阅读说明：本技术 流体组合物及其用于超临界二氧化碳无水染色的用途 (Fluid composition and use thereof for anhydrous dyeing with supercritical carbon dioxide ) 是由 濮坚锋 于 2020-06-08 设计创作，主要内容包括：公开了一种流体组合物及其用于超临界二氧化碳无水染色的用途,该流体组合物包括红色染色组合物和二氧化碳流体；前者包括一种或多种选自式(I)的化合物和一种或多种选自式(II)的化合物。该流体组合物能够实现反胶束染色,同时通过特定种类和配比的式(I)的化合物与式(II)的化合物实现了二者的协同效应,进一步提高了染色性能。(Disclosed are a fluid composition and its use for supercritical carbon dioxide anhydrous dyeing, the fluid composition comprising a red dyeing composition and a carbon dioxide fluid; the former includes one or more compounds selected from formula (I) and one or more compounds selected from formula (II). The fluid composition can realize reverse micelle dyeing, and meanwhile, the synergistic effect of the compound of the formula (I) and the compound of the formula (II) in a specific type and a specific proportion is realized, so that the dyeing performance is further improved.)

1. A fluid composition comprising a red-coloring composition and a carbon dioxide fluid; characterized in that the fluid dyeing composition comprises one or more compounds selected from formula (I) and one or more compounds selected from formula (II),

formula (I)

Formula (II)

Wherein R1 and R2 are selected from H, C_1-4Alkyl or C_1-4An alkoxy group.

2. The fluid composition of 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) to (10-40); more preferably (65-85) to (15-35); and, most preferably (70-80): 20-30).

3. The fluid composition of claim 1, wherein the fluid coloring composition is present in an amount of 0.25-4 omf%.

4. The fluid composition of claim 1, wherein the fluid composition further comprises a surfactant and a co-solvent.

5. The fluid composition of claim 4, wherein the surfactant is selected from fatty alcohol-polyoxyethylene ethers; the dosage of the fatty alcohol-polyoxyethylene ether is 0.5-1.5g/L, and is calculated based on the volume of the carbon dioxide fluid.

6. The fluid composition of claim 4, wherein the co-solvent is selected from the group consisting of alcoholic solvents; the amount of the cosolvent used is 0.5-5g/L based on the volume of the carbon dioxide fluid.

7. The fluid composition of claim 1, wherein the fluid composition further comprises triethylene diamine.

8. The fluid composition according to claim 7, wherein the amount of triethylenediamine to the red dyeing composition is (2.6-5.8):1 (w/w).

9. Use of a fluid composition according to any of claims 1-8 for anhydrous dyeing with supercritical carbon dioxide, characterized in that the dyeing object is a natural fiber.

10. Use according to claim 9, wherein the natural fibres are selected from cotton.

Technical Field

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

Background

Water is an essential and important resource for human survival. Although the water resource on the earth is abundant, the fresh water available for human on land only accounts for 2.5% of the total fresh water resource. The water resource of China is more deficient, and the occupied amount per person is only one fourth of the average level in the world; furthermore, the fresh water resources are not distributed uniformly, and a plurality of areas such as the north and the northwest are seriously lack of water. Meanwhile, the current situations of water environment deterioration, water quality type water shortage and water resource shortage are increasingly aggravated. In order to change the current situation, the public environment protection awareness of society is continuously strengthened, and the country also develops a plurality of laws and regulations related to environment protection. In recent years, environmental storms scrapped against various pollution industries have also become more severe. As the textile printing and dyeing industry with huge water resource consumption and serious pollution, the development of water-saving and even waterless dyeing or printing process with high process efficiency is becoming more and more concerned.

Research shows that the traditional dyeing method consumes a great deal of water. The water amount of 100-200 tons is required for printing and dyeing 1 ton of textiles on average. Although a small part of water can be recycled, the rest is mostly waste water. Therefore, the waste water discharged by the printing and dyeing industry also becomes a main source of the whole textile industry, and accounts for almost more than 80%. Furthermore, in conventional dyeing processes, various dyeing auxiliaries are usually added to the dyebath. The dyeing auxiliary agents and unfixed dye remain in the printing and dyeing wastewater, thus increasing the burden of later-stage sewage treatment and bringing serious threat to the ecological environment.

As a novel, green and environment-friendly printing and dyeing technology, the supercritical carbon dioxide fluid anhydrous dyeing technology injects vitality for innovation of the textile industry, and meanwhile, the technology can really realize ecological spinning, accords with the concepts of energy conservation, emission reduction and sustainable development, and has positive practical significance.

The supercritical carbon dioxide fluid not only has the properties of low viscosity and strong diffusion of gas, but also has the density similar to that of liquid and has good dissolving capacity for hydrophobic substances. The above-mentioned advantageous properties of carbon dioxide fluid are utilized as a dyeing medium to replace the water of a conventional dye bath for dyeing textiles. The supercritical carbon dioxide dyeing does not need water in the whole dyeing process, and dyeing liquor does not need adding dyeing auxiliary agents, acid, alkali and other chemical reagents. The dyed fabric does not need to be washed in a floating color, and the generation of dyeing wastewater is avoided, so that the treatment problem of dyeing wastewater is really solved at the source, and the method is beneficial to environmental protection. In addition, the dyed fabric is in a dry state, and does not need to be dried, thereby being beneficial to saving energy. The residual dye and carbon dioxide fluid can be continuously used in the next dyeing process.

Since carbon dioxide is a nonpolar molecule, according to the principle of similar phase solubility, a nonpolar or low-polarity dye has good solubility in a supercritical carbon dioxide fluid, and thus, the dye for dyeing with supercritical carbon dioxide is mainly a disperse dye. Accordingly, as dyed fabrics, the most widely used and successful are primarily polyester fabrics, followed by aramid and polypropylene fabrics. In the textile market, however, natural fiber fabrics, especially cotton fabrics, generally hold a large share and are highly appreciated by consumers due to their natural material origin and the additional green attributes. However, such fibers are usually dyed using reactive dyes and acid dyes, which are easily soluble in water but not in carbon dioxide fluid, and thus have technical bottlenecks in applying supercritical carbon dioxide fluid dyeing technology.

In recent years, the problem of dyeing natural fibers in supercritical carbon dioxide fluid has been mainly addressed from the following points. The method specifically comprises the following steps:

the natural fiber is pretreated by the swelling agent or the cross-linking agent, so that the number of hydrogen bonds on the surface of the natural fiber is reduced, and the polarity of the natural fiber is reduced.

The addition of a polar co-solvent (primarily 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, active groups are introduced into the disperse dye molecules, and the formed active disperse dye has the advantages of good solubility and strong reactivity of the disperse dye and reacts with natural fibers through nucleophilic addition or substitution reaction. However, most reactive disperse dyes still have the disadvantage of not being very reactive with natural fibers, especially cotton fibers.

The surfactant is added into the carbon dioxide fluid to form reverse micelles, so that the solubility of the dye can be improved; meanwhile, the hydrolysis degree of the dye is inhibited, and the reactivity of the dye can be improved to a certain degree.

Chinese patent application CN105696384A discloses a polyester-cotton blended fabricReverse micelle supercritical CO₂The dyeing system comprises the following components in parts by weight: 5-25 parts of penta-polyethylene glycol mono-octyl ether, n-amyl alcohol: 10-35 parts of reactive dye: 0.01-0.20 parts of disperse dye: 0.01-0.10 parts of carbon dioxide: 40-60 parts of distilled water: 0.01 to 6.0 parts. Placing the polyester-cotton blended fabric in a high-pressure container, and then carrying out reverse micelle supercritical CO₂The dyeing system has good solubility, disperse dye is simultaneously dyed on the polyester fiber while the active dye is used for dyeing the cotton fiber components, and the cotton fiber is dyed under the salt-free condition, so that the phenomena of staining and stain of the dye on the fabric are greatly avoided; meanwhile, the dyeing method has the advantages of high dyeing efficiency, excellent dyeing effect and the like.

However, the above patent application does not disclose specific reactive dyes and disperse dyes, resulting in difficult reproducibility of dyeing properties of the dyeing system.

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

Disclosure of Invention

The invention aims to provide a fluid composition and application thereof to supercritical carbon dioxide anhydrous dyeing. The fluid compositions have excellent dyeing properties.

In order to solve the above technical problem, according to a first aspect of the present invention, the following technical solutions are adopted: a red dyeing composition comprising a dye, characterized in that the dye comprises one or more compounds selected from formula (I) and one or more compounds selected from formula (II),

wherein R1 and R2 are selected from H, C_1-4Alkyl or C_1-4An alkoxy group.

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

In the present invention, the terms "comprising", "including", "having" are intended to be open-ended expressions that do not exclude the presence of any other optional components, steps or procedures. The term "consisting of … …" is meant to exclude the presence of other optional components, steps or procedures.

The dyeing composition according to the invention, wherein R1 and R2 are chosen from H, C_1-2Alkyl or C_1-2An alkoxy group.

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

The dyeing composition of the invention is characterized in that R1 is positioned at ortho-position and/or para-position of the bromo-acrylamido on the benzene nucleus.

The dyeing composition of the invention is characterized in that R2 is positioned at ortho-position and/or meta-position of the bromo-acrylamido on the benzene nucleus.

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

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

the dyeing composition according to the present invention, wherein the compound of formula (II) is selected from the group consisting of a compound of formula (II-1) and a compound of formula (II-2). That is, the compound of formula (II) consists 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 method comprises the following specific steps: with 1-chloroanthraquinone and meta-anthraquinonePhenylenediamine as a starting material in the presence of a Cu catalyst (5 mol%) and an alkaline agent (e.g., K)₂CO₃) Carrying out Ullmann coupling reaction under the action of the dye to prepare a dye intermediate; the latter and 2, 3-dibromo propionyl chloride are subjected to nucleophilic substitution, 1 molecule HBr is removed under the action of triethylamine, after the reaction is finished, the HBr is concentrated, and petroleum ether and dichloromethane in a volume ratio of 1:1.5 are used as eluents for carrying out chromatographic column separation and purification to obtain the corresponding compound.

The compounds of formula (II-1) and compounds of formula (II-2) are likewise synthesized according to prior art methods. The method comprises the following specific steps: 1-chloroanthraquinone and 2, 5-diaminotoluene sulfate are used as raw materials, and a Cu catalyst (5 mol%) and an alkaline agent (such as K) are added₂CO₃) Carrying out Ullmann coupling reaction under the action of the dye to prepare a dye intermediate; the latter and 2, 3-dibromo propionyl chloride are subjected to nucleophilic substitution, 1 molecule HBr is removed under the action of triethylamine, after the reaction is finished, the HBr is concentrated, and petroleum ether and dichloromethane in a volume ratio of 1:1.5 are used as eluents for carrying out chromatographic column separation and purification to obtain the corresponding compound. In the reaction process, because the compound of the formula (II-1) and the compound of the formula (II-2) are isomers, the polarities are extremely similar, and the two are not easy to separate, the corresponding compounds are obtained as a mixture of the two.

The dyeing composition provided by the invention is characterized in that the weight ratio of the compound of the formula (I) to the compound of the formula (II) is (50-99) to (1-50); preferably (60-90) to (10-40); more preferably (65-85) to (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 comprises the step of mixing the compound of the formula (I) and the compound of the formula (II) according to a formula ratio. 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 be present in powder form, or in the form of granules. The mixing step may be carried out in a suitable milling apparatus such as a ball mill or kneader.

According to a second aspect of the present invention, there is further provided a fluid composition for supercritical carbon dioxide anhydrous dyeing, the fluid composition comprising a red dyeing composition as hereinbefore described according to the present invention and a carbon dioxide fluid.

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

Preferably, the amount of the red dyeing composition is 0.5-3.5 omf%; more preferably, the amount of the red dyeing composition is 1.0 to 3 omf%; and, most preferably, the red dyeing composition is used in an amount of 1.5 to 2.5 omf%.

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

The fluid composition according to the present invention, wherein the fluid composition further comprises 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 provided by the invention is characterized in that the molecular formula of the fatty alcohol-polyoxyethylene ether is R- (OCH)₂CH₂)_n-OH; r is selected from C_10-20A fatty alcohol residue; n is 3-30.

Preferably, the molecular formula of the fatty alcohol-polyoxyethylene ether is R- (OCH)₂CH₂)_n-OH; r is selected from C_12-20A fatty alcohol residue; n is 5-25; more preferably, the molecular formula of the fatty alcohol-polyoxyethylene ether is R- (OCH)₂CH₂)_n-OH; r is selected from C_14-20A fatty alcohol residue; n is 8-20; and, most preferably, R- (OCH)₂CH₂)_n-OH; r is selected from C_14-18A fatty alcohol residue; n is 9-15.

In a specific embodiment, the molecular formula of the fatty alcohol-polyoxyethylene ether is R- (OCH)₂CH₂)_n-OH; r is selected from C_16-18A fatty alcohol residue; n is 10. Namely, the fatty alcohol-polyoxyethylene ether is selected from cetearyl alcohol-polyoxyethylene ether-10.

The fluid composition provided by the invention is characterized in that the fatty alcohol-polyoxyethylene ether is used in an amount of 0.5-1.5g/L, based on the volume of the carbon dioxide fluid.

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

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

The fluid composition according to the present invention, wherein 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.

The fluid composition provided by the invention is characterized in that the cosolvent is used in an amount of 0.5-5g/L based on the volume of the carbon dioxide fluid.

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

In one embodiment, the co-solvent is used in an amount of 2.5g/L, based on the volume of the carbon dioxide fluid.

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

The fluid composition provided by the invention is characterized in that the dosage of the triethylene diamine and the red dyeing composition is (2.6-5.8):1 (w/w).

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

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

In the present invention, the fluid composition advantageously consists essentially of the red dyeing composition according to the invention, the carbon dioxide fluid, the surfactant, the co-solvent and the triethylenediamine previously described.

In a specific embodiment, the fluid composition consists of the red coloring composition according to the present invention, a carbon dioxide fluid, a surfactant, a co-solvent, and triethylenediamine as previously described.

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

The use according to the invention, wherein the natural fibres are selected from cotton.

The inventor finds that when the fluid composition is used for supercritical carbon dioxide anhydrous dyeing, the red dyeing composition not only has better solubility in supercritical carbon dioxide, but also has excellent dyeing performance.

Without wishing to be bound by any theory, in one aspect, the red-colored compositions of the present invention are capable of forming reverse micelles in a fluid composition. In the micelle, the supercritical carbon dioxide fluid forms an 'oil phase', the lipophilic end of the surfactant is deeply inserted into the supercritical carbon dioxide fluid, and the hydrophilic end spontaneously aggregates into a spherical micelle, so that a microemulsion with stable thermodynamic properties and containing a polar inner core is formed in the micelle; while the red dyeing composition and triethylenediamine are dissolved in a cosolvent to form a "water-like phase". On the other hand, when the reverse micelle dyeing is carried out, the red dyeing composition realizes the synergistic effect of the compound of the formula (I) and the compound of the formula (II) according to the specific type and proportion, and further improves the dyeing performance. This is very advantageous for improving the solubility of the red dyeing composition in supercritical carbon dioxide and also for improving the dyeing properties of natural fibers, especially cotton fabrics.

Detailed Description

The invention will be further illustrated with reference to specific embodiments.

It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.

In the invention, the technical indexes for evaluating the dyeing performance are soaping color fastness and rubbing color fastness which are respectively evaluated according to GB/T3921-.