Black carbine disperse dyes, compositions and methods of preparation and use

Abstract

The present application provides a kind of black carbine disperse dye and composition and preparation method and application, it is composed of orange carbine disperse dye, red carbine disperse dye, purple carbine disperse dye and blue carbine disperse dye 4 kinds of dyes, solve the 2-diazo malonic acid diester type carbine disperse dye dye deep color, especially black, color light is not pure and the problem of insufficient heat migration color fastness, so that it can be applied to the dyeing scene of polyester and polyester ammonia blend fabric.

Description

Technical Field

[0001] This invention relates to the fields of dyes and textile printing and dyeing, and particularly to a black carbene disperse dye, its composition, preparation method, and applications, especially its dyeing applications on polyester and polyester-spandex blended fabrics. Background Technology

[0002] Polyester is currently the world's most produced synthetic fiber, widely used in clothing, home textiles, and industrial textiles. Polyester-spandex blended fabrics combine the dimensional stability of polyester with the high elasticity of spandex, making them a core fabric for sportswear and underwear. Both types of fabrics use disperse dyes as the main coloring system. Conventional disperse dyes adhere to the fiber interior through weak intermolecular forces such as hydrogen bonds, van der Waals forces, and hydrophobic interactions. Under conditions such as high-temperature heat setting, long-term storage, and repeated washing, the dyes are prone to thermal migration along the fiber capillaries to the fabric surface, directly causing quality defects such as fabric color variations, batch color differences, staining of linings, and degradation of washing / rubbing fastness. Among these, spandex macromolecular chains are flexible and have a low glass transition temperature, making the migration behavior of dyes within the spandex phase more significant. The shortcoming of migration fastness in dark-colored polyester-spandex fabrics is particularly prominent, making it difficult to meet the quality requirements of high-end textile exports.

[0003] Carbene disperse dyes carry carbene reaction precursors such as bis-acrylidine and diazo esters. At high temperatures, they can generate highly reactive carbene intermediates, which can covalently insert into the CH bonds of polyester molecules and the NH bonds of spandex molecules, forming stable chemical bonds between the dye and the fiber. This significantly improves the colorfastness of dyed fabrics from the source. Our team has previously completed the development of multiple generations of carbene disperse dyes, successively launching bis-acrylidine type (CN112239604, CN112409815, CN112522975), α-phenyldiazo ester type (CN117304711, CN117402507, CN118725609), and 2-diazomalonic acid diester type (CN119592098) carbene disperse dyes, suitable for dyeing various synthetic fibers such as polyester, spandex, and polypropylene.

[0004] Existing 2-diazomalonide carbene dyes, represented by CN119592098, employ a high-temperature, high-pressure dyeing process combined with heat setting and color fastness. While this method can achieve good color fastness on light-colored fabrics, it suffers from two core technical bottlenecks: First, this patent is only suitable for light dyeing conditions with a low dye dosage of 1% owf. When increasing the dye concentration to prepare darker products, the covalent reaction efficiency between the dye and the fiber is significantly reduced, resulting in a substantial decline in the fabric's heat migration color fastness. The industry's conventional approach to improvement is to increase the number of reaction sites in the dye molecule, which theoretically increases the probability of carbene covalent reaction. However, an increase in reactive groups increases the steric hindrance of the dye molecule, hindering the diffusion of the dye into the fiber and causing a large accumulation of floating dye on the fabric surface, which further deteriorates the color fastness and color fastness. Secondly, the patent only covers the basic color spectrum of orange, red, and blue, and does not provide a dye system that can be mixed to produce a pure black color. Our team's experiments have confirmed that even if the patented structure is modified to contain orange, red, and blue dyes with bis(2-diazomalonate) reactive groups, it is impossible to obtain a pure black finished product by mixing them in any proportion. The reason for this is that 2-diazomalonate is a strong electron-withdrawing group, which weakens the "electron-donating and electron-withdrawing" conjugated color-emitting system within the dye molecule, causing a blue shift in the maximum absorption wavelength of the dye, resulting in the absence of long-wavelength blue-violet light, and the mixed black color tends to be brownish or grayish. It is evident that the existing 2-diazomalonate carbene dye system cannot simultaneously meet the two core requirements of high fixation rate, excellent thermal migration fastness, and pure black color.

[0005] Another type of black carbene dye scheme is described in CN118725609. This patent designs a three-color blended black dye based on the α-phenyldiazo ester structure, but its applicability to fabrics and its process compatibility are significantly limited: on the one hand, this dye system is only developed for pure spandex, and its carbene reactivity is insufficient when used for dyeing polyester, resulting in poor color fixation; on the other hand, this dye requires a special fixing agent to achieve a qualified color fixation rate on spandex, and the dyed fabrics do not meet the standards for soaping and heat migration fastness without the addition of an external agent. Our team used this patented dye to dye polyester without a fixing agent for verification, and the resulting fabrics had a low color fixation rate, and key color fastness indicators such as migration resistance and rubbing resistance were far below industry standards.

[0006] In summary, the two currently available mainstream carbene black disperse dyes have drawbacks, namely insufficient dark color fastness, impure black hue, compatibility only with spandex, and reliance on special fixing agents. Summary of the Invention

[0007] The purpose of this invention is to provide a black carbene disperse dye, its composition, preparation method, and application. It solves the problem that 2-diazomalonic acid diester type carbene disperse dyes, when dyeing deep and dark colors, especially black, have impure hues and insufficient heat migration fastness, making them applicable to the dyeing of polyester and polyester-spandex blended fabrics.

[0008] To achieve the above objectives, this technical solution provides a black carbene disperse dye, which is composed of four dyes: orange carbene disperse dye, red carbene disperse dye, purple carbene disperse dye, and blue carbene disperse dye. The structure of the orange carbene disperse dye is as follows:

[0009] The structure of red carbene disperse dye is:

[0010] The structure of purple carbene disperse dye is

[0011] The structure of blue carbene disperse dye .

[0012] In some embodiments, the mass ratio of orange carbene disperse dye, red carbene disperse dye, purple carbene disperse dye, and blue carbene disperse dye is 6~8:0.5~2:2~4:15~20.

[0013] Preferably, the mass ratio of orange carbene disperse dye, red carbene disperse dye, purple carbene disperse dye, and blue carbene disperse dye is 7:1:3:18.

[0014] This scheme employs four carbene disperse dyes: orange, red, purple, and blue. In particular, the blue carbene disperse dye in this scheme uses a propyl group instead of an ethyl group as a linking group between aniline and 2-diazomalonic acid diester, reducing the influence of the electron-withdrawing characteristics of the 2-diazomalonic acid diester structure on the azo chromophore. Secondly, a methoxy group is introduced into the benzene ring structure to increase the electron-donating property of the aniline module, further enhancing the intramolecular "donation-absorption" ability of the dye chromophore, thereby obtaining a blue dye with a maximum absorption wavelength of 597 nm.

[0015] Furthermore, the preparation method of the carbene disperse dye in this scheme is as follows: Step 1: Methyl malonate is condensed with N,N-di(hydroxyethyl)aniline or N,N-di(hydroxypropyl)-3-methoxyaniline to obtain compound V or VI. Step 2: React compound V or VI obtained in Step 1 with p-toluenesulfonyl azide to undergo a diazo group transfer reaction to obtain compound VII or VIII; Step 3: The diazonium salts prepared from 2,6-dichloro-4-nitroaniline, 2-chloro-4-nitroaniline, and 2-chloro-4-nitro-6-cyanoaniline are coupled with compound VII obtained in Step 2 to obtain orange, red, and purple carbene disperse dyes, respectively. Alternatively, the diazonium salt prepared from 3-amino-5-nitrobenzisisothiazole is coupled with compound VIII obtained in Step 2 to obtain blue carbene disperse dye.

[0016] The compound V is

[0017] The compound VI is

[0018] The compound VII is

[0019] The compound VIII is .

[0020] Secondly, this solution provides a black carbene disperse dye composition comprising the black carbene disperse dye and dispersant as described in the first aspect.

[0021] In some embodiments, the mass ratio of black carbene disperse dye to dispersant is 1:0.5~2.

[0022] In some embodiments, the dispersant includes dispersant NNO, dispersant MF, and sodium lignosulfonate.

[0023] Thirdly, this solution provides a method for preparing a black carbene disperse dye composition, comprising the following steps: Step 1: As mentioned in the first aspect, the black carbene disperse dye, dispersant, and water are mixed and pre-dispersed to obtain a pre-dispersed mixture. The stirring speed is 800~1200 rpm, and the pre-dispersion time is 8~12 min. Step 2: Pour the pre-dispersed mixture obtained in Step 1 into a sand mill containing zirconium beads for sand milling to obtain a dispersion; the size of the zirconium beads is 0.3~0.4 mm, and the sand milling time is 4~6 h; Step 3: Spray dry the dispersion obtained in Step 2 to obtain a black carbene disperse dye composition; the atomization rate is 15~20 mL / min, the inlet temperature is 150~250 ℃, and the outlet temperature is 120~150 ℃.

[0024] In some embodiments, the stirring speed in step one is 1000 rpm.

[0025] Fourthly, this solution provides a method for applying a black carbene disperse dye composition to polyester and polyester-spandex blended fabrics.

[0026] Furthermore, the method of applying this black carbene disperse dye composition includes the following steps: Step 1: Prepare an aqueous solution of 4%~10% owf black carbene disperse dye composition, adjust the pH value to 5, put the fabric to be dyed into the dyeing vat, seal the dyeing vat, heat to the holding temperature, hold for a period of time, and then take out the fabric. Step 2: Rinse the fabric obtained in Step 1 with clean water, air dry, pre-dry, bake, revert to clean, and air dry to obtain the dyed fabric.

[0027] In some embodiments, the heating rate in step one is 2 ℃ / min, the holding temperature is 130±2 ℃, and the holding time is 30~60 min.

[0028] In some embodiments, the pre-drying temperature in step two is 80~100 ℃, the pre-drying time is 1~3 min, the baking temperature is 180~220 ℃, and the baking time is 2~10 min.

[0029] In some embodiments, the reducing cleaning formula consists of 2 g / L sodium hydrosulfite, 2 g / L sodium carbonate, a bath ratio of 1:50, a cleaning temperature of 80 ℃, and a cleaning time of 10 min.

[0030] Furthermore, in another application scenario, the method of applying this black carbene disperse dye composition includes the following steps: Step 1: Mix the black carbene disperse dye composition, sodium alginate, penetrant and water to obtain a dye mixture solution; Step 2: Using a two-dip and two-paste process, first immerse the fabric in the dye mixture obtained in Step 1, take it out and use a padding machine to remove the excess material, then immerse the fabric in the dye mixture again and remove the excess material again to obtain the padded fabric. Step 3: Pre-dry, bake, reduce and clean the impregnated fabric obtained in Step 2, and air dry to obtain the dyed fabric.

[0031] In some embodiments, the concentration of the black carbene disperse dye composition is 20-100 g / L, the concentration of the sodium alginate is 2-10 g / L, and the concentration of the penetrant is 2-10 g / L. In some embodiments, the liquid-pickling rate of the impregnated fabric is 60% to 80% (i.e., the fabric weight gain is 60% to 80%).

[0032] In some embodiments, the pre-drying temperature is 80~100 ℃, the pre-drying time is 1~3 min, the baking temperature is 180~220 ℃, and the baking time is 2~10 min.

[0033] In some embodiments, the reducing cleaning formula consists of 2 g / L sodium hydrosulfite, 2 g / L sodium carbonate, a bath ratio of 1:50, a cleaning temperature of 80 ℃, and a cleaning time of 10 min.

[0034] Compared with existing technologies, this technical solution has the following characteristics and beneficial effects: This method uses a mixture of four carbene disperse dyes to obtain a black carbene disperse dye. All four dyes contain two 2-diazomalonic acid diester structures, significantly increasing the probability of reaction between the dye molecules and the fiber. The dyed fabric exhibits excellent dye-fiber reaction performance, with a fixation rate approaching 100%. Furthermore, practical application results show that the introduction of the two reactive groups did not significantly affect the effective dye uptake onto the fiber. The four dyes provided in this method have good compatibility, yielding a pure and strong black color, and the dye ratio for obtaining pure black dyed fabrics is provided. The dyed black fabric exhibits high fixation rate, high color fastness to washing / rubbing / heat migration, and has broad application prospects. Attached Figure Description

[0035] Figure 1 This is the 1H NMR spectrum of dye I; Figure 2 This is the carbon NMR spectrum of dye I; Figure 3 It is the 1H NMR spectrum of dye II; Figure 4 It is the carbon NMR spectrum of dye II; Figure 5 It is the 1H NMR spectrum of dye III; Figure 6 It is the carbon NMR spectrum of dye III; Figure 7 It is the 1H NMR spectrum of dye IV; Figure 8 It is the carbon NMR spectrum of dye IV; Figure 9 These are the ultraviolet-visible absorption spectra of dyes I to IV; Figure 10 These are the differential scanning calorimetry curves of dyes I to IV; Figure 11 This is the K / S curve of the dyed polyester fabric in Example 15; Figure 12The samples are: a polyester fabric dyed with black carbene disperse dye, a fabric sample stripped with DMF at 120℃, a polyester fabric treated at 180℃ for 30 s, and a cotton lining (top) and a polyester lining (bottom). Detailed Implementation

[0036] The present invention will be described in detail below through specific embodiments to provide a better understanding of the invention; however, these embodiments do not limit the scope of the invention. In the following embodiments, room temperature refers to a temperature of 25±5 ℃. Unless otherwise specified, all reagents and materials involved are commercially available. The polyester fabric specification is 230 g / m². 2 Polyester-spandex fabric is 250 g / m². 2 The composition is 77% polyester and 23% ammonia, both supplied by Xinxing New Textile Technology (Longyan) Co., Ltd. The main pharmaceutical manufacturers are as follows:

[0037] Test method: (1) Black light: Observe with the naked eye under a D65 light source and compare with a standard black sample card to confirm whether the black light is pure.

[0038] (2) Color depth value: The dyed fabric was tested using a Datacolor colorimeter under a D65 light source and a 10° viewing angle to obtain K / S data every 10 nm in the range of 360~700 nm. All K / S values ​​were summed and recorded as ∑K / S value.

[0039] (3) Fixation rate: The dyed polyester fabric was extracted with N,N-dimethylformamide (DMF) at 120℃ for 10 min. The ∑K / S value of the dyed polyester fabric before and after extraction was measured. The ratio of the ∑K / S value of the dyed polyester fabric after extraction to the ∑K / S value of the dyed polyester fabric before extraction was recorded as the fixation rate. This fixation rate test is only applicable to polyester fabrics. The spandex component in polyester-spandex blended fabrics will dissolve in hot DMF, therefore, it is not applicable to this test.

[0040] (4) Color fastness: Color fastness to washing is tested according to GB / T3921-2008 "Textiles - Tests for Color Fastness to Washing". Color fastness to rubbing is tested according to GB / T3920-2008 "Textiles - Tests for Color Fastness to Rubbing". Color fastness to migration is tested according to GB / T44161-2024 "Determination of Thermal Migration of Disperse Dyes".

[0041] Example 1 (Synthesis of Compound V):

[0042] In a three-necked flask equipped with a magnetic stir bar, N,N-dihydroxyethylaniline (30 mmol, 5.44 g), DCC (75 mmol, 15.47 g), and DMAP (7.5 mmol, 0.92 g) were added sequentially, followed by dichloromethane (200 mL). After stirring to dissolve, the flask was placed in an ice-water bath, and monomethyl malonate (75 mmol, 8.86 g) was added dropwise. After the addition was complete, the ice-water bath was removed, and the mixture was allowed to return to room temperature with stirring for 30 min. After the reaction was complete, the reaction solution was filtered through a Buchner funnel. The filtrate was evaporated using a rotary evaporator to remove the low-boiling-point organic solvent (dichloromethane). The residue was separated by silica gel column chromatography (eluent: V). 石油醚 / V 乙酸乙酯 = 2 / 1), to give compound V, a yellow liquid, 9.96 g, yield 87%.

[0043] Regarding the proton NMR data of compound V: 1 ¹H NMR (CDCl₃, 400MHz) δ 7.22 , 6.74~6.70 (m, 3H), 4.30 , 3.71 (s, 6H), 3.63 , 3.37 (s, 4H). 13 C NMR (CDCl3, 100MHz) δ 166.79, 166.46,147.01, 129.53, 117.29, 112.22, 62.54, 52.54, 49.55, 41.19. ESI-MS: m / z =381.1 [M] + Example 2 (Synthesis of Compound VII):

[0044] In a three-necked flask equipped with a magnetic stir bar, compound V (25 mmol, 9.54 g) and acetonitrile (200 mL) were added sequentially. After stirring to dissolve, DBU (50 mmol, 7.61 g) was added. After stirring for 5 min, the three-necked flask was placed in an ice-water bath, and p-ABSA (55 mmol, 13.21 g) was added in portions. Subsequently, the ice-water bath was removed, and stirring was continued at room temperature for 30 min. After the reaction was complete, water (30 mL) was added, and the mixture was extracted three times with dichloromethane (20 mL × 3). The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the organic solvent was removed from the filtrate using a rotary evaporator. The residue was separated by silica gel column chromatography (eluent: V). 石油醚 / V 乙酸乙酯= 1 / 1), to obtain compound V, a yellow liquid, 7.91 g, yield 73%.

[0045] Regarding the proton NMR data of compound V: 1 ¹H NMR (CDCl₃, 400MHz) δ 7.18 6.74 6.69 4.36 , 3.79 (s, 6H), 3.65 . 13 C NMR (CDCl3, 100MHz) δ 161.27,161.06, 147.16, 129.56, 117.41, 112.31, 65.56, 62.66, 52.59, 49.44. ESI-MS: m / z = 433.1 [M] + .

[0046] Example 3 (Synthesis of Dye I):

[0047] In a three-necked flask equipped with a constant-pressure dropping funnel and a mechanical stirrer, compound V (10 mmol, 4.34 g) and methanol (50 mL) were added, and the flask was placed in an ice-water bath. The pre-prepared diazonium salt of 2,6-dichloro-4-nitroaniline (prepared according to published patent CN121108769) was added dropwise to the flask. After compound V was completely consumed, the reaction mixture was poured into ice water (100 mL), precipitating a dye solid. The solid was filtered using a Buchner funnel to obtain the crude dye product. Further separation using silica gel column chromatography yielded dye I. A 4.63 g orange-red solid, yield 71%. Melting point: 135–136 °C.

[0048] Regarding the 1H NMR data for dye I: 1 H NMR (CDCl3, 400MHz) δ 8.25 (s, 2H), 7.91 6.90 4.47 3.85 , 3.82 (s, 6H). 13C NMR (CDCl3, 100 MHz) δ 161.24, 160.91, 153.83, 151.63, 145.43, 144.14,127.99, 126.32, 124.25, 111.78, 65.90, 62.21, 52.60, 49.49. ESI-MS: m / z =650.0 [M] + .

[0049] The 1H NMR spectrum of dye I is attached. Figure 1 The carbon NMR spectrum is attached. Figure 2 .

[0050] Example 4 (Synthesis of Dye II):

[0051] In a three-necked flask equipped with a constant-pressure dropping funnel and a mechanical stirrer, compound V (10 mmol, 4.34 g) and methanol (50 mL) were added, and the flask was placed in an ice-water bath. The pre-prepared diazonium salt of 2-chloro-4-nitroaniline (prepared according to published patent CN118725604) was added dropwise to the flask. After compound V was completely consumed, the reaction mixture was poured into ice water (100 mL), precipitating a dye solid. The solid was filtered using a Buchner funnel to obtain the crude dye product. Further separation using silica gel column chromatography yielded dye II. A red solid, 5.25 g, yield 85%. Melting point: 109–110 °C.

[0052] Regarding the 1H NMR data for dye II: 1 ¹H NMR (CDCl₃, 400MHz) δ 8.31 , 8.08 7.88 7.72 6.86 4.46 3.81 , 3.80 (s, 6H). 13 C NMR (CDCl3, 100 MHz) δ161.18, 160.92, 152.77, 151.39, 147.41, 144.93, 134.29, 126.78, 126.00,122.59, 118.06, 118.84, 65.85, 62.23, 52.58, 49.43. ESI-MS: m / z = 616.1 [M] + . The 1H NMR spectrum of dye II is attached. Figure 3 The carbon NMR spectrum is attached. Figure 4 .

[0053] Example 5 (Synthesis of Dye III):

[0054] In a three-necked flask equipped with a constant-pressure dropping funnel and a mechanical stirrer, compound V (10 mmol, 4.34 g) and methanol (50 mL) were added, and the flask was placed in an ice-water bath. The pre-prepared diazonium salt of 2-chloro-4-nitro-6-cyanoaniline (prepared according to published patent CN118562311) was added dropwise to the flask. After compound V was completely consumed, the reaction mixture was poured into ice water (100 mL), precipitating a dye solid. The solid was filtered using a Buchner funnel to obtain the crude dye product. Further separation using silica gel column chromatography yielded dye III. A purple solid, 5.33 g, yield 83%. Melting point: 162–163 °C.

[0055] Regarding the 1H NMR data for dye III: 1 ¹H NMR (CDCl₃, 400MHz) δ 8.50 8.46 8.00 6.91 4.49 3.88 , 3.82 (s, 6H). 13 C NMR (CDCl3, 100 MHz) δ 161.29, 160.84, 155.24,152.82, 145.64, 144.40, 133.80, 129.23, 128.52, 127.60, 115.82, 112.14,104.15, 65.96, 62.18, 52.60, 49.53. ESI-MS: m / z = 641.1 [M] + .

[0056] The 1H NMR spectrum of dye III is attached. Figure 5 The carbon NMR spectrum of dye III is attached. Figure 6 .

[0057] Example 6 (Synthesis of N,N-dihydroxypropyl-3-methoxyaniline):

[0058] To a three-necked flask equipped with a magnetic stir bar, 3-methoxyaniline (20 mmol, 2.463 g), potassium iodide (80 mmol, 13.28 g), sodium carbonate (160 mmol, 16.96 g), acetonitrile (60 mL), and 1-bromopropanol (60 mmol, 8.34 g) were added sequentially. The flask was then heated and stirred in an oil bath at 100 °C for 22 h. After the reaction was complete, the mixture was filtered through a Buchner funnel. The filtrate was then evaporated using a rotary evaporator to remove the organic solvent (acetonitrile). The residue was separated by silica gel column chromatography to obtain N,N-dihydroxypropyl-3-methoxyaniline, a pale yellow liquid, 3.74 g, yield 78%.

[0059] Regarding the proton NMR data of this compound: 1 ¹H NMR (CDCl₃, 400MHz) δ 7.13 6.39 6.32 6.28 , 3.78 (s, 3H), 3.71 3.42 , 2.11 (br, 2H), 1.87~1.80 (m, 4H). 13 C NMR (CDCl3, 100MHz) δ 160.88, 149.63,129.99, 106.42, 101.30, 99.94, 60.71, 55.16, 48.37, 30.03. ESI-MS: m / z =239.1 [M] + .

[0060] Example 7 (Synthesis of Compound VI):

[0061] In a three-necked flask equipped with a magnetic stir bar, N,N-dihydroxypropyl-3-methoxyaniline (10 mmol, 2.39 g), DCC (25 mmol, 5.16 g), and DMAP (2.5 mmol, 0.31 g) were added sequentially, followed by dichloromethane (50 mL). After stirring to dissolve, the flask was placed in an ice-water bath, and monomethyl malonate (25 mmol, 2.96 g) was added dropwise. After the addition was complete, the ice-water bath was removed, and the mixture was allowed to return to room temperature with stirring for 30 min. After the reaction was complete, the reaction solution was filtered through a Buchner funnel. The filtrate was evaporated using a rotary evaporator to remove the low-boiling-point organic solvent (dichloromethane). The residue was separated by silica gel column chromatography (eluent: V). 石油醚 / V 乙酸乙酯= 2 / 1), to give compound VI, a pale yellow liquid, 3.26 g, yield 74%.

[0062] Regarding the proton NMR data of compound VI: 1 ¹H NMR (CDCl₃, 400MHz) δ 7.12 , 6.30 , 6.26 , 6.22 (s, 1H), 4.20 , 3.77 (s, 3H), 3.75 (s, 6H), 3.41 (s, 4H), 3.37 ,1.97~1.90 (m, 4H). 13 C NMR (CDCl3, 100MHz) δ 166.98, 166.46, 160.95, 148.85,130.09, 105.70, 100.96, 99.39, 63.35, 55.11, 52.57, 47.73, 41.32, 26.35. ESI-MS: m / z = 439.1 [M] + .

[0063] Example 8 (Synthesis of Compound VIII):

[0064] In a three-necked flask equipped with a magnetic stir bar, compound VI (5 mmol, 2.20 g) and acetonitrile (30 mL) were added sequentially. After stirring to dissolve, DBU (10 mmol, 1.53 g) was added. After stirring for 5 min, the three-necked flask was placed in an ice-water bath, and p-ABSA (10 mmol, 2.41 g) was added in portions. Subsequently, the ice-water bath was removed, and stirring was continued at room temperature for 30 min. After the reaction was complete, water (30 mL) was added, and the mixture was extracted three times with dichloromethane (20 mL × 3). The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the organic solvent was removed from the filtrate using a rotary evaporator. The residue was separated by silica gel column chromatography (eluent: V). 石油醚 / V 乙酸乙酯 = 1 / 1), to give compound VIII, a yellow viscous liquid, 1.70 g, yield 69%.

[0065] Regarding the proton NMR data of compound VIII: 1 ¹H NMR (CDCl₃, 400MHz) δ 7.12 6.32 , 6.26 , 6.23 (s, 1H), 4.29 , 3.84 (s, 3H), 3.77 (s, 6H), 3.40 , 2.00~1.94 (m,4H). 13 C NMR (CDCl3, 100MHz) δ 161.35, 161.14, 160.97, 148.84, 130.10, 105.77,100.99, 99.54, 63.40, 55.12, 52.54, 47.67, 26.53. ESI-MS: m / z = 491.1 [M] + .

[0066] Example 9 (Synthesis of Dye IV):

[0067] In a three-necked flask equipped with a constant-pressure dropping funnel and a mechanical stirrer, compound VIII (10 mmol, 4.92 g) and methanol (50 mL) were added, and the flask was placed in an ice-water bath. The pre-prepared diazonium salt of 3-amino-5-nitro-benzisothiazole (prepared according to published patent CN121108769) was added dropwise to the flask. After compound V was completely consumed, the reaction mixture was poured into ice water (100 mL), precipitating a dye solid. The solid was filtered using a Buchner funnel to obtain the crude dye product. Further separation using silica gel column chromatography yielded dye IV. A blue solid, 4.82 g, yield 69%. Melting point: 161–164 °C.

[0068] Regarding the 1H NMR data for dye IV: 1 ¹H NMR (CDCl₃, 400MHz) δ 9.19 , 8.17 8.05 7.71 6.53 , 6.22 (s, 1H), 4.37 , 4.04 (s, 3H), 3.86 (s, 6H), 3.66 . 13C NMR (CDCl3, 100 MHz) δ 162.46, 161.70, 160.81, 154.65,144.19, 134.89, 127.02, 122.87, 122.60, 120.51, 120.30, 106.87, 94.49, 66.12,62.94, 56.56, 52.55, 48.05. ESI-MS: m / z = 697.1 [M] + .

[0069] The 1H NMR spectrum of dye IV is attached. Figure 7 The carbon NMR spectrum of dye IV is attached. Figure 8 For the UV-Vis absorption spectra of dyes I through IV, please refer to the appendix. Figure 9 It can be seen that their maximum absorption wavelengths are 417 nm, 473 nm, 507 nm and 597 nm, respectively.

[0070] The differential scanning calorimetry curves for dyes I through IV are attached. Figure 10 It can be seen that all four dyes exhibit exothermic peaks at 150~210 ℃.

[0071] Example 10 (Preparation of black carbene disperse dye): Weigh out dye I (35 g), dye II (5 g), dye III (15 g) and dye IV (90 g) respectively, and stir and mix them evenly. That is, dyes I to IV are mixed in a mass ratio of 7:1:3:18 to obtain black carbene disperse dye.

[0072] Example 11 (Preparation of a black carbene disperse dye composition): Weigh out 50 g of the black carbene disperse dye obtained in Example 10, 50 g of dispersant MF, and 200 g of water, mix them, and pre-disperse them for 10 min using mechanical stirring (1000 rpm). Then, transfer the mixture to a sand mill containing zirconium beads (0.3~0.4 mm in diameter) and mill for 5 h to obtain a dispersion. Subsequently, spray dry the mixture at an atomization rate of 15 mL / min, an inlet temperature of 150 °C, and an outlet temperature of 130 °C to obtain the black carbene disperse dye composition.

[0073] Examples 12-14 (Preparation of black carbene disperse dye compositions by changing the dispersant): The dispersant MF (50 g) in Example 11 was replaced with dispersant NNO (50 g), sodium lignosulfonate (50 g), or a mixture of dispersant MF (25 g) and sodium lignosulfonate (25 g), while other conditions remained unchanged, to obtain the black carbene disperse dye compositions of Examples 12-14. The dispersant composition in the different black carbene disperse dye compositions is shown in Table 1 below: Table 1. Dispersant components in different black carbene disperse dye compositions

[0074] Example 15 (Dyeing Polyester): Weigh out 0.5 g of the black carbene disperse dye composition from Example 11 (i.e., dye dosage of 5% owf) and 200 mL of water to prepare an aqueous solution. Adjust the pH of the dye bath to 5 using acetic acid. Place 10 g of polyester fabric into the solution, seal the dye bath, and heat to 130 °C at a rate of 2 °C / min. Hold the solution for 60 min, then remove the fabric. Rinse with water, air dry, pre-dry at 100 °C for 1 min, bake at 200 °C for 2 min, and perform reduction cleaning (2 g / L sodium hydrosulfite, 2 g / L sodium carbonate, liquor ratio 1:50, cleaning temperature 80 °C, cleaning time 10 min). Air dry to obtain the dyed polyester fabric. The K / S curve of this dyed fabric is shown below. Figure 11 As shown. Images of the actual fabric, its stripped sample, and the dry heat-treated sample are shown below. Figure 12 .

[0075] Examples 16-18: In Example 15, the black carbene disperse dye composition was replaced with the black carbene disperse dye composition of Example 12, Example 13, or Example 14, while other conditions remained unchanged, resulting in dyed polyester fabrics of Examples 16-18.

[0076] Examples 19-25: In Example 15, the black carbene disperse dye composition (0.5 g, i.e., dye amount of 5% owf) was replaced with black carbene disperse dye composition (0.4 g, i.e., dye amount of 4% owf), black carbene disperse dye composition (0.6 g, i.e., dye amount of 6% owf), black carbene disperse dye composition (0.7 g, i.e., dye amount of 7% owf), black carbene disperse dye composition (0.8 g, i.e., dye amount of 8% owf), black carbene disperse dye composition (0.9 g, i.e., dye amount of 9% owf), or black carbene disperse dye composition (1.0 g, i.e., dye amount of 10% owf), while other conditions remained unchanged, and the dyed polyester fabrics of Examples 19-24 were obtained respectively. The amount of dyeing composition used in Examples 19-24 is shown in Table 2 below: Table 2. Dosage of dyeing compositions in Examples 19-24

[0077] Example 25 (Dyeing of polyester-spandex blended fabric, polyester content 77%, spandex content 23%): Weigh out 0.5 g of the black carbene disperse dye composition from Example 11 (i.e., dye dosage of 5% owf) and 200 mL of water to prepare an aqueous solution. Adjust the pH of the dye bath to 5 using acetic acid, add 10 g of polyester-ammonia blended fabric, seal the dye vat, heat to 130 °C at 2 °C / min, and keep warm for 60 min. Remove the fabric, rinse with clean water, air dry, pre-dry at 100 °C for 1 min, bake at 200 °C for 2 min, perform reduction cleaning (2 g / L sodium hydrosulfite, 2 g / L sodium carbonate, liquor ratio 1:50, cleaning temperature 80 °C, cleaning time 10 min), and air dry to obtain the dyed polyester-ammonia fabric.

[0078] Example 26 (Dyeing of polyester): Weigh out 2 g of the black carbene disperse dye composition from Example 11, 0.2 g of sodium alginate, 0.2 g of penetrant, and 100 mL of water, and mix them to obtain a dye mixture solution. In this example, the concentration of the black carbene disperse dye composition is 20 g / L, the concentration of the sodium alginate is 2 g / L, and the concentration of the penetrant is 2 g / L. Using a two-dip, two-paste process, immerse the polyester fabric in the above dye mixture solution, remove it, and use a padding machine to remove excess material. Then immerse the fabric in the dye mixture solution again and remove excess material again to obtain a padded fabric, making the padding rate of the padded fabric 70% (i.e., the fabric weight gain 70%). Pre-dry the above fabric at 100 ℃ for 3 min, bake it at 210 ℃ for 3 min, perform reduction cleaning (2 g / L sodium hydrosulfite, 2 g / L sodium carbonate, liquor ratio 1:50, cleaning temperature 80 ℃, cleaning time 10 min), and air dry to obtain the dyed polyester fabric.

[0079] Example 27 (Dyeing of polyester-spandex blended fabric, polyester content 77%, spandex content 23%): Weigh out 2 g of the black carbene disperse dye composition from Example 11, 0.2 g of sodium alginate, 0.2 g of penetrant, and 100 mL of water, and mix them to obtain a dye mixture solution. In this example, the concentration of the black carbene disperse dye composition is 20 g / L, the concentration of the sodium alginate is 2 g / L, and the concentration of the penetrant is 2 g / L. Using a two-dip, two-paste process, immerse the polyester-spandex blended fabric in the above dye mixture solution, remove it, and use a padding machine to remove excess material. Then immerse the fabric in the dye mixture solution again and remove excess material again to obtain a padded fabric, such that the padding rate of the padded fabric is 70% (i.e., the fabric weight gain is 70%). The above fabric was pre-dried at 100 ℃ for 3 min, then baked at 210 ℃ for 3 min, followed by reduction cleaning (2 g / L sodium hydrosulfite, 2 g / L sodium carbonate, liquor ratio 1:50, cleaning temperature 80 ℃, cleaning time 10 min), and then air-dried to obtain the dyed polyester-spandex fabric. The dyeing results of Examples 15-27 are shown in Table 3 below: Table 3. Staining results of Examples 15-27

[0080] Results: Examples 15-27 all yielded deep black dyed polyester and polyester-spandex fabrics; the fixation rate of the dyed polyester fabrics was close to 100%; Examples 15-18 showed that deep black dyed polyester fabrics could be obtained using different dispersants; in Example 19, the dyed polyester fabric had a slightly lower K / S value due to a smaller dye dosage; the K / S values ​​of the dyed polyester fabrics in Examples 20-24 showed little improvement, indicating that the black color of the dyed polyester fabrics had reached saturation; the K / S value of the dyed polyester-spandex fabric in Example 25 was slightly lower than that in Example 15, because more dye was adsorbed by the spandex, resulting in less dye adsorbed on the polyester; Example 26 showed that the K / S value of the dyed polyester fabric obtained by pad-dyeing hot melt method was slightly lower than that of the high-temperature high-pressure dyeing + high-temperature fixation method; in Example 27, the K / S value of the obtained polyester-spandex fabric was also lower than that in Example 26 because the spandex adsorbed more dye. The dyeing performance of Examples 15-27 is shown in Table 4 below: Table 4. Staining performance of Examples 15-27

[0081] Results show that the dyed polyester or polyester-spandex fabrics obtained in Examples 15-27 all have excellent color fastness to washing, rubbing and migration.

[0082] Comparative Example 1 (using the dye published in patent CN119592098) A black dye was obtained by mixing the dyes listed in the published patent CN119592098 at a mass ratio of 4:2:9. A black dye composition was prepared according to Example 11, and then polyester was dyed using this black dye according to Example 15 to obtain a black dyed polyester fabric. The dyed polyester fabric exhibited the following color fastness to washing: color change fastness grade 4; polyester staining fastness grade 3-4; cotton staining fastness grade 4; dry rubbing fastness grade 4-5; wet rubbing fastness grade 4; and migration fastness grade 3-4. All color fastness grades are lower than those of the polyester fabric dyed with the dye of this invention. This is because the dye based on a 2-diazomalonic acid diester cannot achieve a higher reaction rate with the fiber macromolecules.

[0083] The dyes listed in the published patent CN119592098 are as follows: Orange dye:

[0084] Red dye:

[0085] Blue dye is

[0086] Comparative Example 2: In Example 10, the blue dye from Comparative Example 1 was used instead of dye IV of the present invention to prepare a black dye. Subsequently, in Example 11, a black dye composition was prepared, and then polyester fabric was dyed according to Example 15 to obtain a deep black dyed polyester fabric. The dyed polyester fabric exhibited a color fastness to washing of grade 4, a polyester staining grade of 4, a cotton staining grade of 4-5, a dry rubbing fastness of 4-5, a wet rubbing fastness of 4, and a migration fastness of 3-4. The blue dye is the most important component of the black blended dye. In this example, the blue dye had only one reactive group, resulting in a poorer reaction between the dye and the fiber, leading to a lower overall color fastness grade. Therefore, using this dye, it is impossible to obtain the high color fastness dyed polyester fabric of the present invention.

[0087] Comparative Example 3: In Example 10, a black dye was prepared by replacing dye IV of the present invention with the following dye. Subsequently, in Example 11, a black dye composition was prepared, and then polyester fabric was dyed according to Example 15 to obtain dyed polyester fabric. This dyed fabric exhibited a distinct brownish hue, which did not meet the requirement of a pure black hue. This is because, although the chromophore of this dye is consistent with the chromophore of the blue dye shown in Comparative Example 1, this dye contains two 2-diazomalonic acid diester structures, which weakens the "donation-absorption" system of the dye chromophore. The maximum absorption wavelength of this dye is only 564 nm, severely lacking blue light. Therefore, it is impossible to obtain the deep black dyed polyester fabric of the present invention using this dye.

[0088]

[0089] Comparative Example 4 (using commercial dyes): In Example 10, a black dye was prepared by replacing dye IV of the present invention with the following dye (CI Disperse Blue 148, Hangzhou Jihua Chemical Co., Ltd.). Subsequently, in Example 11, a black dye composition was prepared, and polyester fabric was dyed according to Example 15 to obtain a deep black dyed polyester fabric. The dyed polyester fabric exhibited a color fastness to washing of grade 4, a staining fastness of grade 3-4 for polyester, a staining fastness of grade 4 for cotton, a dry rubbing fastness of grade 4-5, a wet rubbing fastness of grade 4, and a migration fastness of grade 3-4. Commercial disperse dyes are not reactive with fiber macromolecules; therefore, it is impossible to obtain a dyed polyester fabric with the high color fastness of the present invention using this dye.

[0090]

[0091] Comparative Example 5 (using the dye published by patent CN118725609A): A black dye was obtained by mixing the dyes listed in the published patent CN118725609A at a mass ratio of 14:1:20. A black dye composition was prepared according to Example 11, and then polyester was dyed using this black dye according to Example 15 to obtain a black dyed polyester fabric. The dyed polyester fabric exhibited the following color fastness to washing: color change fastness grade 4; polyester staining fastness grade 3-4; cotton staining fastness grade 4; dry rubbing fastness grade 4; wet rubbing fastness grade 4; and migration fastness grade 3. The low reactivity of this type of phenyldiazo ester carbene dye with polyester fiber resulted in all color fastness grades being lower than those of the polyester fabric dyed with the dye of this invention.

[0092] The dyes listed in the published patent CN118725609A are as follows:

[0093] Orange dye:

[0094] Red dye:

[0095] Blue dye: Comparative Example 6 (with altered dye ratios): In Example 10, dye I (35 g) was replaced with dye I (15 g), i.e., dyes I to IV were blended in a mass ratio of 3:1:3:18 to obtain a blended dye. Subsequently, the dye composition was prepared according to Example 11, and polyester fabric was dyed according to Example 15. The resulting dyed polyester fabric lacked orange luster, and the black luster was unqualified.

[0096] Comparative Example 7 (with altered dye ratios): In Example 10, dye I (35 g) was replaced with dye I (55 g), i.e., dyes I to IV were blended in a mass ratio of 11:1:3:18 to obtain a blended dye. Subsequently, the dye composition was prepared according to Example 11, and polyester fabric was dyed according to Example 15. The resulting dyed polyester fabric had too much orange sheen and the black sheen was unacceptable.

[0097] Comparative Example 8 (with altered dye ratios): In Example 10, dye II was not used; instead, dyes I, III, and IV were blended in a mass ratio of 7:3:18 to obtain a blended dye. Subsequently, the dye composition was prepared according to Example 11, and polyester fabric was dyed according to Example 15. The resulting dyed polyester fabric lacked red luster, and the black luster was substandard.

[0098] Comparative Example 9 (with altered dye ratios): In Example 10, dye II (5 g) was replaced with dye II (15 g), i.e., dyes I to IV were blended in a mass ratio of 7:3:3:18 to obtain a blended dye. Subsequently, the dye composition was prepared according to Example 11, and polyester fabric was dyed according to Example 15. The resulting dyed polyester fabric had too much red light and the black light was unacceptable.

[0099] Comparative Example 10 (with altered dye ratios): In Example 10, dye III (15 g) was replaced with dye III (5 g), meaning dyes I to IV were blended in a mass ratio of 3:1:1:18 to obtain a blended dye. Subsequently, the dye composition was prepared according to Example 11, and polyester fabric was dyed according to Example 15. The resulting dyed polyester fabric lacked reddish-purple luster, and the black luster was unacceptable.

[0100] Comparative Example 11 (with altered dye ratios): In Example 10, dye III (15 g) was replaced with dye III (25 g), i.e., dyes I to IV were blended in a mass ratio of 11:1:5:18 to obtain a blended dye. Subsequently, the dye composition was prepared according to Example 11, and polyester fabric was dyed according to Example 15. The resulting dyed polyester fabric had too much reddish-purple luster, and the black luster was unacceptable.

[0101] Those skilled in the art should understand that the technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments have been described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0102] The above embodiments are merely illustrative of several implementation methods of this application, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of this application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this application should be determined by the appended claims.

Claims

1. A black carbene disperse dye, characterized in that, It consists of four dyes: orange carbene disperse dye, red carbene disperse dye, purple carbene disperse dye, and blue carbene disperse dye. The structure of the orange carbene disperse dye is as follows: The structure of red carbene disperse dye is: The structure of purple carbene disperse dye is The structure of blue carbene disperse dye 。 2. The black carbene disperse dye according to claim 1, characterized in that, The mass ratio of orange carbene disperse dye, red carbene disperse dye, purple carbene disperse dye, and blue carbene disperse dye is 6~8:0.5~2:2~4:15~20.

3. The black carbene disperse dye according to claim 1, characterized in that, The preparation method of carbene disperse dyes is as follows: Step 1: Methyl malonate is condensed with N,N-di(hydroxyethyl)aniline or N,N-di(hydroxypropyl)-3-methoxyaniline to obtain compound V or VI. Step 2: React compound V or VI obtained in Step 1 with p-toluenesulfonyl azide to undergo a diazo group transfer reaction to obtain compound VII or VIII; Step 3: The diazonium salts prepared from 2,6-dichloro-4-nitroaniline, 2-chloro-4-nitroaniline, and 2-chloro-4-nitro-6-cyanoaniline are coupled with compound VII obtained in Step 2 to obtain orange, red, and purple carbene disperse dyes, respectively. Alternatively, the diazonium salt prepared from 3-amino-5-nitrobenzisisothiazole is coupled with compound VIII obtained in Step 2 to obtain blue carbene disperse dye. The compound V is The compound VI is The compound VII is The compound VIII is 。 4. A black carbene disperse dye composition, characterized in that, Includes the black carbene disperse dye and dispersant as described in any one of claims 1 to 3.

5. The black carbene disperse dye composition according to claim 4, characterized in that, The dispersants include dispersant NNO, dispersant MF, and sodium lignosulfonate. The mass ratio of black carbene disperse dye to dispersant is 1:0.5~2.

6. A method for preparing a black carbene disperse dye composition, characterized in that, Includes the following steps: Step 1: As mentioned in the first aspect, the black carbene disperse dye, dispersant, and water are mixed and pre-dispersed to obtain a pre-dispersed mixture. The stirring speed is 800~1200 rpm, and the pre-dispersion time is 8~12 min. Step 2: Pour the pre-dispersed mixture obtained in Step 1 into a sand mill containing zirconium beads for sand milling to obtain a dispersion; the size of the zirconium beads is 0.3~0.4 mm, and the sand milling time is 4~6 h; Step 3: Spray dry the dispersion obtained in Step 2 to obtain a black carbene disperse dye composition; the atomization rate is 15~20 mL / min, the inlet temperature is 150~250 ℃, and the outlet temperature is 120~150 ℃.

7. A method of applying the black carbene disperse dye composition according to claims 4-5, characterized in that, It is used in polyester and polyester-spandex blended fabrics.

8. The method of applying the black carbene disperse dye composition according to claim 7, characterized in that, Includes the following steps: Step 1: Prepare an aqueous solution of 4%~10% owf black carbene disperse dye composition, adjust the pH value to 5, put the fabric to be dyed into the dyeing vat, seal the dyeing vat, heat to the holding temperature, hold for a period of time, and then take out the fabric. Step 2: Rinse the fabric obtained in Step 1 with clean water, air dry, pre-dry, bake, revert to clean, and air dry to obtain the dyed fabric.

9. The method of applying the black carbene disperse dye composition according to claim 7, characterized in that, Includes the following steps: Step 1: Mix the black carbene disperse dye composition, sodium alginate, penetrant and water to obtain a dye mixture solution; Step 2: Using a two-dip and two-paste process, first immerse the fabric in the dye mixture obtained in Step 1, take it out and use a padding machine to remove the excess material, then immerse the fabric in the dye mixture again and remove the excess material again to obtain the padded fabric. Step 3: Pre-dry, bake, reduce and clean the impregnated fabric obtained in Step 2, and air dry to obtain the dyed fabric.

10. The method of applying the black carbene disperse dye composition according to claim 9, characterized in that, The concentration of the black carbene disperse dye composition is 20-100 g / L, the concentration of the sodium alginate is 2-10 g / L, and the concentration of the penetrant is 2-10 g / L.

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