CN103161066B - Method for modifying and dyeing cotton fibers by adopting tetrabutyl titanate and reactive dyes - Google Patents

Abstract

The invention discloses a method for modifying and dyeing cotton fibers by using tetrabutyl titanate and reactive dyes. Firstly, the cotton fibers are pretreated, and then the pretreated cotton fibers are dyed with reactive dyes, and then titanium Tetrabutyl acid modified solution, the modified solution is added in the late stage of dyeing to modify the dyed cotton fiber, and finally, the dyed modified cotton fiber is post-treated. The method of the invention realizes the simultaneous progress of cotton fiber dyeing and nano-titanium dioxide loading, and the cotton fiber obtained after modified dyeing has good anti-ultraviolet, antibacterial and light-resistant color fastness.

Description

A kind of method adopting tetrabutyl titanate and reactive dyestuff to modify and dye cotton fiber

technical field

The invention belongs to the technical field of functional textile materials, and relates to a method for dyeing and modifying cotton fibers, in particular to a method for modifying and dyeing cotton fibers by using tetrabutyl titanate and reactive dyes.

Background technique

Nano-titanium dioxide is a very important inorganic semiconductor material. Its unique ultraviolet shielding ability, photocatalytic activity and color effect make it popular as soon as it comes out. It has broad applications in sun protection, sterilization, wastewater treatment, environmental protection and automobile industry. application prospects. Using the properties of nano-titanium dioxide such as high temperature resistance, refractory decomposition, non-toxicity, long-lasting function and good compatibility with polymers, textile fibers and fabrics with multiple functions can be prepared. The preparation methods of nano titanium dioxide mainly include gas phase method, liquid phase method and solid phase method. In contrast, the liquid-phase method has the advantages of low synthesis temperature, simple equipment, and easy operation. Liquid phase methods mainly include liquid phase precipitation, sol-gel, microemulsion, and hydrothermal methods. Among them, the nanocrystals prepared by the hydrothermal method have the advantages of complete grain development, small particle size, uniform distribution, and light particle agglomeration. Moreover, the grain phase and morphology can be controlled.

At present, there is no research on the dyeing modification of cotton fibers using reactive dyes and tetrabutyl titanate under hydrothermal conditions. There are two main methods for surface modification of textile materials: one is to prepare functional fibers containing nanoparticles, that is, the nanoparticles are dispersed in the spinning raw materials during the spinning process and spun into fibers. The advantages are long-lasting performance and the disadvantages are The reason is that the affinity between nanoparticles and polymer materials is poor, the dispersion of nanoparticles is uneven, and the agglomeration phenomenon is serious. Most of the nanoparticles are embedded in the fiber matrix, while there are very few nanoparticles on the surface of the fiber, so the properties of nanoparticles cannot be well exerted. performance, the functionality of the material is greatly reduced; the second is to use the post-finishing process to arrange the nanoparticles to the surface of the fiber or fabric, and usually use adhesives and auxiliaries to adhere the nanoparticles to the surface of the fiber or fabric. The problem of nanoparticle agglomeration, and the washing fastness of the finished fabric is not good, the wearing performance is greatly affected, and the hand feeling is obviously deteriorated.

Contents of the invention

The purpose of the present invention is to provide a method for modifying and dyeing cotton fibers using tetrabutyl titanate and reactive dyes, which realizes the simultaneous progress of cotton fiber dyeing and nano-titanium dioxide loading, and the cotton fibers obtained after modified dyeing have good Anti-ultraviolet, antibacterial, color fastness to sunlight.

The technical scheme adopted in the present invention is, a kind of method adopting tetrabutyl titanate and reactive dyestuff to modify and dye cotton fiber, specifically implement according to the following steps:

Step 1, carrying out pretreatment to cotton fiber;

Step 2, using reactive dyes to dye the pretreated cotton fibers;

Step 3, preparing a tetrabutyl titanate modified solution, adding the modified solution in the later stage of dyeing to modify the dyed cotton fiber;

Step 4, post-processing the dyed and modified cotton fibers.

The present invention is also characterized in that,

Step 1 is specifically implemented according to the following steps:

1.1) Weigh cotton fiber;

1.2) Soak the weighed cotton fibers in a sodium hydroxide solution with a mass-volume concentration of 3.0 to 6.0 g/L, and treat them at 80°C to 100°C for 30min to 50min, then wash them with absolute ethanol and deionized water Wash at 60°C for 10min to 20min respectively;

1.3) Take out the cleaned cotton fibers and dry them at 70°C to 90°C to obtain pretreated cotton fibers.

Step 2 is specifically implemented according to the following steps:

2.1) Weigh 1% to 2% of the mass of the pretreated cotton fiber obtained in step 1 to weigh the active Cuilan KN-G dye;

2.2) According to the bath ratio of cotton fiber and deionized water is 1:30~50, measure deionized water;

2.3) Weigh sodium sulfate and sodium carbonate according to the ratio of dissolving 50g-70g sodium sulfate and 10g-20g sodium carbonate per liter of deionized water;

2.4) Dissolve the reactive Cuilan KN-G dye weighed in step 2.1) in the deionized water measured in step 2.2), and put it into the pretreated cotton fiber for dyeing at 40°C-50°C. Then add one-half of the sodium sulfate weighed in step 2.3) and keep stirring. After 10-15 minutes, add another half of the sodium sulfate and continue stirring. min～2℃/min to 80℃～90℃, add 1/2 of the sodium carbonate weighed in step 2.3) after 10min～15min, add another 1/2 of the sodium carbonate after 10min～20min, and Stir continuously, and finish the dyeing treatment after 10min to 20min.

Step 3 is specifically implemented according to the following steps:

3.1) Weigh tetrabutyl titanate according to the mass of pretreated cotton fiber, and the mass ratio of cotton fiber to tetrabutyl titanate is 3-6:1;

3.2) Measure absolute ethanol according to the tetrabutyl titanate weighed in step 3.1), and the volume ratio of tetrabutyl titanate to absolute ethanol is 1:10-30;

3.3) Dissolve the tetrabutyl titanate weighed in step 3.1) in the absolute ethanol measured in step 3.2), and stir to prepare tetrabutyl titanate modified solution;

3.4) Slowly add the tetrabutyl titanate modified solution prepared in step 3.3) dropwise into the dyeing solution containing cotton fibers obtained in step 2, stirring continuously while adding dropwise, and mix the solution at 1°C/min～2°C Raise the temperature at a rate of 110°C to 130°C per minute, treat at a constant temperature for 2h to 4h, and take out the cotton fiber after the reaction is completed.

Step 4 is specifically implemented according to the following steps:

4.1) Wash the dyed and modified cotton fiber obtained in step 3 with a washing solution at a bath ratio of 1:30 to 50 at 70°C to 90°C for 10min to 20min;

4.2) Wash the washed cotton fiber with hot water and cold water repeatedly for 3 times;

4.3) Dry or dry naturally to obtain dyed and modified cotton fibers.

The washing solution in step 4.1) is formed by mixing the soap flake solution with a mass volume concentration of 2 g/L and the sodium carbonate solution with a mass volume concentration of 2 g/L.

The beneficial effect of the present invention is,

The method for modifying and dyeing cotton fibers using tetrabutyl titanate and reactive dyes of the present invention uses reactive turquoise blue KN-G dyes to dye cotton fibers under normal temperature conditions, which can protect the reactive dyes to the greatest extent. Cotton fibers can be dyed with reactive dyes at low temperature without thermal hydrolysis of the dyes, ensuring uniform dyeing of cotton fibers, high dye uptake rate and deep dyeing. In the later stage of dyeing, tetrabutyl titanate modified finishing solution is added. At this time, most of the dyes in the solution have chemically reacted with cotton fibers, and there are very few remaining dyes in the solution. Titanium dioxide has little effect, ensuring that nano-titanium dioxide can be well coated on the surface of cotton fibers, thereby endowing cotton fibers with functions such as UV resistance, antibacterial and self-cleaning. The finishing process is optimized by controlling the amount of dyes, sodium sulfate and sodium carbonate, reaction temperature and time, and the amount of tetrabutyl titanate. The method saves raw materials and is easy to operate. Because the dyed and modified solution contains a certain amount of nano-titanium dioxide particles, under sunlight or ultraviolet radiation, the remaining dyes and organic pollutants in the solution can be photocatalytically degraded, reducing environmental pollution. The test results show that the cotton fiber dyed with reactive dyes and modified with tetrabutyl titanate nano-titanium dioxide has high dye utilization rate, uniform dyeing, nano-titanium dioxide film loaded on the surface, good color fastness to sunlight, anti-ultraviolet, antibacterial and self-cleaning ability.

The method of the present invention solves the problem that cotton fiber dyeing and nano-titanium dioxide loading cannot be realized simultaneously, and the cotton fiber obtained by the existing modification method has low anti-ultraviolet and antibacterial properties, poor color fastness to sunlight, and lack of self-cleaning function , and the printing and dyeing wastewater after dyeing is treated with sunlight or ultraviolet radiation, and the remaining dye macromolecules in the solution can be further photocatalytically degraded, reducing environmental pollution and achieving the purpose of environmental protection. Compared with the production and processing methods of other functional textile products, the production process is greatly simplified, the cost of raw materials is saved, and the added value of products is increased.

Description of drawings

Fig. 1 is the scanning electron micrograph before cotton fiber modification;

Fig. 2 is the scanning electron microscope photo after adopting the inventive method to cotton fiber dyeing modification;

Fig. 3 is the electron diffraction figure of the nano-titanium dioxide particles coated on the surface after the cotton fiber is dyed and modified by the method of the present invention;

Fig. 4 is the ultraviolet-visible light diffuse reflectance spectrum curve of cotton fiber before and after dyeing and modification.

Detailed ways

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

A method of modifying and dyeing cotton fibers using tetrabutyl titanate and reactive dyes of the present invention is to use reactive dyes to dye cotton fibers and then add tetrabutyl titanate precursors to modify the cotton fibers, specifically as follows Steps to implement:

Step 1, pretreatment of cotton fibers:

1.1) Weigh cotton fiber;

1.2) Soak the weighed cotton fiber in a sodium hydroxide solution with a mass-volume concentration of 3.0g/L to 6.0g/L, and treat it at 80°C to 100°C for 30min to 50min, then wash it with absolute ethanol, Wash with deionized water at 60°C for 10min to 20min respectively;

1.3) Take out the cleaned cotton fibers and dry them at 70°C to 90°C to obtain pretreated cotton fibers.

Step 2, using reactive dyes to dye the pretreated cotton fibers:

2.1) Weigh 1% to 2% of the mass of the pretreated cotton fiber obtained in step 1 to weigh the active Cuilan KN-G dye;

2.2) According to the bath ratio of cotton fiber and deionized water is 1:30~50, measure deionized water;

2.3) Weigh sodium sulfate and sodium carbonate according to the ratio of dissolving 50g-70g sodium sulfate and 10g-20g sodium carbonate per liter of deionized water;

2.4) Dissolve the reactive Cuilan KN-G dye weighed in step 2.1) in the deionized water measured in step 2.2), and put it into the pretreated cotton fiber for dyeing at 40°C-50°C. Then add one-half of the sodium sulfate weighed in step 2.3) and keep stirring, add another half of the sodium sulfate after 10min~15min, continue stirring, after dyeing for 10min~15min, the dyeing solution is heated at 1℃/ min～2℃/min to 80℃～90℃, add 1/2 of the sodium carbonate weighed in step 2.3) after 10min～15min, add another 1/2 of the sodium carbonate after 10min～20min, and Stir continuously, and finish the dyeing treatment after 10min to 20min.

Step 3, preparing tetrabutyl titanate modified solution, adding the modified solution to modify the dyed cotton fiber in the later stage of dyeing:

3.1) Weigh tetrabutyl titanate according to the mass of pretreated cotton fiber, and the mass ratio of cotton fiber to tetrabutyl titanate is 3-6:1;

3.2) Measure absolute ethanol according to the tetrabutyl titanate weighed in step 3.1), and the volume ratio of tetrabutyl titanate to absolute ethanol is 1:10-30;

3.3) Dissolve the tetrabutyl titanate weighed in step 3.1) in the absolute ethanol measured in step 3.2), and stir to prepare tetrabutyl titanate modified solution;

3.4) Slowly add the tetrabutyl titanate modified solution prepared in step 3.3) dropwise into the dyeing solution containing cotton fibers obtained in step 2, stirring continuously while adding dropwise, and mix the solution at 1°C/min～2°C Raise the temperature at a rate of 110°C to 130°C per minute, treat at a constant temperature for 2h to 4h, and take out the cotton fiber after the reaction is completed.

Step 4, carry out aftertreatment to the cotton fiber after the dyeing modification:

4.1) Wash the dyed and modified cotton fibers obtained in step 3 with a washing liquid at a bath ratio of 1:30 to 50 at a temperature of 70°C to 90°C for 10 minutes to 20 minutes, wherein the washing liquid is determined by mass volume concentration It is prepared by mixing 2g/L soap flake solution and 2g/L sodium carbonate solution with a mass volume concentration

4.2) Wash the washed cotton fiber 3 times with hot water and cold water repeatedly.

4.3) Dry or dry naturally to obtain dyed and modified cotton fibers.

Figure 1 is a scanning electron micrograph of cotton fiber before dyeing and modification. It can be seen that the surface of the undyed and modified cotton fiber is relatively clean without other attachments. Fig. 2 is a scanning electron micrograph of cotton fiber after dyeing cotton fiber with reactive dye and then adding tetrabutyl titanate modification solution to modify cotton fiber. It can be seen that the surface of the dyed and modified cotton fiber is coated with a film-like substance, and the high-power electron microscope photos show that the film is composed of nano-scale particles. Fig. 3 is an electron diffraction ring of nano titanium dioxide particles coated on the surface of dyed modified cotton fiber. It can be seen that the electron diffraction rings of nano-titanium dioxide correspond to (101), (004), (200), (105) and (211) crystal planes of anatase phase titanium dioxide, respectively. Fig. 4 is the ultraviolet-visible light diffuse reflectance spectrum curve of cotton fiber before and after dyeing and modification. It can be seen that after the cotton fiber is dyed with reactive Cuilan KN-G dye and hydrothermally modified with tetrabutyl titanate, not only the absorption of ultraviolet rays is significantly enhanced, but also the visible light is also increased.

Measure the absorbance of the solution at the maximum absorption wavelength of 680nm before and after the cotton fiber dyeing and modification treatment by the residual liquid colorimetry method with a 7220N spectrophotometer, and calculate the dye uptake E according to the formula (1):

$\mathrm{<span\; class="notranslate">\; E.</span>}<span\; class="notranslate">\; =</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 1</span>}<span\; class="notranslate">\; -</span>\frac{{\mathrm{<span\; class="notranslate">\; C</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}}{{\mathrm{<span\; class="notranslate">\; C</span>}}_{\mathrm{<span\; class="notranslate">\; 0</span>}}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; no</span>}}<span\; class="notranslate">\; )</span><span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; 100</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 1</span>}<span\; class="notranslate">\; )</span><span\; class="notranslate">\; ;</span>$

In the formula, _C1 is the absorbance of the raffinate; _C0 is the absorbance of the stock solution; n is the dilution factor of the stock solution and the raffinate.

Measure 50mL of the residual solution after dyeing and modification, and irradiate it under sunlight with an illumination of 8.5× ¹⁰⁴ lux for 2h, and use a 7220N spectrophotometer to measure the absorbance of the solution at the maximum absorption wavelength of 680nm, and according to the formula (2) Calculate the degradation rate D of the dye:

$\mathrm{<span\; class="notranslate">\; D.</span>}<span\; class="notranslate">\; =</span>\frac{{\mathrm{<span\; class="notranslate">\; A</span>}}_{\mathrm{<span\; class="notranslate">\; 0</span>}}<span\; class="notranslate">\; -</span>{\mathrm{<span\; class="notranslate">\; A</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}}{{\mathrm{<span\; class="notranslate">\; A</span>}}_{\mathrm{<span\; class="notranslate">\; 0</span>}}}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; 100</span>}<span\; class="notranslate">\; \%</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 2</span>}<span\; class="notranslate">\; )</span><span\; class="notranslate">\; ;</span>$

In the formula, A ₀ is the initial absorbance of the dyed modified raffinate; A ₁ is the absorbance of the dyed modified raffinate irradiated for 2 h.

Use the SF300 color measuring and matching instrument to measure the dyeing depth K/S value of cotton fiber at the maximum absorption wavelength of 680mm, choose D65 light source, and 10° field of view. According to the national standard GB/T8427-2008 "Textile color fastness test to artificial light color fastness: xenon arc", the dyed modified cotton fiber was tested for artificial light resistance (xenon arc lamp) with YG611 type light and weather color fastness tester ) irradiation, use the blue wool standard to evaluate the color fastness to artificial light. According to the national standard GB/T8629-2001 "Household Washing and Drying Procedures for Textile Testing", the cotton fibers dyed with reactive dyes tetrabutyl titanate hydrothermally modified are washed and dried (type A washing machine, 7A washing procedure, C-type drying procedure), and according to the national standard GB/T20944.1-2007 "Evaluation of antibacterial properties of textiles Part 1: Agar plate diffusion method", the antibacterial effect of cotton fibers was determined. According to the national standard GB/T18830-2009 "Assessment of UV protection performance of textiles", the UV protection performance of cotton fiber was determined.

Cotton fibers were stained with strawberry juice, and the self-cleaning properties of cotton fibers were evaluated using UV irradiation. Pull 0.3g of cotton fiber into a straight sliver by hand, fix it on a foam board with a pin, add 0.5ml of strawberry juice with a mass concentration of 100%, and then place it under a 30W ultraviolet lamp for irradiation. The main wavelength of the lamp is 254nm, and the distance between the light source and the cotton fiber is 15cm. When the strawberry juice stained with cotton fibers changed completely from red to colorless, the time of ultraviolet irradiation was recorded. The shorter the irradiation time, the stronger the self-cleaning ability of cotton fiber.

The beneficial effect of the present invention is explained from the principle aspect:

(1) Using reactive dyes to dye cotton fibers at a lower temperature can ensure that the dyes are better dyed on the cotton fibers, improve the utilization rate of the dyes, dye the cotton fibers evenly, and have good color fastness. Then add the tetrabutyl titanate modification solution. At this time, there is less residual dye in the solution, which can ensure that the tetrabutyl titanate precursor smoothly generates nano-titanium dioxide particles and is better coated on the surface of the cotton fiber. When the amount of reactive Cuilan KN-G dye is 1-2%, the dyeing rate of cotton fiber is high, and the remaining dye in the solution is very little, which will not affect the growth of nano-titanium dioxide crystals; when the amount of dye is less than 1%, the cotton fiber The K/S value of the dyeing depth is too small, and the color is light; when the amount of dye is more than 2%, the dyeing rate of cotton fiber decreases, and the residual dye in the reaction solution is too much, which affects the formation of nano-titanium dioxide particles.

(2) When the amount of sodium sulfate is 50g/L-70g/L, the dyeing rate of cotton fiber can be improved, and at the same time it will not affect the formation of nano-titanium dioxide and the coating of cotton fiber; when the amount of sodium sulfate is less than 50g/L At L, the dyeing rate of cotton fiber decreased, and the color was not deep; when the amount of sodium sulfate was greater than 70g/L, the growth of nano-titanium dioxide was affected. When the amount of sodium carbonate is 10g/L～20g/L, the cotton fiber is better fixed with reactive dyes, and the coating effect of nano-titanium dioxide is good; when the amount of sodium carbonate is less than 10g/L, the color fastness of cotton fiber is not good; When the amount of sodium is greater than 20g/L, it not only causes waste, but also affects the formation of nano-titanium dioxide.

(3) The proportion of cotton fiber and tetrabutyl titanate affects the amount of nano titanium dioxide produced by the reaction and the effect of cotton fiber surface coating. When the mass ratio of cotton fiber to tetrabutyl titanate is 3-6:1, a certain thickness of nano-titanium dioxide film can be coated on the surface of cotton fiber, and at the same time, too many nanoparticles will not be deposited in the solution; when it is less than 3-6 : 1, the amount of tetrabutyl titanate is too large, and most of the nano-titanium dioxide is deposited at the bottom of the solution, which is easy to cause waste; when it is greater than 3-6: 1, the amount of nano-titanium dioxide particles coated on the surface of the cotton fiber is too small to reach Anti-ultraviolet, antibacterial effect.

(4) Using absolute ethanol solution to dissolve tetrabutyl titanate can effectively prevent the hydrolysis of tetrabutyl titanate. When the volume ratio of tetrabutyl titanate and absolute ethanol is 1:10-30, it can guarantee the complete dilution of tetrabutyl titanate, slow grain growth and small grain size; when tetrabutyl titanate and no When the volume ratio of water to ethanol is less than 1:10-30, tetrabutyl titanate cannot be completely diluted. When it is added to the dyeing solution, it will be hydrolyzed quickly, the grain growth will be accelerated, the grain size will increase, and agglomeration will easily occur. ; When the volume ratio of tetrabutyl titanate to absolute ethanol is greater than 1:10-30, it is easy to cause waste of absolute ethanol.

(5) When the reaction temperature is controlled at 110-130°C, the damage to the mechanical properties of cotton fibers is small, and anatase phase nano-titanium dioxide can be generated; when the reaction temperature is lower than 110°C, the crystal form of nano-titanium dioxide is not well developed; when the reaction When the temperature is higher than 130 °C, the growth rate of titanium dioxide crystals is accelerated, because the nucleation process is an exothermic process, and the increase in temperature is not conducive to the hydrolysis reaction in the direction of nucleation, so that the number of crystal nuclei in the system is relatively small, and the temperature Elevation also leads to an increase in the critical crystal nucleus size that can exist stably. When the reaction time is 2h-4h, the grain size of titanium dioxide is small; when the reaction time is less than 2h, the crystal form of nano-titanium dioxide is not good; Then it decreases, the grain size increases obviously, and the binding fastness with cotton fiber becomes worse.

Example 1

Soak 5g of cotton fiber in a sodium hydroxide solution with a mass concentration of 3.0g/L, treat it at 80°C for 50min, then wash it with absolute ethanol and deionized water at 60°C for 10min, and then wash it at 70°C Dry at ℃; weigh 0.05g of reactive Cuilan KN-G dye according to 1% of the cotton fiber mass, measure 150mL of deionized water according to the bath ratio of 1:30, and weigh 7.5g according to the volume of deionized water Sodium sulfate and 1.5g of sodium carbonate, Dissolve reactive Cuilan KN-G dye in deionized water at 40°C, put it into the pretreated cotton fiber for dyeing, add 3.75g of sodium sulfate and keep stirring, add after 10min Another 3.75g of sodium sulfate, continue to stir, after dyeing for 10min, the solution is heated up to 80°C at a rate of 1°C/min, after 10min, add 0.75g of sodium carbonate, after 15min, add another 0.75g of sodium carbonate, and keep stirring for 15min The post-dyeing is completed; according to the mass ratio of cotton fiber and tetrabutyl titanate of 3:1, weigh 1.67g of tetrabutyl titanate, and according to the volume ratio of tetrabutyl titanate and absolute ethanol of 1:10, weigh 18mL of anhydrous Ethanol, dissolve tetrabutyl titanate in absolute ethanol, and stir to prepare tetrabutyl titanate modified solution, slowly add tetrabutyl titanate modified solution to the dyeing solution, while adding While stirring continuously, raise the temperature of the mixed solution to 110°C at a rate of 1°C/min, and treat it at a constant temperature for 4 hours; after the reaction is completed, take out the cotton fiber, and measure soap flakes with a mass volume concentration of 2g/L according to a bath ratio of 1:30 The washing solution is mixed with the sodium carbonate solution with a mass volume concentration of 2g/L, and the cotton fiber is treated at 70°C for 20 minutes, followed by repeated washing with hot water and cold water for 3 times, and then dried.

Using the residual liquid colorimetric method, the absorbance of the solution at the maximum absorption wavelength of 680nm was measured with a 7220N spectrophotometer before and after the cotton fiber dyeing modification treatment, and the dye uptake rate of the cotton fiber was calculated to be 74%. Measure 50mL of the dyed and modified residual solution, irradiate it under sunlight with an illumination of 8.5× ¹⁰⁴ lux for 2h, measure the absorbance of the solution at the maximum absorption wavelength of 680nm with a 7220N spectrophotometer, and calculate the degradation rate of the dye 85%. The K/S value of the dyeing depth of the dyed modified cotton fiber at the maximum absorption wavelength of 680mm was measured with a SF300 color measuring and matching instrument to be 0.9. According to the national standard GB/T8427-2008 "Textile color fastness test to artificial light color fastness: xenon arc", use YG611 type light and weather color fastness tester to measure the artificial light resistance (xenon arc lamp) of dyed modified cotton fiber The color fastness is grade 5. According to the national standard GB/T8629-2001 "Household Washing and Drying Procedures for Textile Testing", wash and dry the dyed and modified cotton fibers (select A-type washing machine, 7A washing procedure, C-type drying procedure), and according to the national Standard GB/T20944.1-2007 "Evaluation of Antibacterial Performance of Textiles Part 1: Agar Plate Diffusion Method", to determine the antibacterial effect of dyed and modified cotton fibers on Staphylococcus aureus (ATCC6538), Escherichia coli ( 8099), the antibacterial zone is within 1.0mm, no reproduction, and the antibacterial effect is good. According to the national standard GB/T18830-2009 "Assessment of UV protection performance of textiles", the spectral transmittance in the UVB and UVA bands of the dyed and modified cotton fibers was determined to be 3.7% after 30 washes, and the UV protection coefficient was 62. It shows that the dyed and modified cotton fiber has the ability to shield ultraviolet rays, and the combination of nano-titanium dioxide and cotton fiber is firm. The self-cleaning performance of cotton fibers was evaluated by UV irradiation on cotton fibers stained with strawberry juice. After 240 min of UV irradiation, the color of strawberry juice stained on the cotton fiber surface completely disappeared.

Example 2

Soak 5g of cotton fiber in a sodium hydroxide solution with a mass concentration of 6.0g/L, treat it at 100°C for 30min, then wash it with absolute ethanol and deionized water at 60°C for 20min, and then wash it at 90°C Drying under dry conditions; Weigh 0.1g of reactive Cuilan KN-G dye according to 2% of the cotton fiber mass, measure 250mL of deionized water according to the bath ratio of 1:50, and weigh 17.5g of deionized water according to the volume of deionized water Sodium sulfate and 5g of sodium carbonate, dissolving active Cuilan KN-G dye in deionized water at 50°C, putting it into the pretreated cotton fiber for dyeing, adding 8.75g of sodium sulfate and stirring continuously, and adding another after 15min 8.75g of sodium sulfate, continue to stir, after dyeing for 15min, the solution is heated up to 90°C at a rate of 2°C/min, add 2.5g of sodium carbonate after 15min, add another 2.5g of sodium carbonate after 10min, and keep stirring, dyeing after 10min Complete; weigh 0.83g of tetrabutyl titanate according to the mass ratio of cotton fiber to tetrabutyl titanate of 6:1, and weigh 26mL of absolute ethanol according to the volume ratio of tetrabutyl titanate to absolute ethanol of 1:30, Dissolve tetrabutyl titanate in absolute ethanol and stir vigorously to prepare tetrabutyl titanate modified solution. Slowly add tetrabutyl titanate modified solution to the dyeing solution dropwise, continuously Stir continuously, raise the temperature of the mixed solution to 130°C at a rate of 2°C/min, and treat at a constant temperature for 2 hours; take out the cotton fiber after the reaction is completed, and measure the soap flake solution with a mass volume concentration of 2g/L and a mass of The washing solution mixed with sodium carbonate solution with a volume concentration of 2g/L is used to treat the cotton fiber at 90°C for 10 minutes, then wash it repeatedly with hot water and cold water for 3 times, and then dry it.

Using residual liquid colorimetry, 7220N spectrophotometer was used to measure the absorbance at the maximum absorption wavelength of 680nm of the solution before and after cotton fiber dyeing modification, and the dye uptake rate of cotton fiber was calculated to be 63%. Measure 50mL of the dyed and modified residual solution, irradiate it under sunlight with an illumination of 8.5× ¹⁰⁴ lux for 2h, measure the absorbance of the solution at the maximum absorption wavelength of 680nm with a 7220N spectrophotometer, and calculate the degradation rate of the dye 72%. The K/S value of the dyeing depth of the dyed modified cotton fiber at the maximum absorption wavelength of 680mm was measured by SF300 color measuring and matching instrument to be 2.5. According to the national standard GB/T8427-2008 "Textile color fastness test to artificial light color fastness: xenon arc", use YG611 type light and weather color fastness tester to measure the artificial light resistance (xenon arc lamp) of dyed modified cotton fiber The color fastness is grade 5. According to the national standard GB/T8629-2001 "Household Washing and Drying Procedures for Textile Testing", wash and dry the dyed and modified cotton fibers (select A-type washing machine, 7A washing procedure, C-type drying procedure), and according to the national Standard GB/T20944.1-2007 "Evaluation of Antibacterial Performance of Textiles Part 1: Agar Plate Diffusion Method", to determine the antibacterial effect of dyed and modified cotton fibers on Staphylococcus aureus (ATCC6538), Escherichia coli ( 8099), the antibacterial zone is within 1.0mm, no reproduction, and the antibacterial effect is good. According to the national standard GB/T18830-2009 "Assessment of Anti-ultraviolet Properties of Textiles", the spectral transmittance in the UVB and UVA bands of the dyed and modified cotton fibers was determined to be 4.1% after 30 washes, and the UV protection coefficient was 53. It shows that the dyed and modified cotton fiber has the ability to shield ultraviolet rays, and the combination of nano-titanium dioxide and cotton fiber is firm. The self-cleaning performance of cotton fibers was evaluated by ultraviolet irradiation on cotton fibers stained with strawberry juice. After 330 minutes of ultraviolet irradiation, the color of strawberry juice stained on the cotton fiber surface completely disappeared.

Example 3

Soak 5g of cotton fiber in a sodium hydroxide solution with a mass concentration of 4g/L, treat it at 90°C for 40min, then wash it with absolute ethanol and deionized water at 60°C for 15min, and then wash it at 80°C Drying at the bottom; weigh 0.06g of reactive Cuilan KN-G dye according to 1.2% of the cotton fiber mass, measure 200mL of deionized water according to the bath ratio of 1:40, and weigh 12g of sodium sulfate according to the volume of deionized water and 3g of sodium carbonate, dissolve the active Cuilan KN-G dye in deionized water at 45°C, put it into the pretreated cotton fiber for dyeing, add 6g of sodium sulfate and keep stirring, add another 6g of sodium sulfate after 13min , continue to stir, after dyeing for 13 minutes, the solution is heated to 85°C at a rate of 1.5°C/min, 1.5g of sodium carbonate is added after 13 minutes, and another 1.5g of sodium carbonate is added after 20 minutes, and the dyeing is completed after 20 minutes; The mass ratio of fiber to tetrabutyl titanate is 4:1 and 1.25g of tetrabutyl titanate is weighed, and 25mL of absolute ethanol is weighed according to the volume ratio of tetrabutyl titanate and absolute ethanol of 1:20, and tetrabutyl titanate is The butyl ester is dissolved in absolute ethanol and stirred to prepare a tetrabutyl titanate modified solution. The tetrabutyl titanate modified solution is slowly added dropwise to the dyeing solution, and the solution is continuously stirred while adding. The mixed solution was heated up to 120°C at a rate of 1.5°C/min, and treated at a constant temperature for 3 hours; after the reaction was completed, the cotton fiber was taken out, and the soap flake solution with a mass volume concentration of 2g/L and a mass volume concentration of The washing liquid mixed with 2g/L sodium carbonate solution was used to treat cotton fibers at 80°C for 15 minutes, then washed repeatedly with hot water and cold water for 3 times, and then dried.

Using the residual liquid colorimetric method, the absorbance of the solution at the maximum absorption wavelength of 680nm was measured with a 7220N spectrophotometer before and after the cotton fiber dyeing and modification treatment, and the dye uptake rate of the cotton fiber was calculated to be 68%. Measure 50mL of the dyed and modified residual solution, irradiate it under sunlight with an illumination of 8.5× ¹⁰⁴ lux for 2h, measure the absorbance of the solution at the maximum absorption wavelength of 680nm with a 7220N spectrophotometer, and calculate the degradation rate of the dye 79%. The K/S value of the dyeing depth of the dyed modified cotton fiber at the maximum absorption wavelength of 680mm was measured by SF300 color measuring and matching instrument to be 1.8. According to the national standard GB/T8427-2008 "Textile color fastness test to artificial light color fastness: xenon arc", use YG611 type light and weather color fastness tester to measure the artificial light resistance (xenon arc lamp) of dyed modified cotton fiber The color fastness is grade 5. According to the national standard GB/T8629-2001 "Household Washing and Drying Procedures for Textile Testing", wash and dry the dyed and modified cotton fibers (select A-type washing machine, 7A washing procedure, C-type drying procedure), and according to the national Standard GB/T20944.1-2007 "Evaluation of Antibacterial Performance of Textiles Part 1: Agar Plate Diffusion Method", to determine the antibacterial effect of dyed and modified cotton fibers on Staphylococcus aureus (ATCC6538), Escherichia coli ( 8099), the antibacterial zone is within 1.0mm, no reproduction, and the antibacterial effect is good. According to the national standard GB/T18830-2009 "Assessment of Anti-ultraviolet Properties of Textiles", the spectral transmittance in the UVB and UVA bands of the dyed and modified cotton fibers was determined to be 3.9% after 30 washes, and the UV protection coefficient was 57. It shows that the dyed and modified cotton fiber has the ability to shield ultraviolet rays, and the combination of nano-titanium dioxide and cotton fiber is firm. The self-cleaning performance of cotton fibers was evaluated by ultraviolet irradiation on cotton fibers stained with strawberry juice. After 280 minutes of ultraviolet irradiation, the color of strawberry juice stained on the cotton fiber surface completely disappeared.

Claims (5)

1. the method adopting butyl titanate and REACTIVE DYES to dye to cotton fiber modification, is characterized in that, specifically implements according to following steps:

Step 1, preliminary treatment is carried out to cotton fiber;

Step 2, use REACTIVE DYES carry out dyeing process to pretreated cotton fiber;

Step 3, preparation butyl titanate modified solution, the phase adds modified solution and carries out modification to dyeing processes after dyeing, specifically implements according to following steps:

3.1) take butyl titanate according to pretreated cotton quality, the mass ratio of cotton fiber and butyl titanate is 3 ~ 6:1;

3.2) according to step 3.1) in the butyl titanate that takes measure absolute ethyl alcohol, the volume ratio of butyl titanate and absolute ethyl alcohol is 1:10 ~ 30;

3.3) by step 3.1) in the butyl titanate that takes be dissolved in step 3.2) in the absolute ethyl alcohol that measures, and to stir, be mixed with butyl titanate modified solution;

3.4) by step 3.3) the butyl titanate modified solution prepared slowly be added drop-wise to that step 2 obtains containing in the staining solution of cotton fiber, drip while constantly stir, by mixed solution with 1 DEG C/min ~ 2 DEG C/min ramp to 110 DEG C ~ 130 DEG C, constant temperature process 2h ~ 4h, question response terminates rear taking-up cotton fiber;

Step 4, post processing is carried out to the cotton fiber after dyeing, modifying.

2. a kind of method adopting butyl titanate and REACTIVE DYES to dye to cotton fiber modification according to claim 1, it is characterized in that, described step 1 is specifically implemented according to following steps:

1.1) cotton fiber is taken;

1.2) cotton fiber taken being immersed in quality-volumetric concentration is in the sodium hydroxide solution of 3.0g/L ~ 6.0g/L, under 80 DEG C ~ 100 DEG C conditions, process 30min ~ 50min, then under 60 DEG C of conditions, wash 10min ~ 20min with absolute ethyl alcohol, deionized water respectively;

1.3) dry under 70 DEG C ~ 90 DEG C conditions after taking out the cotton fiber cleaned up, obtain pretreated cotton fiber.

3. a kind of method adopting butyl titanate and REACTIVE DYES to dye to cotton fiber modification according to claim 1, it is characterized in that, described step 2 is specifically implemented according to following steps:

2.1) 1% ~ 2% of the pretreated cotton quality obtained according to step 1 takes active emerald green blue KN-G dyestuff;

2.2) be 1:30 ~ 50 according to the bath raio of cotton fiber and deionized water, measure deionized water;

2.3) sodium sulphate and sodium carbonate is taken according to the ratio of dissolving the sodium sulphate of 50g ~ 70g and the sodium carbonate of 10g ~ 20g in often liter of deionized water;

2.4) by step 2.1) in the emerald green blue KN-G dyestuff of the activity that takes be dissolved in step 2.2) in the deionized water that takes, under 40 DEG C ~ 50 DEG C conditions, put into pretreated cotton fiber to dye, then add step 2.3) in take 1/2nd sodium sulphate and constantly stir, the sodium sulphate of other 1/2nd is added after 10min ~ 15min, continue to stir, after dyeing 10min ~ 15min, by staining solution with 1 DEG C/min ~ 2 DEG C/min ramp to 80 DEG C ~ 90 DEG C, add step 2.3 after 10min ~ 15min) in take 1/2nd sodium carbonate, the sodium carbonate of other 1/2nd is added after 10min ~ 20min, and constantly stir, dyeing process is completed after 10min ~ 20min.

4. a kind of method adopting butyl titanate and REACTIVE DYES to dye to cotton fiber modification according to claim 1, it is characterized in that, described step 4 is specifically implemented according to following steps:

4.1) cotton fiber after dyeing, modifying step 3 obtained, with the bath raio of 1:30 ~ 50, washs 10min ~ 20min with cleaning solution under 70 DEG C ~ 90 DEG C conditions;

4.2) by the cotton fiber hot water after washing, cold water cyclic washing 3 times;

4.3) dry or naturally dry, obtaining the cotton fiber after dyeing, modifying.

5. a kind of method adopting butyl titanate and REACTIVE DYES to dye to cotton fiber modification according to claim 4, it is characterized in that, described step 4.1) in cleaning solution, be mixed by the sodium carbonate liquor of mass body volume concentrations to be the soap flakes solution of 2g/L and mass body volume concentrations be 2g/L.