propyldimethylmethoxysilane, gamma- (2, 3-glycidoxy) propylmethyldiethoxysilane, gamma- (2, 3-glycidoxy) propyldimethylethoxysilane, gamma- (2, 3-glycidoxy) propylphenyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma- (2, 3-epoxypropyl) methylenetrimethoxysilane, gamma- (2, 3-epoxypropyl) methylenetriethoxysilane; when particles of nanogold or nanosilver are selected, the core reactant is selected from any of the aforementioned molecules of silane substituted with a hydrosulfide.

2. The method of claim 1, further characterized in that the elevated temperature is 45-60 ℃; the two-dimensional plane material is paper or fabric.

3. The method according to claim 1 or 2, wherein the nano antibacterial substance has a particle size in the range of 8 to 300nm; the mass concentration of the antibacterial substance dispersion liquid is controlled to be 0.1-2%.

4. The method of claim 3, wherein the alcohol is selected from the group consisting of: any one of methanol, ethanol, propanol, isopropanol, butanol, 2-methylpropanol, 2-methyl-tert-propanol, ethylene glycol or a combination thereof, and the volume ratio of alcohol to water is alcohol: water = 95-100.

5. The method of claim 1,2, or 4, wherein the pH is in the range of 9.5 to 13.

6. The method of claim 1,2, or 4, wherein the pH is in the range of 12 to 13.

7. The method according to any one of claims 1,2 and 4, wherein the dispersing in step S3 is performed by using an ultrasonic wall breaking machine, an ultrasonic cleaning machine, or a high-pressure homogenizer dispersing apparatus.

8. A fiber or fiber product obtained by the method of any one of claims 1 to 7.

9. A fibre or fibre product according to claim 8, which comprises paper or a fabric.