CN109970598B - Blue reactive disperse dyes and intermediates for anhydrous dyeing of natural fibers in supercritical CO2 fluid - Google Patents

Abstract

The invention relates to the technical field of reactive disperse dyes, in particular to a blue reactive disperse dye and an intermediate for anhydrous dyeing of natural fibers in supercritical CO ₂ fluid. The blue reactive disperse dye intermediate has the general structural formula shown in formula (I):

Wherein, X is Cl or Br; 2≤m≤5, 1≤n≤5. The blue reactive disperse dye has the general structural formula shown in formula (II):

Wherein, X is Cl or Br; 2≤m≤5, 1≤n≤5. The blue reactive disperse dye of the present invention not only has the characteristics of water insolubility, but also the reactive groups in the dye structure can increase the bond-forming reactivity with natural fibers, thereby improving the coloring performance of the dye on natural fibers.

Description

Blue reactive disperse dyes and intermediates for anhydrous dyeing of natural fibers in supercritical CO2 fluid

technical field

The invention relates to the technical field of reactive disperse dyes, in particular to a blue reactive disperse dye and an intermediate for anhydrous dyeing of natural fibers in supercritical CO ₂ fluid.

Background technique

Since the successful application of supercritical CO ₂ fluid technology in the field of dyeing and finishing in the late 1980s, with the many excellent characteristics of supercritical CO ₂ fluid and the inherent processing advantages of supercritical technology, as well as the green environmental protection in the world today With the proposal of processing concept and the continuous deepening of the idea of sustainable development of ecological environment, the research of supercritical CO ₂ fluid dyeing technology in textile dyeing and finishing is receiving extensive attention.

A S,Clifford AA,Bartle K D,et al.Dyeing ofcotton fibres with disperse dyes in supercritical carbon dioxide[J].Dyes andPigments,1998,36(2):103-110.)。At present, the biggest limitation of supercritical _CO2 fluids in textile dyeing and finishing mainly comes from the contradiction between natural fibers and their textiles and supercritical _CO2 fluids: that is, the hydrogen bonding in the polar molecular structure of the former and the CO ₂ fluid itself is non-polar. Today, there are various solutions to this contradiction, such as hydrophobic modification of polar fibers, reverse micelle systems and the use of special reactive disperse dyes. Obviously, selecting or preparing suitable reactive disperse dyes is the best way, and it is of extraordinary significance for the application and perfection of this technology in dyeing and finishing (References: Bach E, Cleve E, Schollmeyer E. Past, present and future of supercritical fluid dyeingtechnology–an overview[J].Review of Progress in Coloration and Related Topics,2002,32(1):88-102;

AS, Clifford AA, Bartle KD, et al. Dyeing of cotton fibres with disperse dyes in supercritical carbon dioxide [J]. Dyes and Pigments, 1998, 36(2):103-110.).

At present, there are many related studies on the development of reactive disperse dyes suitable for supercritical CO ₂ dyeing of natural fibers, but these studies are insufficient for the future development of supercritical dyeing and finishing technology. The inventor has disclosed a kind of reactive disperse dyes of red hue in the early stage (reference: azo dyes special for anhydrous dyeing of natural fibers in supercritical CO ₂ fluid and preparation method thereof: China CN 109054438A), but still lacks a complete set of azo dyes at present. Reactive disperse dye chromatography system.

The active arylamino group contained in 3-amino-4-methoxyacetanilide can not only further derive compounds containing different N-substituted side groups that can be used for coupling reaction, but also improve and improve the dyeing fastness of the prepared azo dyes. Properties are favorable (Reference: Sunwoo KH, Kim DC, Shin KJ, et al. Monoazo disperse dyes containing ethyleneimine moieties Part 1: Synthesis and application of somemonoazo disperse dyes derived from 3-amino-4-methoxyacetanilide [J]. Dyes andpigments, 1999, 41(1-2):19-29; Hashimoto K, Yoshinaga K, Mori Y, et al. 2-Cyano-4-nitro-6-chlorophenylazo 3-acetyl-or propionylamino-N,N-di-n -pentyl orhexylanilines: US Patent 4,536,569 [P]. 1985-8-20; Wang Nai. Study on the preparation of disperse dye intermediates from 3-amino-4-methoxyacetanilide [D]. Nanjing University of Science and Technology, 2012.). The Chinese patent with the application number of 98116047.6 discloses a disperse dye, and a blue dye is prepared from 3-amino-4-methoxyacetanilide, but the text does not mention 3-amino-4-methyl The preparation process of oxyacetanilide N-mono-substituted modification, and the double-substituted products are mainly containing ester functional groups. Compared with alkane modified groups, the solubility of dyes in supercritical CO ₂ fluid is slightly worse. The key aspect is: The final obtained dye structure does not contain reactive bridge groups that can link with reactive groups.

SUMMARY OF THE INVENTION

In order to improve the chromatogram of reactive disperse dyes for dyeing natural fibers in supercritical systems, the purpose of the present invention is to provide a blue reactive disperse dyes and intermediates for anhydrous dyeing of natural fibers in supercritical CO ₂ fluid. The reactive disperse dyes are: Blue-based dyes, the reactive groups in the dye structure can increase the bond-forming reactivity with natural fibers, thereby improving the coloring properties of dyes on natural fibers, providing a new alternative for supercritical CO ₂ dyeing processing of natural fibers dye.

The first object of the present invention is to provide a blue reactive disperse dye intermediate, which has the general structural formula shown in formula (I):

Wherein, X is Cl or Br; 2≤m≤5, 1≤n≤5.

Preferably, X is Br; m=2, that is, one substituent on the N atom is 2-aminoethyl; n=2, that is, the other substituent on the N atom is a propyl group.

The second object of the present invention is to provide a kind of preparation method of the above-mentioned blue reactive disperse dye intermediate, comprising the following steps:

(1) 3-amino-4-methoxyacetanilide and C ₂ -C ₆ halogenated hydrocarbons are reacted at 50-75 ℃ under the action of acid binding agent and catalyst, and formula (III) is obtained after the reaction is complete Monoalkylated products shown:

Among them, 1≤n≤5;

(2) react the monoalkylated product shown in formula (III) with the hydrohalide of organic hydrazine amine salt at pH=5-7 at 100-110°C, and obtain formula after the reaction is complete Coupling components shown in (IV):

(3) The diazonium salt of the primary aromatic amine is reacted with the coupling component represented by the formula (IV) at 0-5°C under the condition of pH 4-6 to obtain the blue active dispersion represented by the formula (I). Dye intermediates, in which the ortho and para positions of the amino groups of primary aromatic amines are replaced by strong electron withdrawing groups.

Further, in step (1), the structural formula of the C ₂ -C ₆ halogenated hydrocarbon is shown in formula (V):

X ¹ -(CH ₂ ) _n -CH ₃

(V);

Wherein, X ¹ is Cl or Br; 1≤n≤5.

In step (1), the value range of n is 1≤n≤5, for example: when n=1, the halogenated hydrocarbon of formula (V) is 1-haloethane; when n=2, formula (V ) of the halogenated hydrocarbon is 1-halogenated propane; when n=3, the halogenated hydrocarbon of the formula (V) is 1-halogenated butane.

Further, in step (1), the acid binding agent is sodium carbonate and/or sodium bicarbonate.

Further, the molar ratio of acid binding agent and 3-amino-4-methoxyacetanilide is 1-1.5:1.0.

Further, in step (1), the catalyst is potassium iodide, and in the reaction, iodide ions and chlorinated hydrocarbons or brominated hydrocarbons undergo an exchange reaction to obtain more reactive iodoalkanes, and then realize catalysis, considering before and after the potassium iodide reaction. It does not participate in the generation of the product, so the catalyst dosage is 5%-20% of the mass of 3-amino-4-methoxyacetanilide.

Further, in step (1), the reaction solvent is a mixed solvent of alcohol and water. Preferably, the reaction solvent is ethanol/water solution, and the volume ratio of ethanol to water is 1-5:5-10.

Considering that the reaction temperature of step (1) will affect the reaction rate of the target product and the generation rate of the disubstituted by-products, the reaction temperature of step (1) is set to 50-75°C.

Further, in step (2), the structural formula of the hydrohalide salt of the organic hydrazine amine salt is shown in formula (VI):

X ² -(CH ₂ ) _m -NH ₂ ·HX ⁶

(VI);

Wherein, X ² and X ⁶ are independently selected from Cl or Br; 2≤m≤5.

The value range of m is 2≤m≤5, for example, when m=2, the hydrohalide salt of the organic hydrazine amine salt is 2-haloethylamine salt; when m=3, the organic hydrazine amine salt The hydrohalide salt is a 3-halopropylamine salt.

In step (2), the reaction environment is a weakly acidic condition, which can prevent side reactions between the hydrohalide salt of the organic hydrazine amine salt and the substrate.

Further, in step (2), the reaction solvent is an organic solvent, preferably DMF.

Further, in step (2), after the reaction is complete, the step of obtaining a coupling component after adjusting the pH to 6-7 with an aqueous alkali solution is also included. The pH is adjusted to 6-7 by using an aqueous alkaline solution, that is, an alkaline washing method, which can make the primary aliphatic amine in the substituent of the coupling component exist in a free form instead of an acid salt form.

Further, in step (3), the structural formula of primary aromatic amine is shown in formula (VII):

wherein X ³ , X ⁴ and X ⁵ are independently selected from halogen, cyano or nitro. Halogen is chlorine or bromine.

Since the ortho and para positions of the amino group of the primary aromatic amine are replaced by strong electron withdrawing groups, it is a weakly basic primary aromatic amine.

Preferably, the primary aromatic amine is 2-bromo-4,6-dinitroaniline or 2,6-dichloro-4-nitroaniline.

More preferably, the primary aromatic amine is 2-bromo-4,6-dinitroaniline.

Further, in step (3), the reaction time is 1-3h.

Further, in step (3), the coupling component shown in formula (IV) is dissolved in water, and then the diazonium salt of primary aromatic amine is slowly added dropwise thereto, and the buffer solution is added dropwise to maintain the reaction pH as 4- 6. React at 0-5°C.

Further, the buffer solution used is one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide.

Further, the preparation method of the diazonium salt of the primary aromatic amine in step (3) comprises the following steps:

After reacting sodium nitrite and concentrated sulfuric acid at 0-5°C, a nitrosylsulfuric acid solution is obtained; then the primary aromatic amine represented by formula (VII) is slowly added to the nitrosylsulfuric acid solution, and the reaction is performed at 0-5°C For 2-3h, the diazonium salt of the prepared primary aromatic amine is obtained.

Further, the molar ratio of primary aromatic amine, sodium nitrite and concentrated sulfuric acid is 1:1:10-15.

3-amino-4-methoxyacetanilide is selected as the raw material for the preparation of the coupling component, firstly it is modified by N-monoalkylation, and then the secondary amino group in the monoalkylated product is modified to obtain a Coupling components of different structures. At the same time, because the coupling components contain strong electron-donating groups, it is feasible to obtain the parent chromophoric structure of blue reactive disperse dyes. In addition, the N atom of 3-amino-4-methoxyacetanilide was modified with C ₂ -C ₆ halogenated hydrocarbons and connected with the active group as a bridge, which can effectively reduce the effect of the active group on the dye." The effect of donating-absorbing electron chromophoric solutions.

The third object of the present invention is to provide a blue reactive disperse dye, which has the general structural formula shown in formula (II):

Wherein, X is Cl or Br; 2≤m≤5, 1≤n≤5.

Preferably, X is Br; m=2, that is, one substituent on the N atom is 2-aminoethyl; n=2, that is, the other substituent on the N atom is a propyl group.

The 4th object of the present invention is to provide a kind of preparation method of above-mentioned blue reactive disperse dye, comprises the following steps:

The blue reactive disperse dye intermediate represented by formula (I) and cyanuric chloride are subjected to a nucleophilic substitution reaction at 0-5°C under the action of an acid binding agent to obtain a blue color represented by formula (II). Reactive Disperse Dyes:

Wherein, X is Cl or Br; 2≤m≤5, 1≤n≤5.

Further, the reaction solvent includes an organic solvent and water, and the organic solvent is one or more of N,N-dimethylformamide, dioxane and acetone.

Preferably, the reaction solvent is dioxane and water, and the volume ratio of dioxane and water is 10-20:2-10.

Further, the acid binding agent is sodium carbonate and/or sodium bicarbonate. The acid binding agent can neutralize the protonic acid generated during the reaction, promote the equilibrium reaction to move to the right, and improve the dye yield.

By means of the above scheme, the present invention has at least the following advantages:

In the present invention, the weak basic aromatic primary amine is used as the diazo component, the terminal amino-modified derivative of 3-amino-4-methoxyacetanilide is used as the coupling component, and the diazotization-coupling process is used to carry out the reaction, thereby obtaining a compound containing The blue reactive disperse dye intermediate of reactive bridge group can significantly increase the "donating-withdrawing" electron effect of the aromatic rings on both sides of the azo group, and because the reactive group and the dye parent are connected by an alkane chain, the The electron-withdrawing effect of the active group on the alkane chain gradually decreases, which further reduces the influence on the electron-donating property of the coupling component. At the same time, the 3-amino-4-methoxyacetanilide in the dye intermediate can increase the dye Color fastness is favorable.

The reactive disperse dye of the present invention is not only suitable for water bath dyeing, but also provides a blue-based azo dye for supercritical CO ₂ dyeing of natural fibers. The dye not only has the characteristics of water insolubility, but also the reactive groups in the dye structure can increase the bond reactivity with natural fibers, thereby improving the coloring properties of the dyes on natural fibers, and it is used for supercritical CO ₂ dyeing processing of natural fibers. New alternative dyes are available. In the reactive disperse dye structure of the present invention, the alkane chain is bridged between the dye chromophore and the reactive group, which effectively reduces the influence of the active group on the "donating-absorbing" electron solution in the dye chromophore, that is, reducing the The effect of reactive groups on the induction effect of the parent structure was investigated.

The above description is only an overview of the technical solution of the present invention. In order to understand the technical means of the present invention more clearly and implement it according to the content of the description, the following detailed description is given with the preferred embodiments of the present invention and the accompanying drawings.

Description of drawings

Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the blue reactive disperse dye intermediate prepared in Example 1 of the present invention;

Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the blue reactive disperse dye prepared in Example 6 of the present invention;

Fig. 3 is the Fourier transform infrared spectrogram of the blue reactive disperse dye intermediate prepared in Example 1 of the present invention;

Fig. 4 is the Fourier transform infrared spectrogram of the blue reactive disperse dye prepared in Example 6 of the present invention;

Fig. 5 is the ultraviolet-visible absorption spectrogram of the blue reactive disperse dye intermediate prepared in Example 1 of the present invention and the blue reactive disperse dye prepared in Example 6;

Fig. 6 is the apparent color depth value (K/S value) curve of the blue reactive disperse dye prepared in Example 6 of the present invention dyed silk fabric in supercritical carbon dioxide fluid.

Detailed ways

The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. The following examples are intended to illustrate the present invention, but not to limit the scope of the present invention.

The reagents and materials used in the following examples of the present invention can be obtained from commercial sources unless otherwise specified.

Example 1

Preparation of 3-(N-propyl)amino-4-methoxyacetanilide:

(1) take by weighing 2mmol 3-amino-4-methoxyacetanilide, 2.2mmol sodium bicarbonate and potassium iodide, wherein the quality of potassium iodide is 10% of the 3-amino-4-methoxyacetanilide quality, above-mentioned raw material It was added into a 50 mL three-necked flask, dispersed and dissolved with a mixed solution of 5 mL of deionized water and 1 mL of absolute ethanol, and then the mixed solution was slowly heated to 60-70° C.

(2) 2.2mmol of 1-bromopropane is dissolved in 1mL ethanol solution, and the alcoholic solution of 1-bromopropane is slowly added dropwise to the solution obtained in step (1) in a nitrogen atmosphere (dropping time is about 15min) , and kept stirring at constant temperature for 5-10 h, and the reaction was tracked by TLC. After the reaction was completed, the mixture was extracted with dichloromethane, then rotary evaporated and concentrated to obtain the reaction product, namely 3-(N-propyl)amino-4-methoxyacetanilide, and the isolated yield was 52.3%.

Example 2

Preparation of 3-(N-propyl)amino-4-methoxyacetanilide:

(1) take by weighing 2mmol 3-amino-4-methoxyacetanilide, 2mmol sodium carbonate and potassium iodide, wherein the quality of potassium iodide is 10% of the 3-amino-4-methoxyacetanilide quality, above-mentioned raw material is added to In a 50 mL three-necked flask, disperse and dissolve with a mixed solution of 5 mL of deionized water and 1 mL of absolute ethanol, and then slowly heat the mixed solution to 60-70 °C.

(2) 2.2mmol of 1-bromopropane is dissolved in 1mL ethanol solution, and the alcoholic solution of 1-bromopropane is slowly added dropwise to the solution obtained in step (1) in a nitrogen atmosphere (dropping time is about 15min) , and kept stirring at constant temperature for 5-10 h, and the reaction was tracked by TLC. After the reaction, the mixture was extracted with dichloromethane, then rotary evaporated and concentrated to obtain the reaction product, namely 3-(N-propyl)amino-4-methoxyacetanilide, and the isolated yield was 50.6%.

Example 3

Preparation of 3-[N-propyl-N-(2-aminoethyl)]amino-4-methoxyacetanilide:

(1) 2mmol 3-(N-propyl) amino-4-methoxyacetanilide and 2.2mmol 2-bromoethylamine hydrobromide were added to 50mL there-necked flask simultaneously, and 10mL DMF solution was added to ultrasonically Dissolve, put the solution in a constant temperature stirrer and then slowly heat up to 110 ° C, pH value is 6, carry out reflux reaction in a nitrogen environment, and keep stirring at constant temperature for 6-10 h, use TLC to track the reaction product until the substrate reacts Completed, the color of the reaction solution changed from orange-yellow to gray-brown.

After the reaction is completed, the reaction product is concentrated under reduced pressure and neutralized, and then using dichloromethane, acetone and/or ethanol as the eluent, the crude product is purified and separated through a silica gel chromatographic column, and the purified components are collected to obtain brown. The grey solid product is 3-[N-propyl-N-(2-aminoethyl)]amino-4-methoxyacetanilide.

Or after the reaction, if it is determined that there are less reaction by-products in the solution, 20 mL of water can be added to the reaction solution, which can be directly used as a coupling reaction solution for the next reaction. The isolated yield of the product was 81.2%.

Example 4

Preparation of reactive disperse dye intermediates:

(1) Add 30mmol 98% concentrated sulfuric acid solution in a 50mL round-bottomed flask, and place it in a 0～5°C water bath environment, slowly add 2mmol sodium nitrite under the action of magnetic stirring, stir at low temperature for 10～15min, and then set Continue stirring in a water bath at 60-70° C. until the sodium nitrite is completely dissolved to obtain a nitrosyl sulfuric acid solution. Then, it was placed in a low temperature environment of 0 to 5 °C for 5 to 10 minutes, and 2 mmol of 2-bromo-4,6-dinitroaniline was added to the flask in batches, and the reaction was kept under constant temperature stirring for 2 to 3 hours. The basic reaction of the substrate was traced by TLC, and the arylamine diazonium salt was obtained.

(2) Disperse 2mmol of 3-[N-propyl-N-(2-aminoethyl)]amino-4-methoxyacetanilide with 20mL of deionized water, then adjust the pH of the solution to 4～ 6, the substrate is completely dissolved, and the mixed solution is placed under a low temperature condition of 0 to 5 ° C, the arylamine diazonium salt solution prepared in step (1) is slowly added dropwise, and the solution pH is maintained at 4- 7. At the same time, stir at a constant temperature of 0 to 5 °C for 1 to 3 hours, the TLC tracking reaction is basically complete, and then diluted with deionized water to make the product completely precipitate, and suction filtration to obtain a blue reactive disperse dye intermediate crude product. Using methyl chloride and acetone as developing solvents, the impurities in the crude product were separated, eluted and collected using a silica gel column, and further concentrated and dried to obtain a blue reactive disperse dye intermediate purified product with a separation yield of 81.9%.

The structure of the purified product of the prepared dye intermediate was characterized by hydrogen nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy and ultraviolet-visible absorption spectroscopy. The results are shown in Figures 1, 3, and 5.

Figure 1 shows the test results of H NMR spectrum of reactive disperse dye intermediates, each proton peak is assigned as: ¹ H NMR (400MHz, DMSO-d ₆ )δppm8.76-8.69(m,2H,H-1,H-2 ), 7.71(s, 1H, H-3), 7.17(s, 1H, H-4), 3.88(s, 4H, H-13, H-10 (the amino group is affected by the residual water molecules in the solution, which may cause Absence of proton)), 3.45 (t, J=6.3 Hz, 2H, H-8), 3.32 (s, 2H, H-5 (overlapped with the proton peak of residual water)), 3.01 (t, J=6.2 Hz , 2H, H-9), 2.18 (s, 3H, H-12), 2.05–1.95 (m, 2H, H-6), 0.84 (t, 2H, H-7 (one proton missing)).

The Fourier transform infrared spectrum test results of the blue reactive disperse dye intermediate in Fig. 3 show that the anti-symmetric stretching vibration peak and the symmetrical stretching vibration peak of the secondary amino group at 3445.44cm ^-1 and 3421.97cm ^-1 are respectively, 2968.18cm ^{- 1} and 2925.22 cm ^-1 are the antisymmetric stretching vibration peaks of CH bond in methyl and methylene, respectively, 2853.22 cm ^-1 is the symmetrical stretching vibration absorption peak of methylene, and 1617.88 cm ^-1 is the variable angle of NH bond Vibration peaks, 1532.48cm ^-1 and 1330.08cm ^-1 are antisymmetric stretching vibration peaks of arylamine nitro group, 1459.16 is the weak vibration peak of N=N double bond, 1259.46cm ^-1 is Ar-O-CH ₃ The stretching vibration peak of the ether bond in the middle, 1075.76cm ^-1 is the stretching vibration peak of the C-Br bond on the aromatic ring.

Curve a in Figure 5 is the ultraviolet-visible absorption spectrum of the dye intermediate in ethanol solution. It can be seen in the figure that the maximum absorption wavelength of the dye intermediate is λmax=588nm, and the visual color region where the maximum absorption wavelength is located is displayed as blue. From this comprehensive structural analysis, it can be concluded that the prepared dye intermediates meet the set target requirements.

Example 5

Preparation of reactive disperse dye intermediates:

This embodiment provides a blue reactive disperse dye intermediate and a preparation method thereof, and the specific steps are similar to those in embodiment 4. The difference is that:

In embodiment 4, the coupling reaction substrate in step (2) selects the 3-[N-propyl-N-(2-aminoethyl)] amino-4-methoxyacetyl group that has not been concentrated and separated in embodiment 3 A mixed solution of DMF and water of aniline, the volume ratio of DMF and water is 10:20, and the aromatic amine diazonium salt prepared in step (1) of Example 4 is slowly added dropwise to the coupling system at 0～5° C. Use a buffer to maintain the pH of the reaction to be weakly acidic, and stir at a constant temperature of 0 to 5 °C for 1 to 3 hours to complete the reaction of the substrate. After the end, the mixed solution was sufficiently diluted with deionized water, and suction filtered to obtain a crude product of reactive disperse dye intermediate, which was further separated and purified, and the separation yield was 82.3%.

Example 6

Preparation of target reactive disperse dyes:

(1) Weigh 1 mmol of the dye intermediate and place it in a 50 mL three-necked flask, disperse and dissolve it with 10 mL of 1,4-dioxane and 5 mL of deionized water, and place the solution in a low-temperature water environment of 0 to 5°C. Dissolve 1.5 mmol cyanuric chloride in 3 mL of 1,4-dioxane, and dissolve 1 mmol of anhydrous Na ₂ CO ₃ in 3 mL of deionized water, and slowly add the above two solutions to the dye intermediate solution dropwise at the same time. , stirred at 0～5℃ for 1～3h, and the reaction was tracked by TLC. After the reaction was completed, the reaction solution was diluted with 50 mL of deionized water to separate out solid dye particles, suction filtered, washed with water, and dried to obtain a crude reactive disperse dye product. Using dichloromethane and acetone as developing solvents, the crude product was separated and purified by silica gel chromatographic column, and finally a blue-purple solid product was obtained, and the isolated yield was 73.5%.

The purified products of the prepared reactive disperse dyes were characterized by hydrogen nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy and ultraviolet-visible absorption spectroscopy. The results are shown in Figures 2, 4, and 5.

Figure 2 shows the test results of 1H NMR spectrum of the target reactive disperse dyes. Each proton peak is assigned as follows: ¹ H NMR (400MHz, DMSO-d ₆ )δppm: 9.21(s,1H,H-11),8.75-8.67(m ,2H,H-1,H-2),7.95(s,1H,H-10),7.68(s,1H,H-3),7.15(s,1H,H-4),3.87(s,3H ,H-13),3.58–3.52(m,4H,H-8,H-9),2.15(s,3H,H-12),2.00(q,J＝7.2Hz,2H,H-6), 0.85 (t, J=6.6 Hz, 3H, H-7). In addition, the proton peak of H-5 at 3.32 ppm overlapped with the proton peak of residual water in the solvent and was not displayed.

Figure 4 shows the test results of Fourier transform infrared spectroscopy of reactive disperse dyes. The peak at 3421.84cm ^-1 is the stretching vibration absorption peak of NH, and the peak at 2961.74cm ^-1 and 2920.90cm ^-1 are CH in methyl and methylene, respectively. The antisymmetric stretch vibration peak of the bond, 2851.70cm ^-1 is the symmetric stretch vibration peak of the methylene CH bond, 1463.80cm ^-1 is the stretch vibration peak of N=N, 1640.84cm ^-1 is the stretch vibration peak of the triazine ring skeleton , 1261.40cm ^-1 is the stretching vibration peak of the ether bond in Ar-O- _CH3 , 1029.40cm ^-1 is the stretching vibration absorption peak of the C-Br bond on the aromatic ring, 802.93cm ^-1 is the C- The stretching vibration absorption peak of Cl.

By comparing the chemical shift changes of each proton peak in Figure 1 and Figure 2 and the assignment of the vibration peaks of the characteristic functional groups contained in Figure 3 and Figure 4, the results show that the active group of cyanuric chloride is successfully introduced into the active dispersion prepared by the present invention. in the structure of dye intermediates.

Figure 5 is the UV-Vis absorption spectrum of dye intermediates and reactive disperse dyes in ethanol solution, wherein curve a is the dye intermediate (the maximum absorption wavelength is 588 nm, corresponding to the molar absorption coefficient ε _max =7.51×10 ³ L/(mol cm), curve b is reactive disperse dye (the maximum absorption wavelength is 583nm, corresponding to molar absorption coefficient ε _max =7.91×10 ³ L/(mol·cm). From curves a and b, it can be seen that dye intermediates and reactive disperse dyes The change of the maximum absorption wavelength between △λmax=588-583=5nm, the shift of the maximum absorption peak is relatively small, indicating that the use of long-chain alkyl groups as bridge groups can effectively reduce the effect of reactive groups on the dye parent. chromophore effect.

Example 7

Preparation of target reactive disperse dyes:

Weigh 1 mmol of the dye intermediate into a 50 mL three-necked flask, disperse and dissolve with 15 mL of 1,4-dioxane and 2 mL of deionized water, and place the solution in a low-temperature water environment of 0-5 °C. Dissolve 1.5 mmol cyanuric chloride in 2 mL of 1,4-dioxane, and dissolve 1 mmol of anhydrous Na ₂ CO ₃ in 3 mL of deionized water, and slowly add the above two solutions dropwise to the dye intermediate solution at the same time. , stirred at 0～5℃ for 1～3h, and the reaction was tracked by TLC. After the reaction was completed, the reaction solution was diluted with 50 mL of deionized water to separate out solid dye particles, suction filtered, washed with water, and dried to obtain a crude reactive disperse dye product. Using dichloromethane and acetone as developing solvents, the crude product was separated and purified by silica gel chromatographic column, and finally a blue-purple solid product was obtained, and the isolated yield was 77.6%.

Example 8

Dyeing of silk fabrics with reactive disperse dyes:

Get silk fabric 1g (65g/m ² ), the target reactive disperse dye 2% omf prepared in Example 6 and dyeing accelerator 5mL, adopt supercritical carbon dioxide fluid dyeing system, set fluid pressure 20MPa, dyeing temperature 120 ℃, fluid The cycle ratio is 1min/10min, and the dyeing time is 60min. The obtained dyed fabrics were tested for color depth, soaping fastness and rubbing fastness. The results are shown in Figure 6 and Table 1, respectively.

表1为本发明实施6制备的蓝色活性分散染料在超临界二氧化碳流体中染色蚕丝织物牢度特征的评价。结合表1可知，本发明所制备蓝色活性分散染料在超临界二氧化碳流体中染色的蚕丝织物具有较好的色牢度特征，织物的耐皂洗牢度和耐摩擦牢度指标均能达到4级及以上水平。Fig. 6 is the apparent color depth value curve of dyed silk fabric, the fabric has the maximum absorption peak at λ=610nm, and the corresponding apparent color depth value is

Table 1 is the evaluation of the fastness characteristics of the blue reactive disperse dyes prepared in the embodiment 6 of the present invention dyeing silk fabrics in supercritical carbon dioxide fluid. In conjunction with Table 1, it can be seen that the silk fabrics dyed with blue reactive disperse dyes prepared by the present invention in supercritical carbon dioxide fluid have good color fastness characteristics, and the soaping fastness and rubbing fastness indexes of the fabric can reach 4. level and above.

Table 1 Fastness characteristics of silk fabrics dyed with blue reactive disperse dyes in supercritical carbon dioxide fluid

The above are only preferred embodiments of the present invention and are not intended to limit the present invention. It should be pointed out that for those skilled in the art, some improvements can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention.

Claims (3)

1. a blue reactive disperse dye is characterized in that, has the general structural formula shown in formula (II):

Wherein, X is Cl or Br; 2≤m≤5, 1≤n≤5. 2 . The blue reactive disperse dye according to claim 1 , wherein: X is Br; m=2; n=2. 3 . 3. a preparation method of the described blue reactive disperse dye of claim 1 or 2, is characterized in that, comprises the following steps: The blue reactive disperse dye intermediate represented by formula (I) is reacted with cyanuric chloride under the action of an acid binding agent at 0-5° C. to obtain the blue reactive disperse dye represented by formula (II):

Wherein, X is Cl or Br; 2≤m≤5, 1≤n≤5.

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