A Disperse Dye, Its Synthesis Method and Application

Abstract

This invention discloses a disperse dye, its synthesis method, and its application, belonging to the field of disperse dye technology. Its structural formula is as follows: The disperse dye designed in this invention is a novel dye obtained by reacting a diazo component with a novel coupling component containing a water-soluble group. Different colors and properties of monoazo dyes can be obtained by adjusting the chemical structure of the diazo component, and the obtained dyes can effectively dye polyester.

Description

Technical Field

[0001] This invention relates to a disperse dye, its synthesis method, and its application, belonging to the field of disperse dye technology. Background Technology

[0002] The guiding opinions on the development of the dyeing and printing industry propose adhering to the concept of green development, strengthening pollution prevention and control, further improving clean production in the dyeing and printing industry, and guiding and promoting dyeing and printing enterprises to implement clean production. With increasingly severe environmental problems, the pollution of the environment by disperse dyeing wastewater has attracted great attention from dyeing and printing workers. In addition to traditional methods of treating contaminated wastewater after it has been polluted, preventing the generation of polluted wastewater is also an important means to effectively reduce environmental pressure, leading to a growing demand for environmentally friendly disperse dyes for polyester.

[0003] Polyester fiber possesses excellent properties, such as high breaking strength and elastic modulus, good heat and light resistance, good corrosion resistance, and washability, making it one of the fastest-growing and highest-producing varieties of polyester fiber. Polyester is a polymer obtained by the condensation polymerization of diacids and diols. The basic chain segments are linked by ester groups. The molecular chain lacks hydrophilic groups and reactive groups that can bind to dyes, so it can only be dyed with disperse dyes. Disperse dyes have a simple structure and diffuse into the fiber interior and interstitial spaces during dyeing, where they are fixed to the polyester fiber under the influence of van der Waals forces, hydrogen bonds, and dipole forces.

[0004] Conventional disperse dyes do not contain water-soluble groups and have extremely low water solubility. Dispersants must be added during grinding, at a dosage of 1-3 times the dye's mass, to prevent crystal growth, aggregation, and coagulation during grinding and use, maintaining the stability of the dye liquor and meeting the requirements for uniform and reproducible dyeing. Dispersants are readily soluble in water and have no affinity for polyester, making them difficult to recover through filtration or adsorption. Evaporating water for recovery wastes a significant amount of energy, and these dispersants are typically discharged with the dyeing waste liquor, resulting in high BOD and COD values ​​and environmental pollution. Reducing the use of dispersants has become a research direction for environmentally friendly disperse dyes.

[0005] The Chinese patent application filed prior to this invention, entitled "A Diazo Disperse Dye and Its Synthesis Method and Application", with patent number ZL202211370653.X, relates to a diazo disperse dye. In this invention, the diazo disperse dye and monoazo intermediate are prepared by using an aromatic amine compound containing a water-soluble group as the diazo component and a hydrophobic coupling component. The water-soluble group in the diazo disperse dye and monoazo intermediate is in the diazo component. The intermediate obtained is limited to yellow, has weak color development ability, and has no affinity for polyester.

[0006] The present invention aims to design an azo disperse dye that has better affinity and dyeing effect on polyester fabrics. Summary of the Invention

[0007] The first objective of this invention is to provide a disperse dye with the following structural formula:

[0008]

[0009] In Equation 1:

[0010] R is a -H or -CH3 group;

[0011] X is a -H, -CH3, or -CN group;

[0012] Y is Where n < 18, and W is a -COOH or -SO3H group;

[0013] Ar-N is the diazo component of the dye, obtained through any one of the following groups:

[0014]

[0015] Each of R1-R5 can be independently selected from -NO2, -CN, -Cl, -F, -CF3, -H, -CH3, -OCH3, or -COOCH3 groups.

[0016] The dye structure design principle of this invention is as follows:

[0017] The self-dispersible dye designed in this invention is a novel dye obtained by reacting a diazo component with a novel coupling component containing water-soluble groups. Different colors and properties of monoazo dyes can be obtained by adjusting the chemical structure of the diazo component. Specifically, the molecular structure design of the disperse dye in this invention, especially the structural design of the hydrophilic groups (-SO3H or -COOH) and ester groups (-COO-), enables the dye to form hydrogen bonds with fibers while maintaining water solubility, thereby improving color fastness. As a result, the obtained dye can effectively dye polyester.

[0018] A second aspect of this invention aims to provide a method for synthesizing disperse dyes, comprising the following steps:

[0019] Synthesis of coupling components: An aniline compound containing an alcohol hydroxyl group was dissolved in toluene solvent by stirring. A carboxyl compound and a catalyst were added, and the mixture was heated to reflux. The reaction was monitored by thin-layer spotting. After the reaction was completed, the toluene solvent was removed by rotary evaporation to obtain a coupling component containing hydrophilic groups.

[0020] Synthetic disperse dyes: The coupling component containing hydrophilic groups is coupled with the diazo component. After the reaction is complete, the mixture is filtered and washed to obtain crude dye. The crude product is then recrystallized to obtain pure disperse dye.

[0021] Furthermore:

[0022] The reaction equivalent of the carboxyl compound is 1 to 2 times that of the aniline compound, preferably 1.2 times.

[0023] The reaction equivalent of the catalyst is 1-2% of the aniline compound.

[0024] The aniline compound containing the alcohol hydroxyl group is preferably N-ethyl-N-hydroxyethyl m-toluidine, the carboxyl compound is preferably phthalic anhydride, and the catalyst is preferably 4-dimethylaminopyridine.

[0025] The reaction temperature of the coupling reaction is -10 to room temperature, preferably 0 degrees Celsius.

[0026] The diazo component is selected from any one of the following groups:

[0027]

[0028] Each of R1-R5 can be independently selected from -NO2, -CN, -Cl, -F, -CF3, -H, -CH3, -OCH3, or -COOCH3 groups.

[0029] The diazo component is preferably obtained by diazotization reaction of nitroaniline with sodium nitrite and hydrochloric acid.

[0030] The synthesis method of the present invention involves esterifying an aniline compound containing an alcohol hydroxyl group with a carboxylic acid compound to obtain a coupling component containing a hydrophilic group, which is then coupled with a diazo component to obtain a novel disperse dye. This type of dye does not require the addition of a dispersant when preparing the dyeing solution, and the pollution of the dyeing waste liquid is significantly reduced.

[0031] A third objective of this invention is to provide an application of disperse dyes in polyester dyeing.

[0032] The dye liquor was prepared using the disperse dye of the present invention. No dispersant was added during the grinding process. The average particle size of the dye liquor was less than 500 nm. Polyester was dyed with the dyed fabric sample. The ΔE value of the dyed fabric sample was less than 0.1. Color fastness test was performed. The test results showed that the dye's performance in all aspects met the requirements for commercial use.

[0033] The beneficial effects of this invention are as follows:

[0034] According to the above design scheme, the present invention conducts synthesis and application performance research on the target molecule and successfully obtains a new type of disperse dye. Through polyester dyeing test, it was found that it has self-dispersing properties, no dispersant needs to be added when preparing dye liquor, the BOD and COD values ​​of dyeing residue are significantly reduced, and the dyeing rate, dyeing performance and color fastness performance of polyester fabric are significantly improved, filling the gap in the existing market.

[0035] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. Attached Figure Description

[0036] Figure 1 The image shows the nuclear magnetic resonance (NMR) spectrum of the new dye 1 prepared in Example 1.

[0037] Figure 2 The infrared spectrum of the new dye 1 prepared in Example 1.

[0038] Figure 3 The absorption spectrum curve of the new dye 1 prepared in Example 1 is shown.

[0039] Figure 4 The dyeing uplift of the new dye 1 prepared in Example 1.

[0040] Figure 5 The dyeing rate of the new dye 1 prepared in Example 1.

[0041] Figure 6 The nuclear magnetic resonance image of the new dye 2 prepared in Example 2.

[0042] Figure 7 The infrared spectrum of the new dye 2 prepared in Example 2.

[0043] Figure 8 The absorption spectrum curve of the new dye 2 prepared in Example 2 is shown.

[0044] Figure 9 The dyeing uptake capacity of the new dye 2 prepared in Example 2.

[0045] Figure 10 The dyeing rate of the new dye 2 prepared in Example 2.

[0046] Figure 11 The nuclear magnetic resonance image of the new dye 3 prepared in Example 3.

[0047] Figure 12 The infrared spectrum of the new dye 3 prepared in Example 3.

[0048] Figure 13 The absorption spectrum curve of the new dye 3 prepared in Example 3 is shown.

[0049] Figure 14 The dyeing uptake capacity of the new dye 3 prepared in Example 3.

[0050] Figure 15 The dyeing rate of the new dye 3 prepared in Example 3. Detailed Implementation

[0051] Example 1

[0052] A novel method for synthesizing disperse dyes includes the following steps:

[0053] (1) In a 250 mL three-necked flask, add 50 mL of toluene as solvent, add 10 mmol of N-ethyl-N-hydroxyethylm-toluidine, stir to dissolve, add 12 mmol of phthalic anhydride and 0.1 mmol of 4-dimethylaminopyridine, heat to 130 °C and reflux to react. Monitor the reaction by thin-layer spotting. After the reaction is complete, remove the toluene solvent by rotary evaporation to obtain the coupling component containing hydrophilic groups. Dissolve the coupling component in acetone, add it to a 500 mL three-necked flask, add 200 mL of deionized water and 0.1 g of O2, stir well, cool to 0 °C in an ice bath, and keep cool for later use.

[0054] (2) Measure 6 mL of hydrochloric acid into water and stir until homogeneous. Slowly add 10 mmol of p-nitroaniline, stir thoroughly, cool to 0°C, then add 11 mmol of sodium nitrite and continue stirring until diazotization is complete. Add an appropriate amount of aminosulfonic acid to eliminate excess nitrite. Add the prepared p-nitroaniline diazonium salt dropwise to the previously prepared coupling component. During the dropwise addition, add a small amount of crushed ice to maintain the temperature of the reaction system at 0°C. After the diazonium salt is completely added, slowly restore the reaction solution to room temperature and continue the reaction until the diazonium salt is completely consumed. Use H acid to monitor the reaction progress. After the reaction is complete, filter and wash to obtain the crude dye product with a yield of 97%.

[0055] The crude product was then recrystallized from N,N-dimethylformamide to obtain a pure red disperse dye, which was labeled as New Dye 1.

[0056] The reaction equations involved are as follows:

[0057]

[0058] Product characterization:

[0059] (1) Dye molecular structure

[0060]

[0061] (2) Nuclear magnetic resonance analysis:

[0062] 1H NMR (500MHz, DMSO-d6) δ8.35(d,J=8.7Hz,2H),7.92(d,J=8.7Hz,2H),7.71(dd,J=10.9,8.3Hz,2H),7.39(t,J=7.4Hz,1H),7.31(t,J=7.4Hz,1H), 7.27(d,J=7.5Hz,1H),6.82–6.76(m,2H),4.35(t,J=6.1Hz,2H),3.80(t, J=6.2Hz,2H),3.56(q,J=7.0Hz,2H),2.64(s,3H),1.14(t,J=6.9Hz,3H).

[0063] (3) Infrared spectroscopy analysis:

[0064] 3470cm -1 The stretching vibration of the OH group of the carboxyl group is 3082 cm⁻¹. -1 This is the CH stretching vibration of the benzene ring, 2970 cm⁻¹ -1 2904cm -1 2835cm -1 This is the CH stretching vibration of an alkane, 1743 cm⁻¹. -1 The C=O stretching vibration of the carboxyl group, 1683 cm⁻¹ -1 This is the C=O stretching vibration of the ester group, 1601 cm⁻¹ -1 1556cm -1 This is a C=C skeletal stretching vibration of the benzene ring, 1512 cm⁻¹ -1 This is an N=O asymmetric stretching vibration of NO2, 1421 cm. -1 This is an in-plane deformation vibration of the OH group of the carboxyl group, 1379 cm⁻¹. -1 It is a symmetrical deformation vibration of CH3, 1334 cm. -1 This is a symmetrical stretching vibration of NO2 at N=O, 1288 cm. -1 The CN stretching vibration of a tertiary amine, 1263 cm⁻¹ -1 The CO stretching vibration of the carboxyl group, 1228 cm⁻¹ -1 The CCN bending vibration of the amine, 1190 cm⁻¹ -1 This is the COC stretching vibration of the ester group, 1149 cm⁻¹ -1 This is an in-plane deformation vibration of the 1,2,4-trisubstituted benzene ring CH, 1103 cm⁻¹ -1 1072cm -1 This is an in-plane deformation vibration of disubstituted benzene ring CH, 923 cm⁻¹ -1 This is the out-of-plane deformation vibration of the OH group of the carboxyl group, 854 cm⁻¹. -1 This is an out-of-plane deformation vibration of CH at the para-substitution of the benzene ring, 806 cm⁻¹. -1This is an out-of-plane deformation vibration of the 1,2,4-trisubstituted benzene ring (CH), 746 cm⁻¹ -1 This is an out-of-plane deformation vibration of CH at ortho-substituted benzene ring, 686 cm⁻¹. -1 The OC=O bending vibration of the carboxyl group, 650 cm⁻¹ -1 This is the deformation vibration of NO2.

[0065] (4) Spectral absorption performance

[0066] Weigh 0.01 g of the new dye 1, dissolve and dilute to 100 mL of N,N-dimethylformamide, then dilute 5 times to a concentration of 0.02 g / L. Measure the absorption spectrum using a UV-2450 UV-Vis spectrophotometer (Shimadzu Corporation, Japan). See [link to sample image]. Figure 3 .

[0067] The new dye 1 was measured to have a maximum absorption wavelength of 503 nm and a molar extinction coefficient ε = 36118.

[0068] (5) Dye solution and dyeing properties

[0069] Accurately weigh 2g of dye 1 into a mortar, add a little water, grind, and transfer to a 1000mL volumetric flask to obtain a 2g / L stock solution. After dilution, the particle size of the dye was determined using a ZS90 nanoparticle size and potential analyzer (Malvin Instruments Ltd., UK). The average particle size of the prepared dye dispersion was 430.2nm, meeting the standard for commercial disperse dyes.

[0070] The mother liquor was used to prepare dye solutions of different concentrations. A 1g sample of polyester fabric was moistened and placed into the dye bath (pH=5, liquor ratio 1:20). The sealed dyeing cylinder was then installed in a high-temperature, high-pressure dyeing machine. The dye bath temperature was increased from 50℃ to 130℃ at a rate of 2℃ / min, held for 60 minutes, and then rapidly cooled to room temperature. After rinsing the fabric sample with cold water, the dyed polyester fabric was subjected to a reduction cleaning solution (2g / L sodium carbonate, 2g / L sodium hydrosulfite, liquor ratio 1:50) at 85℃ for 15 minutes, followed by drying. The dyeing results are shown below. Figure 4 As shown. When the dye is used at a dosage of 0.25%, the K / S value on polyester fabric exceeds 8. At 1%, it is basically saturated, and the K / S value reaches more than 18. A very deep color can be obtained with a very small amount.

[0071] Prepare a 1% (owf) dye solution by taking the mother liquor. Wet a 1g piece of cut polyester fabric sample and add it to the dye solution (pH=5, liquor ratio 1:20). Then, install the sealed dye cup into a high-temperature, high-pressure dyeing machine. Increase the dye solution temperature from 50℃ to 130℃ at a rate of 2℃ / min, hold for 60min, and then rapidly cool to room temperature. Remove one dye cup every 10min during the heating phase and every 15min during the holding phase. After rinsing the fabric sample with cold water, use the prepared reducing cleaning solution (2g / L sodium carbonate, 2g / L sodium hydrosulfite, liquor ratio 1:50) to reduce and clean the dyed polyester fabric at 85℃ for 15min, then dry. The dyeing results are as follows. Figure 5 As shown, the dye reaches saturation after 55 minutes of dyeing, i.e., 15 minutes at 130℃, exhibiting a fast dyeing rate and low energy consumption during the dyeing process.

[0072] (6) Color fastness performance

[0073] According to ISO 105-C04 (2010) "Textiles - Tests for color fastness to washing", the color fastness to washing of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105 / P01 (1993) "Textiles - Tests for color fastness to dry heat (excluding hot pressing)", the color fastness to sublimation of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105-X12 (2016) "Textiles - Tests for color fastness to rubbing", the color fastness to dry / wet rubbing of polyester dyed fabrics with a dye concentration of 1% (owf) is tested.

[0074] Table 1. Color fastness properties of new dye 1 for polyester dyeing

[0075]

[0076] Based on the experimental data in the table above, the washing and rubbing fastness of the new dye 1 are both above grade 4-5, while the sublimation fastness is slightly worse, reaching grade 2-3.

[0077] Example 2

[0078] A novel method for synthesizing disperse dyes includes the following steps:

[0079] (1) In a 250 mL three-necked flask, add 50 mL of toluene as solvent, add 10 mmol of N-ethyl-N-hydroxyethylm-toluidine, stir to dissolve, add 12 mmol of phthalic anhydride and 0.1 mmol of 4-dimethylaminopyridine, heat to 130 °C and reflux to react. Monitor the reaction by thin-layer spotting. After the reaction is complete, remove the toluene solvent by rotary evaporation to obtain the coupling component containing hydrophilic groups. Dissolve the coupling component in acetone, add it to a 500 mL three-necked flask, add 200 mL of deionized water and 0.1 g of O2, stir well, cool to 0 °C in an ice bath, and keep cool for later use.

[0080] (2) Measure 6 mL of hydrochloric acid into water and stir until homogeneous. Slowly add 10 mmol of 2-chloro-4-nitroaniline, stir thoroughly, cool to 0°C, then add 11 mmol of sodium nitrite and continue stirring until diazotization is complete. Add an appropriate amount of aminosulfonic acid to eliminate excess nitrite. Add the prepared 2-chloro-4-nitroaniline diazonium salt dropwise to the coupling component, adding a small amount of crushed ice during the dropwise addition to maintain the temperature of the reaction system. After the diazonium salt is completely added, slowly restore the reaction solution to room temperature and continue the reaction until the diazonium salt is completely consumed. Use H acid to monitor the reaction progress. After the reaction is complete, filter and wash to obtain the crude dye product with a yield of 92%.

[0081] The crude product was then recrystallized from N,N-dimethylformamide to obtain pure blue disperse dye, which was labeled as new dye 2.

[0082] The reaction equation is as follows:

[0083]

[0084] Product characterization:

[0085] (1) Dye molecular structure

[0086]

[0087] (2) Nuclear magnetic resonance analysis:

[0088] 1 H NMR(500MHz,DMSO-d6)δ8.43(d,J=2.5Hz,1H),8.24(dd,J=8.9,2.5Hz,1H),7.80–7.76(m,2H),7.74(d,J=10.0Hz,1H),7.66–7.60(m,3H ),6.81(dd,J=6.6,3.1Hz,2H),4.45(t,J=5.8Hz,2H),3.84(t,J=5.8Hz,2H),3.57(q,J=7.1Hz,2H),2.63(s,3H),1.15(t,J=7.0Hz,3H).

[0089] (3) Infrared spectroscopy analysis:

[0090] 3470cm -1 The stretching vibration of the OH group of the carboxyl group is 3082 cm⁻¹. -1 This is the CH stretching vibration of the benzene ring, 2970 cm⁻¹ -1 2904cm -1 2835cm -1 This is the CH stretching vibration of an alkane, 1743 cm⁻¹. -1 The C=O stretching vibration of the carboxyl group, 1683 cm⁻¹ -1 This is the C=O stretching vibration of the ester group, 1601 cm⁻¹ -1 1556cm -1 This is a C=C skeletal stretching vibration of the benzene ring, 1512 cm⁻¹ -1 This is an N=O asymmetric stretching vibration of NO2, 1421 cm. -1 This is an in-plane deformation vibration of the OH group of the carboxyl group, 1379 cm⁻¹. -1 It is a symmetrical deformation vibration of CH3, 1334 cm. -1 This is a symmetrical stretching vibration of NO2 at N=O, 1288 cm. -1 The CN stretching vibration of a tertiary amine, 1263 cm⁻¹ -1 The CO stretching vibration of the carboxyl group, 1228 cm⁻¹ -1 The CCN bending vibration of the amine, 1190 cm⁻¹ -1 This is the COC stretching vibration of the ester group, 1149 cm⁻¹ -1 This is an in-plane deformation vibration of the 1,2,4-trisubstituted benzene ring CH, 1103 cm⁻¹ -1 1072cm -1 This is an in-plane deformation vibration of disubstituted benzene ring CH, 923 cm⁻¹ -1 This is the out-of-plane deformation vibration of the OH group of the carboxyl group, 854 cm⁻¹. -1 This is an out-of-plane deformation vibration of CH at the para-substitution of the benzene ring, 806 cm⁻¹. -1 This is an out-of-plane deformation vibration of the 1,2,4-trisubstituted benzene ring (CH), 746 cm⁻¹ -1 This is an out-of-plane deformation vibration of CH at ortho-substituted benzene ring, 686 cm⁻¹. -1 The OC=O bending vibration of the carboxyl group, 650 cm⁻¹ -1 This is the deformation vibration of NO2.

[0091] (4) Spectral absorption performance

[0092] Weigh 0.01 g of the new dye 2, dissolve and dilute to 100 mL of N,N-dimethylformamide, then dilute 5 times to a concentration of 0.02 g / L. Measure the absorption spectrum using a UV-2450 UV-Vis spectrophotometer (Shimadzu Corporation, Japan). See [link to table]. Figure 8 .

[0093] The new dye 2 was measured to have a maximum absorption wavelength of 528 nm and a molar extinction coefficient ε = 39137.

[0094] (5) Dye solution and dyeing properties

[0095] Accurately weigh 2g of dye 2 and place it in a mortar. Add a small amount of water, grind, and transfer to a 1000mL volumetric flask to obtain a 2g / L stock solution. After dilution, the particle size of the dye was determined using a ZS90 nanoparticle size and potential analyzer (Malvin Instruments Ltd., UK). The average particle size of the prepared dye dispersion was 297.7nm, meeting the standard for commercial disperse dyes.

[0096] The mother liquor was used to prepare dye solutions of different concentrations. A 1g sample of polyester fabric was moistened and placed into the dye bath (pH=5, liquor ratio 1:20). The sealed dyeing cylinder was then installed in a high-temperature, high-pressure dyeing machine. The dye bath temperature was increased from 50℃ to 130℃ at a rate of 2℃ / min, held for 60 minutes, and then rapidly cooled to room temperature. After rinsing the fabric sample with cold water, the dyed polyester fabric was subjected to a reduction cleaning solution (2g / L sodium carbonate, 2g / L sodium hydrosulfite, liquor ratio 1:50) at 85℃ for 15 minutes, followed by drying. The dyeing results are shown below. Figure 9 As shown, when the dye dosage is 0.25%, the K / S value on polyester fabric exceeds 9, and at 1%, it basically reaches saturation, with a K / S value exceeding 19.

[0097] Prepare a 1% (owf) dye solution by taking the mother liquor. Wet a 1g piece of cut polyester fabric sample and add it to the dye solution (pH=5, liquor ratio 1:20). Then, install the sealed dye cup into a high-temperature, high-pressure dyeing machine. Increase the dye solution temperature from 50℃ to 130℃ at a rate of 2℃ / min, hold for 60min, and then rapidly cool to room temperature. Remove one dye cup every 10min during the heating phase and every 15min during the holding phase. After rinsing the fabric sample with cold water, use the prepared reducing cleaning solution (2g / L sodium carbonate, 2g / L sodium hydrosulfite, liquor ratio 1:50) to reduce and clean the dyed polyester fabric at 85℃ for 15min, then dry. The dyeing results are as follows. Figure 10 As shown, the dye reaches near saturation after 55 minutes of dyeing, which is equivalent to 15 minutes at 130°C.

[0098] (6) Color fastness performance

[0099] According to ISO 105-C04 (2010) "Textiles - Tests for color fastness to washing", the color fastness to washing of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105 / P01 (1993) "Textiles - Tests for color fastness to dry heat (excluding hot pressing)", the color fastness to sublimation of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105-X12 (2016) "Textiles - Tests for color fastness to rubbing", the color fastness to dry / wet rubbing of polyester dyed fabrics with a dye concentration of 1% (owf) is tested.

[0100] Table 2. Color fastness properties of new dye 2 for polyester dyeing

[0101]

[0102] Based on the experimental data in the table above, the washing and rubbing fastness of the new dye 2 are both above grade 4-5, while the sublimation fastness is slightly worse, reaching grade 3 or above.

[0103] Example 3

[0104] A novel method for synthesizing disperse dyes includes the following steps:

[0105] (1) In a 250 mL three-necked flask, add 50 mL of toluene as solvent, add 10 mmol of N-ethyl-N-hydroxyethylm-toluidine, stir to dissolve, add 12 mmol of phthalic anhydride and 0.1 mmol of 4-dimethylaminopyridine, heat to 130 °C and reflux to react. Monitor the reaction by thin-layer spotting. After the reaction is complete, remove the toluene solvent by rotary evaporation to obtain the coupling component containing hydrophilic groups. Dissolve the coupling component in acetone, add it to a 500 mL three-necked flask, add 200 mL of deionized water and 0.1 g of O2, stir well, cool to 0 °C in an ice bath, and keep cool for later use.

[0106] (2) Weigh 10 mmol of 3-amino-5-nitrobenzisothiazole into 6 mL of concentrated sulfuric acid. Stir until completely dissolved, then cool to 0°C and add 11 mmol of 41% nitrosylsulfonic acid. Continue stirring at low temperature until the reaction is complete. The completeness of the diazotization reaction can be detected by the ice-water method. Add the prepared 3-amino-5-nitrobenzisothiazole diazonium salt dropwise to the coupling component. During the dropwise addition, add a small amount of crushed ice to maintain the temperature of the reaction system. After the diazonium salt is completely added, slowly restore the reaction solution to room temperature and continue the reaction until the diazonium salt is completely consumed. Use H acid to monitor the reaction progress. After the reaction is completed, filter and wash to obtain the crude dye product with a yield of 85.65%.

[0107] The crude product was then recrystallized from dimethylformamide to obtain a new type of pure disperse dye, which was labeled as New Dye 3.

[0108] The reaction equation is as follows:

[0109]

[0110] Product characterization:

[0111] (1) Dye molecular structure

[0112]

[0113] (2) Nuclear magnetic resonance analysis:

[0114] 1 H NMR(500MHz,DMSO-d6)δ8.43(d,J=2.5Hz,1H),8.24(dd,J=8.9,2.5Hz,1H),7.80–7.76(m,2H),7.74(d,J=10.0Hz,1H),7.66–7.60(m,3H ),6.81(dd,J=6.6,3.1Hz,2H),4.45(t,J=5.8Hz,2H),3.84(t,J=5.8Hz,2H),3.57(q,J=7.1Hz,2H),2.63(s,3H),1.15(t,J=7.0Hz,3H).

[0115] (3) Infrared spectroscopy analysis:

[0116] 3441cm -1 The stretching vibration of the OH group of the carboxyl group is 3093 cm⁻¹. -1 This is the CH stretching vibration of the benzene ring, 2974 cm⁻¹ -1 2929cm -1 2875cm -1 The CH stretching vibration of alkanes, 1734 cm⁻¹ -1 This is the C=O stretching vibration of the carboxyl group, 1701 cm⁻¹ -1 This is the C=O stretching vibration of the ester group, 1595 cm⁻¹ -1 This is a C=C skeletal stretching vibration of the benzene ring, 1517 cm⁻¹. -1 This is an N=O asymmetric stretching vibration of NO2, 1406 cm. -1 This is an in-plane deformation vibration of the OH group of the carboxyl group, 1375 cm⁻¹. -1 It is a symmetrical deformation vibration of CH3, 1332 cm. -1 This is a symmetrical stretching vibration of NO2 at N=O, 1315 cm. -1 This is the CN stretching vibration of a tertiary amine, 1267 cm⁻¹ -1 The CO stretching vibration of the carboxyl group, 1232 cm⁻¹ -1 The CCN bending vibration of an amine, 1172 cm⁻¹ -1This is the COC stretching vibration of the ester group, 1103 cm⁻¹ -1 1072cm -1 This is an in-plane deformation vibration of the 1,2,4-trisubstituted benzene ring CH, 985 cm⁻¹ -1 This is an in-plane deformation vibration of CH at ortho-substituted benzene ring, 933 cm⁻¹. -1 This is the out-of-plane deformation vibration of the OH group of the carboxyl group, 871 cm⁻¹. -1 815cm -1 This is an out-of-plane deformation vibration of the 1,2,4-trisubstituted benzene ring (CH), 734 cm⁻¹ -1 This is an out-of-plane deformation vibration of CH at ortho-substituted benzene ring, 690 cm⁻¹. -1 The OC=O bending vibration of the carboxyl group, 642 cm⁻¹ -1 This is the deformation vibration of NO2.

[0117] (4) Spectral absorption performance

[0118] Weigh 0.01 g of the new dye 3, dissolve and dilute to 100 mL of N,N-dimethylformamide, then dilute 5 times to a concentration of 0.02 g / L. Measure the absorption spectrum using a UV-2450 UV-Vis spectrophotometer (Shimadzu Corporation, Japan). See [link to sample image]. Figure 13 .

[0119] The new dye 3 was measured to have a maximum absorption wavelength of 621 nm and a molar extinction coefficient ε = 39590.

[0120] (5) Dye solution and dyeing properties

[0121] Accurately weigh 2g of the new dye 3 and place it in a mortar. Add a small amount of water, grind, and transfer to a 1000mL volumetric flask to obtain a 2g / L stock solution. After dilution, the particle size of the dye was determined using a ZS90 nanoparticle size and potential analyzer (Malvin Instruments Ltd., UK). The average particle size of the prepared dye dispersion was 457.2nm, meeting the standard for commercial disperse dyes.

[0122] The mother liquor was used to prepare dye solutions of different concentrations. A 1g sample of polyester fabric was moistened and placed into the dye bath (pH=5, liquor ratio 1:20). The sealed dyeing cylinder was then installed in a high-temperature, high-pressure dyeing machine. The dye bath temperature was increased from 50℃ to 130℃ at a rate of 2℃ / min, held for 60 minutes, and then rapidly cooled to room temperature. After rinsing the fabric sample with cold water, the dyed polyester fabric was subjected to a reduction cleaning solution (2g / L sodium carbonate, 2g / L sodium hydrosulfite, liquor ratio 1:50) at 85℃ for 15 minutes, followed by drying. The dyeing results are shown below. Figure 14 As shown, when the dye is used at a concentration of 0.25%, the K / S value on polyester fabric exceeds 9. At 2%, it is basically saturated, with a K / S value exceeding 20, resulting in a relatively deep color.

[0123] Prepare a 1% (owf) dye solution by taking the mother liquor. Wet a 1g piece of cut polyester fabric sample and add it to the dye solution (pH=5, liquor ratio 1:20). Then, install the sealed dye cup into a high-temperature, high-pressure dyeing machine. Increase the dye solution temperature from 50℃ to 130℃ at a rate of 2℃ / min, hold for 60min, and then rapidly cool to room temperature. Remove one dye cup every 10min during the heating phase and every 15min during the holding phase. After rinsing the fabric sample with cold water, use the prepared reducing cleaning solution (2g / L sodium carbonate, 2g / L sodium hydrosulfite, liquor ratio 1:50) to reduce and clean the dyed polyester fabric at 85℃ for 15min, then dry. The dyeing results are as follows. Figure 15 As shown, the dye reaches near saturation after 55 minutes of dyeing, which is equivalent to 15 minutes at 130°C.

[0124] (6) Color fastness performance

[0125] According to ISO 105-C04 (2010) "Textiles - Tests for color fastness to washing", the color fastness to washing of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105 / P01 (1993) "Textiles - Tests for color fastness to dry heat (excluding hot pressing)", the color fastness to sublimation of dyed fabrics with a dye concentration of 1% (owf) is tested. According to ISO 105-X12 (2016) "Textiles - Tests for color fastness to rubbing", the color fastness to dry / wet rubbing of polyester dyed fabrics with a dye concentration of 1% (owf) is tested.

[0126] Table 3. Color fastness properties of new dye 3 for polyester dyeing

[0127]

[0128] Based on the experimental data in the table above, the washing, sublimation, and rubbing fastness of the new dye 3 are all above grade 4-5, meeting the requirements for use as a commercial dye.

Claims

1. A disperse dye, the structural formula of which is as follows: Formula 1; In Equation 1: R is a -H or -CH3 group; X is a -H, -CH3, or -CN group; Y is ,in: W represents -COOH; Ar-N is the diazo component of the dye, obtained through any one of the following groups: ； Each of R1-R5 can be independently selected from -NO2, -CN, -Cl, -F, -CF3, -H, -CH3, -OCH3, or -COOCH3 groups.

2. A method for synthesizing the disperse dye according to claim 1, characterized in that, Includes the following steps: Synthesis of coupling components: An aniline compound containing an alcohol hydroxyl group was dissolved in toluene solvent by stirring. A carboxyl compound and a catalyst were added, and the mixture was heated to reflux. The reaction was monitored by thin-layer spotting. After the reaction was completed, the toluene solvent was removed by rotary evaporation to obtain a coupling component containing a hydrophilic group. Disperse dye synthesis: The coupling component containing hydrophilic groups is coupled with the diazo component. After the reaction is complete, the mixture is filtered and washed to obtain crude dye. The crude product is then recrystallized to obtain pure disperse dye.

3. The method for synthesizing a disperse dye according to claim 2, characterized in that: The reaction equivalent of the carboxyl compound is 1 to 2 times that of the aniline compound.

4. The method for synthesizing a disperse dye according to claim 3, characterized in that: The reaction equivalent of the carboxyl compound is 1.2 times that of the aniline compound.

5. The method for synthesizing a disperse dye according to claim 3, characterized in that: The reaction equivalent of the catalyst is 1 to 2% of the aniline compound.

6. The method for synthesizing a disperse dye according to claim 3, characterized in that: The reaction temperature of the coupling reaction is -10 to room temperature.

7. The method for synthesizing a disperse dye according to claim 6, characterized in that: The reaction temperature of the coupling reaction is 0 degrees Celsius.

8. The method for synthesizing a disperse dye according to claim 6, characterized in that: The diazo component is selected from any one of the following groups: ； Each of R1-R5 can be independently selected from -NO2, -CN, -Cl, -F, -CF3, -H, -CH3, -OCH3, or -COOCH3 groups.

9. The method for synthesizing a disperse dye according to claim 6, characterized in that: The diazo component was obtained by diazotization reaction of nitroaniline with sodium nitrite and hydrochloric acid.

10. The use of the disperse dye of claim 1 in polyester dyeing.

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