CN108486752B - Preparation method of nano self-cleaning functional knitted woolen fabric - Google Patents

Abstract

The preparation method of nano self-cleaning function knitted woolen fabric of the present invention, the steps comprise: 1) prepare graphene solution, form mixed solvent with dehydrated alcohol and N, N-dimethylformamide and add flake graphite, this mixed solution Place in an ultrasonic cleaner for ultrasonic peeling; centrifuge the suspended mixed solution to remove thick graphite flakes, take the supernatant to obtain a graphene solution; 2) pre-treat the woolen knitted fabric, put the woolen knitted fabric into the graphene Soak in the solution, fully wash and dry with distilled water; 3) prepare graphene/nano-TiO Composite knitted fabric, mix ethanol and butyl titanate, stir to obtain solution A; mix graphene solution with glacial acetic acid to obtain solution B Put the pretreated woolen knitted fabric into solution A while stirring, then slowly add solution B dropwise to solution A while stirring, then take a water bath, then take out the woolen knitted fabric, and dry it. The method of the invention is simple and easy to popularize.

Description

Preparation method of nano self-cleaning functional knitted woolen fabric

technical field

The invention belongs to the technical field of composite knitted fabric preparation, and relates to a preparation method of knitted woolen fabric with nanometer self-cleaning function.

Background technique

Woolen fabrics are generally thick and heavy, and the raw materials used are wool fibers. The felting of wool fibers will affect the shape retention of woolen garments after washing and the retention of shape in the high-grade woolen production process. Therefore, using the special properties of self-cleaning materials to "automatically" achieve the environmental protection functions of removing stains, cleaning and antifouling has become the focus of research at home and abroad.

Graphene (GN) has excellent light transmission properties, and its absorption range is very wide, which is a good saturable absorber; at the same time, the unique low-temperature far-infrared function of graphene can greatly stimulate and enhance the far-infrared function of the human body. , Promote blood circulation. The preparation methods of graphene mainly include liquid phase graphite exfoliation method, chemical vapor deposition method, mechanical exfoliation method and graphene oxide reduction method. Among them, the chemical vapor deposition method usually uses metal as the substrate, which is not suitable for the present invention, and has higher requirements on the instrument; the mechanical stripping method has high requirements on the process and low yield; the graphene produced by the graphene oxide reduction method is greatly damaged. In contrast, the liquid-phase exfoliation method is convenient and feasible, and can produce defect-free graphene.

Nanoscale TiO ₂ has anti-thread, antibacterial, self-cleaning, and anti-aging properties. At present, TiO ₂ mainly uses the advantages of anti-ultraviolet, anti-bacterial, anti-static, matting, anti-aging, self-cleaning, and heat insulation in textiles. According to the preparation conditions of nano-TiO ₂ and the form of the reactant system, the preparation methods mainly include gas-phase method and liquid-phase method. The liquid phase method has a wide range of raw materials, simple operation, low equipment requirements, and is more suitable for laboratory preparation, but the reaction process is generally difficult to control, resulting in uneven product particle size and shape, and high cost, which affects the use effect and application range of the product. The sol-gel method is the most commonly used and convenient method in the liquid phase method. The sol-gel method is to use compounds containing highly chemically active components as precursors, uniformly mix these raw materials in the liquid phase, and perform hydrolysis and condensation chemical reactions to form a stable transparent sol system in the solution, and the sol is aged The colloidal particles are slowly aggregated to form a three-dimensional network structure gel, and the gel network is filled with solvents that have lost fluidity to form a gel. The gel is dried, sintered and solidified to prepare molecular and even nano-substructure materials.

Therefore, a method of compounding graphene and nano-TiO ₂ onto the surface of woolen knitted fabrics by sol-gel method was developed, and a suitable process path was explored to realize the preparation of knitted woolen fabrics (graphene/nano-TiO2) with nano-self-cleaning function. ₂ composite knitted fabrics), it is worth trying.

Contents of the invention

The purpose of the present invention is to provide a preparation method of nano self-cleaning functional knitted woolen fabric, which solves the problems in the prior art that the preparation method of graphene/nano _TiO2 self-cleaning functional knitted fabric is complicated and the product performance is poor.

The technical scheme adopted in the present invention is, a kind of preparation method of nano self-cleaning functional knitted woolen fabric, implement according to the following steps:

Step 1, prepare graphene solution,

A mixed solvent is composed of absolute ethanol and N,N-dimethylformamide, flake graphite is added to the mixed solvent to obtain a mixed solution with a concentration of 2-5mg/mL;

Place the mixed solution in an ultrasonic cleaner and ultrasonically peel it off for 24-60 hours at 30±5°C; after the ultrasonic wave is completed, centrifuge the suspended mixed solution at a speed of 2000-8000r/min for 1 hour to remove thick graphite flakes , keeping single-layer and few-layer graphite flakes suspended in the mixed solution;

Take the supernatant to obtain a graphene solution with high concentration and good stability;

Step 2, pretreatment to the woolen knitted fabric,

Soak the woolen knitted fabric in the graphene solution prepared in step 1, the soaking temperature is 60-90°C, and the time is 60min; after the reaction, fully wash with distilled water, and dry at 70-80°C;

Step 3, preparing graphene/nano TiO Composite knitted fabric,

First mix 28-34ml ethanol with 2ml butyl titanate, stir for 10min to obtain solution A;

Then mix 16-22ml graphene solution with 1-4ml glacial acetic acid to obtain solution B;

Put the woolen knitted fabric pretreated in step 2 into solution A while stirring, then slowly add solution B into solution A while stirring, and then add woolen knitted fabric, solution A, and solution B together Put it into a 70-90°C water bath and keep stirring for 1 hour, then take out the woolen knitted fabric and dry it.

The beneficial effect of the present invention is, adopt liquid phase exfoliation method to prepare graphene solution, and prepare flexible electrode material by sol-gel method, make full use of the advantage of sol-gel method, this preparation method is simple and easy, prepared graphene/ The nano-TiO ₂ composite knitted fabric combines the excellent light absorption performance and far-infrared function of graphene, and the antibacterial, self-cleaning, and anti-aging properties of nano-TiO ₂ can be widely used in wearable smart clothing and other fields.

Description of drawings

Fig. 1 is that the inventive method prepares graphene/nanometer _TiO Composite knitted fabric schematic flow sheet;

Fig. 2 is the surface morphology of raw material graphene;

Fig. 3 is the surface morphology of raw wool fiber;

Fig. 4 is the surface morphology of the wool fiber after the method pretreatment of the present invention;

Fig. 5 is the graphene/nanometer _TiO that the inventive method prepares The surface morphology of wool fiber;

Fig. 6 is a graphene/nano-TiO ₂ composite knitted fabric self-cleaning effect comparison diagram prepared by the method of the present invention.

Detailed ways

The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.

The preparation method of the nano self-cleaning functional knitted woolen fabric of the present invention is implemented according to the following steps:

Step 1, prepare graphene solution,

A mixed solvent is composed of absolute ethanol and N,N-dimethylformamide, and the mass parts ratio of the two components is 9-1:1-9. Flake graphite is added to the mixed solvent to obtain a concentration of 2- 5mg/mL mixed solution;

Place the mixed solution in a (30-60kHz) ultrasonic cleaner, and ultrasonically strip it at 30±5°C for 24-60h; after the ultrasonic is completed, centrifuge the suspended mixed solution at a speed of 2000-8000r/min for 1h , remove the thick graphite flakes, and keep single-layer and few-layer graphite flakes suspended in the mixed solution;

Take the supernatant to obtain a graphene solution with high concentration and good stability.

Step 2, pretreatment to the woolen knitted fabric,

Soak the woolen knitted fabric in the graphene solution prepared in step 1, the soaking temperature is 60-90°C, and the time is 60min; after the reaction, fully wash with distilled water, and dry at 70-80°C;

The woolen knitted fabric of the embodiment is double-colored woolen knitted woolen fabric with a wool-polyester fiber ratio of 45:55, the grammage is 550 g/m ² , and the weave structure is a pad weave. Padding weave is a kind of color weave of knitted fabric. In this weave, one or several laying yarns form hanging arcs on the coils at certain intervals, and are connected by floating threads on the reverse side of the fabric.

Step 3, preparing graphene/nano TiO Composite knitted fabric,

First mix 28-34ml of ethanol (chemically pure) with 2ml of butyl titanate (chemically pure), and stir for 10min to obtain solution A;

Then 16-22ml graphene solution (the graphene solution prepared in step 1) was mixed with 1-4ml glacial acetic acid (chemically pure) to obtain solution B;

Put the woolen knitted fabric pretreated in step 2 into solution A while stirring, then slowly add solution B into solution A while stirring, and then add woolen knitted fabric, solution A, and solution B together Put it into a 70-90°C water bath and keep stirring for 1 hour, then take out the woolen knitted fabric and dry it.

The drying method in step 3 is first drying in an oven at 75°C, and then heating to 130°C for 10 minutes at a constant temperature.

Visible from above, as Fig. 1, preparation method of the present invention, adopts liquid phase exfoliation method to prepare graphene solution earlier, then prepares graphene/nanometer _TiO by sol-gel method Composite knitted fabric; First adopt liquid phase exfoliation method, with The mixed solution of absolute ethanol and N,N-dimethylformamide is the dispersion liquid, and the graphene solution is prepared by ultrasonic stripping; secondly, the woolen knitted fabric is pretreated, that is, soaked in the graphene solution, so that the graphene is easier to load to the fiber surface, wash the treated fabric with distilled water, and dry; finally, use the sol-gel method to load graphene and nano-TiO ₂ on the surface of the wool fiber, and finally wash and dry with distilled water to obtain a fabric with good self-cleaning performance. Functional knitted woolen fabric.

Figure 2 is the surface morphology of graphene. It can be seen that the graphene prepared by flake graphite liquid phase exfoliation has obvious wrinkles, lighter color and fewer graphene layers;

Fig. 3 is the surface morphology of the raw material wool fiber, the scaly fiber seen is wool, and the surface integrity and cleanliness of the wool are better;

Fig. 4 is the surface morphology of the wool fiber after pretreatment, and it can be seen that the fiber surface is covered with flake graphene in various degrees, indicating that the pretreatment process has arranged (attached) graphene to the fiber surface;

Figure 5 shows the surface morphology of graphene/nano-TiO2 wool fiber. It can be seen that the graphene sheets on the surface of the fiber are embedded in a dense film, indicating that nano-TiO2 and graphene have been tightly and stably loaded on the wool fiber surface ;

Figure 6 is a graphene/nano-TiO ₂ composite knitted fabric self-cleaning comparison diagram, as can be seen from the changes in Figure 6, the fabric as it is and the sample after finishing after about 10 days of natural light irradiation, remaining in the sample after finishing The oil stains on the fabric are completely decomposed, while the oil stains remaining on the original fabric remain unchanged, indicating that the graphene/nano-TiO2/composite knitted fabric has a good decontamination effect and a short time.

Example 1

Step 1, prepare the graphene solution: form a mixed solvent with absolute ethanol and N, N-dimethylformamide (the mass ratio of the two is 7:3), add flake graphite, and obtain a mixed solution with a concentration of 2mg/mL 30kHz Ultrasonic peeling at 30°C for 24 hours in an ultrasonic cleaner. After the ultrasonication was completed, the suspended mixed solution was centrifuged at a speed of 2000 r/min for 1 h to remove the thick graphite flakes and obtain single-layer and few-layer graphene sheets suspended in the mixed solution. Take the supernatant to obtain a graphene solution with high concentration and good stability.

Step 2. Pretreatment of the woolen knitted fabric: soaking the woolen knitted fabric in the graphene solution prepared in step 1 at a temperature of 60° C. for 60 minutes. After the reaction, wash thoroughly with distilled water and dry at 75°C;

Step 3. Preparation of graphene/nano-TiO2 composite knitted fabric: first mix 28ml of ethanol (EtOH) with 2ml of butyl titanate, and stir for 10min to obtain solution A. Then 16ml of graphene (GN) solution was mixed with 1ml of glacial acetic acid to obtain solution B. Put the woolen knitted fabric pretreated in step 2 into solution A while stirring, then slowly add solution B dropwise into solution A, and then put it into a 75°C water bath and continue stirring for 1 hour. Then take out the sample, dry it, and serve.

Example 2

Step 1, prepare graphene solution: form a mixed solvent with absolute ethanol and N, N-dimethylformamide (the mass ratio of the two is 5:5), add flake graphite to obtain a mixed solution with a concentration of 3mg/mL 40kHz ultrasonic wave Ultrasonic stripping at 31°C for 36 hours in a cleaner. After the ultrasonication was completed, the suspended mixed solution was centrifuged at a speed of 4000 r/min for 1 h to remove the thick graphite flakes and obtain single-layer and few-layer graphene sheets suspended in the mixed solution. Take the supernatant to obtain a graphene solution with high concentration and good stability.

Step 2. Pretreatment of the woolen knitted fabric: soaking the woolen knitted fabric in the graphene solution prepared in step 1 at a temperature of 70° C. for 60 minutes. After the reaction, wash thoroughly with distilled water and dry at 70°C;

Step 3, prepare graphene/nano-TiO Composite knitted fabric: first 30ml ethanol (EtOH) is mixed with 2ml butyl titanate, stir 10min, obtain solution A; Then 18ml graphene (GN) solution is mixed with 2ml glacial acetic acid, Solution B is obtained. Put the wool knitted fabric pretreated in step 2 into solution A while stirring, then slowly add solution B dropwise into solution A, and then put it into a water bath at 85° C. and continue stirring for 1 hour. The samples were then removed and dried.

Example 3

Step 1, prepare graphene solution: form a mixed solvent with absolute ethanol and N, N-dimethylformamide (the mass ratio of the two is 3:7), add flake graphite to obtain a mixed solution with a concentration of 4mg/mL 50kHz ultrasonic wave Ultrasonic stripping at 30°C for 48 hours in a cleaner. After the ultrasonication was completed, the suspended mixed solution was centrifuged at a speed of 6000 r/min for 1 h to remove the thick graphite flakes and obtain single-layer and few-layer graphene sheets suspended in the mixed solution. Take the supernatant to obtain a graphene solution with high concentration and good stability.

Step 2. Pretreatment of the woolen knitted fabric: soaking the woolen knitted fabric in the graphene solution prepared in step 1 at a temperature of 80° C. for 60 minutes. After the reaction, wash thoroughly with distilled water and dry at 75°C;

Step 3, prepare graphene/nano-TiO Composite knitted fabric: first 32ml ethanol (EtOH) is mixed with 2ml butyl titanate, stir 10min, obtain solution A; Then 20ml graphene (GN) solution is mixed with 3ml glacial acetic acid, Solution B is obtained. Put the woolen knitted fabric pretreated in step 2 into solution A while stirring, then slowly add solution B dropwise into solution A, and then put it into a water bath at 80° C. and continue stirring for 1 hour. The samples were then removed and dried.

Example 4

Step 1, prepare graphene solution: form a mixed solvent with absolute ethanol and N, N-dimethylformamide (the mass ratio of the two is 1:9), add flake graphite to obtain a mixed solution with a concentration of 5mg/mL 60kHz ultrasonic Ultrasonic stripping at 32°C for 60h in a cleaner. After the ultrasonication was completed, the suspended mixed solution was centrifuged at a speed of 8000 r/min for 1 h to remove the thick graphite flakes and obtain single-layer and few-layer graphene sheets suspended in the mixed solution. Take the supernatant to obtain a graphene solution with high concentration and good stability.

Step 2. Pretreatment of the woolen knitted fabric: soaking the woolen knitted fabric in the graphene solution prepared in step 1 at a temperature of 90° C. for 60 minutes. After the reaction, wash thoroughly with distilled water and dry at 80°C;

Step 3, prepare graphene/nano-TiO Composite knitted fabric: first 34ml ethanol (EtOH) is mixed with 2ml butyl titanate, stir 10min, obtain solution A; Then 22ml graphene (GN) solution is mixed with 4ml glacial acetic acid, Solution B is obtained. Put the woolen knitted fabric pretreated in step 2 into solution A while stirring, then slowly add solution B into solution A dropwise, and then put it into a 90° C. water bath and continue stirring for 1 hour. The samples were then removed and dried.

Example 5

Step 1, prepare graphene solution: form a mixed solvent with absolute ethanol and N, N-dimethylformamide (the mass ratio of the two is 7:3), add flake graphite to obtain a mixed solution with a concentration of 2mg/mL 30kHz ultrasonic Ultrasonic stripping at 34°C for 24 hours in a cleaner. After the ultrasonication was completed, the suspended mixed solution was centrifuged at a speed of 2000 r/min for 1 h to remove the thick graphite flakes and obtain single-layer and few-layer graphene sheets suspended in the mixed solution. Take the supernatant to obtain a graphene solution with high concentration and good stability.

Step 2, pretreatment to woolen knitted fabric: step is with reference to embodiment 1;

Step 3, prepare graphene/nano-TiO Composite knitted fabric: first 28ml ethanol (EtOH) is mixed with 2ml butyl titanate, stir 10min, obtain solution A; Then 16ml graphene (GN) solution is mixed with 1ml glacial acetic acid, Solution B is obtained. Put the woolen knitted fabric pretreated in step 2 into solution A while stirring, then slowly add solution B dropwise into solution A, and then put it into a 75°C water bath and continue stirring for 1 hour. The samples were then removed and dried.

Example 6

Step 1, prepare graphene solution: form a mixed solvent with absolute ethanol and N, N-dimethylformamide (the mass ratio of the two is 4:6), add flake graphite to obtain a mixed solution with a concentration of 3mg/mL 40kHz ultrasonic wave Ultrasonic stripping at 30°C for 36 hours in a cleaner. After the ultrasonication was completed, the suspended mixed solution was centrifuged at a speed of 4000 r/min for 1 h to remove the thick graphite flakes and obtain single-layer and few-layer graphene sheets suspended in the mixed solution. Take the supernatant to obtain a graphene solution with high concentration and good stability.

Step 2, pretreatment to woolen knitted fabric: step is with reference to embodiment 2;

Step 3, prepare graphene/nano-TiO Composite knitted fabric: first 30ml ethanol (EtOH) is mixed with 2ml butyl titanate, stir 10min, obtain solution A; Then 18ml graphene (GN) solution is mixed with 2ml glacial acetic acid, Solution B is obtained. Put the wool knitted fabric pretreated in step 2 into solution A while stirring, then slowly add solution B dropwise into solution A, and then put it into a water bath at 85° C. and continue stirring for 1 hour. The samples were then removed and dried.

Claims (1)

1. A preparation method of a nano self-cleaning knitted woolen fabric is characterized by comprising the following steps:

Step 1, preparing a graphene solution,

Forming a mixed solvent by using absolute ethyl alcohol and N, N-dimethylformamide, wherein the mass part matching ratio of the absolute ethyl alcohol to the N, N-dimethylformamide is 9-1:1-9, and adding crystalline flake graphite into the mixed solvent to obtain a mixed solution with the concentration of 2-5 mg/mL;

placing the mixed solution in an ultrasonic cleaner, and ultrasonically stripping for 24-60h at the temperature of 30 +/-5 ℃; after the ultrasonic treatment is finished, centrifuging the suspended mixed solution for 1h at the speed of 2000-8000r/min, removing thick graphite flakes, and keeping single-layer and few-layer graphite flakes suspended in the mixed solution;

Taking the supernatant to obtain a graphene solution with high concentration and good stability;

Step 2, pretreating the woolen knitted fabric,

the woolen knitted fabric adopts a woolen-polyester fiber ratio of 45: 55, putting the woolen knitted fabric into the graphene solution prepared in the step 1 for soaking at the temperature of 60-90 ℃ for 60 min; after the reaction, fully washing the mixture by using distilled water, and drying the mixture at 70-80 ℃;

Step 3, preparing the graphene/nano TiO2 composite knitted fabric,

Mixing 28-34ml of ethanol and 2ml of butyl titanate, and stirring for 10min to obtain a solution A;

Mixing 16-22ml of graphene solution with 1-4ml of glacial acetic acid to obtain a solution B;

Putting the woolen knitted fabric pretreated in the step 2 into the solution A while stirring, slowly dripping the solution B into the solution A while stirring, putting the woolen knitted fabric, the solution A and the solution B into a 70-90 ℃ water bath together, continuously stirring for 1h, taking out the woolen knitted fabric, and drying to obtain the woolen knitted fabric,

the drying method comprises drying in a 75 deg.C oven, heating to 130 deg.C, and keeping the temperature for 10 min.