Reactive dye with high fixation rate and preparation method thereof

Abstract

The invention provides a reactive dye with a high fixation rate and a preparation method thereof. The reactive dye is prepared from the following raw materials in parts by mass: 25 parts of modified reactive dye, 0.3-0.7 part of a metal ion agent and 60-80 parts of water, wherein the modified reactive dye is obtained by inclusion of reactive dye molecules with beta-cyclodextrin-pyridine carboxylic acid, and beta-cyclodextrin and pyridine carboxylic acid in the beta-cyclodextrin-pyridine carboxylic acid are connected through an alkyl chain; metal ions provided by the metal ion agent can be chelated with the picolinic acid. Reactive dye molecules and beta-cyclodextrin-pyridine carboxylic acid form an inclusion structure, the hydrolysis probability of active groups is reduced, and an alkyl chain regulates steric hindrance and molecular spacing, so that pyridine nitrogen and carboxylic acid more efficiently form a more stable chelate with metal ions and further form coordinate bonds with hydroxyl groups on the fiber surface, and the fixation rate of the reactive dye is improved.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to the technical field of reactive dyes, in particular to a reactive dye with high fixation rate and a preparation method thereof. BACKGROUND

[0002] Reactive dyes are a class of dyes containing groups that can react with hydroxyl or amino groups on the fiber molecule to form covalent bonds in the molecule, which have the advantages of bright color, good uniform dyeing, high wash fastness, etc., and are widely used for dyeing and printing of cotton, hemp, viscose and other fibers. However, the existing reactive dyes still have problems such as easy hydrolysis of active groups, easy aggregation of dye molecules during dyeing process, etc., which leads to a decrease in fixation rate, thus resulting in low dye utilization or serious dye solution waste.

[0003] At present, the main idea to improve the fixation rate of reactive dyes is to increase the number of active groups or introduce bridging structures to improve the reaction probability with fibers or enhance the chemical bonding force between dyes and fibers. For example, patent CN117106322A discloses a synthesis method of a reactive dye with cyanuric chloride as a connecting group. First, cyanuric chloride is subjected to a substitution reaction with 2-amino-5-naphthol-7-sulfonic acid compounds to introduce naphthalene ring hydroxyl substitution structure; then reacted with compounds containing two primary amine groups to form a bridging structure to lengthen the molecular backbone; and then subjected to a third condensation reaction with arylamine compounds containing ethylene sulfone sulfate active groups to introduce ethylene sulfone type active groups, to obtain an intermediate containing two ethylene sulfone sulfate active groups; finally, the intermediate is subjected to a coupling reaction with arylamine diazonium salt not containing ethylene sulfone sulfate active groups to prepare a reactive dye containing double ethylene sulfone active groups.

[0004] Such dyes can improve the fixation rate and dyeing fastness to some extent by introducing multiple active groups, but due to the complex structure of the dye molecules and large steric hindrance, the active groups may be more prone to hydrolysis side reactions during dyeing, resulting in a decrease in effective reaction sites, or the problem of easy aggregation, which may affect the combination efficiency of dyes and fibers.

[0005] Therefore, reducing the hydrolysis rate and improving the dispersibility are effective means to improve the fixation rate of dyes, and how to reduce the hydrolysis rate of reactive dyes while maintaining the reaction between reactive dyes and fibers is a technical problem that needs to be solved in the field. SUMMARY

[0006] The present application provides a reactive dye with high fixation rate and a preparation method thereof.

[0007] In a first aspect, the application provides a reactive dye with high fixation rate, comprising the following raw materials by mass fraction: 25 parts of modified reactive dye, 0.3-0.7 parts of metal ion agent, 60-80 parts of water; wherein the modified reactive dye is obtained by β-cyclodextrin-pyridine carboxylic acid inclusion of reactive dye molecules, wherein the β-cyclodextrin and pyridine carboxylic acid in the β-cyclodextrin-pyridine carboxylic acid are connected by an alkyl chain; the metal ions provided by the metal ion agent can be chelated with the pyridine carboxylic acid.

[0008] According to the application, by the above formula and structural design, the hydrolysis of the reactive dye molecules can be inhibited while maintaining the reactivity of the reactive dye molecules, the dyeing combination efficiency is improved, and the high fixation rate of the reactive dye is realized.

[0009] Specifically, the β-cyclodextrin (β-CD) is connected with the pyridine carboxylic acid by an alkyl chain to form a β-cyclodextrin-pyridine carboxylic acid, and the reactive dye molecules are partially embedded in the hydrophobic cavity of the β-CD by Van der Waals force to form a relatively stable non-covalent binding structure. The inclusion of β-CD can make the reactive dye molecules in an orderly dispersed state, inhibit the aggregation and precipitation caused by the accumulation of molecules, and at the same time, the steric hindrance effect of β-CD can limit the contact of water molecules and hydroxyl ions with the active groups of the reactive dye molecules, and the hydrophobicity of the cavity is not conducive to the entry of polar molecules, which can slow down the reaction rate of the active groups by nucleophilic substitution, maintain a high active group efficiency, and improve the fixation rate of the dye; the alkyl chain is a non-polar hydrophobic chain, which can form a "synergistic hydrophobic field" with the hydrophobic characteristics of the β-CD cavity, and can also isolate the β-CD cavity from the polar groups of the pyridine carboxylic acid by a certain spatial distance, reduce the interference of the polar groups to the inclusion cavity, and further enhance the inclusion stability of the β-cyclodextrin-pyridine carboxylic acid. In addition, the hydrophobic characteristics of the alkyl chain can make the pyridine carboxylic acid more inclined to the outside of the inclusion, reduce the polar interference of the pyridine carboxylic acid to the hydrophobic cavity of the β-cyclodextrin, and at the same time, retain the orientation freedom given by the alkyl chain, which is conducive to the formation of hydrogen bonds and dipole interactions between the reactive dye molecules and the fiber surface during the dyeing process, and enhances the adsorption and combination efficiency of the modified reactive dye; the pyridine carboxylic acid is a medium-polar group, which can adjust the surface polarity of the inclusion structure, make the whole system show weak negative electric property and form a polar gradient layer, weaken the π-π stacking and aggregation tendency between the reactive dye molecules, and improve the combination efficiency of the reactive dye and the fiber.

[0010] On the other hand, the pyridine nitrogen atom and the carboxyl oxygen atom provided by the pyridine carboxylic acid can form a relatively stable chelate with the metal ion provided by the metal ion agent, which can make the modified reactive dye form a surface charge balance layer, inhibit the aggregation and precipitation between the reactive dye molecules, improve the stability, and the coordination of the metal ion and the pyridine carboxylic acid can bind the free water molecules around the part, reduce the probability of nucleophilic attack of water molecules on the active group, thereby slowing down the hydrolysis of the active group. In addition, the alkyl chain connecting the β-cyclodextrin and the pyridine carboxylic acid may play a role in space and structure optimization in this process. Its certain flexible characteristics can fine-tune the molecular conformation, expose the chelating sites of the pyridine carboxylic acid, and promote the formation of chelates. At the same time, the non-polar hydrophobic characteristics of the alkyl chain reduce the competitive coordination of the metal ion itself, improving the chelation efficiency. During the dyeing process, the chelate can promote the enrichment of the dye on the fiber surface through electrostatic adsorption, coordination or hydrogen bonding, etc. to build a "reactive dye molecule-metal-fiber" type ternary bridging structure, enhance the binding force between the dye and the fiber, and improve the fixation rate.

[0011] Therefore, the dye system of the present application can significantly reduce the hydrolysis rate of the reactive dye molecule during the dyeing process, improve the fiber binding efficiency, and achieve high fixation performance.

[0012] In some embodiments, the reactive dye molecule contains an aromatic ring structure.

[0013] In some of the above embodiments, the cavity of the β-CD can contain the hydrophobic structure of the reactive dye molecule, improving its dispersibility and fixation performance. The "conical" cavity of the β-CD makes the aromatic ring embedded, and the active group of the reactive dye molecule tends to be exposed at the opening of the cavity at both ends. In addition, the hydroxyl groups at the opening of the β-CD cavity can limit the direct contact of the active group with water or nucleophilic reagents to a certain extent through steric hindrance and hydrogen bonding, which is conducive to reducing the hydrolysis rate while maintaining the reactivity of the active group with the fiber. The modified reactive dye obtained by modifying the reactive dye molecule containing an aromatic ring structure can achieve higher active group utilization rate and better dyeing fastness during the dyeing process. Preferably, the reactive dye molecule includes reactive red 120, reactive red 195, reactive yellow 145, reactive orange 13, reactive orange 122, reactive blue 160, reactive blue 49, reactive blue 19, reactive violet 5, and reactive green 27.

[0014] In some embodiments, the preparation method of the modified reactive dye comprises the following steps: S1: reacting β-cyclodextrin with a bromoalkyl aminating agent, the hydroxyl group of β-cyclodextrin undergoes nucleophilic substitution with the alkyl group containing bromine in the bromoalkyl aminating agent to obtain amino-β-cyclodextrin; S2: reacting amino-β-cyclodextrin with pyridine carboxylic acid to make the amino group of amino-β-cyclodextrin react with the carboxyl group of pyridine carboxylic acid, obtaining β-cyclodextrin-pyridine carboxylic acid; S3: mixing reactive dye raw material with β-cyclodextrin-pyridine carboxylic acid to form a reactive dye molecule-β-cyclodextrin-pyridine carboxylic acid inclusion compound, obtaining a modified reactive dye.

[0015] In some of the above embodiments, the amino group and alkyl chain are introduced into the β-cyclodextrin by reacting with a bromoalkyl aminating agent, providing more reaction sites for subsequent combination with pyridine carboxylic acid; In step S2, the carboxyl group of pyridine carboxylic acid reacts with the amino group in amino-β-cyclodextrin to form an amide bond connected β-cyclodextrin-pyridine carboxylic acid, which provides a functional group for amino-β-cyclodextrin, improves the reactivity of the complex, and helps the subsequent metal ion chelation reaction; In step S3, the hydrophobic group of the reactive dye molecule is embedded in the β-CD cavity through van der Waals force and hydrophobic effect, which realizes isolation of the reactive dye molecule through steric hindrance, reduces the side-by-side contact between aromatic nuclei, inhibits π-π stacking, and further forms a relatively stable inclusion compound, thereby improving the dispersion stability of the dye solution.

[0016] In some embodiments, the alkyl chain in the bromoalkyl aminating agent contains 2-4 carbon atoms.

[0017] In some of the above embodiments, when the alkyl chain in the bromoalkyl aminating agent used contains 2-4 carbon atoms, the spatial distance between β-CD and pyridine carboxylic acid can be controlled within 2-4 carbon atoms in length. The alkyl chain of this length range is not prone to chain entanglement or intramolecular folding, and the amide bond connection structure formed is more compact, which can reduce the spatial entanglement and aggregation between modified reactive dye molecules. At the same time, its moderately rigid structure can support the formation of a relatively stable inclusion structure between β-cyclodextrin and reactive dye molecules, improving the long-term storage stability of the reactive dye. Its limited flexibility can drive the chelate to make a small turn, so that the pyridine nitrogen and carboxyl oxygen of pyridine carboxylic acid form a spatial angle that is suitable for metal ion coordination configuration, effectively avoiding the spatial orientation deviation of coordination groups that often occurs in long chains, and promoting the efficient construction of the "dye-metal-fiber" structure.

[0018] In some embodiments, the mass ratio of amino-β-cyclodextrin to pyridine carboxylic acid is 10:1.0-1.2.

[0019] In some of the above embodiments, when the mass ratio of the amino-β-cyclodextrin and the pyridine carboxylic acid is controlled in the range of 10:1.0~1.2, the carboxyl group of the pyridine carboxylic acid can be coupled with the amino group of the amino-β-cyclodextrin through an amidation reaction, while the excessive pyridine carboxylic acid can be limited to cause excessive substitution or cavity polarity enhancement, so as to maintain the inclusion ability and dispersion stability of the β-cyclodextrin. The ratio interval can make the dye inclusion more stable, thereby improving the dye fixation rate.

[0020] In some embodiments, the preparation method of the modified reactive dye comprises the following steps: S1: reacting 10 parts of β-cyclodextrin with 2~3 parts of a bromoalkyl amine reagent at 40~60℃ for 6~12h to obtain amino-β-cyclodextrin; S2: reacting 10 parts of the amino-β-cyclodextrin with 1~1.2 parts of pyridine carboxylic acid at 0~30℃ for 10~14h to obtain β-cyclodextrin-pyridine carboxylic acid; S3: dissolving 30 parts of the β-cyclodextrin-pyridine carboxylic acid and 8~20 parts of a reactive dye in 100~200 parts of water, adding 0.8~1.5 parts of a quaternary ammonium salt, adjusting the pH value to 6~7, and reacting at 30~60℃ for 2~4h to obtain the modified reactive dye.

[0021] In some of the above embodiments, by introducing an amino-alkyl chain to the outer layer of the β-cyclodextrin, the modification can improve the dispersion and dye inclusion stability of the β-cyclodextrin.

[0022] In step S2, the pyridine carboxylic acid group is introduced to the amino-β-cyclodextrin, which enhances the metal ion coordination ability of the amino-β-cyclodextrin.

[0023] In step S3, the β-cyclodextrin-pyridine carboxylic acid is allowed to include the reactive dye molecule to obtain the modified reactive dye. In this process, the quaternary ammonium salt is added, which can weaken the negative charge repulsion between them, promote the host-guest inclusion to form a stable inclusion structure, and at the same time, form an electrostatic shielding layer on the surface of the dye molecule to inhibit the aggregation of the dye molecule and enhance the stability.

[0024] The modified reactive dye prepared by the above process conditions has good dispersion stability, reactivity and dyeing performance, which can improve the problems of hydrolysis loss and uneven dyeing of traditional reactive dyes in the dyeing process.

[0025] In some embodiments, in step S2, the pyridine carboxylic acid includes 2,6-pyridine dicarboxylic acid and 4-pyridine carboxylic acid, and the mass ratio of the 2,6-pyridine dicarboxylic acid and the 4-pyridine carboxylic acid is 1:0.6~0.8.

[0026] In some of the above embodiments, 2,6-pyridinedicarboxylic acid has two carboxyl groups, which can effectively enhance the chelation with metal ions. The linear para-carboxyl group of 4-pyridinedicarboxylic acid can enhance the dispersibility of the β-CD cavity and promote the inclusion of dye molecules. In addition, 4-pyridinedicarboxylic acid has a promoting effect on the chelation of 2,6-pyridinedicarboxylic acid with metal ions. On the one hand, its linear structure can uniformly disperse 2,6-pyridinedicarboxylic acid, inhibit the chelation sites from being blocked by its own molecules due to aggregation of 2,6-pyridinedicarboxylic acid, and promote its contact with metal ions. On the other hand... In terms of 4-pyridine carboxylic acid, due to its smaller steric hindrance, it can more efficiently form hydrogen bonds and dipole interactions with the fiber surface, promoting the adsorption of modified reactive dyes onto the fiber surface. This also brings the chelating sites of 2,6-pyridine dicarboxylic acid closer to the fiber hydroxyl groups, making it easier for them to bind and improving the fixation rate of the reactive dyes. When the mass ratio of 2,6-pyridine dicarboxylic acid to 4-pyridine carboxylic acid is controlled at 1:0.6~0.8, a functional layer structure with strong coordination ability and without excessive polarization can be formed, improving the adsorption and binding efficiency of reactive dyes on the fiber surface.

[0027] In some embodiments, in step S3, the quaternary ammonium salt includes chitosan quaternary ammonium salt and epoxy quaternary ammonium salt, wherein the mass ratio of chitosan quaternary ammonium salt to epoxy quaternary ammonium salt is 1:0.1~0.3.

[0028] In some of the above embodiments, quaternary ammonium salts can not only form a cationic electrostatic shielding layer on the surface of the inclusion complex, enhancing the structural stability of the modified reactive dyes, but also, by combining chitosan quaternary ammonium salts with epoxy-based quaternary ammonium salts, achieve dual functions of electrostatic regulation and chemical crosslinking during subsequent dyeing processes. Chitosan quaternary ammonium salts provide a high density of cationic groups, which preferentially promotes the enrichment of modified reactive dyes on negatively charged sites on the fiber surface, forming a preliminary electrostatic adsorption layer. Furthermore, chitosan quaternary ammonium salts may inhibit excessive aggregation of metal ions through charge repulsion effects, while their cationic properties help promote contact between metal ions and negatively charged pyridine carboxylic acid sites, improving chelation efficiency. Subsequently, under dyeing conditions... Under these conditions, epoxy quaternary ammonium salts may undergo ring-opening reactions at the interface between fibers and modified reactive dyes, providing attachment sites on the fiber surface. This enhances dye fixation through chemical bonding or strong non-covalent adsorption. Furthermore, epoxy quaternary ammonium cations may form "ion pairs" with pyridine carboxylic acid-metal ion chelates. The hydroxyl groups generated after ring opening can form auxiliary coordination with metal ions in the chelate, improving the stability of the modified reactive dye. When both are added in a mass ratio of 1:0.1 to 0.3, the binding state between the inclusion complex and the fiber interface can be stabilized, effectively inhibiting the aggregation or dissociation of dye inclusion complexes. Through stepwise synergistic improvement, the binding efficiency between the dye and the fiber is enhanced, thereby increasing the fixation rate of the modified reactive dye.

[0029] In some embodiments, the metal ion agent includes zirconium salts.

[0030] In some of the above embodiments, the zirconium salt metal ion agent provides a high coordination number of zirconium ions, which can coordinate with the pyridine nitrogen atoms and carboxyl oxygen atoms in the pyridine carboxylic acid to form a relatively stable chelate, Zr 4+ The chelate acts as a "molecular bridge", connecting the dye molecule at one end and the cellulose hydroxyl group at the other end through an unsaturated coordination site, Zr 4+ The high positive charge of Zr 4+ In aqueous solution, it is easy to form polynuclear hydroxyl complexes, and these hydrolysis products can also form hydrogen bonds with the hydroxyl groups on the fiber surface or undergo dehydration condensation, further strengthening the anchoring of the modified reactive dye to the fiber, thereby improving the fixation rate of the reactive dye.

[0031] In a second aspect, the application provides a method for preparing a high-fixation-rate reactive dye, which comprises mixing and stirring the raw materials of the reactive dye according to any one of the embodiments of the first aspect to obtain the high-fixation-rate reactive dye.

[0032] According to the application, the method can be used to prepare the reactive dye of the first aspect, thus having the beneficial effects of the first aspect, and the obtained reactive dye has excellent fixation performance.

[0033] In a third aspect, the application provides the use of the high-fixation-rate reactive dye according to any one of the embodiments of the second aspect in the field of textiles.

[0034] According to the application, when the high-fixation-rate reactive dye prepared by the method according to any one of the embodiments of the second aspect is used in the dip dyeing process of fibers, it can significantly improve the dye uptake and fixation rate of the dye under conventional dyeing conditions, reduce the hydrolysis loss of the reactive groups, reduce the discharge of dye waste liquid, and the dyed fabric has higher dyeing uniformity.

[0035] Compared with the prior art, the application has at least the following beneficial effects: by connecting the β-cyclodextrin and the pyridine carboxylic acid through a short chain, a structure with an internal inclusion cavity and an external coordination function is constructed, the hydrophobic cavity of the β-cyclodextrin includes the reactive dye molecule to form a relatively stable inclusion body, which can effectively inhibit the π-π stacking and hydrolysis inactivation of the dye molecules, the external pyridine carboxylic acid group can act on the hydroxyl groups on the fiber surface to enhance the binding force between the dye and the fiber, and can also coordinate with the metal ions, forming an "dye-metal-fiber" anchoring structure during the dyeing process, thereby improving the fixation rate. DETAILED DESCRIPTION

[0036] Each embodiment in the specification is described in a progressive manner, and each embodiment focuses on the differences from other embodiments.

[0037] In the description of the present specification, the description referring to the terms "one embodiment", "some embodiments", "exemplary embodiment", "example", "specific example", or "some examples" etc. means that the specific feature, structure, material or characteristic described in connection with the implementation or example is included in at least one implementation or example of the present application. The exemplary description of the above terms in the present specification does not necessarily mean the same implementation or example. Also, the specific feature, structure, material or characteristic described can be combined with any one or more implementations or examples in a suitable manner.

[0038] In addition, the terms "first", "second" are used only for the purpose of description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, the features defined with "first", "second" can explicitly or implicitly include at least one of the features. In the description of the present application, the meaning of "plurality" is at least two, for example, two, three, etc., unless otherwise specifically limited.

[0039] In the description of the present specification, "parts" means "mass parts" unless otherwise specifically described.

[0040] Hereinafter, the embodiments of the present application will be described. The embodiments described below are exemplary and are for the purpose of explanation of the present application only, and cannot be understood as a limitation of the present application. In the embodiments, the specific techniques or conditions not noted are performed according to the techniques or conditions described in the literature in the art or according to the product manual. The reagents or instruments not noted the manufacturer are all conventional products that can be obtained by purchase in the market.

[0041] Reactive Red 120: CAS No. 61951-82-4; β-Cyclodextrin: CAS No. 7585-39-9; Hydroxypropyltrimethylammonium chloride chitosan: CAS No. 70694-72-3, weight average molecular weight is about 100000, degree of deacetylation is ≥80%; Polyethylene glycol (PEG-4000): CAS No. 25322-68-3, weight average molecular weight is about 4000.

[0042] Preparation Example 1 Preparation of modified reactive dyes: S1: 10 parts of β-cyclodextrin was dissolved in 100 parts of mixed solution (80 parts of deionized water, 20 parts of N,N-dimethylformamide) at 40°C for 20 min, 0.5 parts of tetrabutylammonium bromide was added and stirred for 10 min, 2.5 parts of 3-bromopropylamine hydrobromide was dissolved in 30 parts of mixed solution (25 parts of deionized water, 5 parts of N,N-dimethylformamide), the pH value was adjusted to 10 with 0.5M NaOH aqueous solution, the above-mentioned 3-bromopropylamine hydrobromide solution was added to the above-mentioned β-cyclodextrin solution, and the reaction was carried out at 50°C for 8h, the pH value was adjusted to 7 with 0.1M HCl aqueous solution, the solution was passed through an ultrafiltration membrane (MWCO 1000Da), and the concentrated liquid was vacuum dried to obtain amino-β-cyclodextrin; S2: 10 parts of amino-β-cyclodextrin, 0.64 parts of 2,6-pyridine dicarboxylic acid, and 0.46 parts of 4-pyridine carboxylic acid were dissolved in 150 parts of N,N-dimethylformamide, 2.5 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and 1.8 parts of N-hydroxysuccinimide were added, and the reaction was carried out at 0°C for 20 min, 2.5 parts of N,N-diisopropylethylamine was added, and the reaction was carried out at 20°C for 12h, rotary evaporation (50°C, 0.1bar), the residual liquid was added to 10 times the volume of deionized water, the pH was adjusted to 7 with 0.1M HCl aqueous solution, 30 parts of dichloromethane was added, and after oscillation, the layers were separated, the water phase was passed through an ultrafiltration membrane (MWCO 1000Da), and the concentrated liquid was vacuum dried to obtain β-cyclodextrin-pyridine carboxylic acid; S3: 30 parts of β-cyclodextrin-pyridine carboxylic acid was dissolved in 150 parts of deionized water, stirred for 20 min, 15 parts of reactive red 120 was added, stirred for 60 min, 1 part of hydroxypropyltrimethylammonium chloride chitosan was slowly added, and then stood for 30 min, 0.2 parts of glycidyltrimethylammonium chloride was continuously added, stirred for 15 min, the pH value was adjusted to 6.5 with 0.5M NaHCO3 aqueous solution, and the reaction was carried out at 40°C for 3h, the reaction liquid was left to stand, the upper solution was passed through an ultrafiltration membrane (MWCO 3000Da), and the concentrated liquid was spray dried to obtain modified reactive dye A.

[0043] Preparation Example 2 Preparation of modified reactive dye: The preparation was substantially the same as that of Preparation Example 1, except that the amount of pyridine carboxylic acid in S2 was changed, and the specific difference was that: S2: 10 parts of amino-β-cyclodextrin, 0.475 parts of 2,6-pyridine dicarboxylic acid, 0.335 parts of 4-pyridine carboxylic acid were dissolved in 150 parts of N,N-dimethylformamide, 2.5 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 1.8 parts of N-hydroxysuccinimide were added, and the reaction was carried out at 0°C for 20 min, 2.5 parts of N,N-diisopropylethylamine was added, and the reaction was carried out at 20°C for 12 h, rotary evaporation (50°C, 0.1 bar) was carried out, the residual liquid was added to 10 times the volume of deionized water, 0.1M HCl aqueous solution was used to adjust the pH to 7, 30 parts of dichloromethane was added, and after oscillation, the upper layer was separated, the water phase was passed through an ultrafiltration membrane (MWCO 1000Da), and the concentrated liquid was vacuum dried to obtain β-cyclodextrin-pyridine carboxylic acid; S3: 30 parts of β-cyclodextrin-pyridine carboxylic acid was dissolved in 150 parts of deionized water, stirred for 20 min, 15 parts of reactive red 120 was added, stirred for 60 min, 1 part of hydroxypropyltrimethylammonium chloride chitosan was slowly added, and then stood for 30 min, 0.2 parts of glycidyltrimethylammonium chloride was continuously added, stirred for 15 min, and 0.5M NaHCO3 aqueous solution was used to adjust the pH value to 6.5, and the reaction was carried out at 40°C for 3 hours, the reaction liquid was stood, the upper solution was passed through an ultrafiltration membrane (MWCO 3000Da), and the concentrated liquid was spray dried to obtain a modified reactive dye B.

[0044] Preparation Example 3 Preparation of modified reactive dyes: The preparation was substantially the same as that of Preparation Example 1, except that the amount of pyridine carboxylic acid in S2 was changed, and the specific difference was that: S2: 10 parts of amino-β-cyclodextrin, 0.475 parts of 2,6-pyridine dicarboxylic acid, 0.335 parts of 4-pyridine carboxylic acid were dissolved in 150 parts of N,N-dimethylformamide, 2.5 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 1.8 parts of N-hydroxysuccinimide were added, and the reaction was carried out at 0°C for 20 min, 2.5 parts of N,N-diisopropylethylamine was added, and the reaction was carried out at 20°C for 12 h, rotary evaporation (50°C, 0.1 bar) was carried out, the residual liquid was added to 10 times the volume of deionized water, 0.1M HCl aqueous solution was used to adjust the pH to 7, 30 parts of dichloromethane was added, and after oscillation, the upper layer was separated, the water phase was passed through an ultrafiltration membrane (MWCO 1000Da), and the concentrated liquid was vacuum dried to obtain β-cyclodextrin-pyridine carboxylic acid; S3: 30 parts of β-cyclodextrin-pyridine carboxylic acid was dissolved in 150 parts of deionized water, stirred for 20 min, 15 parts of reactive red 120 was added, stirred for 60 min, 1 part of hydroxypropyltrimethylammonium chloride chitosan was slowly added, and then stood for 30 min, 0.2 parts of glycidyl trimethylammonium chloride was continuously added, stirred for 15 min, 0.5M NaHCO3 aqueous solution was used to adjust the pH value to 6.5, reacted at 40℃ for 3 hours, the reaction solution was stood, the upper solution was passed through ultrafiltration membrane (MWCO 3000Da), and the concentrated solution was spray dried to obtain modified reactive dye C.

[0045] Preparation Example 4 Preparation of modified reactive dye: The preparation was substantially the same as that of Preparation Example 1, and the only difference was that the amount ratio of 2,6-pyridine dicarboxylic acid and 4-pyridine carboxylic acid in S2 was changed, and the specific difference was that: S2: 10 parts of amino-β-cyclodextrin, 0.7 parts of 2,6-pyridine dicarboxylic acid, and 0.4 parts of 4-pyridine carboxylic acid were dissolved in 150 parts of N,N-dimethylformamide, 2.5 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and 1.8 parts of N-hydroxysuccinimide were added, and reacted at 0℃ for 20 min, 2.5 parts of N,N-diisopropylethylamine was added, and reacted at 20℃ for 12h, rotary evaporation (50℃, 0.1 bar), the residual liquid was added into 10 times volume of deionized water, 0.1M HCl aqueous solution was used to adjust the pH to 7, 30 parts of dichloromethane was added, and then stood after oscillation, the water phase was passed through ultrafiltration membrane (MWCO 1000Da), and the concentrated solution was vacuum dried to obtain β-cyclodextrin-pyridine carboxylic acid; S3: 30 parts of β-cyclodextrin-pyridine carboxylic acid was dissolved in 150 parts of deionized water, stirred for 20 min, 15 parts of reactive red 120 was added, stirred for 60 min, 1 part of hydroxypropyltrimethylammonium chloride chitosan was slowly added, and then stood for 30 min, 0.2 parts of glycidyl trimethylammonium chloride was continuously added, stirred for 15 min, 0.5M NaHCO3 aqueous solution was used to adjust the pH value to 6.5, reacted at 40℃ for 3 hours, the reaction solution was stood, the upper solution was passed through ultrafiltration membrane (MWCO 3000Da), and the concentrated solution was spray dried to obtain modified reactive dye C.

[0046] Preparation Example 5 Preparation of modified reactive dye: The preparation was substantially the same as that of Preparation Example 1, and the only difference was that the amount ratio of 2,6-pyridine dicarboxylic acid and 4-pyridine carboxylic acid in S2 was changed, and the specific difference was that: S2: 10 parts of amino-β-cyclodextrin, 0.6 parts of 2,6-pyridinedicarboxylic acid, 0.5 parts of 4-pyridinecarboxylic acid were dissolved in 150 parts of N,N-dimethylformamide, 2.5 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 1.8 parts of N-hydroxysuccinimide were added, and the reaction was carried out at 0°C for 20 min, 2.5 parts of N,N-diisopropylethylamine was added, and the reaction was carried out at 20°C for 12 h, rotary evaporation (50°C, 0.1 bar) was carried out, the residual liquid was added to 10 times the volume of deionized water, 0.1M HCl aqueous solution was used to adjust the pH to 7, 30 parts of dichloromethane was added, after oscillation, the upper layer was separated, the water phase was passed through an ultrafiltration membrane (MWCO 1000 Da), and the concentrated liquid was vacuum dried to obtain β-cyclodextrin-pyridinecarboxylic acid; S3: 30 parts of β-cyclodextrin-pyridinecarboxylic acid was dissolved in 150 parts of deionized water, stirred for 20 min, 15 parts of reactive red 120 was added, stirred for 60 min, 1 part of hydroxypropyltrimethylammonium chloride chitosan was slowly added, and then stood for 30 min, 0.2 parts of glycidyltrimethylammonium chloride was continuously added, stirred for 15 min, and 0.5M NaHCO3 aqueous solution was used to adjust the pH value to 6.5, and the reaction was carried out at 40°C for 3 hours, the reaction liquid was stood, the upper solution was passed through an ultrafiltration membrane (MWCO 3000 Da), and the concentrated liquid was spray dried to obtain modified reactive dye E.

[0047] Preparation Example 6 Preparation of modified reactive dye: The preparation was substantially the same as that of Preparation Example 1, and the only difference was that the amount ratio of chitosan quaternary ammonium salt and epoxy quaternary ammonium salt in S3 was changed, and the specific difference was that: S3: 30 parts of β-cyclodextrin-pyridinecarboxylic acid was dissolved in 150 parts of deionized water, stirred for 20 min, 15 parts of reactive red 120 was added, stirred for 60 min, 1.2 parts of hydroxypropyltrimethylammonium chloride chitosan was slowly added, and then stood for 30 min, 0.5M NaHCO3 aqueous solution was used to adjust the pH value to 6.5, and the reaction was carried out at 40°C for 3 hours, the reaction liquid was stood, the upper solution was passed through an ultrafiltration membrane (MWCO 3000 Da), and the concentrated liquid was spray dried to obtain modified reactive dye F.

[0048] Preparation Example 7 Preparation of modified reactive dye: The preparation was substantially the same as that of Preparation Example 1, and the only difference was that the amount ratio of chitosan quaternary ammonium salt and epoxy quaternary ammonium salt in S3 was changed, and the specific difference was that: S3: 30 parts of β-cyclodextrin-pyridinecarboxylic acid was dissolved in 150 parts of deionized water, stirred for 20 min, 15 parts of Reactive Red 120 was added, stirred for 60 min, 0.6 parts of hydroxypropyltrimethylammonium chloride chitosan was slowly added, and then stood for 30 min, 0.6 parts of glycidyltrimethylammonium chloride was continuously added, stirred for 15 min, the pH value was adjusted to 6.5 with 0.5M NaHCO3 aqueous solution, and reacted at 40℃ for 3 hours. The reaction solution was allowed to stand, the upper solution was passed through an ultrafiltration membrane (MWCO 3000Da), and the concentrated solution was spray dried to obtain modified reactive dye G.

[0049] Preparation Example 8 Preparation of modified reactive dye: The preparation was substantially the same as that of Preparation Example 1, except that no quaternary ammonium salt was added in S3, and the difference was that: S3: 30 parts of β-cyclodextrin-pyridinecarboxylic acid was dissolved in 150 parts of deionized water, stirred for 20 min, 15 parts of Reactive Red 120 was added, stirred for 60 min, 0.6 parts of hydroxypropyltrimethylammonium chloride chitosan was slowly added, and then stood for 30 min, 0.6 parts of glycidyltrimethylammonium chloride was continuously added, stirred for 15 min, the pH value was adjusted to 6.5 with 0.5M NaHCO3 aqueous solution, and reacted at 40℃ for 3 hours. The reaction solution was allowed to stand, the upper solution was passed through an ultrafiltration membrane (MWCO 3000Da), and the concentrated solution was spray dried to obtain modified reactive dye G.

[0050] Preparation Example 9 Preparation of modified reactive dye: The preparation was substantially the same as that of Preparation Example 1, except that 3-bromopropylamine hydrobromide used in S1 was replaced by bromomethylamine hydrobromide, and other steps were the same, to prepare modified reactive dye I.

[0051] Preparation Example 10 Preparation of modified reactive dye: The preparation was substantially the same as that of Preparation Example 1, except that 3-bromopropylamine hydrobromide used in S1 was replaced by 5-bromopentylamine hydrobromide, and other steps were the same, to prepare modified reactive dye K.

[0052] Comparative Preparation Example 1 Preparation of modified reactive dye: S1: 30 parts of β-cyclodextrin was dissolved in 150 parts of deionized water, stirred for 20 min, 15 parts of Reactive Red 120 was added, stirred for 60 min, the pH value was adjusted to 6.5 with 0.5M NaHCO3 aqueous solution, and reacted at 40℃ for 3 hours. The reaction solution was allowed to stand, the upper solution was passed through an ultrafiltration membrane (MWCO 1000Da), and the concentrated solution was spray dried to obtain modified reactive dye J.

[0053] Example 1 Preparation of reactive dye: M1: 25 parts of modified reactive dye A, 0.9 parts of PEG-4000, 1.2 parts of sodium polyacrylate, 71.5 parts of deionized water are mixed, the pH value is adjusted to 4.5, 0.5 parts of ZrOCl2·8H2O is added, stirred for 30-60 min, 0.25 parts of sodium phosphite, 0.35 parts of sodium bisulfite are mixed, 3 parts of sodium chloride is continuously added, stirred for 15 min, and a reactive dye with high color yield is obtained.

[0054] Example 2 Preparation of reactive dye: The same as example 1, the only difference is that the modified reactive dye A is replaced by modified reactive dye B.

[0055] Example 3 Preparation of reactive dye: The same as example 1, the only difference is that the modified reactive dye A is replaced by modified reactive dye C.

[0056] Example 4 Preparation of reactive dye: The same as example 1, the only difference is that the modified reactive dye A is replaced by modified reactive dye D.

[0057] Example 5 Preparation of reactive dye: The same as example 1, the only difference is that the modified reactive dye A is replaced by modified reactive dye E.

[0058] Example 6 Preparation of reactive dye: The same as example 1, the only difference is that the modified reactive dye A is replaced by modified reactive dye F.

[0059] Example 7 Preparation of reactive dye: The same as example 1, the only difference is that the modified reactive dye A is replaced by modified reactive dye G.

[0060] Example 8 Preparation of reactive dye: The same as example 1, the only difference is that the modified reactive dye A is replaced by modified reactive dye H.

[0061] Example 9 Preparation of reactive dye: The same as example 1, the only difference is that the type of metal ion agent is changed, and the specific difference is that ZrOCl2·8H2O is replaced by CuSO4·5H2O.

[0062] Example 10 Preparation of reactive dye: The same as Example 1, except that modified reactive dye A is replaced by modified reactive dye I.

[0063] Example 11 Preparation of reactive dye: The same as Example 1, except that modified reactive dye A is replaced by modified reactive dye K.

[0064] Comparative Example 1 Preparation of reactive dye: The same as Example 1, except that no metal ion agent is added.

[0065] Comparative Example 2 Preparation of reactive dye: The same as Example 1, except that modified reactive dye A is replaced by modified reactive dye J.

[0066] Comparative Example 3 Preparation of reactive dye: The same as Example 1, except that modified reactive dye A is replaced by reactive red 120.

[0067] Test section The high fixation rate reactive dyes obtained in Examples 1-9 and Comparative Examples 1-3 are diluted by adding 1 part by mass of the reactive dye to 99 parts of deionized water, 5 g of cotton fabric is added, the temperature is raised to 40°C (temperature raising rate 1°C / min), 0.1M Na2CO3 solution is slowly added to adjust the pH value to 8, and the temperature is maintained for 10 min, the temperature is then continuously raised to 60°C (temperature raising rate 1°C / min), and the temperature is maintained for 50 min. After dyeing, the fabric is washed with water, then boiled in a soapy solution with a concentration of 0.5 g / L for 15 min, rinsed with cold water, and dried to obtain a fabric sample.

[0068] The fabric samples prepared from the high fixation rate reactive dyes obtained in Examples 1-9 and Comparative Examples 1-3 are tested, and the rubbing fastness is evaluated according to the national standard GB / T 3920-2008; the absorbance is tested using a UV-visible spectrophotometer, and the dye uptake and fixation rate are calculated, the dye uptake (E%) = (A0n0-A1n1) / A0n0x100%, and the fixation rate (F%) = (A0n0-A1n1-A2n2) / A0n0x100%, wherein A0, A1, and A2 are the absorbance of the dye liquor before dyeing, after dyeing, and after soaping, respectively, and n0, n1, and n2 are the dilution multiples of the dye liquor before dyeing, after dyeing, and after soaping, respectively. The test results are shown in Table 1.

[0069] Table 1

[0070] As can be seen from Table 1, Examples 1-9 and Comparative Examples 1-3, the active dyes provided by the present application have good dye-uptake, fixation rate, and better rubbing fastness. In Comparative Example 1, no metal ion agent is added, and the chelation of metal ions with nitrogen atoms and oxygen atoms of carboxylic acid in pyridine is absent, so the binding force between the dye and the fiber is reduced, resulting in reduced dye-uptake and fixation rate. In Comparative Example 2, no pyridine carboxylic acid is introduced, and the metal coordination site is absent, so it is difficult to construct a chemical bridging network of dye-metal-fiber, resulting in reduced dye-uptake and fixation rate. In Comparative Example 3, Reactive Red 120 directly reacts with the fiber, but it may be hydrolyzed in an alkaline environment and during heat treatment, or the diffusion rate may be slowed down due to aggregation, which adversely affects the dye-uptake and fixation rate.

[0071] As can be seen from Examples 1, 2 and 3, the ratio of amino-β-cyclodextrin and pyridine carboxylic acid has a certain influence on the fixation rate of the active dye. When the mass ratio of amino-β-cyclodextrin and pyridine carboxylic acid is in the range of 10:1.0-1.2, the dye-uptake and fixation rate of the active dye are higher.

[0072] As can be seen from Examples 1, 4 and 5, the type of pyridine carboxylic acid has a certain influence on the dye-uptake and fixation rate of the active dye. When 2,6-pyridine dicarboxylic acid and 4-pyridine carboxylic acid are used in combination, and the mass ratio of 2,6-pyridine dicarboxylic acid and 4-pyridine carboxylic acid is 1:0.6-0.8, the dye-uptake and fixation rate of the active dye are higher.

[0073] As can be seen from Examples 1, 6-8, the introduction of quaternary ammonium salt has a certain influence on the dye-uptake and fixation rate of the active dye. When quaternary ammonium salt is added, the dye-uptake and fixation rate of the active dye are improved. When chitosan quaternary ammonium salt and epoxy quaternary ammonium salt are used in combination, and the mass ratio of chitosan quaternary ammonium salt and epoxy quaternary ammonium salt is in the range of 1:0.1-0.3, the dye-uptake and fixation rate of the active dye are higher.

[0074] As can be seen from Examples 1 and 9, the type of metal ion has a certain influence on the dye-uptake and fixation rate of the active dye. When zirconium salt is used, the dye-uptake and fixation rate of the active dye are higher than when copper salt is used. It is possible that Zr 4+ A stronger positive charge layer can be formed on the surface of the fiber, improving the electrostatic adsorption of the dye and further improving the dye-uptake. When copper salt is used, the dye-uptake and fixation rate of the active dye are lower. The reason may be that Cu 2+ In an alkaline condition, it may have a catalytic effect on the hydrolysis of the active dye, resulting in a decrease in the active groups that can participate in covalent reaction.

[0075] As can be seen from Examples 1, 10 and 11, the bromoalkyl amination agent has a certain influence on the dye-uptake and fixation rate of the active dye. When the alkyl chain of the bromoalkyl amination agent contains 2-4 carbon atoms, the dye-uptake and fixation rate of the active dye are higher.

[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacements for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A high fixation active dye, characterized in that, The modified reactive dye is prepared by β-cyclodextrin-pyridine carboxylic acid inclusion reactive dye molecules, wherein the β-cyclodextrin-pyridine carboxylic acid is connected by an alkyl chain. The metal ions provided by the metal ion agent can be chelated with the pyridine carboxylic acid. The reactive dye molecules contain aromatic ring structures. The preparation method of the modified reactive dye comprises the following steps:

2. Reactive dye according to claim 1, characterized in that S1: reacting β-cyclodextrin with a bromoalkyl aminating agent to make the hydroxyl group of β-cyclodextrin undergo nucleophilic substitution with the bromine-containing alkyl group in the bromoalkyl aminating agent to obtain amino-β-cyclodextrin; 3. The reactive dye according to claim 1, characterized in that, S2: reacting amino-β-cyclodextrin with pyridine carboxylic acid to make the amino group of amino-β-cyclodextrin react with the carboxyl group of pyridine carboxylic acid to obtain β-cyclodextrin-pyridine carboxylic acid; S3: mixing reactive dye raw materials with β-cyclodextrin-pyridine carboxylic acid to form a reactive dye molecule @ β-cyclodextrin-pyridine carboxylic acid inclusion compound and obtain a modified reactive dye. The alkyl chain in the bromoalkyl aminating agent contains 2-4 carbon atoms. The mass ratio of amino-β-cyclodextrin to pyridine carboxylic acid is 10:1.0-1.

2.

4. Reactive dye according to claim 3, characterized in that The preparation method of the modified reactive dye comprises the following steps:

5. The reactive dye according to claim 3, characterized in that, S1: reacting 10 parts of β-cyclodextrin with 2-3 parts of a bromoalkyl aminating agent at 40-60°C for 6-12 hours to obtain amino-β-cyclodextrin; 6. Reactive dye according to any one of claims 1 to 5, characterized in that S2: reacting 10 parts of amino-β-cyclodextrin with 1-1.2 parts of pyridine carboxylic acid at 0-30°C for 10-14 hours to obtain β-cyclodextrin-pyridine carboxylic acid; S3: dissolving 30 parts of β-cyclodextrin-pyridine carboxylic acid and 8-20 parts of reactive dye in 100-200 parts of water, adding 0.8-1.5 parts of quaternary ammonium salt, adjusting the pH value to 6-7, and reacting at 30-60°C for 2-4 hours to obtain a modified reactive dye. In step S2, the pyridine carboxylic acid includes 2,6-pyridine dicarboxylic acid and 4-pyridine carboxylic acid, and the mass ratio of 2,6-pyridine dicarboxylic acid to 4-pyridine carboxylic acid is 1:0.6-0.

8. In step S3, the quaternary ammonium salt includes chitosan quaternary ammonium salt and epoxy quaternary ammonium salt, and the mass ratio of chitosan quaternary ammonium salt to epoxy quaternary ammonium salt is 1:0.1-0.

3.

7. The reactive dye according to claim 3, characterized in that, The metal ion agent includes a zirconium salt.

8. The reactive dye according to claim 6, characterized in that, The raw materials of the reactive dye according to any one of claims 1-9 are mixed and stirred to obtain a reactive dye with high color fixation rate.

9. The reactive dye according to claim 1, characterized in that, ​ 10. A process for the preparation of high fixation yield reactive dyes, characterized in that, ​

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