Reactive dye capable of being used for color fixation in dry heat setting process and preparation method and dyeing application thereof

Abstract

The invention belongs to the fields of fine chemical engineering and textile printing and dyeing, and relates to a reactive dye capable of fixing the color of a dyed polyester fabric by using a dry heat setting process, and a preparation method and dyeing application thereof. The structural general formula of the reactive dye provided by the invention is # imgabs0 #. The invention also provides application of the reactive dye, and the reactive dye is used for fixing the color of a dyed polyester fabric by using a dry heat setting process. Through the ingenious design and application of the carbene type dye, the high color fastness effect of the dyed polyester fabric is achieved, the adverse factors of high-temperature heat setting are eliminated, and the optional range of the heat setting process (temperature and time) is expanded.

Description

Technical Field

[0001] The invention belongs to the field of fine chemicals and textile printing and dyeing, and relates to a reactive dye capable of fixing the color of dyed polyester fabric by utilizing a dry heat setting process, and a preparation method and dyeing application thereof. Background Art

[0002] Conventional disperse dye-dyed polyester fabrics have the problem of poor resistance to heat migration. It has been reported that when the ambient temperature reaches 140°C or above, dyed polyester is more likely to migrate, resulting in defects such as color spots and color differences (reference: Printing and Dyeing, 2022 (9), 46-48). During the dyeing and finishing process, the dyed fabrics usually need to be processed by heat setting. Heat setting of polyester fabrics is an important process in the production process of polyester fabrics. The purpose is to improve the stability of the physical and chemical forms of the fabric, such as size and shape. Heat setting needs to be carried out under high temperature conditions. For polyester fabrics, it usually requires 170-210°C and a processing time of 15-90s. The higher the temperature, the shorter the required processing time (reference: Dyeing and Finishing Technology, 2011, 33 (12), 1-6). Heat setting processing can easily lead to dye migration in dyed polyester.

[0003] At present, in actual production practice, in order to avoid the problem of thermal migration of dyed polyester, the setting temperature is usually actively lowered (for example, 150°C 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 characteristics have a more significant effect of improving migration resistance (reference: Patent 202211331358.3; 201810822874.3). However, the negative effect of these dye structure designs is that they seriously affect the dyeability of dyes on polyester. In actual application, the dyeing rate is generally not high (reference: Dyes and Pigments, 2019, 166, 130–139; Journal of Zhejiang Sci-Tech University, 2022, 47(3), 283–292), which limits the practical application of these dyes.

[0004] Carbene dyes that have emerged in recent years refer to dyes containing a carbene precursor structure in their structure. The carbene precursor structure can form an active carbene intermediate under high temperature conditions, which can then react chemically with the carbon-hydrogen bonds in the polyester structure. The emergence of carbene dyes provides the possibility of forming covalent bonds between dyes and polyester fibers. Therefore, polyester fabrics dyed with carbene dyes have excellent migration resistance. Patent ZL202011324055.X proposes a carbene dye based on a diazirine structure. The optimized dyeing method of the dye is to dissolve the dye in methanol, adsorb and dye the polyester at 70°C for 1h, take it out and dry it, and then bake it at 150°C for 50min to fix the color (reference: Dyes and Pigments, 2021, 194, 109555). The resulting dyed polyester fabric has excellent migration resistance. The problems of this method include: 1. The synthesis of diazirine fragments is complex, with many steps, low total yield, unfriendly reagents, and inconvenient operation; 2. The dyeing solvent is not environmentally friendly, the fixation time is long, and the energy consumption is high, and the practical application is limited. Patents ZL202311229023.5 and ZL202311231061.4 propose a carbene dye based on an α-phenyldiazo ester structure. This dye has better synthesis convenience than diazirine dyes. However, the dye has poor dyeing method and effect on polyester, mainly manifested in: the methanol solvent used in the dyeing process is not environmentally friendly, the fixation time is long, the energy consumption is high, and the dye has a poor fixation reaction effect on polyester (easier to dye 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 which can be used for color fixation in a dry heat setting process, and a preparation method and dyeing application thereof.

[0006] In order to solve the above technical problems, the present invention provides a reactive dye having the following structural formula I:

[0007]

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

[0009] R is any of the following: methyl (preferred), ethyl, tert-butyl, phenyl, benzyl.

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

[0011]

[0012] R in the general structural formula II 1 , R 2, R 3 Each of the following is any of: a hydrogen atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a methyl group or a methoxy group.

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

[0014]

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

[0016]

[0017] The present invention also provides a method for preparing a reactive dye, 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 to react, and post-treat the reaction solution to obtain an intermediate product;

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

[0020] Step 2: adding the intermediate product, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-acetylaminobenzenesulfonyl azide and solvent II into a container, stirring for reaction, and post-treating the reaction solution to obtain a reactive dye; the reaction temperature is room temperature (25±5° C.); the reaction time is 0.5±0.1 h; the molar ratio of the intermediate product, 1,8-diazabicyclo[5.4.0]undec-7-ene and 4-acetylaminobenzenesulfonyl azide is 1:1.25:1.25;

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

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

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

[0024] The general formula of compound A is:

[0025]

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

[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 are selected from hydrogen atom, chlorine atom, bromine atom, nitro group, cyano group, methyl group or methoxy group; the structure of compound D is:

[0032]

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

[0034] The raw material A is

[0035] Compound C is

[0036] The reactive dye obtained is

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

[0038] The raw material A is

[0039] Compound C is

[0040] The reactive dye obtained is

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

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

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

[0044] The present invention also provides the use of the reactive dye: using a dry heat setting process to fix the dyed polyester fabric. That is, the dyeing application object is polyester.

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

[0046] (1) 2.0 g of 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 at a speed of 3000 rpm for 2 h to obtain a dye dispersion;

[0047] (2) preparing a dye solution, adjusting the pH value of the dye solution to 4-5, placing the fabric in the dye vat, sealing the dye vat, heating the dye vat to a holding temperature, and dyeing the fabric; the holding temperature is 130° C., and the holding time is 1 hour;

[0048] (3) pre-drying the polyester fabric obtained in step (2), then dry-heat setting, taking out the fabric, and cooling it naturally to obtain a dyed polyester fabric; the pre-drying temperature is 100° C., and the pre-drying time is sufficient to make the fabric have a constant weight; the dry-heat setting temperature is 180-200° C., and the heat setting time is 30-60 seconds.

[0049] The present invention can solve the problems of long fixation time and high energy consumption in existing carbene dye dyeing polyester methods. Existing carbene dye use methods all require an additional high-temperature fixation step, and the fixation time is long. Although the existing literature does not mention the post-processing steps including heat setting after these dyes are dyed polyester, it is a common and necessary operation to heat set the dyed fabric in the dyeing and finishing field. That is, the existing carbene dyes inevitably have the problem of high energy consumption during the application process. On the one hand, the present invention requires a short fixation time, and on the other hand, the fixation step and the heat setting step are combined into one, thereby saving energy consumption.

[0050] In the present invention:

[0051] (1) The structure of the carbene dye is innovative. Two ester groups are used as ortho-substituents at the ortho position of the diazo structure to design and develop a new carbene dye with a higher thermal response temperature, which is suitable for the dyeing process for polyester proposed in the present invention. The dye has excellent stability under high temperature and high pressure dyeing conditions (the diazo group is not destroyed) and has rapid response ability under conventional heat setting conditions.

[0052] (2) The process of dyeing polyester with carbene dyes is innovative. The existing carbene dye application method for dyeing polyester usually requires an additional color fixing step. The present invention first obtains a dyed polyester fabric based on a conventional high temperature and high pressure dyeing method, and then uses the heat of a dry heat setting process to trigger a chemical reaction between the dye and the polyester fiber, thereby achieving one-step completion of color fixing and setting. In conventional dyeing and finishing processes, dyeing and finishing are usually carried out 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. The present invention also incorporates dry heat setting into a part of the dyeing process, and completes the color fixing process of the dye on the polyester fiber and the 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 caused by the process actually promotes the fastness of the dye on the polyester fiber. In the process of the present invention, the dye must use a carbene dye, and must be the carbene dye provided by the present invention. Conventional disperse dyes or existing reported carbene dyes cannot achieve the same color fixing effect as the present invention.

[0053] (3) Innovative use of heat in the heat setting step. 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 very likely to migrate. The present invention adopts reverse thinking and uses high temperature as a triggering condition for the reaction between dye and fiber, so that high temperature changes from a negative impact on dye migration to promoting the reaction between dye and fiber, thereby reducing the positive impact of dye migration.

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

[0055] 1. Patent 202011324055.X discloses reactive dyes And a better color fixation effect is achieved on polyester. The difference between it and the present invention is that the thermal response temperature of this type of diaziridine dye is low, and there is a tendency to form carbene when the temperature rises to above 120°C (reference: Dyes and Pigments, 2021, 194, 109555). Therefore, the patent adds a dyeing accelerator during the dyeing process to make its dyeing temperature less than 100°C. In addition, the patent shows that this type of dye dyeing polyester fabric needs to be fixed at 150-160°C for 2h. The above process is completely different from the process provided by the present invention, and the above dyes cannot obtain the same effect as the present invention when used in the process of the present invention. First of all, the present invention does not require the addition of a dyeing accelerator. Secondly, the addition of a dyeing accelerator is not conducive to obtaining the same color fixation effect as the present invention in the present invention. Thirdly, even if the diaziridine dye of the patent is used in the process of the present invention, the result is that most of the dyes have been transformed during the dyeing process and fail to react well with polyester, resulting in a low color fixation rate and the migration of the dyed fabric cannot be well suppressed.

[0056] 2. Patent 202011325642.0 discloses reactive dyes The performance of the dye and the corresponding dyeing method described in this patent are similar to those described in the aforementioned patent, and the difference between this patent and the present invention is the same as above, which will not be described in detail here.

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

[0058] 4. Patent 202311231061.4 discloses reactive dyes The dyeing is carried out by a solvent method, and then the color is fixed under high temperature conditions, thereby achieving a good color fixing effect on polyester. The difference from the present invention is that firstly, the dyeing process is different, and secondly, the dye structure is different. The thermal response temperature of the dye is quite different from the dye of the present invention (reference: Dyes and Pigments, 2025, 233, 112517). Thirdly, even if the dye of the patent is used in the process of the present invention, the result is that most of the dye has been transformed during the dyeing process and failed to react well with polyester, resulting in a low color fixing rate and the migration of the dyed fabric cannot be well suppressed.

[0059] The present invention has the following technical advantages:

[0060] The existing carbene dye application method for polyester dyeing usually requires an additional color fixing step, with high color fixing temperature, long time, high energy consumption, and also cannot be fixed using conventional heat setting process. In contrast, the present invention combines the color fixing and heat setting processes into one, saving operation steps and operation time, saving energy consumption, and greatly reducing the dyeing and finishing production costs. From another perspective, the present invention still adopts the commonly used "dyeing-setting" dyeing and finishing process, and does not substantially increase or change the existing production process, but achieves the effect of high resistance to migration of dyes (or colors) on dyed polyester fabrics. The dyed polyester fabric has excellent resistance to organic solvent extraction, high color fixing rate, and excellent color fastness such as resistance to soaping, friction and sublimation.

[0061] Another technical advantage of the process of the present invention is that the selection range of heat setting temperature and time is expanded. Conventional heat setting has to limit the temperature and time because the conventional disperse dyes used are easy to migrate. Since the present invention uses a specific carbene type dye, the higher the temperature, the faster the reaction of the dye and the fiber. After the dye forms a covalent bond with the fiber, no matter how long the heat treatment is, the dye will not migrate again.

[0062] The realization of the above-mentioned effect depends on the creation of novel carbene type dye. The dye molecule of the present invention is a carbene precursor with a diazo group, which can form an active carbene intermediate at high temperature, and then chemically react with the polyester CH bond, so as to realize the covalent bond between the dye and the polyester fiber. Compared with the diazo type dye reported, the present invention is designed to use an ester group on both sides of the diazo structure. The obtained dye has a higher thermal response temperature. Another feature of the dye is that it can react chemically with the polyester fiber quickly under the heat setting condition, and the reaction speed is fast, which is very suitable for the short-time characteristics of heat setting. In addition, the dye is easy to synthesize, the raw material is relatively cheap, the operation is simple, and the yield is higher, and it has the potential for large-scale production.

[0063] In summary, the reactive dye provided by the present invention, which can fix the dyed polyester fabric by dry heat setting process, and the preparation method and dyeing application method thereof have broad application prospects.

[0064] In addition, the present invention has restrictions on the heat setting process conditions, and the present invention is only applicable to a specific dry heat setting process. First, since the temperature of the wet heat setting process is generally low, generally rarely exceeding 140°C, under this temperature condition, the dye of the present invention cannot effectively react with the polyester fiber, thereby failing to achieve an excellent color fixation effect. Second, in conventional heat setting processes, some auxiliaries such as surfactants or softeners are often added. The presence of these auxiliaries may: on the one hand, accelerate the migration of the dye before the dye reacts chemically with the fiber, and on the other hand, directly react chemically with the dye. These will all lead to a decrease in the color fixation effect or migration resistance of the dyed fabric. Therefore, additional auxiliaries cannot be applied in the heat setting process of the present invention, otherwise the high color fixation and high migration resistance effects of the present invention cannot be achieved.

[0065] In summary, based on the existing knowledge in the art, the present invention proposes a reactive dye that can be used to fix the dyed polyester fabric using a dry heat setting process. The dye structure contains a diazo group, and both sides of the diazo group are connected to an ester structure. The minimum thermal response temperature of existing carbene-type dyes (the temperature required for heat conversion to carbene) is usually 110-130°C. If these dyes are dyed using a high temperature and high pressure dyeing method (130°C), it is very easy to form carbene during the dyeing process, resulting in more side reactions between the dye and water, auxiliaries, etc., resulting in a low fixation rate of the dyed polyester. First, the dye structure design in the present invention is to greatly increase the minimum thermal response temperature of the carbene-type dye, far exceeding the dyeing temperature of the high temperature and high pressure dyeing method. This ensures the stability of most dyes in the high temperature and high pressure dyeing system, that is, the diazo group in the dye structure will not be destroyed during the dyeing process. Secondly, the present invention uses the heat of the dry heat setting process to promote the dye to form a carbene intermediate, which then reacts chemically with polyester. For polyester fabrics dyed with conventional disperse dyes, the heat of the heat setting process is the main cause of dye migration. The present invention, through ingenious design, converts the heat of heat setting with negative effects into the initiation condition of the reaction between the dye and the fiber, thereby firmly bonding the dye to the fiber as a positive factor. The dye of the present invention does not need to substantially change the existing dyeing and finishing process when applied. The present invention achieves the high color fastness effect of dyed polyester fabrics only through the ingenious design and application of carbene-type dyes, eliminates the unfavorable factors of high-temperature heat setting, and expands the optional range of formulating heat setting processes (temperature, time). The dye synthesis steps are short, the total yield is high, the operation is convenient, and the application effect is good. The present invention will have broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] The specific implementation modes of the present invention are further described in detail below with reference to the accompanying drawings.

[0067] Figure 1 is the H NMR spectrum of compound VI;

[0068] Figure 2 is the carbon NMR spectrum of compound VI;

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

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

[0071] Figure 5 is the UV-visible absorption spectrum of dye III in N,N-dimethylformamide;

[0072] Figure 6 is the thermogravimetric curve of dye III;

[0073] Figure 7 is the differential scanning calorimetry (DSC) curve of dye III;

[0074] Figure 8 This is the K / S curve of the dyed polyester fabric obtained using dye III of the present invention. DETAILED DESCRIPTION

[0075] The present invention is described in detail and specifically through specific examples below to provide a better understanding of the present invention, but the following examples do not limit the scope of the present invention. The heat setting processes involved in the present invention are all conventional processes in the dyeing and finishing field. Therefore, it is assumed that the setting effect under this process meets the corresponding indicators, and the setting results are not within the scope of discussion of the present invention. In the following examples, room temperature refers to a temperature of 25±5°C. Unless otherwise specified, the reagents and materials involved are all commercially available. The specifications of the polyester fabric are twill, 230g / m 2 .

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

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

[0078] Raw material c was synthesized by referring to the literature (ACS Omega, 2022, 7(34), 29858-29867).

[0079] The boiling range of petroleum ether used for elution is 60-90°C.

[0080] Example 1, Synthetic Dye III

[0081] Step 1:

[0082]

[0083] Add raw material a (5mmol, 1.73g), monomethyl malonate (7.5mmol, 0.88g), 1,3-dicyclohexylcarbodiimide (7.5mmol, 1.55g), 4-dimethylaminopyridine (0.75mmol, 0.092g) and dichloromethane (30mL) to a 100mL two-necked flask equipped with a magnetic rod, and then stir the reaction at room temperature for 1h. After the reaction, add 50mL of deionized water and extract with dichloromethane 3 times (50mL×3). Then combine all organic phases, evaporate the low boiling point solvent---dichloromethane by rotary evaporator, and the residual solid is chromatographed by silica gel column (100-200 mesh, eluent: V 石油醚 / V乙酸乙酯 =10 / 3) with an elution flow rate of 20-30 mL / min, and the eluate containing compounds with a specific migration value (Rf) of 0.3-0.4 was collected. The eluate was evaporated under reduced pressure on a rotary evaporator to remove organic solvents (petroleum ether and ethyl acetate) to obtain compound VI as a red solid, 1.70 g, with a yield of 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 H NMR spectrum of compound VI is shown in Figure 1 The C NMR spectrum of compound VI is shown in Figure 2 .

[0084] Step 2:

[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-acetylaminobenzenesulfonyl azide (3.75 mmol, 0.90 g) were added to a 100 mL two-necked flask equipped with a magnetic rod, and then stirred for 30 min at room temperature. After the reaction, the reaction solution was poured into 100 mL of deionized water, and solid precipitation was observed. After suction filtration, the residue was subjected to silica gel column chromatography (100-200 mesh, eluent: V 石油醚 / V 乙酸乙酯=10 / 4) with an elution flow rate of 20-30 mL / min, and the eluate containing compounds with a specific migration value (Rf) of 0.3-0.4 was collected. The eluate was evaporated under reduced pressure on a rotary evaporator to remove organic solvents (petroleum ether and ethyl acetate) to obtain dye III as a red solid, 1.25 g, with a yield of 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 H NMR spectrum of dye III is shown in Figure 3 The carbon NMR spectrum of dye III is shown in Figure 4 .

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

[0088] Thermogravimetric curve of dye III is shown in Figure 6 , DSC curve see Figure 7 The results show that dye III has good thermal stability in a temperature environment below 150°C. When the temperature is higher than 150°C, the dye gradually changes. The essential process is the release of nitrogen and the formation of carbene intermediates. Note: The peak at 144°C in the DSC curve is the melting peak of the dye from solid to liquid, which does not involve changes in the dye structure).

[0089] Example 2, Synthetic Dye IV

[0090] Step 1:

[0091] The raw material a in step 1 of Example 1 was replaced by raw material b, and the rest was referred to step 1 of Example 1 to obtain compound VII as 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] Wherein, the structural formula of raw material b is as follows:

[0093]

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

[0095]

[0096] Step 2:

[0097] The compound VI in step 2 of Example 1 was replaced by compound VII, and the rest was referred to step 2 of Example 1 to synthesize dye IV as 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] The raw material a in step 1 of Example 1 was replaced by raw material c, and the rest was referred to step 1 of Example 1 to obtain compound VIII, 2.03 g, with a yield of 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] Among them, the structural formula of raw material c is as follows:

[0103]

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

[0105]

[0106] Step 2:

[0107] The compound VI in step 2 of Example 1 was replaced by compound VIII, and the rest was made by referring to step 2 of Example 1 to synthesize dye V, 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 (2.0g), dispersant NNO (2.0g) and water (46g) were put into a sand mill equipped with 30mL zirconium beads (diameter 0.2mm) for grinding at a speed of 3000 rpm for 2h to obtain a dye dispersion. Weigh 0.5g of the above dye dispersion, add water, dilute to 100mL, and obtain a dye solution. Add the dye solution to the dye cup, add acetic acid until the pH value of the dye solution reaches 5 (detected using pH test paper), add 2g of polyester fabric, then seal the dye cup, and put it into a coloring machine for dyeing. In this dyeing system, the dye dosage is 1% owf (owf is the ratio of dye to fabric weight), and the bath ratio is 1:50. Set the initial dyeing temperature to 30℃, the heating rate to 2℃ / min, the insulation temperature to 130℃, and the insulation time to 60min. After dyeing, when the temperature of the dye cup drops below 60°C, take out the polyester fabric, rinse it with tap water (just rinse off the additives that may adhere to the surface of the fabric), and pre-dry it in a 100°C oven to constant weight. Then place the fabric in a 200°C setting machine for 30 seconds. Take out the fabric to obtain red dyed polyester fabric, and test the various properties of the fabric.

[0111] Dyeing performance test method:

[0112] (1) Determination of dye uptake

[0113] The absorbance values ​​of the pre-dyeing solution diluted m times and the post-dyeing solution diluted n times were tested by a UV-visible spectrophotometer, and the dye uptake was calculated according to the formula: dye uptake = (absorbance value of post-dyeing solution × n) / (absorbance value of pre-dyeing solution × m).

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

[0115] The Datacolor colorimeter was used to test the surface color depth (K / S) of dyed fabrics.

[0116] (3) Determination of color fixation rate

[0117] Put the dyed polyester fabric into 100mL N,N-dimethylformamide at 120℃ and keep it for 30min. Then take out the polyester fabric, rinse it with tap water (no precise parameters are required), dry it, and test the K / S value of the polyester fabric again. According to the formula of color fixation rate = (K / S value of dyed fabric after extraction) / (K / S value of dyed fabric before extraction), calculate the color fixation rate of dyed polyester fabric.

[0118] (4) Determination of migration

[0119] The present invention makes reference to GB T 44161-2024 "Determination of Thermal Migration of Disperse Dyes" to formulate the following method for determining the migration of dyed fabrics. Accurately weigh 0.200g of a fabric that has not been subjected to setting treatment after dyeing and a fabric that has been subjected to heat setting treatment after dyeing, respectively, and place them in a test tube pre-added with 10mL of N,N-dimethylformamide, and oscillate and strip the dyes that are not firmly bound to the fiber for 5 minutes at 30°C, and strip the dyes from the fiber surface, and use a spectrophotometer to test the absorbance of the stripping solution at the maximum absorption wavelength, and use the difference between the absorbance measured by the stripping solution of the fabric after heat setting and the absorbance of the stripping solution of the fabric that has not been subjected to heat setting to represent the relative thermal migration amount of the dye during the heat setting process. The smaller the value, the better the thermal migration resistance.

[0120] (5) Determination of color fastness

[0121] The color fastness to washing with soap, 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 treatment time was changed from 30 s to 45 s, and the rest was the same as described in Application Example 1; and a red polyester fabric was obtained.

[0124] Application Example 3

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

[0126] Application Example 4

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

[0128] Application Example 5

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

[0130] Application Example 6

[0131] The amount of the dispersion in Application Example 1 was replaced from 0.5 g to 0.25 g, and the other steps remained unchanged, and the operation was still carried out according to Application Example 1. That is, the amount of dye relative to the fabric was changed from 1% owf to 0.5% owf; and a red polyester fabric was obtained.

[0132] Application Example 7

[0133] The amount of the dispersion in Application Example 1 was replaced from 0.5 g to 0.05 g, and the other steps remained unchanged, and the operation was still carried out according to Application Example 1. That is, the amount of dye relative to the fabric was changed from 1% owf to 0.1% owf; and a light red polyester fabric was obtained.

[0134] Application Example 8

[0135] The amount of the dispersion in Application Example 1 was replaced from 0.5 g to 1.0 g, and the other steps remained unchanged, and the operation was still carried out according to Application Example 1. That is, the amount of dye relative to the fabric was changed from 1% owf to 2% owf, and a red polyester fabric was obtained.

[0136] Application Example 9

[0137] The dye III in Application Example 1 was replaced by dye IV, and the rest was the same as described in Application Example 1; an orange polyester fabric was obtained.

[0138] Application Example 10

[0139] The dye III in Application Example 1 was replaced by the dye V, and the rest was the same as described in Application Example 1; a blue polyester fabric was obtained.

[0140] Application Example 11

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

[0142] Table 1 Color depth, color fixation rate and relative migration data of fabrics after shaping

[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 and high pressure dyeing stage in Application Example 1, the dyed liquid is almost clear. The dye uptake is calculated to be 97%. The dyeing fixation rate of the fabric without heat setting treatment is 2.2%, indicating that most of the dye on the fabric has not chemically reacted with the fiber at this time. The final K / S curve of the polyester fabric dyed with dye III in Application Example 1 after heat setting treatment is as follows Figure 8 Note 2: The dye uptake rate of application example 6 is 99%; the dye uptake rate of application example 7 is 99%; the dye uptake rate of application example 8 is 94%; the dye uptake rate of application example 9 is 97%; the dye uptake rate of application example 10 is 96%.

[0145] Note: Application Examples 2 to 5 change the setting conditions, and the dyeing parameters are the same as those in Application Example 1.

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

[0147] The results of Application Example 1 show that the K / S value of the fabric after dyeing and heat setting treatment is 21, and judging by the naked eye, the color light before and after the heat setting treatment does not change significantly, indicating that the effect of the heat setting treatment on the color of the dyed fabric can be ignored; the color fixation rate of the fabric after dyeing and heat setting treatment is 95%, indicating that the heat setting treatment can effectively promote the chemical reaction between the dye and the polyester fiber; the relative thermal migration amount of the fabric after dyeing and heat setting treatment 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 effect and migration resistance effect can be achieved.

[0149] The results of Application Examples 6 to 8 show that the method provided by the present invention can be used to obtain dyed fabrics with different color depths and fast colors, 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 with different colors provided by the present invention have excellent dyeing rate, color yield, color fixation effect and migration resistance in the dyeing and finishing system of the present invention.

[0151] The results of Application Example 11 show that the dyes of the present invention can also achieve excellent coloring effect, color fixation effect and migration resistance after being mixed. The results of this example lay a foundation for the subsequent use of the present invention to obtain various fast colors by mixing and matching colors.

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

[0153]

[0154] It can be seen from Table 2 that the dyed polyester fabric obtained by dyeing with the dye provided by the present invention under high temperature and high pressure conditions and then subjected to heat setting treatment has excellent color fastness to soaping, color fastness to rubbing and color fastness to sublimation.

[0155] Comparative Example 1

[0156] The heat setting treatment time was changed from 30 s to 2 min, and the rest was the same as described in Application Example 1.

[0157] Comparative Example 2

[0158] The heat setting treatment time was changed from 30 s to 5 min, and the rest was the same as described in Application Example 1.

[0159] Comparative Example 3

[0160] The heat setting treatment time was changed from 30 s to 15 s, and the rest was the same as described in Application Example 1.

[0161] Comparative Example 4

[0162] The heat setting treatment temperature was changed from 200°C to 170°C, and the rest was the same as described in Application Example 1.

[0163] Comparative Example 5

[0164] The heat setting treatment temperature was changed from 200°C to 160°C, and the rest was the same as described in Application Example 1.

[0165] Comparative Example 6

[0166] The heat setting treatment temperature was changed from 200°C to 150°C, and the rest was the same as described in Application Example 1.

[0167] Comparative Example 7

[0168] The heat setting treatment temperature was changed from 200°C to 220°C, and the rest was the same as described in Application Example 1.

[0169] Comparative Example 8

[0170] The dye III in Application Example 1 is replaced by compound VI, and the rest is the same as described in Application Example 1.

[0171] Comparative Example 9

[0172] The dye III in Application Example 1 is replaced by compound VII, and the rest is the same as described in Application Example 1.

[0173] Comparative Example 10

[0174] The dye III in Application Example 1 is replaced by compound VIII, and the rest is the same as described in Application Example 1.

[0175] Comparative Example 11

[0176] The dye III in Application Example 1 is replaced by the commercial disperse dye CI Disperse Red 13, and the rest is as described in Application Example 1. The structure of CI Disperse Red 13 is as follows:

[0177]

[0178] Comparative Example 12

[0179] The dye III in Application Example 1 is replaced by compound IX, and the rest is the same 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 document Dyes and Pigments, 2021, 194, 109555, and is synthesized according to the method reported in the above patent or document.

[0183] Comparative Example 13

[0184] The dye III in Application Example 1 is replaced by compound X, and the rest is the same as described in Application Example 1.

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

[0186]

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

[0188] Comparative Example 14

[0189] The dye III in Application Example 1 is replaced by compound XI, and the rest is the same as described in Application Example 1.

[0190]

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

[0192] Comparative Example 15

[0193] The phrase "pre-drying in an oven at 100° C. to constant weight" in Application Example 1 is deleted, that is, after the high-temperature and high-pressure dyeing process is completed, the pre-drying operation is not performed and the heat setting operation is directly performed. The rest is as described in Application Example 1.

[0194] Comparative Example 16

[0195] Dye III (2.0g), dispersant NNO (2.0g) and water (46g) were put into a sand mill equipped with 30mL zirconium beads (diameter 0.2mm) for grinding at a speed of 3000 rpm for 2h to obtain a dye dispersion. Weigh 0.5g of the above dye dispersion, add water, dilute to 100mL, and obtain a dye solution. Add the dye solution to the dye cup, add acetic acid until the pH value of the dye solution reaches 4-5 (detected by pH test paper), add 2g of polyester fabric, then seal the dye cup, and put it into the color machine for dyeing. In this dyeing system, the dye dosage is 1% owf (owf is the ratio of dye to fabric weight), and the bath ratio is 1:50. Set the initial dyeing temperature to 30℃, the heating rate to 2℃ / min, the insulation temperature to 130℃, and the insulation time to 60min. After dyeing, when the temperature of the dye cup drops below 60°C, take out the polyester fabric and rinse it with tap water (the purpose is to rinse off the auxiliaries that may adhere to the surface of the fabric, and no precise rinsing parameters are required). Then, the fabric is double-dipped and double-rolled in a 30g / L aqueous solution of commercial softener W208, and then pre-dried in a 100°C oven to constant weight. Then, the fabric is placed in a 200°C setting machine for 30s. Take out the fabric to obtain a red-dyed polyester fabric, and test the various properties of the fabric.

[0196] The difference from Application Example 1 is that Comparative Example 16 adds a softener treatment step after dyeing, and the rest is as described in Application Example 1.

[0197] Comparative Example 17

[0198] In Application Example 1, 0.1 g of butylene succinate was added after the pH of the dye solution was adjusted to 5 and before the polyester fabric was added. The role of butylene succinate is to be used as a dyeing accelerator. That is, compared with Application Example 1, Comparative Example 17 uses a dyeing accelerator during the dyeing process.

[0199] Table 3. Color depth, color fixation rate and relative migration data of fabrics after shaping

[0200]

[0201]

[0202] The results of Comparative Examples 1 and 2 show that, based on the process of Example 1, the extended heat setting time still has excellent color yield, color fixation rate and migration resistance. Since the conventional heat setting process can meet the requirements in a shorter time, extending the heat setting time is not conducive to saving energy consumption. In addition, the fabric treated at 200°C for 5 minutes in Comparative Example 2 has visible color change, which is not conducive to maintaining the color stability of the fabric.

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

[0204] The results of Comparative Examples 4 to 6 show that as the heat setting temperature decreases, the fixation rate of the dyed polyester fabric gradually decreases, which may be due to the decrease in the reactivity of the dye as the temperature decreases. At the same time, the relative migration amount increases slightly.

[0205] In Comparative Example 7, due to the excessively high heat setting temperature, the color and shade of the dyed polyester fabric are significantly changed under naked eye observation. Comparative Examples 8 to 10 use compounds with structures similar to those of the dyes provided by the present invention, except that these compounds do not contain diazo groups or other reactive groups in their molecules. Therefore, these compounds are similar in structure to conventional disperse dyes. The results show that although these compounds can also give polyester a darker color, they are not reactive with polyester fibers, have no color fixation effect, and have a large relative migration amount.

[0206] Comparative Example 11 uses a commercial disperse dye. The results show that the dyed polyester fiber has no reactivity, no color fixation effect, and a large relative migration amount.

[0207] The results of Comparative Example 12 show that the use of the reported dyes with a diaziridine structure has a low fixation rate and a large relative migration amount in the dyeing and finishing system of the present invention. This may be due to the low thermal response temperature of the dye. The literature (Dyes and Pigments, 2021, 194, 109555) reports that the substance begins to decompose at 120°C, which causes many dyes to decompose under high temperature and high pressure dyeing (130°C). Although some dyes react chemically with polyester during the dyeing process, the reaction selectivity is not high, resulting in a low fixation rate. There are a large number of dyes on polyester fabrics that do not react with fibers, resulting in a large relative migration of dyes.

[0208] The results of Comparative Example 13 show that the reported α-phenyldiazo ester dye has a low fixation rate and a large relative migration amount in the dyeing system of the present invention, which 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 the use of dyes containing two α-phenyldiazo ester structures reported in the dyeing system of the present invention has a low fixation rate and a large relative migration amount. 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 the compound has a higher reaction fixation rate for polyester, the dyeing method used in the patent is a non-aqueous organic solvent dyeing method, which is different from the dyeing method of the present invention. The present invention adopts a high temperature and high pressure aqueous dyeing system, and dye XI is easily reacted with water, auxiliaries, etc. in the system, resulting in a significant decrease in the reaction rate with the fiber.

[0210] The results of Comparative Example 15 show that without pre-drying, the fabric will have residual moisture, which will eventually lead to a certain decrease in the color fixation rate and an increase in the relative migration amount. This is because although the setting temperature is very high, the moisture will evaporate quickly, but a certain amount of moisture will still remain. This moisture will react with the dye carbene intermediate formed at high temperature, resulting in an increase in dye side reactions, thereby reducing the color fixation rate.

[0211] The results of Comparative Example 16 show that when textile auxiliaries such as softeners are present on the dyed polyester fabric during the heat setting process, the dyed fabric fixation rate is reduced and the relative migration amount is greatly increased. This is because some dyes may also react with the auxiliaries, resulting in a decrease in the fixation rate. The auxiliaries can also cause the dye to migrate faster before reacting with the fiber, further increasing the relative migration amount.

[0212] The results of Comparative Example 17 show that the use of dye accelerators in the dyeing system will lead to a decrease in the color fixation rate of the dyed polyester fabric and an increase in the relative migration amount. This may be because the dye accelerator used may also enter the fiber, and during the setting stage, part of the dye reacts chemically with the dye accelerator, resulting in a decrease in the color fixation rate. The number of dye molecules that do not react with the fiber increases, resulting in an increase in the relative migration amount.

[0213] Comparative Example 18

[0214] The dye III in Application Example 1 is replaced by the compound XII having the following structure, and the rest is the same as described in Application Example 1.

[0215]

[0216] Synthesis of Compound XII: Replace monomethyl malonate (7.5 mmol) in step 1 of Example 1 with mono-tert-butyl malonate (7.5 mmol), and the rest is as described in Example 1 to obtain Compound XII. ESI-MS: 516.1 [M] + .

[0217] Comparative Example 18 obtained a red dyed polyester fabric with a dye uptake of 88%, a K / S value of 16, a color fixation rate of 89, and a relative migration amount of 0.078. Compared with Application Example 1, the various indicators are slightly worse. This is mainly because after the methyl ester group in the structure of dye III is replaced by the tert-butyl ester in the structure of dye XII, on the one hand, the volume of the dye molecule increases slightly, and it is relatively difficult for the dye to dye the fiber, resulting in a slight decrease in the dye uptake; on the other hand, the amount of dye on the fabric surface increases, and the number of alkyl groups in the dye molecular structure increases, which may cause the reaction between the dye and the fiber to deteriorate, the color fixation rate is relatively reduced, and the relative migration amount increases slightly.

[0218] Comparative Example 19

[0219] The dye III in Application Example 1 is replaced by a compound XIII having the following structure, and the rest is the same as described in Application Example 1.

[0220]

[0221] Synthesis of Compound XIII: Replace monomethyl malonate (7.5 mmol) in step 1 of Example 1 with monophenyl malonate (7.5 mmol), and proceed as described in Example 1 to obtain Compound XIII. ESI-MS: 536.1 [M] + .

[0222] Comparative Example 19 obtained a red dyed polyester fabric with a dye uptake of 87%, a K / S value of 16, a color fixation rate of 88, and a relative migration amount of 0.073. Compared with Application Example 1, each index is slightly worse. The possible reason is the same as that of Comparative Example 18.

[0223] Modification 1

[0224] Dye III (2.0g), dispersant NNO (2.0g) and water (46g) were put into a sand mill equipped with 30mL zirconium beads (diameter 0.2mm) for grinding at a speed of 3000 rpm for 2h to obtain a dye dispersion. Weigh 0.5g of the above dye dispersion, add water, dilute to 100mL, and obtain a dye solution. Add the dye solution to the dye cup, add acetic acid until the pH value of the dye solution reaches 4-5 (detected by pH test paper), add 2g of polyester fabric, then seal the dye cup, and put it into the color machine for dyeing. In this dyeing system, the dye dosage is 1% owf (owf is the ratio of dye to fabric weight), and the bath ratio is 1:50. Set the initial dyeing temperature to 30℃, the heating rate to 2℃ / min, the insulation temperature to 130℃, and the insulation time to 60min. After dyeing, when the temperature of the dye cup drops below 60°C, take out the polyester fabric, perform reduction cleaning (sodium hydroxide 2g / L; sodium dithionite 2g / L; bath ratio 1:50; 80°C, 5min), then rinse with tap water (rinse off the auxiliaries that may adhere to the surface of the fabric), and pre-dry in a 60°C oven to constant weight. Then place the fabric in a 200°C setting machine for 30s. Take out the fabric to obtain red dyed polyester fabric, and test the various properties of the fabric.

[0225] The difference between the above-mentioned variant example 1 and application example 1 is that after the high temperature and high pressure dyeing process is completed, a reduction cleaning process is added in variant example 1, the purpose of which is to clean off a small amount of floating color on the surface of the dyed fabric, which is beneficial to increase the color fastness grade of the dyed fabric. The results of variant example 1 are as follows: the dye uptake rate is 97%, the K / S value of the dyed fabric is 20, the color fixation rate is 95%, and the relative migration amount is 0.05 (the calculation of the relative migration amount is based on the fabric after reduction cleaning). The above results show that in the dyeing and finishing process provided by the present invention, adding a reduction cleaning process after dyeing can also achieve excellent dye uptake rate, color yield, color fixation rate and migration resistance. Compared with application example 1, the additional reduction cleaning process in variant example 1 relatively increases the steps, energy consumption and cost, and from the perspective of the migration resistance effect pursued by the present invention, there is no significant improvement.

[0226] Modification 2

[0227] Take 0.01g dye III and place it in 100mL decamethylcyclopentasiloxane, heat it to 60℃ to dissolve the dye, add the dye solution to the dye cup, add 5 drops of deionized water, add 2g polyester fabric, then seal the dye cup and put it in the color machine for dyeing. In this dyeing system, the amount of dye is 1% owf (owf is the ratio of dye to fabric weight), and the bath ratio is 1:50. Set the initial dyeing temperature to 30℃, the heating rate to 2℃ / min, the insulation temperature to 130℃, and the insulation time to 60min. After dyeing, when the dye cup is cooled to below 60℃, take out the polyester fabric, rinse it with tap water (rinse the auxiliaries that may adhere to the surface of the fabric), and pre-dry it in a 60℃ oven to constant weight. Then place the fabric in a 200℃ setting machine for 30s. Take out the fabric to obtain red dyed polyester fabric, and test the various properties of the fabric.

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

[0229] Finally, it should be noted that the above examples are only some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and there are many variations. All variations that can be directly derived or associated with the content disclosed by a person skilled in the art should be considered as the protection scope of the present invention.

Claims

1. A reactive dye, characterized in that It is the following structural formula I: The chromophore in the general structural formula I is any of the following: an azobenzene-derived structure, a heterocyclic azo derivative, or an anthraquinone-derived structure; R is any of the following: methyl, ethyl, tert-butyl, phenyl, benzyl.

2. The reactive dye according to claim 1, characterized in that The following structural formula II: R in the general structural formula II 1 , R 2 , R 3 Each of the following is any of: a hydrogen atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a methyl group or a methoxy group.

3. The reactive dye according to claim 2, characterized in that Any of the following structural formulas:

4. The reactive dye according to claim 1, characterized in that The following structural formula:

5. The method for preparing a reactive dye according to claims 1 to 4, characterized in that The steps include: Step 1: Adding raw material I, monomethyl malonate, 1,3-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and solvent I into a container, stirring for reaction, and post-treating the reaction solution to obtain an intermediate product; The reaction temperature is room temperature; the reaction time is 1±0.1h; the molar ratio of the raw material I, monomethyl malonate, 1,3-dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 1:1.5:1.5:0.15; Step 2: The intermediate product, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-acetylaminobenzenesulfonyl azide and solvent II are added into a container, stirred for reaction, and the reaction solution is post-treated to obtain a reactive dye; The reaction temperature is room temperature; the reaction time is 0.5±0.1h; the molar ratio of the intermediate product, 1,8-diazabicyclo[5.4.0]undec-7-ene and 4-acetamidobenzenesulfonyl azide is 1:1.25:1.25; Raw material I is compound A or compound B; When the raw material I is compound A, the intermediate product obtained in step 1 is compound C; and step 2 obtains a reactive dye described in the general structural formula II; When the raw material I is compound B, the intermediate product obtained in step 1 is compound D; the reactive dye described in structural formula V obtained in step 2; The general formula of compound A is: Among them, R 1 , R 2 , R 3 are selected from hydrogen, chlorine, bromine, nitro, cyano, methyl or methoxy groups; The structure of compound B is: The general formula of compound C is: Among them, R 1 , R 2 , R 3 are selected from hydrogen atom, chlorine atom, bromine atom, nitro group, cyano group, methyl group or methoxy group; the structure of compound D is:

6. The method for preparing a reactive dye according to claim 5, characterized in that: The raw material A is Compound C is The reactive dye obtained is 7. The method for preparing a reactive dye according to claim 5, characterized in that: The raw material A is Compound C is The reactive dye obtained is 8. The method for preparing a reactive dye according to any one of claims 5 to 7, characterized in that: The solvent I in step 1 is dichloromethane, and 1 L of dichloromethane is used for every 0.1-0.5 mol of raw material I; The solvent II in step 2 is acetonitrile, and 1 L of acetonitrile is used for every 0.1 to 0.5 mol of the intermediate product.

9. The use of the reactive dye according to claims 1 to 4, characterized in that: The dyed polyester fabric is fixed by dry heat setting process.

10. The use of the reactive dye according to claim 9, characterized in that: The method for fixing the dyed polyester fabric by using a dry heat setting process comprises the following steps: (1) 2.0 g of 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) preparing a dye liquor using a dye dispersion, adjusting the pH value of the dye liquor to 4-5, placing the fabric in the dye vat, sealing the dye vat, heating the dye vat to a holding temperature, and dyeing the fabric; the holding temperature is 130° C., and the holding time is 1 hour; (3) pre-drying the polyester fabric obtained in step (2), then dry-heat setting, taking out the fabric, and cooling it naturally to obtain a dyed polyester fabric; the pre-drying temperature is 80 to 100° C., and the pre-drying time is sufficient to make the fabric have a constant weight; the dry-heat setting temperature is 180 to 200° C., and the heat setting time is 30 to 60 seconds.

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