WO2021248809A1

WO2021248809A1 - Red dye composition and use thereof for supercritical carbon dioxide waterless dyeing

Info

Publication number: WO2021248809A1
Application number: PCT/CN2020/128334
Authority: WO
Inventors: 濮坚锋
Original assignee: 浙江越新印染有限公司
Priority date: 2020-06-08
Filing date: 2020-11-12
Publication date: 2021-12-16
Also published as: CN111635647A

Abstract

Disclosed is a red dye composition and the application thereof for supercritical carbon dioxide waterless dyeing. The dye composition comprises a dye consisting of one or more compounds selected from formula (I) and one or more compounds selected from formula (II). The dye composition can achieve reverse micelle dyeing in supercritical carbon dioxide, and by means of a specific type and ratio of the compound as represented by formula (I) and the compound shown in formula (II), and can also achieve a synergistic effect of the two, thereby further improving dyeing performance.

Description

Red dyeing composition and its use for supercritical carbon dioxide anhydrous dyeing

Technical field

The invention belongs to the technical field of dyeing; relates to a supercritical dyeing technology; more specifically, to a red dyeing composition and its use for supercritical carbon dioxide anhydrous dyeing.

Background technique

Water is an important resource essential for human survival. Although the earth is rich in water resources, the fresh water available for human use on land only accounts for 2.5% of the total fresh water resources. my country's water resources are even more scarce, with per capita only a quarter of the world average; fresh water resources are unevenly distributed, and many regions such as the north and northwest are severely short of water. At the same time, the water environment is deteriorating, water quality-type water shortages, and water shortages are becoming more and more serious. In order to change this status quo, the public's awareness of environmental protection has been continuously strengthened, and the state has also promulgated many laws and regulations related to environmental protection. In recent years, environmental protection storms against many polluting industries have also intensified. As the textile printing and dyeing industry with huge water consumption and serious pollution, the development of water-saving or even water-free dyeing or printing processes with high-efficiency processes is becoming more and more attention.

Studies have shown that traditional dyeing methods consume huge amounts of water. On average, 100 to 200 tons of water are used for printing and dyeing 1 ton of textiles. Although a small part of the water can be recycled, most of the remaining water becomes waste water. Therefore, the wastewater discharged from the printing and dyeing industry has become the main source of the entire textile industry, accounting for almost 80%. Not only that, in traditional dyeing methods, various dyeing auxiliaries are usually added to the dyeing bath. These dyeing auxiliaries and unfixed dyes remain in the printing and dyeing wastewater, which increases the burden of sewage treatment in the later stage and poses a serious threat to the ecological environment.

As a new, green, and environmentally friendly printing and dyeing technology, supercritical carbon dioxide fluid anhydrous dyeing technology has injected vitality into the reform and innovation of the textile industry. At the same time, this technology can truly realize ecological textiles and conform to the concepts of energy saving, emission reduction and sustainable development. Has positive practical significance.

Supercritical carbon dioxide fluid not only has the gas properties of low viscosity and strong diffusion, but also has a density similar to liquids and has good solubility for hydrophobic substances. People use the above-mentioned excellent characteristics of carbon dioxide fluid as a dyeing medium to replace the water in the traditional dyeing bath to dye textiles. Supercritical carbon dioxide dyeing not only does not require water for the entire dyeing process, but also does not need to add dyeing auxiliaries, acids, alkalis and other chemical reagents. The dyed fabric does not need to be washed with floating color, which prevents the generation of dyeing wastewater, so that the problem of dyeing wastewater treatment is solved at the source, which is beneficial to environmental protection. In addition, the dyed fabric is in a dry state and does not need to be dried, which is conducive to energy saving. The remaining dye and carbon dioxide fluid can be used in the next dyeing process.

Since carbon dioxide is a non-polar molecule, according to the principle of similar compatibility, non-polar or low-polar dyes have better solubility in supercritical carbon dioxide fluids. Therefore, the dyes used for supercritical carbon dioxide dyeing are mainly disperse dyes. Correspondingly, as dyed fabrics, polyester fabrics are the most widely used and most successful, followed by aramid and polypropylene fabrics. In the textile market, natural fiber fabrics, especially cotton fabrics, usually occupy a large share, and they are favored by consumers because they are derived from natural materials and have additional green properties. However, this type of fiber is usually dyed with reactive dyes and acid dyes. These dyes are easily soluble in water but not easily soluble in carbon dioxide fluid, so there is a technical bottleneck in the application of supercritical carbon dioxide fluid dyeing technology.

In recent years, in order to solve the problem of dyeing natural fibers in supercritical carbon dioxide fluid, people have mainly started from the following aspects. Specifically include the following:

The natural fiber is pretreated by a swelling agent or a cross-linking agent to reduce the number of hydrogen bonds on the surface of the natural fiber, thereby reducing the polarity of the natural fiber.

Adding polar co-solvents (mainly water and ethanol) to the carbon dioxide fluid increases the polarity of the carbon dioxide fluid, thereby improving the solubility of the dye in the carbon dioxide fluid.

Under the premise of basically not changing the polarity of the original dye, the reactive group is introduced into the disperse dye molecule, and the formed reactive disperse dye has the advantages of good disperse dye solubility and strong reactivity of the reactive dye. Through nucleophilic addition Or the substitution reaction reacts with natural fibers. However, most reactive disperse dyes still have the defect that they are not highly reactive with natural fibers, especially cotton fibers.

The addition of surfactants in the carbon dioxide fluid to form reverse micelles can improve the solubility of the dye; at the same time, inhibit the degree of hydrolysis of the dye, which can also improve the reactivity of the dye to a certain extent.

Chinese patent application CN105696384A discloses a polyester-cotton blended fabric reverse micellar supercritical CO ₂ dyeing system, including the following parts by weight: pentaethylene glycol monooctyl ether: 5-25 parts, n-pentanol: 10 to 35 parts, reactive dyes: 0.01 to 0.20 parts, disperse dyes: 0.01 to 0.10 parts, carbon dioxide: 40 to 60 parts, distilled water: 0.01 to 6.0 parts. After the polyester-cotton blended fabric is placed in a high-pressure container, the reverse micellar supercritical CO ₂ dyeing system has good dissolution performance. While the reactive dyes dye the cotton fiber components, the disperse dyes are dyed on the polyester fiber at the same time, and the cotton fiber is Dyeing under salt-free conditions greatly avoids the staining and staining phenomenon of dyes on the fabric; at the same time, it has the advantages of high dyeing efficiency and excellent dyeing effect.

However, the above patent application does not disclose specific reactive dyes and disperse dyes, which makes it difficult to reproduce the dyeing performance of the dyeing system.

Therefore, there is still a need to provide a red dyeing composition and its use for supercritical carbon dioxide anhydrous dyeing for natural fibers, especially cotton fiber fabrics.

Summary of the invention

The purpose of the present invention is to provide a red dyeing composition and its use for supercritical carbon dioxide anhydrous dyeing. The dyeing composition not only has better solubility in supercritical carbon dioxide, but also has excellent dyeing properties.

In order to solve the above technical problems, according to the first aspect of the present invention, the present invention adopts the following technical solutions: a red dyeing composition, the dyeing composition includes a dye, characterized in that the dye includes one or more options From the compound of formula (I) and one or more compounds selected from the group of formula (II),

Wherein, R1 and R2 are selected from H, C _1-4 alkyl or C _1-4 alkoxy.

In a specific embodiment, the dye is composed of one or more compounds selected from formula (I) and one or more compounds selected from formula (II).

In the present invention, the terms "including", "including" and "having" are open-ended expression meanings, and do not mean to exclude the existence of any other optional components, steps or procedures. The term "consisting of" means to exclude the existence of other optional components, steps or procedures.

The dyeing composition according to the present invention, wherein R1 and R2 are selected from H, C _1-2 alkyl or C _1-2 alkoxy.

The dyeing composition according to the present invention, wherein R1 and R2 are selected from H or methyl.

The dyeing composition according to the present invention, wherein R1 is located at the ortho and/or para position of the bromoacrylamido group on the benzene nucleus.

According to the dyeing composition of the present invention, R2 is located at the ortho and/or meta position of the bromoacrylamido group on the benzene nucleus.

The dyeing composition according to the present invention, wherein the compound of formula (I) is selected from the compound of formula (I-1),

The dyeing composition according to the present invention, wherein the compound of formula (II) is selected from the compound of formula (II-1) and/or the compound of formula (II-2),

The dyeing composition according to the present invention, wherein the compound of formula (II) is selected from a combination of a compound of formula (II-1) and a compound of formula (II-2). That is, the compound of formula (II) is composed of the compound of formula (II-1) and the compound of formula (II-2).

In the present invention, the compound of formula (I-1) is synthesized according to the prior art method. The details are as follows: Using 1-chloroanthraquinone and m-phenylenediamine as raw materials, Ullmann coupling reaction occurs under the action of a _{Cu catalyst (5mol%) and an alkaline agent (such as K 2} CO _{3) to prepare a dye intermediate;} Perform nucleophilic substitution with 2,3-dibromopropionyl chloride, and remove 1 molecule of HBr under the action of triethylamine. After the reaction, it is concentrated and eluted with petroleum ether and dichloromethane with a volume ratio of 1:1.5 The reagent is subjected to a chromatographic column, and the corresponding compound is obtained by separation and purification.

The compound of formula (II-1) and the compound of formula (II-2) are also synthesized according to the prior art method. The details are as follows: Using 1-chloroanthraquinone and 2,5-diaminotoluene sulfate as raw materials, Ullmann coupling reaction occurs under the action of _{Cu catalyst (5mol%) and alkaline agent (such as K 2} CO _{3) to prepare dyes} Intermediate; the latter performs nucleophilic substitution with 2,3-dibromopropionyl chloride, and removes 1 molecule of HBr under the action of triethylamine. After the reaction, it is concentrated and the volume ratio is 1:1.5. Chloromethane is used as the eluent to perform chromatographic column separation and purification to obtain the corresponding compounds. During the reaction process, since the compound of formula (II-1) and the compound of formula (II-2) are isomers with extremely similar polarities, the two are not easy to separate, so the corresponding compound obtained is a mixture of the two .

The dyeing composition according to the present invention, wherein the weight ratio of the compound of formula (I) to the compound of formula (II) is (50-99): (1-50); preferably (60-90): (10 -40); more preferably (65-85): (15-35); and, most preferably (70-80): (20-30).

In a specific embodiment, the weight ratio of the compound of formula (I) to the compound of formula (II) is 75:25.

The preparation method of the red dyeing composition of the present invention includes mixing the compound of formula (I) and the compound of formula (II) according to the formula ratio. The mixing means are well known to those skilled in the art, such as mechanical mixing methods. When mixed, the compound of formula (I) and the compound of formula (II) may exist in powder form or in granular form. The mixing step can be carried out in a suitable grinding device such as a ball mill or a kneader.

According to the second aspect of the present invention, the present invention further provides a fluid composition for supercritical carbon dioxide anhydrous dyeing, the fluid composition comprising the aforementioned red dyeing composition and carbon dioxide fluid according to the present invention.

The fluid composition according to the present invention, wherein the amount of the red dyeing composition is 0.25-4omf%.

Preferably, the amount of the red coloring composition is 0.5-3.5 omf%; more preferably, the amount of the red coloring composition is 1.0-3 omf%; and, most preferably, the amount of the red coloring composition It is 1.5-2.5omf%.

In a specific embodiment, the amount of the red dyeing composition is 2omf%.

The fluid composition according to the present invention, wherein the fluid composition further includes a surfactant and a co-solvent.

The fluid composition according to the present invention, wherein the surfactant is selected from fatty alcohol polyoxyethylene ether.

The fluid composition according to the present invention, wherein the molecular formula of the fatty alcohol polyoxyethylene ether is R-(OCH ₂ CH ₂ ) _n -OH; R is selected from C _10-20 fatty alcohol residues; n=3 -30.

Preferably, the molecular formula of the fatty alcohol polyoxyethylene ether is R-(OCH ₂ CH ₂ ) _n -OH; R is selected from C _12-20 fatty alcohol residues; n=5-25; more preferably, the The molecular formula of fatty alcohol polyoxyethylene ether is R-(OCH ₂ CH ₂ ) _n -OH; R is selected from C _14-20 fatty alcohol residues; n=8-20; and, most preferably, R-(OCH ₂ CH ₂ ) _n -OH; R is selected from C _14-18 fatty alcohol residues; n=9-15.

In a specific embodiment, the molecular formula of the fatty alcohol polyoxyethylene ether is R-(OCH ₂ CH ₂ ) _n -OH; R is selected from C _16-18 fatty alcohol residues; n=10. That is, the fatty alcohol polyoxyethylene ether is selected from cetearyl alcohol polyoxyethylene ether-10.

According to the fluid composition of the present invention, the amount of the fatty alcohol polyoxyethylene ether is 0.5-1.5 g/L, calculated based on the volume of the carbon dioxide fluid.

Preferably, the amount of the fatty alcohol polyoxyethylene ether is 0.6-1.4 g/L, calculated based on the volume of the carbon dioxide fluid; more preferably, the amount of the fatty alcohol polyoxyethylene ether is 0.7-1.2 g/L, Calculated based on the volume of the carbon dioxide fluid; and, most preferably, the amount of the fatty alcohol polyoxyethylene ether is 0.8-1.0 g/L, calculated based on the volume of the carbon dioxide fluid.

In a specific embodiment, the amount of the fatty alcohol polyoxyethylene ether is 0.9 g/L, calculated based on the volume of the carbon dioxide fluid.

According to the fluid composition of the present invention, the co-solvent is selected from alcohol solvents.

Preferably, the co-solvent is selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol; more preferably, the co-solvent is selected from methanol, ethanol, propanol, isopropanol and Butanol; and, most preferably, the co-solvent is selected from methanol, ethanol and propanol.

In a specific embodiment, the co-solvent is selected from ethanol.

According to the fluid composition of the present invention, the amount of the co-solvent is 0.5-5 g/L, calculated based on the volume of the carbon dioxide fluid.

Preferably, the amount of the co-solvent is 1-4/L, calculated based on the volume of the carbon dioxide fluid; more preferably, the amount of the co-solvent is 1.5-3.5 g/L, calculated based on the volume of the carbon dioxide fluid; and, Most preferably, the amount of the co-solvent is 2-3 g/L, calculated based on the volume of the carbon dioxide fluid.

In a specific embodiment, the amount of the co-solvent is 2.5 g/L, calculated based on the volume of the carbon dioxide fluid.

The fluid composition according to the present invention, wherein the fluid composition further includes triethylene diamine.

According to the fluid composition of the present invention, the amount of triethylenediamine and the red coloring composition is (2.6-5.8):1 (w/w).

Preferably, the amount of triethylenediamine and the red dyeing composition is (3-5.4):1 (w/w); more preferably, the amount of triethylenediamine and the red dyeing composition is (3.4 -5):1 (w/w); and, most preferably, the amount of triethylenediamine and the red dyeing composition is (3.8-4.6):1 (w/w).

In a specific embodiment, the amount of triethylenediamine and the red dyeing composition is 4.2:1 (w/w).

In the present invention, advantageously, the fluid composition basically consists of the aforementioned red coloring composition, carbon dioxide fluid, surfactant, cosolvent and triethylenediamine according to the present invention.

In a specific embodiment, the fluid composition is composed of the aforementioned red coloring composition, carbon dioxide fluid, surfactant, cosolvent and triethylenediamine according to the present invention.

According to the third aspect of the present invention, the present invention also provides the use of the above-mentioned red dyeing composition and fluid composition for supercritical carbon dioxide anhydrous dyeing, characterized in that the dyeing object is natural fiber.

The use according to the present invention, wherein the natural fiber is selected from cotton.

The inventor found that using the fluid composition of the present invention for supercritical carbon dioxide anhydrous dyeing, the red dyeing composition not only has better solubility in supercritical carbon dioxide, but also has excellent dyeing properties.

Without wishing to be limited to any theory, on the one hand, the red dyeing composition of the present invention can form reverse micelles in a fluid composition. In the micelles, the supercritical carbon dioxide fluid constitutes the "oil phase". The lipophilic end of the surfactant penetrates into the supercritical carbon dioxide fluid, and the hydrophilic end spontaneously aggregates into spherical micelles, thereby forming stable thermodynamic properties and extremely high content inside the micelles. The red dyeing composition and triethylenediamine are dissolved in the co-solvent to form the "water-like phase". On the other hand, while the reverse micelle is dyed, the red dyeing composition realizes the synergistic effect of the compound of formula (I) and the compound of formula (II) in a specific type and ratio, and further improves the dyeing performance. The above situation is very helpful to improve the solubility of the red dyeing composition in supercritical carbon dioxide, and also helps to improve the dyeing performance of natural fibers, especially cotton fiber fabrics.

detailed description

The present invention will be further explained below in conjunction with specific embodiments.

It should be understood that the specific embodiments of the present invention are only used to explain the spirit and principle of the present invention, and not used to limit the scope of the present invention. In addition, it should be understood that after reading the content of the present invention, those skilled in the art can make various changes, substitutions, deletions, corrections or adjustments to the technical solutions of the present invention, and these equivalent technical solutions also fall into the claims of the present invention. The limited range.

In the present invention, the technical indicators for evaluating dyeing performance are color fastness to soaping and color fastness to rubbing, and the two are evaluated in accordance with GB/T 3921-2008 and GB/T 3920-2008, respectively.

Example 1

A red dyeing composition composed of a compound of formula (I-1), a compound of formula (II-1) and a compound of formula (II-2); the compound of formula (I-1) and the compound of formula (II-1) The weight ratio of the compound of) and the compound of formula (II-2) is 75:25. The above composition is obtained by mixing raw materials in powder form through a ball mill.

Further, a fluid composition for supercritical carbon dioxide anhydrous dyeing is prepared, and the fluid composition includes the aforementioned red dyeing composition, carbon dioxide fluid, surfactant, cosolvent and triethylenediamine; wherein, the red dyeing The amount of the composition is 2omf%. The surfactant is selected from fatty alcohol polyoxyethylene ether, the fatty alcohol polyoxyethylene ether is selected from cetearyl alcohol polyoxyethylene ether-10; the dosage of the fatty alcohol polyoxyethylene ether is 0.9g/ L, calculated based on the volume of carbon dioxide fluid. The co-solvent is selected from ethanol; the amount of the co-solvent is 2.5 g/L, calculated based on the volume of the carbon dioxide fluid. The amount of triethylenediamine and the red dyeing composition is 4.2:1 (w/w).

Calculate according to 1:500 (g/ml) relative to the fluid bath ratio of carbon dioxide, take the cotton fabric of the corresponding weight and fix it on the dyeing beam; then dissolve the red dyeing composition, surfactant and triethylenediamine in the formula amount In the co-solvent, add it to the dyeing kettle. Subsequently, carbon dioxide fluid is injected into the dyeing kettle, the dyeing kettle is sealed, and the dyeing kettle is fully stirred and then allowed to stand for 1 hour (during this process, the carbon dioxide fluid and the surfactant form a reverse micelle system). Further start the pressure and heating device until the pressure is 25MPa and the temperature is 130°C. Then dye for 60min under the condition of heat preservation and pressure. After the dyeing is finished, the pressure is released and the residual red dyeing composition and carbon dioxide fluid are separated through the separating kettle; finally, the dyed cotton fabric is taken out.

Comparative example 1

The other conditions were the same as in Example 1, but the red dyeing composition was replaced with an equivalent amount of the compound of formula (I-1).

Dyeing performance evaluation

The color fastness to soaping and the color fastness to rubbing of the dyed cotton fabrics of Example 1 and Comparative Example 1 were measured according to the aforementioned method. The results are shown in Table 1.

Table 1

It can be seen from Table 1 that compared with Comparative Example 1, the color fastness to soaping and the color fastness to rubbing of the dyed cotton fabric of Example 1 of the present invention are significantly higher.

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are all included in the protection scope of the present invention.

Claims

A red dyeing composition, the dyeing composition comprising a dye, characterized in that the dye comprises one or more compounds selected from the formula (I) and one or more compounds selected from the formula (II) ,

Wherein, R1 and R2 are selected from H, C 1-4 alkyl or C 1-4 alkoxy.
The dyeing composition according to claim 1, wherein the dye is composed of one or more compounds selected from the formula (I) and one or more compounds selected from the formula (II).
The dyeing composition according to claim 1, wherein R1 is located at the ortho and/or para position of the bromoacrylamido group on the benzene nucleus.
The dyeing composition according to claim 1, wherein R2 is located at the ortho and/or meta position of the bromoacrylamido group on the benzene nucleus.
The dyeing composition according to claim 1, wherein the compound of formula (I) is selected from the compound of formula (I-1),
The dyeing composition according to claim 1, wherein the compound of formula (II) is selected from the compound of formula (II-1) and/or the compound of formula (II-2),
The dyeing composition according to claim 6, wherein the compound of formula (II) is selected from a combination of a compound of formula (II-1) and a compound of formula (II-2).
The dyeing composition according to claim 1, wherein the weight ratio of the compound of formula (I) to the compound of formula (II) is (50-99): (1-50); preferably (60-90): ( 10-40); more preferably (65-85): (15-35).
The dyeing composition according to claim 8, wherein the weight ratio of the compound of formula (I) to the compound of formula (II) is (70-80):(20-30).
The use of the red dyeing composition of any one of claims 1-9 for supercritical carbon dioxide anhydrous dyeing, characterized in that the dyeing object is natural fiber.