CN102277754B - Method of wool surface modification and low temperature dyeing - Google Patents

Abstract

The invention relates to a wool surface modification and a low-temperature dyeing method thereof. The technical scheme is as follows: the wool is treated with an ionic liquid at 60-80°C and a bath ratio of 1:10-30 for 5-20 minutes, and the wool adsorbed The ionic liquid is rolled out and recovered for recycling, the wool is washed with ethanol and the ionic liquid is recovered, rinsed with water and then dried; the treated wool is dyed with acid dyes or reactive dyes at 60-80°C, liquor ratio 1:20-40 60-80min, after dyeing, take out the wool, soap, wash, dehydrate and dry. The invention uses the ionic liquid to treat the wool, the process is simple, the ionic liquid can be recycled and reused, and the modification process has no environmental pollution; the dyeing temperature of the modified wool is low, which is beneficial to energy saving, the color yield is high, and the utilization rate of the dye is improved. The luster and wearability of wool are improved.

Description

A kind of wool surface modification and its low-temperature dyeing method

technical field

The invention relates to the technical field of textile printing and dyeing, in particular to a wool surface modification and a low-temperature dyeing method thereof.

Background technique

Wool is an important natural fiber. It is widely used in high-grade textile fabrics due to its excellent hygroscopicity, resilience, hand feeling and wearing comfort. However, wool fiber has complex physical and chemical structures, and its surface layer has special properties. The scale layer structure, because the texture of the scale layer is hard, dense, and hydrophobic, is extremely unfavorable to the adsorption and dyeing of dye molecules, and at the same time prevents the dye from diffusing into the fiber. Therefore, wool is generally dyed at a high temperature of 95-100 °C. However, high-temperature dyeing not only consumes a lot of energy, but also increases the cost of dyeing. In addition, under the condition of high-temperature dyeing, the natural style of wool is easily damaged by the action of heating and chemical reagents, such as lower color brightness and hard handle. , the strength decreases, the resilience decreases, which is not conducive to the processing of the next process, affects its aesthetic value, reduces the wearing performance, and decreases the competitiveness of the market. Therefore, it is of great significance to research and develop low-temperature dyeing of wool.

In order to improve the dyeing performance of wool, numerous surface modification technologies have emerged. Chlorination surface modification is the most widely used in industry, but the released chlorides are likely to cause environmental pollution of water bodies, which has been banned in European and American countries. People have also tried technologies such as low-temperature plasma, corona irradiation, liquid ammonia treatment, and biological enzyme hydrolysis. Although they have little pollution to the environment, they have their own defects. For example, low-temperature plasma, corona irradiation technology and liquid ammonia treatment have problems such as high equipment requirements, poor compatibility with other technologies, and limited processing capacity by equipment, which restrict their practical application in the dyeing and finishing industry; and biological enzymes Although the treatment technology has the characteristics of mild conditions, high selectivity, and environmental protection, due to the strong hydrophobicity and chemical inertness of the wool scale layer, it is difficult for biological enzymes to act on it, and the wool must be chemically treated.

Ionic Liquids (Ionic Liquids, abbreviated as IL) is a new type of "green solvent". It is composed of organic cations and inorganic/organic anions, and is a salt compound in a liquid state at or near room temperature. Ionic liquids have excellent physical and chemical characteristics, such as no vapor pressure at room temperature, good thermal stability and electrical conductivity, and can be recycled and used repeatedly. Ionic liquids are solvents with strong polarity and low coordination ability, which can dissolve various organic and inorganic compounds, and have unique properties that many organic solvents cannot match. Due to the advantages of high solubility, no pollution, and recyclability, ionic liquids have been widely used in fiber dissolution and regeneration, and fiber modification.

Contents of the invention

In order to solve the above-mentioned technical problems, the present invention provides a wool surface modification and a low-temperature dyeing method thereof. The invention realizes the low-temperature dyeing of wool, and has the characteristics of improving dyeing performance, no sewage discharge, reducing energy consumption, ionic liquid recycling and the like.

The technical scheme that the present invention solves the above problems comprises the following steps:

a. Ionic liquid surface treatment: The wool is impregnated and modified with ionic liquid. The treatment conditions are: the bath ratio is 1:10-30, the treatment temperature is 60-80°C, and the treatment time is 5-20min. After the treatment, the The ionic liquid adsorbed by the wool is squeezed out into the treated ionic liquid, then the wool is washed with ethanol, finally washed with water and dried at 80°C, and the ethanol washing solution is preserved.

b. Low-temperature dyeing: low-temperature dyeing: dye the wool treated with ionic liquids with acid dyes or reactive dyes, dyeing conditions: liquor ratio 1:20-40, dyeing temperature 60-80°C, dyeing time 60- 80 minutes, after wool dyeing, it is soaped, washed with water, dehydrated and dried.

c. Regeneration of ionic liquid: add deionized water to the treated ionic liquid until the precipitate is no longer formed, remove the precipitate by filtration, remove the water from the filtrate on a rotary evaporator at 80°C under reduced pressure, and obtain the regenerated ionic liquid .

d. Recovery of ionic liquid in ethanol: the ethanol washing solution in step a is filtered to remove the precipitate, and then the ethanol is removed under reduced pressure with a rotary evaporator at 60°C to obtain the treated ionic liquid, and the ionic liquid is recycled by the method of step c .

The acid dye dyeing process formula and conditions described in the above step b include: the acid dye accounts for 0.3-3% of the fiber weight, the sodium sulfate accounts for 5-10% of the fiber weight, and is adjusted to pH 4.5-5.5 with acetic acid or acetic acid-sodium acetate, The dyeing temperature is 30-40°C, the heating rate is 1-3°C/min, the dyeing temperature is 60-80°C, the holding time is 60-80min, and the liquor ratio is 1:20-40;

Reactive dye dyeing process formula and conditions described in above-mentioned steps b include: hairy reactive dyes account for 0.3-3% of fiber weight, ammonium sulfate accounts for 1-2% of fiber weight, and sodium sulfate accounts for 5-10% of fiber weight. Acetic acid-sodium acetate is adjusted to pH 4.5-5.5, the dyeing temperature is 30-40°C, the heating rate is 1-3°C/min, the dyeing temperature is 60-80°C, the holding time is 60-80min, and the liquor ratio is 1: 20-40;

The above-mentioned wool can be pure wool loose fiber, pure wool top, pure wool yarn, pure wool fabric.

The ionic structure characteristics of the ionic liquid in the above step a are as follows:

Among them, R1=C _n H _2n-1 , n=1,2; R2=C _m H _2m-1 , 1<n<10, A ^- = Cl ^- , Br ^- ,CH3COO ^- .

Further, the ions in the ionic liquid are 1-butyl-3-methylimidazolium chloride ([Bmim]Cl), 1-butyl-3-methylimidazolium bromide ([Bmim]Br), 1 -Butyl-3-methylimidazolium acetate ([Bmim]Ac), 1-ethyl-3-methylimidazolium chloride ([Emim]Cl), 1-ethyl-3-methylimidazolium bromide ([Emim]Br), 1-ethyl-3-methylimidazolium acetate ([Emim]Ac), 1-allyl-3-methylimidazolium chloride ([Amim]Cl), 1-ene Any of propyl-3-methylimidazolium bromide ([Amim]Br) and 1-allyl-3-methylimidazolium acetate ([Amim]Ac).

The beneficial effects of the present invention are: (1) the method for treating the wool surface with the ionic liquid adopted in the present invention can effectively partially peel off the scale layer on the wool surface, improve the hydrophilicity of the wool surface, and eliminate the impact of the scale on the wool surface. The barrier of dye molecule adsorption and diffusion into the fiber improves the dyeing performance and realizes the low-temperature dyeing of wool. Compared with the traditional surface modification of chlorination method, there is no sewage discharge and no volatile gas generation. The ionic liquid can be recycled and green. Environmental friendly. (2) Low-temperature dyeing can avoid the problems of high energy consumption, low brilliance, hard hand feeling and low strength caused by high-temperature dyeing, and has the advantages of energy saving and emission reduction, as well as improving wool quality and wearability.

Detailed ways

Example 1:

Wool Variety: Pure Wool Loose Fiber.

Ionic liquid treatment: the ionic liquid is selected from 1-ethyl-3-methylimidazolium bromide ([Emim]Br), the liquor ratio is 1:30, the treatment temperature is 80°C, and the treatment time is 20mim. The attached ionic liquid is squeezed into the treated ionic liquid, and the treated fiber is washed with ethanol, finally washed with water, dried at 80°C, and the ethanol washing solution is preserved.

Acid dye dyeing: the fiber treated with ionic liquid is dyed with acid dye, the acid dye accounts for 1% by weight of the fiber, the sodium sulfate accounts for 10% by weight of the fiber, the bath ratio is 1:40, and the pH value is adjusted to 4.5-5.5, the dyeing temperature is 30°C, the temperature is raised to 60°C at 2°C/min, and the dyeing is kept for 80 minutes. After the dyeing is completed, it is soaped, washed, dehydrated, and dried.

Regeneration of ionic liquid: add deionized water to the treated ionic liquid until the precipitate is no longer formed, filter to remove the precipitate, remove the water from the filtrate on a rotary evaporator at 80°C under reduced pressure, and obtain the regenerated ionic liquid, and regenerate The ionic liquid can be recycled.

Recovery of ionic liquid in ethanol: the above-mentioned ethanol washing solution is filtered to remove the precipitate, and then the ethanol is removed under reduced pressure with a rotary evaporator at 60°C to obtain the treated ionic liquid, which is recovered through the above-mentioned ionic liquid regeneration and utilization steps and reuse.

Example 2:

Wool Variety: Pure Wool Yarn.

Ionic liquid treatment: the ionic liquid is 1-butyl-3-methylimidazolium chloride ([Bmim]Cl), the liquor ratio is 1:10, the treatment temperature is 80°C, and the treatment time is 5mim. The attached ionic liquid is squeezed into the treated ionic liquid, and the treated fiber is washed with ethanol, finally washed with water, dried at 80°C, and the ethanol washing solution is preserved.

Acid dye dyeing: the wool yarn treated with ionic liquid is dyed with acid dye, the acid dye accounts for 1% by weight of the fiber, the sodium sulfate accounts for 5% by weight of the fiber, the bath ratio is 1:20, and the pH is adjusted with acetic acid The value is 4.5-5.5, the dyeing temperature is 40°C, the temperature is raised to 70°C at 2°C/min, and the dyeing is kept for 70 minutes. After the dyeing is completed, it is soaped, washed, dehydrated, and dried.

Other steps are consistent with embodiment 1.

Embodiment 3:

Wool Variety: Pure wool fabric.

Ionic liquid treatment: the ionic liquid is 1-butyl-3-methylimidazole acetate ([Bmim]Ac), the bath ratio is 1:20, the treatment temperature is 70°C, and the treatment time is 8mim. After the treatment, the fiber The attached ionic liquid is rolled off into the treated ionic liquid, the treated fiber is washed with ethanol, finally washed with water, dried at 80°C, and the ethanol washing solution is preserved.

Dyeing with acid dye: dye the pure wool fabric treated with ionic liquid with acid dye, the acid dye accounts for 0.3% by weight of the fiber, the percentage of sodium sulfate accounts for 8% by weight of the fiber, the bath ratio is 1:30, and the pH is adjusted with acetic acid The value is 4.5-5.5, the dyeing temperature is 35°C, the temperature is raised to 80°C at 3°C/min, and the dyeing is kept for 60 minutes. After the dyeing is completed, it is soaped, washed, dehydrated, and dried.

Other steps are consistent with embodiment 1.

Embodiment 4:

Wool Variety: Pure wool fabric.

Ionic liquid treatment: the ionic liquid is 1-ethyl-3-methylimidazole acetate ([Emim]Ac), the liquor ratio is 1:20, the treatment temperature is 60°C, and the treatment time is 10mim. After the treatment, the fiber The attached ionic liquid is rolled off into the treated ionic liquid, the treated fiber is washed with ethanol, finally washed with water, dried at 80°C, and the ethanol washing solution is preserved.

Dyeing with reactive dyes: the pure wool fabric treated with ionic liquid is dyed with wool with reactive dyes, the wool with reactive dyes accounts for 2% by weight of fibers, ammonium sulfate accounts for 2% by weight of fibers, and sodium sulfate accounts for 2% by weight of fibers. 7%, the bath ratio is 1:20, the pH value is adjusted to 4.5-5.5 with acetic acid, the dyeing temperature is 40°C, the temperature is raised to 70°C at 2°C/min, and the dyeing is kept for 80min. After the dyeing is completed, soaping, washing, Dehydrate and dry.

Other steps are consistent with embodiment 1.

Embodiment 5:

Wool Variety: Pure Wool Yarn.

Ionic liquid treatment: the ionic liquid is selected from 1-allyl-3-methylimidazolium chloride salt ([Amim]Cl), the liquor ratio is 1:10, the treatment temperature is 80°C, and the treatment time is 5mim. After the treatment, the fiber The attached ionic liquid is rolled off into the treated ionic liquid, the treated fiber is washed with ethanol, finally washed with water, dried at 80°C, and the ethanol washing solution is preserved.

Dyeing with reactive dyes: the wool yarn treated with ionic liquids is dyed with wool reactive dyes, the wool reactive dyes account for 2% of the fiber weight percentage, the ammonium sulfate accounts for 2% of the fiber weight percentage, and the sodium sulfate accounts for 2% of the fiber weight percentage. 10%, bath ratio 1:20, adjust the pH value to 4.5-5.5 with acetic acid, enter the dyeing temperature at 30°C, raise the temperature to 60°C at 2°C/min, keep it warm for 80min, after the dyeing is completed, carry out soaping, washing and dehydration ,drying.

Other steps are consistent with embodiment 1.

Embodiment 6:

Wool Variety: Pure Wool Loose Fiber.

Ionic liquid treatment: the ionic liquid is selected from 1-allyl-3-methylimidazole acetate ([Amim]Ac), the liquor ratio is 1:30, the treatment temperature is 70°C, and the treatment time is 5mim. After the treatment, the The ionic liquid adhering to the fiber is rolled off into the treated ionic liquid, the treated fiber is washed with ethanol, finally washed with water, dried at 80°C, and the ethanol washing solution is preserved.

Dyeing with reactive dyes: the wool yarn treated with ionic liquids is dyed with wool reactive dyes, the wool reactive dyes account for 3% by weight of the fibers, the ammonium sulfate accounts for 2% by weight of the fibers, and the percent by weight of sodium sulfate accounts for 2% by weight of the fibers. 10%, the bath ratio is 1:40, the pH value is adjusted with acetic acid: 4.5-5.5, the dyeing temperature is 35°C, the temperature is raised to 70°C at 2°C/min, and the dyeing is kept for 80min. After the dyeing is completed, soaping, washing, Dehydrate and dry.

Other steps are consistent with embodiment 1.

Embodiment 7:

Wool Variety: Pure wool fabric.

Ionic liquid treatment: the ionic liquid is 1-allyl-3-methylimidazolium bromide ([Amim]Br), the bath ratio is 1:10, the treatment temperature is 70°C, and the treatment time is 10mim. After the treatment, the fiber The attached ionic liquid is rolled off into the treated ionic liquid, the treated fiber is washed with ethanol, finally washed with water, dried at 80°C, and the ethanol washing solution is preserved.

Dyeing with reactive dyes: the wool fabric treated with ionic liquid is dyed with reactive dyes. The reactive dyes for wool account for 0.3% of the fiber weight percentage, the ammonium sulfate accounts for 1% of the fiber weight percentage, and the sodium sulfate accounts for 5% of the fiber weight percentage. The bath ratio is 1:30, the pH value is adjusted to 4.5-5.5 with acetic acid-sodium acetate, the dyeing temperature is 40°C, the temperature is raised to 70°C at 1°C/min, and the dyeing is kept for 70 minutes. After the dyeing is completed, soaping, washing, Dehydrate and dry.

Other steps are consistent with embodiment 1.

Embodiment 8:

Wool Variety: Pure Wool Yarn.

Ionic liquid treatment: the ionic liquid is 1-butyl-3-ethylimidazolium chloride ([Beim]Cl), the liquor ratio is 1:20, the treatment temperature is 70°C, and the treatment time is 20mim. The attached ionic liquid is squeezed into the treated ionic liquid, and the treated fiber is washed with ethanol, finally washed with water, dried at 80°C, and the ethanol washing solution is preserved.

Acid dye dyeing: the wool yarn treated with ionic liquid is dyed with acid dye, the acid dye accounts for 3% by weight of the fiber, the sodium sulfate accounts for 8% by weight of the fiber, the bath ratio is 1:30, and the pH is adjusted with acetic acid The value is 4.5-5.5, the dyeing temperature is 40°C, the temperature is raised to 80°C at 1°C/min, and the dyeing is kept for 80 minutes. After the dyeing is completed, it is soaped, washed, dehydrated, and dried.

Other steps are consistent with embodiment 1.

Embodiment 9:

Wool Variety: Pure wool fabric.

Ionic liquid treatment: the ionic liquid is 1-octyl-3-methylimidazolium chloride ([Omim]Cl), the liquor ratio is 1:30, the treatment temperature is 80°C, and the treatment time is 20mim. The attached ionic liquid is squeezed into the treated ionic liquid, and the treated fiber is washed with ethanol, finally washed with water, dried at 80°C, and the ethanol washing solution is preserved.

Dyeing with reactive dyes: the wool fabric treated with ionic liquids is dyed with reactive dyes, the reactive dyes for wool account for 0.3% by weight of the fiber, the percentage of ammonium sulfate accounts for 2% by weight of the fiber, and the percentage of sodium sulfate accounts for 5% by weight of the fiber. %, the liquor ratio is 1:20, adjust the pH value to 4.5-5.5 with acetic acid-sodium acetate, the dyeing temperature is 40°C, the temperature is raised to 60°C at 2°C/min, and the dyeing is kept for 60 minutes. After the dyeing is completed, soaping, Washing, dehydration, drying.

Other steps are consistent with embodiment 1.

Embodiment 10:

Wool species: pure wool tops.

Ionic liquid treatment: the ionic liquid is 1-butyl-3-methylimidazolium bromide ([Bmim]Br), the liquor ratio is 1:30, the treatment temperature is 80°C, and the treatment time is 20mim. The attached ionic liquid is squeezed into the treated ionic liquid, and the treated fiber is washed with ethanol, finally washed with water, dried at 80°C, and the ethanol washing solution is preserved.

Dyeing with reactive dyes: the wool fabric treated with ionic liquids is dyed with reactive dyes, the reactive dyes for wool account for 0.3% by weight of the fiber, the percentage of ammonium sulfate accounts for 2% by weight of the fiber, and the percentage of sodium sulfate accounts for 5% by weight of the fiber. %, the bath ratio is 1:20, adjust the pH value to 4.5-5.5 with acetic acid-sodium acetate, the dyeing temperature is 40°C, the temperature is raised to 80°C at 3°C/min, and the dyeing is kept for 80min. After the dyeing is completed, soaping, Washing, dehydration, drying.

Other steps are consistent with embodiment 1.

Claims (3)

1. A wool surface modification and low-temperature dyeing method thereof, comprising the steps of: a. Ionic liquid surface treatment: The wool is impregnated and modified with ionic liquid. The treatment conditions are: the bath ratio is 1:10-30, the treatment temperature is 60°C, and the treatment time is 5-20min. After the treatment, the wool The adsorbed ionic liquid is squeezed out into the treated ionic liquid, then the wool is washed with ethanol, finally washed with water and dried at 80°C, and the ethanol washing solution is preserved; b. low temperature dyeing: the wool treated with ionic liquid is dyed with acid dye or reactive dye, acid dye dyeing condition: acid dye accounts for 3% by weight of fiber, sodium sulfate accounts for 5-10% by weight of fiber, bath The ratio is 1:20-40, acetic acid-sodium acetate adjusts the pH to 4.5-5.5, the dyeing temperature is 60°C, the dyeing temperature is 30-40°C, the heating rate is 1-3°C/min, and the dyeing time is 60-80min Reactive dye dyeing conditions: hairy reactive dye accounts for 0.3-3% by weight of fiber, ammonium sulfate accounts for 1-2% by weight of fiber, sodium sulfate accounts for 5-10% by weight of fiber, and the bath ratio is 1: 20-40, acetic acid-sodium acetate to adjust the pH to 4.5-5.5, the dyeing temperature is 60°C, the dyeing temperature is 30-40°C, the heating rate is 1-3°C/min, and the dyeing time is 60-80min; Finally, after soaping, washing, dehydration and drying; c. Regeneration of ionic liquid: add deionized water to the treated ionic liquid until the precipitate is no longer formed, remove the precipitate by filtration, remove the water from the filtrate on a rotary evaporator at 80°C under reduced pressure, and obtain the regenerated ionic liquid ; d. Recovery of ionic liquid in ethanol: the ethanol washing liquid in step a is filtered to remove the precipitate, and then the ethanol is removed under reduced pressure with a rotary evaporator at 60°C to obtain the treated ionic liquid, and the ionic liquid is regenerated and utilized in step c. 2. wool surface modification and low-temperature dyeing method thereof according to claim 1, described wool is pure wool loose fiber, pure wool top, pure wool yarn, pure wool fabric. 3. wool surface modification and low-temperature dyeing method thereof according to claim 1, ion in the ionic liquid in the described step a is 1-butyl-3-methylimidazolium chloride salt, 1-butyl-3-formazolium imidazolium bromide, 1-butyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-ethyl- 3-Methylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium acetic acid any kind of salt.