Reactive dyes useful for the fixation of the dry heat setting process, their preparation and dyeing applications

Abstract

The present application belongs to the field of fine chemical industry and textile printing and dyeing, and relates to a reactive dye which can be used for fixing color of dyed polyester fabric by dry heat setting process, a preparation method and dyeing application thereof. The reactive dye provided by the present application has a general structure, and the present application also simultaneously provides the use of the reactive dye, i.e. fixing color of dyed polyester fabric by dry heat setting process. Through ingenious design and application of the carbene type dye, the present application realizes high color fastness effect of dyed polyester fabric, eliminates the adverse factors of high temperature heat setting, and expands the optional range of setting heat setting process (temperature, time).

Description

Technical Field

[0001] This invention belongs to the fields of fine chemicals and textile printing and dyeing, and relates to a reactive dye that can be used to fix the color of dyed polyester fabrics using a dry heat setting process, its preparation method and dyeing application. Background Technology

[0002] Polyester fabrics dyed with conventional disperse dyes suffer from poor heat migration resistance. Reports indicate that when the ambient temperature reaches 140℃ or above, dyed polyester is more prone to migration, leading to defects such as color spots and color differences (Reference: Dyeing and Finishing, 2022(9), 46-48). In the dyeing and finishing process, dyed fabrics usually require heat setting. Heat setting of polyester fabrics is an important step in the production process of polyester fabrics, aiming to improve the stability of the fabric's size, shape, and other physical and chemical properties. Heat setting needs to be carried out under high temperature conditions. For polyester fabrics, 170-210℃ is usually required, with a processing time of 15-90 seconds. The higher the temperature, the shorter the processing time can be (Reference: Dyeing and Finishing Technology, 2011, 33(12), 1-6). Heat setting processing easily leads to dye migration in dyed polyester.

[0003] Currently, in actual production practice, to avoid the problem of heat migration in dyed polyester, the setting temperature is usually actively reduced (e.g., 150℃ or lower), but this will seriously affect the setting effect. From the perspective of dyes, dyes designed and developed by increasing the relative molecular mass of dye molecules or using some chromophores with planar structural features have a significant effect on improving migration resistance (see: Patent 202211331358.3; 201810822874.3). However, the negative effect of these dye structure designs is that they seriously affect the dye uptake of polyester, and the dye uptake rate is generally not high in actual applications (see: Dyes and Pigments, 2019, 166, 130–139; Journal of Zhejiang Sci-Tech University, 2022, 47(3), 283–292), thus limiting the practical application of these dyes.

[0004] Carbene dyes, which have emerged in recent years, refer to dyes containing a carbene precursor structure. This carbene precursor structure can form an active carbene intermediate under high-temperature conditions, which can then chemically react with the carbon-hydrogen bonds in the polyester structure. The emergence of carbene dyes provides the possibility of forming covalent bonds between the dye and polyester fibers. Therefore, polyester fabrics dyed with carbene dyes exhibit excellent migration resistance. Patent ZL202011324055.X proposes a carbene dye based on a diacrylidine structure. The optimized dyeing method for this dye involves dissolving the dye in methanol, adsorbing and dyeing the polyester at 70°C for 1 hour, drying the fabric, and then baking it at 150°C for 50 minutes to fix the color (reference: Dyes and Pigments, 2021, 194, 109555). The resulting dyed polyester fabric exhibits excellent migration resistance. The problems with this method include: 1. Complex synthesis of the bisacrylidine fragment, involving multiple steps, low overall yield, unfriendly reagents, and inconvenient operation; 2. The dyeing solvent is not environmentally friendly, requires long fixing time, and consumes a lot of energy, limiting its practical application. Patents ZL202311229023.5 and ZL202311231061.4 propose a carbene dye based on the α-phenyl diazo ester structure. This dye has better synthetic convenience compared to bisacrylidine dyes. However, the dyeing method and effect on polyester are not good, mainly because: the methanol solvent used in the dyeing process is not environmentally friendly, the fixing time is long and energy consumption is high, and the dye's fixing effect on polyester is poor (more prone to dyeing spandex) (Reference: Dyes and Pigments, 2025, 233, 112517). Summary of the Invention

[0005] The problem to be solved by the present invention is to provide a reactive dye that can be used for color fixing in dry heat setting process, its preparation method and dyeing application.

[0006] To solve the above-mentioned technical problems, the present invention provides a reactive dye with the following general structural formula I:

[0007]

[0008] The chromophore in general structural formula I is any of the following: azobenzene-derived structure, heterocyclic azo derivative, or anthraquinone-derived structure;

[0009] R can be any of the following: methyl (preferably), ethyl, tert-butyl, phenyl, or benzyl.

[0010] As an improvement to the reactive dye of the present invention, the following general structural formula II is provided:

[0011]

[0012] R in structural formula II 1 R 2R 3 All of the following are possible combinations: hydrogen atom, chlorine atom, bromine atom, nitro group, cyano group, methyl group, or methoxy group.

[0013] As a further improvement to the reactive dye of the present invention, it has any of the following structural formulas:

[0014]

[0015] As a further improvement to the reactive dye of the present invention, the following structural formula is provided:

[0016]

[0017] This invention also provides a method for preparing reactive dyes, comprising the following steps:

[0018] Step 1: Add raw material I, monomethyl malonate, 1,3-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and solvent I into a container, stir and react. The reaction solution is then post-treated to obtain the intermediate product.

[0019] The reaction temperature was room temperature (25±5℃); the reaction time was 1±0.1h; the molar ratio of raw material I, monomethyl malonate, 1,3-dicyclohexylcarbodiimide and 4-dimethylaminopyridine was 1∶1.5∶1.5∶0.15;

[0020] Step 2: The intermediate product, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-acetaminobenzenesulfonyl azide, and solvent II were added to a container and stirred to react. The reaction solution was post-treated to obtain the reactive dye. The reaction temperature was room temperature (25±5℃); the reaction time was 0.5±0.1h; the molar ratio of the intermediate product, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 4-acetaminobenzenesulfonyl azide was 1:1.25:1.25.

[0021] Raw material I is compound A or compound B;

[0022] When raw material I is compound A, the intermediate product obtained in step 1 is compound C; step 2 yields the reactive dye described in general formula II.

[0023] When raw material I is compound B, the intermediate product obtained in step 1 is compound D; the reactive dye with structural formula V obtained in step 2;

[0024] The general formula of compound A is:

[0025]

[0026] Among them, R 1 R 2 R 3They are selected from hydrogen atoms, chlorine atoms, bromine atoms, nitro groups, cyano groups, methyl groups, or methoxy groups, respectively;

[0027] The structure of compound B is:

[0028]

[0029] The general formula of compound C is:

[0030]

[0031] Among them, R 1 R 2 R 3 The atoms are selected from hydrogen, chlorine, bromine, nitro, cyano, methyl, or methoxy groups, respectively; the structure of compound D is:

[0032]

[0033] As an improvement to the preparation method of the reactive dye of the present invention:

[0034] The raw material A is

[0035] Compound C is

[0036] The resulting reactive dye is

[0037] As an improvement to the preparation method of the reactive dye of the present invention:

[0038] The raw material A is

[0039] Compound C is

[0040] The resulting reactive dye is

[0041] As a further improvement to the preparation method of the reactive dye of the present invention:

[0042] Solvent I in step 1 is dichloromethane, and 1L of dichloromethane is used for every 0.1 to 0.5 mol of raw material I;

[0043] Solvent II in step 2 is acetonitrile, and 1 L of acetonitrile is used for every 0.1 to 0.5 mol of intermediate product.

[0044] This invention also provides the use of the above-mentioned reactive dyes: fixing the color of dyed polyester fabrics using a dry heat setting process. That is, the dyeing application is for polyester.

[0045] As an improvement to the use of the reactive dye of the present invention, the method for fixing the dyed polyester fabric using a dry heat setting process includes the following steps:

[0046] (1) 2.0g of dye, 2.0g of dispersant NNO and 46g of water were put into a sand mill containing 30mL of zirconium beads and ground at 3000 rpm for 2 hours to obtain dye dispersion.

[0047] (2) Prepare the dyeing solution, adjust the pH value of the dyeing solution to 4-5, put the fabric into the dyeing vat, seal the dyeing vat, heat up to the holding temperature, and carry out dyeing; the holding temperature is 130℃, and the holding time is 1h.

[0048] (3) The polyester fabric obtained in step (2) is pre-dried, then heat-set, the fabric is taken out and cooled naturally to obtain the dyed polyester fabric; the pre-drying temperature is 100℃, and the pre-drying time is until the fabric reaches a constant weight; the heat-setting temperature is 180~200℃, and the heat-setting time is 30~60s.

[0049] This invention solves the problems of long fixation time and high energy consumption in existing methods for dyeing polyester with carbene dyes. Existing methods for using carbene dyes all require an additional high-temperature fixation step, which is time-consuming. Although existing literature does not mention post-treatment steps, including heat setting, after dyeing polyester with these dyes, heat setting of dyed fabrics is a routine and necessary operation in the dyeing and finishing industry. That is, existing carbene dyes inevitably suffer from high energy consumption during application. This invention, on the one hand, requires a shorter fixation time, and on the other hand, combines the fixation and heat setting steps into one, thus saving energy.

[0050] In this invention:

[0051] (1) The carbene dye structure is innovative. By using two ester groups as ortho-substituents in the diazo structure, a novel carbene dye with a high thermal response temperature was designed and developed, which is suitable for the polyester dyeing process proposed in this invention. The dye has excellent stability under high temperature and high pressure dyeing conditions (the diazo group is not destroyed) and rapid reaction capability under conventional heat setting conditions.

[0052] (2) The process for dyeing polyester with carbene dyes is innovative. Existing methods for dyeing polyester with carbene dyes typically require an additional fixation step. This invention first obtains dyed polyester fabric using a conventional high-temperature, high-pressure dyeing method, and then utilizes the heat of a dry heat setting process to initiate a chemical reaction between the dye and the polyester fibers, achieving a one-step fixation and color fixing process. In conventional dyeing and finishing processes, dyeing and finishing are usually performed separately. The finishing process only needs to ensure that the dyeing effect is not reduced. However, even so, processes such as dry heat setting may still cause problems such as dye migration. This invention incorporates dry heat setting into the dyeing process, completing the dye fixation process on the polyester fibers and fabric setting in one step. The amount of dye migration caused by the heat setting process is greatly reduced, and the reaction between the dye and the fiber initiated by this process actually promotes the fastness of the dye on the polyester fibers. In the process of this invention, carbene dyes must be used, and they must be carbene dyes provided by this invention. Conventional disperse dyes or existing reported carbene dyes cannot achieve the same fixation effect as this invention.

[0053] (3) Innovative utilization of heat in the heat setting process. In the heat setting process, high temperature helps to set the fabric, but the side effect of high temperature is that conventional disperse dyes are prone to migration. This invention adopts a reverse thinking approach, using high temperature as an initiating condition for the reaction between dye and fiber, so that high temperature changes from a negative influence on dye migration to a positive influence on the reaction between dye and fiber, thereby reducing the positive impact of dye migration.

[0054] The differences between this invention and the prior art are as follows:

[0055] 1. Patent 202011324055.X discloses reactive dyes. It achieves good color-fixing effect on polyester. The difference between this and the present invention lies in the fact that this type of bisacrylidine dye has a low thermal response temperature, and tends to form carbene when heated above 120°C (reference: Dyes and Pigments, 2021, 194, 109555). Therefore, this patent adds a dyeing accelerator during the dyeing process, keeping the dyeing temperature below 100°C. Furthermore, this patent indicates that this type of dye requires color-fixing at 150-160°C for 2 hours when dyeing polyester fabrics. The above process is completely different from the process provided by the present invention, and the above dyes cannot achieve the same effect in the process of the present invention. Firstly, the present invention does not require the addition of a dyeing accelerator. Secondly, adding a dyeing accelerator in the present invention is not conducive to obtaining the same color-fixing effect as the present invention. Thirdly, even if the bisacrylidine dye of this patent is used in the process of the present invention, the result is that most of the dye has already transformed during the dyeing process and has not reacted well with polyester, resulting in a low color-fixing rate and poor suppression of fabric migration.

[0056] 2. Patent 202011325642.0 discloses reactive dyes. The properties of the dye and the corresponding dyeing method described in this patent are similar to those in the aforementioned patent, and the differences between this patent and the present invention are also as stated above. Further details will not be elaborated here.

[0057] 3. Patent 202311229023.5 discloses reactive dyes. The patent explicitly states that "the dye is relatively difficult to react with polyester," indicating that even if the dye used in this invention is used to replace the dye provided in this invention, the same excellent color-fixing effect cannot be obtained as in this invention.

[0058] 4. Patent 202311231061.4 discloses reactive dyes. Solvent-based dyeing followed by high-temperature fixation achieved good color-fixing on polyester. The differences from this invention are: firstly, the dyeing process is different; secondly, the dye structure is different, and the thermal response temperature of the dye differs significantly from that of the dye in this invention (see: Dyes and Pigments, 2025, 233, 112517); and thirdly, even when the dye of this patent is used in the process of this invention, most of the dye undergoes transformation during the dyeing process and fails to react well with the polyester, resulting in a lower color-fixing rate and inadequate suppression of fabric migration.

[0059] This invention has the following technical advantages:

[0060] Existing methods for dyeing polyester with carbene dyes typically require an additional fixing step, involving high temperatures, long fixing times, and high energy consumption. Furthermore, conventional heat-setting processes cannot be used for fixing. In contrast, this invention combines fixing and heat-setting processes into one, saving operational steps and time, conserving energy, and significantly reducing dyeing and finishing production costs. From another perspective, this invention still employs the commonly used "dyeing-setting" dyeing and finishing process, without substantially increasing or altering existing production processes, yet it achieves high dye (or color) migration resistance on dyed polyester fabrics. The dyed polyester fabrics exhibit excellent resistance to organic solvent extraction, high color fastness, and excellent color fastness to washing, rubbing, and sublimation.

[0061] Another technical advantage of this invention is that it expands the range of selectable heat setting temperatures and times. Conventional heat setting methods necessitate limiting temperature and time due to the tendency of conventional disperse dyes to migrate. This invention, however, utilizes specific carbene dyes; the higher the temperature, the faster the reaction between the dye and the fiber. Once the dye forms covalent bonds with the fiber, it will not migrate regardless of the duration of the heat treatment.

[0062] The aforementioned effects are achieved through the creation of novel carbene dyes. The dye molecule of this invention uses a diazo group as a carbene precursor, which can form a reactive carbene intermediate at high temperatures, subsequently reacting chemically with the CH bonds of polyester to achieve covalent bonding between the dye and polyester fibers. Compared to previously reported diazo dyes, this invention uses ester groups on both sides of the diazo structure. The resulting dye exhibits a higher thermal response temperature. Another characteristic of this dye is its rapid chemical reaction with polyester fibers under heat-setting conditions, making it highly suitable for the short duration of heat setting. Furthermore, the dye is easy to synthesize, uses relatively inexpensive raw materials, is simple to operate, and has a high yield, showing potential for large-scale production.

[0063] In summary, the reactive dye provided by this invention, which can be used to fix the color of dyed polyester fabrics using a dry heat setting process, and its preparation method and dyeing application method have broad application prospects.

[0064] Furthermore, this invention has limitations on the heat setting process conditions; it is only applicable to specific dry heat setting processes. First, because the temperature of wet heat setting processes is generally low, rarely exceeding 140°C, the dyes of this invention cannot effectively react with polyester fibers under these conditions, thus failing to achieve excellent color fixation. Second, conventional heat setting processes often involve the addition of surfactants or softeners, which may either accelerate dye migration before the dye reacts chemically with the fiber or directly react with the dye. Both of these factors can lead to a decrease in the color fixation or migration resistance of the dyed fabric. Therefore, no additional auxiliaries can be applied in the heat setting process of this invention; otherwise, the high color fixation and high migration resistance effects of this invention cannot be achieved.

[0065] In summary, based on existing knowledge in this field, this invention proposes a reactive dye that can be used to fix the color of dyed polyester fabrics using a dry heat setting process. This dye contains a diazo group in its structure, with ester groups attached to both sides of the diazo group. The minimum thermal response temperature (the temperature required for conversion to carbene) of existing carbene dyes is typically between 110 and 130°C. When these dyes are dyed using a high-temperature, high-pressure dyeing method (130°C), they readily form carbene during the dyeing process, resulting in numerous side reactions between the dye and water, auxiliaries, etc., leading to a low fixation rate of the dyed polyester. Firstly, the dye structure design in this invention is intended to significantly increase the minimum thermal response temperature of the carbene dye, far exceeding the dyeing temperature of the high-temperature, high-pressure dyeing method. This ensures the stability of most dyes in the high-temperature, high-pressure dyeing system, meaning that the diazo group in the dye structure will not be destroyed during the dyeing process. Secondly, this invention utilizes the heat of the dry heat setting process to promote the formation of carbene intermediates in the dye, which then react chemically with the polyester. For polyester fabrics dyed with conventional disperse dyes, the heat of the heat setting process is the main cause of dye migration. This invention, through ingenious design, transforms the negative heat of heat setting into an initiating condition for the reaction between dye and fiber, thereby becoming a positive factor in firmly binding the dye to the fiber. The dyes of this invention do not require substantial changes to existing dyeing and finishing processes. This invention achieves high color fastness to dyed polyester fabrics and eliminates the adverse effects of high-temperature heat setting by simply designing and applying carbene dyes, expanding the range of selectable heat setting processes (temperature, time). The dye synthesis steps are short, the overall yield is high, the operation is convenient, and the application effect is good. This invention has broad application prospects. Attached Figure Description

[0066] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0067] Figure 1 The image shows the 1H NMR spectrum of compound VI.

[0068] Figure 2 The image shows the carbon NMR spectrum of compound VI.

[0069] Figure 3 This is the 1H NMR spectrum of dye III;

[0070] Figure 4 This is the carbon NMR spectrum of dye III;

[0071] Figure 5 The UV-Vis absorption spectrum of dye III in N,N-dimethylformamide is shown.

[0072] Figure 6 Thermogravimetric curve of dye III;

[0073] Figure 7 The differential scanning calorimetry (DSC) curve for dye III;

[0074] Figure 8 The K / S curves of the polyester fabric dyed using dye III in this invention are shown. Detailed Implementation

[0075] 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. The heat setting processes involved in this invention are all conventional processes in the dyeing and finishing field. Therefore, it is assumed that the setting effect under these processes meets the corresponding indicators, and the setting results are not within the scope of discussion in this 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 twill, 230g / m². 2 .

[0076] Raw material a was synthesized in-house using the method described in the reference (Dyes and Pigments, 2021, 194, 109555).

[0077] Raw material b was synthesized in-house using the method described in the reference (ACS Sustainable Chemistry & Engineering, 2017, 5(1), 758-766).

[0078] Raw material c was synthesized by itself according to the method described in the reference (ACS Omega, 2022, 7(34), 29858-29867).

[0079] The petroleum ether used for elution has a boiling range of 60–90°C.

[0080] Example 1: Synthetic Dye III

[0081] Step 1:

[0082]

[0083] Add starting material a (5 mmol, 1.73 g), monomethyl malonate (7.5 mmol, 0.88 g), 1,3-dicyclohexylcarbodiimide (7.5 mmol, 1.55 g), 4-dimethylaminopyridine (0.75 mmol, 0.092 g), and dichloromethane (30 mL) to a 100 mL two-necked flask equipped with a magnetic stir bar. Then, stir the mixture at room temperature for 1 h. After the reaction is complete, add 50 mL of deionized water and extract three times (50 mL × 3) with dichloromethane. Combine all organic phases and remove the low-boiling-point solvent—dichloromethane—using a rotary evaporator. Analyze the remaining solid by silica gel column chromatography (100–200 mesh, eluent: V). 石油醚 / V乙酸乙酯 =10 / 3) Purification, the flow rate during elution was 20-30 mL / min, and the eluent containing compounds with a specific gravity (Rf) of 0.3-0.4 was collected. The organic solvents (petroleum ether and ethyl acetate) in the eluent were removed by vacuum evaporation using a rotary evaporator to give compound VI, a red solid, 1.70 g, yield 76%. 1 H NMR (CDCl3, 400MHz) δ8.35 (d, J = 2.4Hz, 1H), 8.12 (dd, J 1 =8.8Hz, J 2 =2.4Hz,1H),7.92(d,J=9.2Hz,2H),7.75(d,J=8.8Hz,1H),6.79(d,J=9.2Hz,2H),4.37(t,J =6.0Hz,2H),3.73~3.70(m,5H),3.53(q,J=7.2Hz,2H),3.40(s,2H),1.25(t,J=7.2Hz,3H). 13 CNMR(CDCl3,100MHz)δ166.69,166.42,153.02,151.63,147.21,144.49,134.06,126.96,126.0 2,122.62,118.04,111.55,62.32,52.67,48.65,45.82,41.21,12.33.ESI-MS: m / z=471.1[M+Na] + The proton NMR spectrum of compound VI is shown below. Figure 1 The carbon NMR spectrum of compound VI is shown below. Figure 2 .

[0084] Step Two:

[0085]

[0086] Compound VI (3 mmol, 1.34 g), acetonitrile (20 mL), 1,8-diazabicyclo[5.4.0]undec-7-ene (3.75 mmol, 0.57 g), and 4-acetaminophensulfonyl azide (3.75 mmol, 0.90 g) were added sequentially to a 100 mL two-necked flask equipped with a magnetic stir bar. The mixture was then stirred at room temperature for 30 min. After the reaction was complete, the reaction solution was poured into 100 mL of deionized water, and a solid precipitated out. The solid was filtered, and the residue was subjected to silica gel column chromatography (100-200 mesh, eluent: V). 石油醚 / V 乙酸乙酯=10 / 4) Purification, the flow rate during elution is 20-30 mL / min, the eluent containing compounds with a specific gravity (Rf) of 0.3-0.4 is collected, the organic solvent (petroleum ether and ethyl acetate) is removed from the eluent by rotary evaporation under reduced pressure, to give dye III, red solid, 1.25 g, yield 88%. 1 H NMR (CDCl3, 400MHz) δ8.36 (d, J = 2.4Hz, 1H), 8.12 (dd, J 1 =8.8Hz,J 2 =2.4Hz,1H),7.92(d,J=9.2Hz,2H),7.75(d,J=8.8Hz,1H),6.81(d,J=9.2Hz,2H),4.46(t,J= 6.0Hz,2H),3.83(s,3H),3.75(t,J=6.0Hz,2H),3.55(q,J=7.2Hz,2H),1.25(t,J=7.2Hz,3H). 13 CNMR(CDCl3,100MHz)δ161.12,161.10,153.05,151.68,147.25,144.55,134.09,126.99,12 6.04,122.64,118.07,111.59,62.35,52.67,48.69,45.71,12.31.ESI-MS: m / z=475.1[M+H] + The proton NMR spectrum of dye III is shown below. Figure 3 The carbon NMR spectrum of dye III is shown below. Figure 4 .

[0087] The UV-Vis absorption spectrum of dye III in N,N-dimethylformamide is shown below. Figure 5 Its maximum absorption wavelength is 494 nm, and its molar extinction coefficient is 33600 L / (mol·cm).

[0088] The thermogravimetric curve of dye III is shown below. Figure 6 DSC curves are shown below. Figure 7 The results showed that dye III exhibited good thermal stability below 150℃. Above 150℃, the dye gradually underwent a transformation, the essential process being the release of nitrogen gas and the formation of a carbene intermediate. (Note: The peak at 144℃ in the DSC curve is the melting peak of the dye as it transforms from a solid to a liquid, and does not involve changes in the dye's structure.)

[0089] Example 2: Synthetic Dye IV

[0090] Step 1

[0091] Replacing raw material a in step one of Example 1 with raw material b, and following the same procedure as in step one of Example 1, compound VII was obtained, an orange solid, 1.94 g, with a yield of 80%. 1 H NMR(CDCl3,400MHz)δ8.24(s,2H),7.90(d,J=8.8Hz,2H),6.80(d,J=8.8Hz,2H),4.37(t,J =6.0Hz,2H),3.74~3.70(m,5H),3.53(q,J=7.2Hz,2H),3.40(s,2H),1.25(t,J=7.2Hz,3H). 13 C NMR(CDCl3,100MHz)δ166.72,166.44,153.97,151.89,145.26,143.57,128.06,126.4 8,124.26,111.41,62.30,52.68,48.66,45.83,41.21,12.28.ESI-MS: m / z=483.1[M+H] + .

[0092] The structural formula of raw material b is as follows:

[0093]

[0094] The structural formula of compound VII is as follows:

[0095]

[0096] Step Two

[0097] By replacing compound VI in step two of Example 1 with compound VII, and following the same procedure as in step two of Example 1, dye IV was synthesized, an orange solid, 1.39 g, with a yield of 91%. 1 H NMR (CDCl3, 400MHz) δ8.20 (s, 2H), 7.87 (d, J = 8.8Hz, 2H), 6.80 (d, J = 8.8Hz, 2H), 4.43 (t, J = 6 .0Hz,2H),3.80(s,3H),3.73(t,J=6.0Hz,2H),3.52(q,J=7.2Hz,2H),1.22(t,J=7.2Hz,3H). 13 C NMR(CDCl3,100MHz)δ161.05,153.88,151.95,145.20,143.57,128.04,126.46,12 4.23,111.43,65.72,62.35,52.63,48.69,45.72,12.27.ESI-MS: m / z=509.1[M+H]+ .

[0098]

[0099] Example 3: Synthetic dye V

[0100] Step 1

[0101] Replacing raw material a in step one of Example 1 with raw material c, and following the same procedure as in step one of Example 1, compound VIII was obtained, 2.03 g, yield 86%. 1 H NMR (CDCl3, 400MHz) δ9.11 (d, J = 2.0Hz, 1H), 8.16 (dd, J 1 =9.6Hz, J 2 =2.0Hz,1H),7.92(d,J=9.2Hz,2H),7.73(d,J=9.6Hz,1H),6.80(d,J=9.2Hz,2H),4.40(t,J=6.0Hz, 2H), 3.75 (t, J = 6.0Hz, 2H), 3.74 (s, 3H), 3.57 (q, J = 7.2Hz, 2H), 3.41 (s, 2H), 1.28 (t, J = 7.2Hz, 3H). 13 C NMR(CDCl3,100MHz)δ180.73,166.67,166.40,162.41,152.49,144.44,143.99,127.54,123.0 5,122.63,119.85,112.07,62.26,52.72,48.76,46.06,41.19,12.42.ESI-MS: m / z=472.1[M+H] + .

[0102] The structural formula of raw material c is as follows:

[0103]

[0104] The structural formula of compound VIII is as follows:

[0105]

[0106] Step Two

[0107] By replacing compound VI in step two of Example 1 with compound VIII, and following the same procedure as in step two of Example 1, dye V was synthesized, yielding 1.38 g with a yield of 92%. 1 H NMR (CDCl3, 400MHz) δ9.20 (d, J = 2.0Hz, 1H), 8.21 (dd, J 1 =9.6Hz, J2 =2.0Hz,1H),7.99(d,J=9.2Hz,2H),7.77(d,J=9.6Hz,1H),6.86(d,J=9.2Hz,2H),4.49(t,J= 6.0Hz,2H),3.85(s,3H),3.80(t,J=6.0Hz,2H),3.60(q,J=7.2Hz,2H),1.28(t,J=7.2Hz,3H). 13 C NMR(CDCl3,100MHz)δ180.79,168.84,162.48,161.16,152.55,144.52,144.09,127.88,127.69 ,123.10,122.70,119.91,112.12,62.31,52.71,48.77,45.94,12.40.ESI-MS: m / z=498.1[M+H] + .

[0108]

[0109] Application Example 1

[0110] Dye III (2.0 g), dispersant NNO (2.0 g), and water (46 g) were ground in a sand mill containing 30 mL of zirconium beads (0.2 mm in diameter) at 3000 rpm for 2 hours to obtain a dye dispersion. 0.5 g of the above dye dispersion was weighed, diluted with water to 100 mL, and the dye solution was obtained. This dye solution was added to a dyeing cup, and acetic acid was added dropwise until the pH of the dye solution reached 5 (tested using pH test paper). 2 g of polyester fabric was added, and the dyeing cup was then sealed and placed in a dyeing machine for dyeing. In this dyeing system, the dye dosage was 1% owf (owf is the dye-to-fabric weight ratio), and the liquor ratio was 1:50. The initial dyeing temperature was set at 30℃, the heating rate at 2℃ / min, the holding temperature at 130℃, and the holding time at 60 min. After dyeing, once the dye cup has cooled to below 60℃, remove the polyester fabric and rinse it with tap water (just enough to remove any auxiliaries that may be adhering to the fabric surface). Pre-dry it in a 100℃ oven until constant weight. Then, place the fabric in a 200℃ setting machine for 30 seconds. Remove the fabric to obtain red-dyed polyester fabric, and test its various properties.

[0111] Staining performance test method:

[0112] (1) Determination of dyeing rate

[0113] The absorbance values ​​of the pre-dye solution diluted by m times and the post-dye solution diluted by n times were measured using a UV-Vis spectrophotometer. The dye uptake rate was calculated according to the formula: Dyeing rate = (Absorbance value of post-dye solution × n) / (Absorbance value of pre-dye solution × m).

[0114] (2) Determination of K / S value

[0115] The surface color depth (K / S) of the dyed fabric was tested using a Datacolor colorimeter.

[0116] (3) Determination of fixation rate

[0117] Immerse the dyed polyester fabric in 100 mL of N,N-dimethylformamide at 120℃ for 30 minutes. Then remove the fabric, rinse it thoroughly with tap water (precise parameters are not required), and air dry it. Test the K / S value of the polyester fabric again. Calculate the color fixation rate of the dyed polyester fabric using the formula: Fixation Rate = (K / S value of dyed fabric after extraction) / (K / S value of dyed fabric before extraction).

[0118] (4) Measurement of migration

[0119] This invention, referencing GB / T 44161-2024 "Determination of Thermal Migration of Disperse Dyes," establishes the following method for determining the migration properties of dyed fabrics. Accurately weigh 0.200 g of dyed fabric that has not yet undergone heat setting and 0.200 g of dyed fabric that has undergone heat setting. Place each in a test tube pre-filled with 10 mL of N,N-dimethylformamide. Shake at 30°C for 5 min to remove the dye that is not firmly bound to the fiber surface. Measure the absorbance of the stripping solution at the maximum absorption wavelength using a spectrophotometer. The difference between the absorbance of the stripping solution from the heat-set fabric and the absorbance of the stripping solution from the unheat-set fabric represents the relative thermal migration of the dye during the heat setting process. The smaller this value, the better the thermal migration resistance.

[0120] (5) Determination of color fastness

[0121] The color fastness to washing, color fastness to rubbing and color fastness to sublimation of dyed polyester fabrics were tested according to standards GB / T 3921-2008, GB / T 3920-2008 and GB / T 6152-1997.

[0122] Application Example 2

[0123] The heat setting time was changed from 30s to 45s, and other steps were the same as described in Application Example 1; a red polyester fabric was obtained.

[0124] Application Example 3

[0125] The heat setting time was changed from 30s to 60s, and other steps were the same as described in Application Example 1; a red polyester fabric was obtained.

[0126] Application Example 4

[0127] The heat setting temperature was changed from 200℃ to 190℃, and other conditions were the same as described in Application Example 1; a red polyester fabric was obtained.

[0128] Application Example 5

[0129] The heat setting temperature was changed from 200℃ to 180℃, and other conditions were the same as described in Application Example 1; a red polyester fabric was obtained.

[0130] Application Example 6

[0131] Replace the amount of dispersion weighed in Application Example 1 from 0.5g to 0.25g, keeping all other steps unchanged, and continue operating as in Application Example 1. That is, the amount of dye relative to the fabric is changed from 1% owf to 0.5% owf; a red polyester fabric is obtained.

[0132] Application Example 7

[0133] Replace the amount of dispersion weighed in Application Example 1 from 0.5g to 0.05g, keeping all other steps unchanged, and continue operating as in Application Example 1. That is, the amount of dye relative to the fabric is changed from 1% owf to 0.1% owf; a light red polyester fabric is obtained.

[0134] Application Example 8

[0135] Replace the amount of dispersion weighed in Application Example 1 from 0.5g to 1.0g, keeping all other steps unchanged, and continue operating as in Application Example 1. That is, the amount of dye relative to the fabric is changed from 1% owf to 2% owf. Red polyester fabric is obtained.

[0136] Application Example 9

[0137] Replace dye III in Application Example 1 with dye IV, otherwise as described in Application Example 1; an orange polyester fabric is obtained.

[0138] Application Example 10

[0139] Replace dye III in Application Example 1 with dye V, otherwise as described in Application Example 1; a blue polyester fabric is obtained.

[0140] Application Example 11

[0141] A 2.0g black mixed dye was prepared by mixing 0.1g of dye III, 0.9g of dye IV, and 1.0g of dye V. Dye III (2.0g) in Application Example 1 was replaced with the aforementioned black mixed dye (2.0g), and the weight of the dispersion in Application Example 1 was changed from 0.5g to 1.0g, otherwise as described in Application Example 1. A black polyester fabric was obtained.

[0142] Table 1. Color depth, fixation rate, and relative migration data of the fabric after setting.

[0143] K / S value Fixation rate / % relative migration Application Example 1 21 95 0.010 Application Example 2 21 96 0.012 Application Example 3 21 96 0.011 Application Example 4 21 93 0.013 Application Example 5 21 91 0.012 Application Example 6 11 97 0.006 Application Example 7 4.1 94 0.010 Application Example 8 28 98 0.003 Application Example 9 23 93 0.015 Application Example 10 24 91 0.016 Application Example 11 26 92 0.019

[0144] Note 1: In the high-temperature, high-pressure dyeing stage of Application Example 1, the dye bath was almost clear, and the dye uptake rate was calculated to be 97%. The color fixation rate of the fabric after dyeing without heat setting was 2.2%, indicating that most of the dye on the fabric did not chemically react with the fiber at this point. The final K / S curve of the polyester fabric dyed with dye III in Application Example 1 after heat setting is shown below. Figure 8 As shown. Note 2: The dye uptake rate of Example 6 was 99%; the dye uptake rate of Example 7 was 99%; the dye uptake rate of Example 8 was 94%; the dye uptake rate of Example 9 was 97%; and the dye uptake rate of Example 10 was 96%.

[0145] Note: Application Examples 2-5 change the setting conditions, while the parameters for dyeing are the same as in Application Example 1.

[0146] Note 3: In Application Example 11, the K / S value is read from the dominant wavelength of the blue dye (590 nm) in the K / S curve.

[0147] The results of Application Example 1 show that the K / S value of the dyed and heat-set fabric is 21, and the color does not change significantly before and after heat setting, indicating that the effect of heat setting on the color of the dyed fabric is negligible. The color fixation rate of the dyed and heat-set fabric is 95%, indicating that heat setting can effectively promote the chemical reaction between the dye and the polyester fiber. The relative heat migration of the dyed and heat-set fabric is 0.01, indicating that the dye provided by the present invention has good migration resistance in the dyeing and finishing process of the present invention.

[0148] The results of Application Examples 2 to 5 show that, under the heat setting temperature and time conditions provided by the present invention, excellent color fixation and migration resistance can be achieved.

[0149] The results of Application Examples 6 to 8 show that the method provided by the present invention can obtain dyed fabrics with different color depths and strong color fastness, and the dyed fabrics have excellent migration resistance at different color depths.

[0150] The results of Application Examples 1, 9 and 10 show that the carbene dyes of different colors provided by the present invention all have excellent dyeing rate, color gain, color fixation and migration resistance in the dyeing and finishing system of the present invention.

[0151] The results of Application Example 11 demonstrate that the dyes of the present invention, when applied after mixing, can also achieve excellent color yield, color fixation, and migration resistance. These results lay the foundation for obtaining various durable colors through mixing and blending using the present invention.

[0152] Table 2 Color fastness data of dyed polyester fabrics after heat setting

[0153]

[0154] As can be seen from Table 2, the dyed polyester fabrics provided by the present invention, after being dyed under high temperature and high pressure conditions and then heat-set, have excellent color fastness to washing, color fastness to rubbing and color fastness to sublimation.

[0155] Comparative Example 1

[0156] Change the heat setting time from 30 seconds to 2 minutes, and keep the rest as described in Application Example 1.

[0157] Comparative Example 2

[0158] Change the heat setting time from 30 seconds to 5 minutes, and keep the rest as described in Application Example 1.

[0159] Comparative Example 3

[0160] The heat setting time was changed from 30s to 15s, and other settings were as described in Application Example 1.

[0161] Comparative Example 4

[0162] The heat setting temperature was changed from 200℃ to 170℃, and other conditions were as described in Application Example 1.

[0163] Comparative Example 5

[0164] The heat setting temperature was changed from 200℃ to 160℃, and other conditions were as described in Application Example 1.

[0165] Comparative Example 6

[0166] The heat setting temperature was changed from 200℃ to 150℃, and other conditions were as described in Application Example 1.

[0167] Comparative Example 7

[0168] The heat setting temperature was changed from 200℃ to 220℃, and other conditions were as described in Application Example 1.

[0169] Comparative Example 8

[0170] Replace dye III in Application Example 1 with compound VI, otherwise as described in Application Example 1.

[0171] Comparative Example 9

[0172] Replace dye III in Application Example 1 with compound VII, otherwise as described in Application Example 1.

[0173] Comparative Example 10

[0174] Replace dye III in Application Example 1 with compound VIII, otherwise as described in Application Example 1.

[0175] Comparative Example 11

[0176] Replace dye III in Application Example 1 with commercial disperse dye CI Disperse Red 13, otherwise as described in Application Example 1. The structure of CI Disperse Red 13 is as follows:

[0177]

[0178] Comparative Example 12

[0179] Replace dye III in Application Example 1 with compound IX, otherwise as described in Application Example 1.

[0180] The structure of compound IX is as follows:

[0181]

[0182] Compound IX is the compound reported in patent 202011324055X or in the literature Dyes and Pigments, 2021, 194, 109555, and was synthesized according to the method reported in the aforementioned patent or literature.

[0183] Comparative Example 13

[0184] Replace dye III in Application Example 1 with compound X, otherwise as described in Application Example 1.

[0185] The structure of compound X is as follows:

[0186]

[0187] Compound X is the compound reported in the literature (Dyes and Pigments, 2025, 233, 112517) or patent 202311229023.5, and was synthesized according to the methods described in the literature or patent.

[0188] Comparative Example 14

[0189] Replace dye III in Application Example 1 with compound XI, otherwise as described in Application Example 1.

[0190]

[0191] Compound XI is the compound reported in the literature (Dyes and Pigments, 2025, 233, 112517) or patent 202311231061.4, and was synthesized according to the methods described in the literature or patent.

[0192] Comparative Example 15

[0193] The phrase "pre-drying to constant weight in an oven at 100°C" in Application Example 1 is removed. That is, after the high-temperature and high-pressure dyeing process is completed, no pre-drying operation is performed, and the heat setting operation is performed directly. Everything else is as described in Application Example 1.

[0194] Comparative Example 16

[0195] Dye III (2.0g), dispersant NNO (2.0g), and water (46g) were ground in a sand mill containing 30mL of zirconium beads (0.2mm in diameter) at 3000 rpm for 2 hours to obtain a dye dispersion. 0.5g of the above dye dispersion was weighed, diluted with water to 100mL, and the dye solution was obtained. This dye solution was added to a dyeing cup, and acetic acid was added dropwise until the pH of the dye solution reached 4-5 (using pH test paper). 2g of polyester fabric was added, and the dyeing cup was then sealed and placed in a dyeing machine for dyeing. In this dyeing system, the dye dosage was 1% owf (owf is the dye-to-fabric weight ratio), and the liquor ratio was 1:50. The initial dyeing temperature was set at 30℃, the heating rate at 2℃ / min, the holding temperature at 130℃, and the holding time at 60min. After dyeing, once the dye cup has cooled to below 60℃, remove the polyester fabric and rinse it with tap water (the purpose is simply to remove any auxiliaries that may adhere to the fabric surface; precise rinsing parameters are not required). Then, perform a two-dip, two-nip process in a 30g / L aqueous solution of commercially available softener W208, followed by pre-drying in a 100℃ oven until constant weight. Next, place the fabric in a 200℃ setting machine for 30 seconds. Remove the fabric to obtain red-dyed polyester fabric, and test its various properties.

[0196] The difference from Application Example 1 is that Comparative Example 16 adds a softener treatment step after staining, otherwise it is the same as described in Application Example 1.

[0197] Comparative Example 17

[0198] In Application Example 1, 0.1 g of dibutyl succinate was added after adjusting the pH of the dye bath to 5 and before placing the polyester fabric in the dyeing process. The dibutyl succinate was used as a dyeing accelerator. That is, compared to Application Example 1, Comparative Example 17 used a dyeing accelerator during the dyeing process.

[0199] Table 3. Color depth, fixation rate, and relative migration data of the fabric after setting.

[0200]

[0201]

[0202] The results of Comparative Examples 1 and 2 show that, based on the process in Example 1, extending the heat setting time still results in excellent color yield, color fixation rate, and migration resistance. Since conventional heat setting processes can meet the requirements in a relatively short time, extending the heat setting time is not conducive to energy conservation. Furthermore, in Comparative Example 2, the fabric treated at 200℃ for 5 minutes exhibited visible color changes, which is detrimental to maintaining fabric color stability.

[0203] The results of Comparative Example 3 indicate that when the heat setting time is insufficient, the fixation rate of the dyed polyester fabric decreases slightly. This may be due to the short high-temperature time, during which the dye has not fully reacted with the fiber. At the same time, the relative migration amount increases slightly.

[0204] The results of Comparative Examples 4 to 6 indicate that the fixation rate of dyed polyester fabrics gradually decreases as the heat setting temperature decreases, which may be due to the reduced dye reactivity caused by the lower temperature. Meanwhile, the relative migration amount increases slightly.

[0205] In Comparative Example 7, the excessively high heat-setting temperature resulted in a noticeable change in the color of the dyed polyester fabric, visible to the naked eye. Comparative Examples 8 to 10 used compounds with structures similar to the dyes provided in this invention, the difference being that these compounds did not contain diazo groups or other reactive groups. Therefore, these compounds were structurally similar to conventional disperse dyes. The results showed that although these compounds could also impart a deep color to polyester, they were non-reactive with polyester fibers, had no color-fixing effect, and exhibited relatively high migration.

[0206] Comparative Example 11 used a commercially available disperse dye. Results showed that the dyed polyester fibers were non-reactive, had no color-fixing effect, and exhibited high relative migration.

[0207] The results of Comparative Example 12 indicate that using the reported dyes with a diacrylidine structure in the dyeing and finishing system of this invention results in lower fixation and higher relative migration. This may be due to the low thermal response temperature of the dyes. Literature (Dyes and Pigments, 2021, 194, 109555) reports that this substance begins to decompose at 120°C, which leads to the decomposition of many dyes under high-temperature and high-pressure dyeing conditions (130°C). Although some dyes react chemically with polyester during the dyeing process, the reaction selectivity is low, resulting in low fixation. A large number of dyes remain unreacted on the polyester fabric, leading to a higher relative migration of the dyes.

[0208] The results of Comparative Example 13 indicate that, using the reported α-phenyldiazo ester type dye, the fixation rate is low and the relative migration is high in the dyeing system of the present invention. This may also be related to the low thermal response temperature of the dye (reference: Dyes and Pigments, 2025, 233, 112517).

[0209] The results of Comparative Example 14 show that, using the reported dye containing two α-phenyl diazo ester structures, the fixation rate is low and the relative migration is high in the dyeing system of this invention. This may also be related to the low thermal response temperature of the dye (reference: Dyes and Pigments, 2025, 233, 112517). It should be noted that although patent 202311231061.4 reports that this compound has a high reactive fixation rate for polyester, the dyeing method used in that patent is a non-aqueous organic solvent dyeing method, which is different from the dyeing method of this invention. This invention uses a high-temperature, high-pressure aqueous phase dyeing system. In this system, dye XI is prone to side reactions with water, auxiliaries, etc., leading to a significant decrease in the reaction rate with the fiber.

[0210] The results of Comparative Example 15 indicate that the absence of pre-drying, leaving residual moisture on the fabric, ultimately leads to a decrease in fixation rate and an increase in relative migration. This is because although the setting temperature is high and the moisture evaporates quickly, a certain amount of moisture remains. This moisture reacts with the dye carbene intermediates formed at high temperatures, leading to an increase in dye side reactions and thus a decrease in fixation rate.

[0211] The results of Comparative Example 16 indicate that the presence of textile auxiliaries such as softeners on dyed polyester fabrics during heat setting leads to a decrease in color fixation and a significant increase in relative migration. This is because some dyes may react with the auxiliaries, resulting in a decrease in color fixation. The auxiliaries also cause the dyes to migrate more rapidly before reacting with the fibers, further increasing the relative migration.

[0212] The results of Comparative Example 17 indicate that the use of a dyeing accelerator in the dyeing system leads to a decrease in the fixation rate and an increase in the relative migration of dyed polyester fabrics. This may be because the dyeing accelerator used may also enter the fiber, and during the setting stage, some dyes react chemically with the accelerator, resulting in a decrease in fixation rate. The increased number of dye molecules that have not reacted with the fiber leads to an increase in the relative migration.

[0213] Comparative Example 18

[0214] Replace dye III in Application Example 1 with compound XII having the following structure, otherwise as described in Application Example 1.

[0215]

[0216] Synthesis of compound XII: In Example 1, step one, methyl malonate (7.5 mmol) was replaced with tert-butyl malonate (7.5 mmol), otherwise as described in Example 1, to obtain compound XII. ESI-MS: 516.1 [M] + .

[0217] Comparative Example 18 yielded a red-dyed polyester fabric with a dye uptake rate of 88%, a K / S value of 16, a fixation rate of 89, and a relative migration of 0.078. Compared to Application Example 1, these indicators were slightly worse. This is mainly because replacing the methyl ester group in dye III with the tert-butyl ester in dye XII slightly increased the dye molecule volume, making it more difficult for the dye to adhere to the fiber, thus slightly decreasing the uptake rate. Furthermore, the increased amount of dye on the fabric surface and the increased number of alkyl groups in the dye molecule may have worsened the reaction between the dye and the fiber, resulting in a relatively lower fixation rate and a slightly higher relative migration.

[0218] Comparative Example 19

[0219] Replace dye III in Application Example 1 with compound XIII having the following structure, otherwise as described in Application Example 1.

[0220]

[0221] Synthesis of compound XIII: In Example 1, step one, methyl malonate (7.5 mmol) was replaced with phenyl malonate (7.5 mmol), otherwise as described in Example 1, to obtain compound XIII. ESI-MS: 536.1 [M] + .

[0222] Comparative Example 19 yielded a red-dyed polyester fabric with a dye uptake rate of 87%, a K / S value of 16, a fixation rate of 88%, and a relative migration of 0.073. Compared to Application Example 1, these indicators are slightly worse. The possible reasons are the same as in Comparative Example 18.

[0223] Variation Example 1

[0224] Dye III (2.0g), dispersant NNO (2.0g), and water (46g) were ground in a sand mill containing 30mL of zirconium beads (0.2mm in diameter) at 3000 rpm for 2 hours to obtain a dye dispersion. 0.5g of the above dye dispersion was weighed, diluted with water to 100mL, and the dye solution was obtained. This dye solution was added to a dyeing cup, and acetic acid was added dropwise until the pH of the dye solution reached 4-5 (using pH test paper). 2g of polyester fabric was added, and the dyeing cup was then sealed and placed in a dyeing machine for dyeing. In this dyeing system, the dye dosage was 1% owf (owf is the dye-to-fabric weight ratio), and the liquor ratio was 1:50. The initial dyeing temperature was set at 30℃, the heating rate at 2℃ / min, the holding temperature at 130℃, and the holding time at 60min. After dyeing, when the dye cup has cooled to below 60℃, the polyester fabric is removed and subjected to reduction cleaning (sodium hydroxide 2g / L; sodium dithionite 2g / L; liquor ratio 1:50; 80℃, 5min). It is then rinsed with tap water (just enough to remove any auxiliaries that may be adhering to the fabric surface) and pre-dried in a 60℃ oven to constant weight. Subsequently, the fabric is placed in a 200℃ setting machine for 30s. The fabric is then removed, yielding red-dyed polyester fabric, and its various properties are tested.

[0225] The difference between Modification 1 and Application 1 lies in the addition of a reduction cleaning process after the high-temperature, high-pressure dyeing process. This additional process removes a small amount of loose dye from the surface of the dyed fabric, thus improving its colorfastness. The results of Modification 1 are as follows: dye uptake rate of 97%, K / S value of the dyed fabric of 20, color fixation rate of 95%, and relative migration of 0.05 (the relative migration is calculated based on the fabric after reduction cleaning). These results demonstrate that adding a reduction cleaning process after dyeing in the dyeing and finishing process provided by this invention can achieve excellent results in dye uptake rate, color yield, color fixation rate, and migration resistance. Compared to Application 1, the additional reduction cleaning process in Modification 1 increases the number of steps, energy consumption, and cost, and does not significantly improve the migration resistance effect sought by this invention.

[0226] Variation Example 2

[0227] 0.01g of dye III was placed in 100mL of decamethylcyclopentasiloxane and heated to 60℃ to dissolve the dye. This dye solution was then added to a dyeing cup, along with 5 drops of deionized water and 2g of polyester fabric. The dyeing cup was then sealed and placed in a dyeing machine for dyeing. In this dyeing system, the dye dosage was 1% owf (owf is the dye-to-fabric weight ratio), and the liquor ratio was 1:50. The initial dyeing temperature was set at 30℃, the heating rate at 2℃ / min, the holding temperature at 130℃, and the holding time at 60min. After dyeing, when the dyeing cup cooled to below 60℃, the polyester fabric was removed and rinsed with tap water (just to remove any auxiliaries that might be adhering to the fabric surface). It was then pre-dried in a 60℃ oven to constant weight. The fabric was then placed in a 200℃ setting machine for 30s. The fabric was then removed, yielding red-dyed polyester fabric, and its various properties were tested.

[0228] The difference between Modification Example 2 and Application Example 1 is that Modification Example 2 uses decamethylcyclopentasiloxane as the dyeing medium in the high-temperature and high-pressure dyeing stage, the pretreatment method is different, and no other auxiliaries are used. That is, Modification Example 2 uses a non-aqueous dyeing process instead of the aqueous dyeing process in Example 1. The results of Modification Example 2 are as follows: dye uptake rate is 90%, the K / S value of the dyed fabric is 18, the fixation rate is 94%, and the relative migration is -0.08. These results indicate that in the dyeing and finishing process provided by this invention, using a non-aqueous solvent as the dyeing medium in the dyeing stage can also achieve excellent dye uptake rate, color yield, fixation rate, and migration resistance. Compared with Application Example 1, some indicators of Modification Example 2 are not as good as Application Example 1. The cost of the non-aqueous medium is higher than that of water, and an additional non-aqueous medium recovery system is required. From the perspective of the migration resistance effect pursued by this invention, there is no significant improvement.

[0229] Finally, it should be noted that the above examples are merely some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments and many variations are possible. All variations that can be directly derived or conceived by those skilled in the art from the disclosure of the present invention should be considered within the scope of protection of the present invention.

Claims

1. A reactive dye, characterized in that... It is any of the following structural formulas: ； ； 。 2. The method for preparing the reactive dye according to claim 1, characterized in that... Includes the following steps: Step 1: Raw material I, monomethyl malonate, 1,3-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and solvent I were added to a container and stirred to react. The reaction solution was then post-treated to obtain an intermediate product. The reaction temperature was room temperature; the reaction time was 1 ± 0.1 h; the molar ratio of raw material I, monomethyl malonate, 1,3-dicyclohexylcarbodiimide and 4-dimethylaminopyridine was 1:1.5:1.5:0.15; Step 2: The intermediate product, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-acetamidobenzenesulfonyl azide and solvent II were added to a container and stirred to react. The reaction solution was then post-treated to obtain the reactive dye. The reaction temperature was room temperature; the reaction time was 0.5 ± 0.1 h; the molar ratio of the intermediate product, 1,8-diazabicyclo[5.4.0]undec-7-ene and 4-acetaminobenzenesulfonyl azide was 1:1.25:1.25; When raw material I is hour, intermediate product is , The resulting reactive dye is ; When raw material I is hour, intermediate product is , The resulting reactive dye is ; When raw material I is hour, intermediate product is , The resulting reactive dye is .

3. The method for preparing the reactive dye according to claim 2, characterized in that: Solvent I in step 1 is dichloromethane, and 1L of dichloromethane is used for every 0.1~0.5mol of raw material I; Solvent II in step 2 is acetonitrile, and 1 L of acetonitrile is used for every 0.1~0.5 mol of intermediate product.

4. The use of the reactive dye as described in claim 1, characterized in that: The dyed polyester fabric is fixed using a dry heat setting process.

5. The use of the reactive dye according to claim 4, characterized in that, The method for fixing the dyed polyester fabric using a dry heat setting process includes the following steps: (1) 2.0 g of reactive dye, 2.0 g of dispersant NNO and 46 g of water were put into a sand mill containing 30 mL of zirconium beads and ground to obtain a dye dispersion. (2) Prepare dye solution using dye dispersion, adjust the pH of dye solution to 4~5, put the fabric in, seal the dye vat, heat to the holding temperature, and carry out dyeing; the holding temperature is 130℃, and the holding time is 1 h. (3) The polyester fabric obtained in step (2) is pre-dried, then dry heat set, the fabric is taken out and cooled naturally to obtain dyed polyester fabric; the pre-drying temperature is 80~100℃, and the pre-drying time is until the fabric is at a constant weight; the dry heat setting temperature is 180~200℃, and the heat setting time is 30~60s.

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