Pyrimidine acid blue reactive dye as well as preparation method and application thereof

Abstract

The invention relates to the technical field of dyes, and particularly discloses a pyrimidinyl acid ornamental blue reactive dye as well as a preparation method and application thereof. According to the invention, trichloropyrimidine is introduced into the ornamental blue structure as an active group, and the reactivity of the trichloropyrimidine is lower than that of an active group of a cyanuric chloride structure, so that the pyrimidine acid ornamental blue reactive dye is more stable and not easy to hydrolyze after being combined with cellulosic fibers, the acid-resistant and alkali-resistant stability of a dye-fiber covalent bond is better, and the dyeing performance is more excellent; in addition, water-soluble groups such as a sulfonic acid group and a carboxyl group are introduced, so that the water solubility of the pyrimidinic acid blue reactive dye is improved. Moreover, the pyrimidinyl acid ornamental blue reactive dye prepared by the invention has a good dyeing effect on chemical fibers such as acrylic fibers, spandex and the like and blend fiber fabrics thereof, the adaptability of ornamental blue is further improved, the dye is stable in dyeing, deep in coloring and good in color fixing effect, meanwhile, the acid and alkali resistance of the fabrics is improved, and the pyrimidinyl acid ornamental blue reactive dye has a wide application prospect.

Description

Technical Field

[0001] The present application relates to the technical field of dyes, and in particular to a pyrimidine acid indigoidine-based reactive dye, a preparation method thereof, and an application thereof. Background Art

[0002] Indigoidine is a bacterial natural product with antioxidant and antibacterial activities. It has stable properties and is environmentally friendly, and is a dark blue natural pigment with broad application prospects. Indigoidine is a water-insoluble blue pigment with poor solubility in solvents, and has only a small solubility in DMF and DMSO. Therefore, it is necessary to modify its structure to improve the solubility of the dye and make it into a dye variety with practical value.

[0003] Reactive dyes, also known as reactive dyes, contain reactive groups that can react with hydroxyl groups in cellulose and amino groups in protein fibers. When dyeing, covalent bonds are formed with the fibers to form "dye-fiber" compounds. Reactive dyes have the characteristics of bright colors, good level dyeing property, simple dyeing method, complete chromatogram, and low cost.

[0004] In view of the dyeing disadvantages of indigoidine dyes, a variety of indigoidine reactive dyes have been reported and synthesized. The invention with the application number 2018106072177 prepares a reactive dye by reacting indigoidine dye with the condensate of cyanuric chloride and aminobenzenesulfonic acid, and the prepared reactive dye can achieve efficient dyeing of cotton fiber fabrics in an aqueous system. The reactive dye disclosed in the invention with the application number 2018105729317 is mainly applied to the dyeing of polyester fibers, and it is difficult to dye other fabrics to dark colors. In addition, the sublimation fastness of the dyed fabrics is also relatively low. Although the reactive dye disclosed in the invention with the application number 201911369938 improves the affinity between the dye and hydrophobic polyamide fibers and increases the fixation rate and dyeing depth of the dye on polyamide fibers, this type of dye uses cyanuric chloride as the reactive group and has the disadvantages of poor hydrolysis stability of the "dye-fiber" covalent bond and poor acid and alkali resistance, and the dyeing rate and fixation rate on acrylic fibers, spandex and their blended fabrics are relatively low. Summary of the Invention

[0005] The purpose of the present application is to overcome the deficiencies of the above-mentioned prior art and provide a pyrimidine acid indigoidine-based reactive dye, a preparation method thereof, and an application thereof. The pyrimidine acid indigoidine-based reactive dye of the present application is not easily hydrolyzed, has a deep color, stronger acid and alkali stability of the dyed fabric, and can achieve efficient dyeing of a variety of chemical fibers and their blended fiber fabrics in an aqueous system, with high dyeing rate and fixation rate. The preparation process is simple and highly operable.

[0006] To achieve the above purpose, the technical solution adopted by the present application is as follows:

[0007] The present application provides a pyrimidine acid phthalocyanine-based reactive dye, and the structural general formula of the pyrimidine acid phthalocyanine-based reactive dye is shown in formula (I).

[0008]

[0009] Among them, R1 includes one of -NH-SO3M, -NH-Ar-SO3M, -NH-Ar-COOM;

[0010] M includes one of H, Na, K or Li;

[0011] R2 includes

[0012]

[0013] As a preferred embodiment of the pyrimidine acid phthalocyanine-based reactive dye of the present application, the structural general formula of the pyrimidine acid phthalocyanine-based reactive dye is shown in formula (II) or formula (III);

[0014]

[0015] Among them, R1 includes one of -NH-SO3M, -NH-Ar-SO3M, -NH-Ar-COOM;

[0016] M includes one of H, Na, K or Li.

[0017] As a preferred embodiment of the pyrimidine acid phthalocyanine-based reactive dye of the present application, R1 is selected from one of -NH-SO3M, -NH-Ar-SO3M, -NH-Ar-COOM;

[0018] M is one of H, Na, K or Li.

[0019] By adopting the above technical solution, the present application uses trichloropyrimidine as the reactive group. After the synthesized pyrimidine acid phthalocyanine-based reactive dye binds to the fiber, the electron cloud density on the carbon atom increases, obtaining good C-O bond stability, more excellent dyeing performance, and effectively improving the fixation rate and color fastness.

[0020] As a preferred embodiment of the pyrimidine acid phthalocyanine-based reactive dye of the present application, the pyrimidine acid phthalocyanine-based reactive dye is any one of the following structures:

[0021]

[0022]

[0023] The present application adopts the pyrimidine acid phthalocyanine-based reactive dye with the above structural formula, and the dyeing effect is more excellent.

[0024] The present application also provides a preparation method of the pyrimidine acid indigo-like reactive dye, comprising the following steps:

[0025] S1. Mix indigo, trichloropyrimidine and ethanol, then add an acid-binding agent, and then carry out a condensation reaction, and purify to obtain intermediate 1 or intermediate 2;

[0026] S2. Add an amino coupling agent to intermediate 1 or intermediate 2, then add an acid-binding agent to react to obtain a reaction solution;

[0027] S3. Purify the reaction solution, collect the solid and dry it to obtain the pyrimidine acid indigo-like reactive dye.

[0028] As a preferred embodiment of the preparation method of the pyrimidine acid indigo-like reactive dye of the present application, the structures of intermediate 1 or intermediate 2 are as follows:

[0029] Intermediate 1 is N-dichloropyrimidine indigo;

[0030] Intermediate 2 is N,N'-bis-dichloropyrimidine indigo;

[0031]

[0032] As a preferred embodiment of the preparation method of the pyrimidine acid indigo-like reactive dye of the present application, in step S1, when synthesizing intermediate 1, the reaction temperature is 5-15 °C, the reaction time is 3-5 h, and the molar ratio of indigo:trichloropyrimidine:acid-binding agent is 1:(1.0-1.2):(1.0-1.2).

[0033] Under the above low-temperature conditions for synthesizing intermediate 1, the reactivity of indigo and trichloropyrimidine decreases, and indigo only reacts with one molecule of trichloropyrimidine in the reaction system to form a pyrimidine indigo structure with a unilateral structure, which can effectively reduce the generation of intermediate 2.

[0034] As a preferred embodiment of the preparation method of the pyrimidine acid indigo-like reactive dye of the present application, in step S1, when synthesizing intermediate 2, the reaction temperature is 25-40 °C, the reaction time is 3-5 h, and the molar ratio of indigo:trichloropyrimidine:acid-binding agent is 1:(2.0-2.2):(2.0-2.2).

[0035] When the reaction temperature for synthesizing intermediate 2 increases, and at the same time the molar ratios of trichloropyrimidine and the acid-binding agent to indigo also increase, it promotes the reaction of indigo with two molecules of trichloropyrimidine to form indigo with a bilateral pyrimidine structure.

[0036] As a preferred embodiment of the preparation method of the pyrimidine acid phthalocyanine blue active dye described in the present application, the purification includes: filtering the reaction solution obtained by the condensation reaction to obtain a solid precipitate, washing the precipitate with 3 to 5 times the mass of pure water, and then washing with 3 to 5 times the mass of ethyl acetate, and drying at room temperature to obtain an intermediate 1 or an intermediate 2.

[0037] As a preferred embodiment of the preparation method of the pyrimidine acid phthalocyanine blue active dye described in the present application, in step S2, the reaction temperature is 50 to 60 °C, the reaction time is 4 to 6 h, and the molar ratio of the intermediate 1: amino coupling agent: acid-binding agent is 1: (1.0 to 1.2): (1.0 to 1.2).

[0038] The phthalocyanine blue with a single-sided pyrimidine structure is more likely to react with the amino coupling agent, and the reaction can be promoted under the condition of 50 to 60 °C.

[0039] As a preferred embodiment of the preparation method of the pyrimidine acid phthalocyanine blue active dye described in the present application, in step S2, the reaction temperature is 80 to 100 °C, the reaction time is 4 to 6 h, and the intermediate 2: amino

[0040] coupling agent: acid-binding agent molar ratio is 1: (2.0 to 2.2): (2.0 to 2.2).

[0041] Since there are two pyrimidine structures on the intermediate 2, the reactivity is low. In the present application, a higher temperature (80 to 100 °C) is required to promote the reaction, effectively promoting the production of the product.

[0042] As a preferred embodiment of the preparation method of the pyrimidine acid phthalocyanine blue active dye described in the present application, the acid-binding agent includes sodium bicarbonate.

[0043] As a preferred embodiment of the preparation method of the pyrimidine acid phthalocyanine blue active dye described in the present application, the acid-binding agent includes sodium bicarbonate, and the amino coupling agent includes at least one of sodium aminosulfonate, sodium p-aminobenzenesulfonate, and sodium p-aminobenzoate.

[0044] The preparation method of the pyrimidine acid phthalocyanine blue active dye of the present application is simple to operate, can be industrially produced, and the prepared pyrimidine acid phthalocyanine blue active dye has excellent comprehensive performance.

[0045] The present application also provides the application of the above pyrimidine acid phthalocyanine blue active dye in dyeing.

[0046] As a preferred embodiment of the application described in the present application, the application is the application of the pyrimidine acid phthalocyanine blue active dye in dyeing chemical fibers and blended fibers.

[0047] Preferably, the chemical fiber includes acrylic fiber or / and spandex.

[0048] The pyrimidine acid guanlan - type reactive dyes of the present application have good dyeing and fixation effects on acrylic fibers, spandex fibers and their blended fiber fabrics, and the dyed fabrics have better acid and alkali resistance.

[0049] As a preferred embodiment of the application described in the present application, the mass concentration of the pyrimidine acid guanlan - type reactive dye during application is 0.5 - 10% (o.w.f).

[0050] The pyrimidine acid guanlan - type reactive dyes prepared in the present application can combine well with chemical fibers and their blended fiber textiles, and can effectively improve the fixation rate and color fastness.

[0051] Compared with the prior art, the present application has the following beneficial effects:

[0052] The present application provides a pyrimidine acid guanlan - type reactive dye, its preparation method and application. In the present application, trichloropyrimidine is introduced as an active group into the guanlan structure. The reactivity of the active group with trichloropyrimidine structure is lower than that of cyanuric chloride structure, making the pyrimidine acid guanlan - type reactive dye more stable after binding with cellulose fibers, not easy to hydrolyze, and the acid and alkali stability of the "dye - fiber" covalent bond is better, and the dyeing performance is more excellent; in addition, water - soluble groups such as sulfonic acid groups and carboxyl groups are introduced to improve the water solubility of the pyrimidine acid guanlan - type reactive dye. And, the preparation method of the pyrimidine acid guanlan - type reactive dye in the present application is simple in operation, can be industrially produced, and the prepared pyrimidine acid guanlan - type reactive dye has excellent comprehensive performance; the pyrimidine acid guanlan - type reactive dye prepared in the present application has good dyeing effects on chemical fibers such as acrylic fibers and spandex fibers and their blended fiber fabrics, further improving the adaptability of guanlan. The dyeing of this dye is stable, the color is deep, the fixation effect is good, at the same time, the acid and alkali resistance of the fabric is improved, the applicability of the guanlan dye is increased, and it has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 1H NMR spectrum of the pyrimidine acid guanlan - type reactive dye I - 1 in Example 3;

[0054] Figure 2 1H NMR spectrum of the pyrimidine acid guanlan - type reactive dye I - 2 in Example 4;

[0055] Figure 3 1H NMR spectrum of the pyrimidine acid guanlan - type reactive dye I - 3 in Example 5;

[0056] Figure 4 1H NMR spectrum of the pyrimidine acid guanlan - type reactive dye II - 1 in Example 6;

[0057] Figure 5 1H NMR spectrum of the pyrimidine acid guanlan - type reactive dye II - 2 in Example 7;

[0058] Figure 6 1H NMR spectrum of pyrimidine acid indigo-like reactive dye II-3 in Example 8;

[0059] Figure 7 Dyeing result chart of the experimental example. Detailed implementation manners

[0060] To better illustrate the objectives, technical solutions and advantages of this application, the following will further illustrate this application in combination with the accompanying drawings and specific embodiments.

[0061] In the following examples and comparative examples, unless otherwise specified, the experimental methods used are all conventional methods, and the materials, reagents, etc. used, unless otherwise specified, can all be obtained from commercial channels.

[0062] The indigo used in the examples was provided by Nanjing Hegu Life Biotechnology Co., Ltd., and other reagent consumables were obtained through market procurement.

[0063] The 1H NMR test of the synthesized pyrimidine acid indigo-like reactive dye was detected using a nuclear magnetic resonance spectrometer Avance II (400 MHz) and AVANCEⅢ (500); the mass spectrometry test was detected using a matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF.

[0064] Example 1, Preparation method of intermediate 1

[0065] This example provides a preparation method of intermediate 1, which is prepared according to the following steps:

[0066] 1), Grind the indigo dye through a 100-mesh sieve, take 0.01 mol and put it into a three-necked flask equipped with a stirrer and a thermometer, add 100 mL of ethanol, and stir at room temperature to form a dye suspension for later use;

[0067] 2), Dissolve 0.011 mol of trichloropyrimidine in 50 mL of ethanol and add it to the above dye dispersion, then add 0.011 mol of sodium bicarbonate, and react at 5 °C for 4 h; after the reaction, a mixed solution containing a large amount of intermediate 1 and a small amount of intermediate 2 is obtained.

[0068] 3), Wash the above reaction mixed solution twice with 3 times the mass of pure water and twice with 3 times the mass of ethyl acetate, and dry to obtain the solid of intermediate 1 (N-dichloropyrimidine indigo), and the small amount of intermediate 2 can be ignored.

[0069] The structural formula of intermediate 1 is as follows:

[0070]

[0071] ESI-MS m / z: 394.16 [M-H] - 。

[0072] The synthetic route of step 2) is as follows:

[0073]

[0074] Example 2, Preparation method of intermediate 2

[0075] This example provides a preparation method of intermediate 2, which is prepared according to the following steps:

[0076] 1), Grind the phthalocyanine blue dye through a 100-mesh sieve, take 0.01 mol and put it into a three-necked flask equipped with a stirrer and a thermometer, add 100 mL of ethanol, and stir at room temperature to form a dye suspension for later use;

[0077] 2), Dissolve 0.022 mol of trichloropyrimidine (double the amount added in Example 1) and 50 mL of ethanol and add them to the above dye dispersion, then add 0.022 mol of sodium bicarbonate, and react at 15 °C for 5 h (raising the temperature for the reaction can promote the combination of two molecules of trichloropyrimidine and one molecule of phthalocyanine blue); after the reaction, a mixed solution containing a large amount of intermediate 2 and a trace amount of intermediate 1 is obtained.

[0078] 3), Wash the above reaction mixture twice with 3 times the mass of pure water and twice with 3 times the mass of ethyl acetate, and dry to obtain the solid of intermediate 2 (N,N'-bis-dichloropyrimidine phthalocyanine blue).

[0079] The structural formula of intermediate 2 is as follows:

[0080]

[0081] ESI-MS m / z: 541.11 [M-H] - 。

[0082] The synthetic route of step 2) is as follows:

[0083]

[0084] Example 3, Preparation method and structure identification of a pyrimidine acid phthalocyanine blue type reactive dye I-1

[0085] This example provides a preparation method of a pyrimidine acid phthalocyanine blue type reactive dye I-1, which is prepared according to the following steps:

[0086] 1), Take 0.02 mol of the solid powder of intermediate 1 prepared above, add 0.02 mol of sodium sulfamate and sodium bicarbonate, and stir and react at 60 °C for 4 h;

[0087] 2), After the reaction, ethanol was removed by rotary evaporation at 50 °C, and after drying at room temperature, a pyrimidine acid phthalocyanine-based reactive dye having the following structure was obtained.

[0088] The synthesis route of step 1) is as follows:

[0089]

[0091] The structural formula of the pyrimidine acid phthalocyanine-based reactive dye I-1 is as follows:

[0092]

[0093] As 1 shown in the 1H-NMR spectrum (as Figure 1 ), 1 1H NMR (400 MHz, DMSO-d6): δ 9.93 (s, 1H), 9.77 (s, 1H), 9.75 (s, 1H), 7.77 (d, 1H), 7.67 (d, 1H), 7.08 (s, 1H), 5.46 (s, 1H), 5.36 (s, 1H).

[0094] ESI-MS m / z: 454.01 [M-H] - .

[0095] Analyzing the 1H NMR data, the low-field region δ 9.93 (s, 1H) and δ 9.77 (s, 1H) give two sets of proton signals of amides. It is speculated that the isolated singlet at δ 9.75 (s, 1H) is the proton signal of the active hydrogen sulfonic acid group. According to its chemical shift value and the structural characteristics of the parent phthalocyanine nucleus, δ 7.77 (d, 1H) and δ 7.67 (d, 1H) are inferred to be the vinylic hydrogen proton signals in the parent nucleus ring. The isolated singlet at δ 7.08 (s, 1H) is the vinylic hydrogen proton signal in the dichloropyrimidine ring. The presence of an amino group in the molecule is speculated from δ 5.46 (s, 1H) and δ 5.36 (s, 1H). Combining with the calculated molecular weight in the mass spectrum, the structure of the reactive dye I-1 was determined as the target product.

[0096] Example 4, Preparation method and structure identification of a pyrimidine acid phthalocyanine-based reactive dye I-2

[0097] This example provides a preparation method of a pyrimidine acid phthalocyanine-based reactive dye I-2, which is prepared according to the following steps:

[0098] 1), Take 0.02 mol of the solid powder of the intermediate 1 prepared above, add 0.022 mol of sodium p-aminobenzenesulfonate and sodium bicarbonate, and stir and react at 55 °C for 5 h;

[0099] 2), After the reaction is completed, ethanol is removed by rotary evaporation at 50 °C and dried at room temperature to obtain a pyrimidine acid phthalocyanine-based reactive dye having the following structure.

[0100] The synthesis route of step 1) is the same as that of step 1) in Example 3.

[0101] The structural formula of the pyrimidine acid phthalocyanine-based reactive dye I-2 is as follows:

[0102]

[0103] As 1 shown in the 1H-NMR spectrum (as Figure 2 ), 1 1H NMR (400 MHz, DMSO-d6): δ 9.96 (s, 1H), 9.93 (s, 1H), 9.77 (s, 1H), 9.30 (s, 1H), 7.77 (d, 1H), 7.71 (d, 1H), 7.70 (d, 1H), 7.67 (d, 1H), 7.52 (d, 1H), 7.51 (d, 1H), 7.02 (s, 1H), 5.46 (s, 1H), 5.36 (s, 1H).

[0104] ESI-MS m / z: 530.04 [M-H] - .

[0105] Analyzing the 1H NMR data, based on the chemical shift values at δ 9.96 (s, 1H) and 9.93 (s, 1H) in the low field region and the structural characteristics of the parent nucleus, it is inferred that they are the imine proton signals in the parent heterocycle. It is speculated that the proton at δ 9.77 (s, 1H) is the signal of the imine formed by the condensation of dichloropyrimidine and phthalocyanine. The peak region of vinylic protons is at δ 7.00 - 8.00, and a total of seven vinylic proton signals are given: δ 7.77 (d, 1H), 7.71 (d, 1H), 7.70 (d, 1H), 7.67 (d, 1H), 7.52 (d, 1H), 7.51 (d, 1H), 7.02 (s, 1H), which are consistent with the target structure. δ 5.46 (s, 1H) and 5.36 (s, 1H) are also the amino proton signals in the phthalocyanine parent nucleus. Combining the molecular weight in the mass spectrum, the structure of the reactive dye I-2 is determined to be the target product.

[0106] Example 5. Preparation method and structure identification of a pyrimidine acid phthalocyanine-based reactive dye I-3

[0107] This example provides a preparation method of a pyrimidine acid phthalocyanine-based reactive dye I-3, which is prepared according to the following steps:

[0108] 1), Take 0.02 mol of the solid powder of the intermediate 1 prepared above, add 0.024 mol of sodium p-aminobenzoate and sodium bicarbonate, and stir and react at 50 °C for 6 h;

[0109] 2), After the reaction is completed, ethanol is removed by rotary evaporation at 50 °C, and after drying at room temperature, a pyrimidine acid cyan blue active dye having the following structure is obtained.

[0110] The synthesis route of step 1) is the same as that of step 1) in Example 3.

[0111] The structural formula of the pyrimidine acid cyan blue active dye I-3 is as follows:

[0112]

[0113] As 1 shown in the 1H-NMR spectrum (as Figure 3 ), 1 1H NMR (400 MHz, DMSO-d6): δ 9.96 (s, 1H), 9.93 (s, 1H), 9.77 (s, 1H), 9.24 (s, 1H), 7.95 (d, 1H), 7.94 (d, 1H), 7.77 (d, 1H), 7.67 (d, 1H), 7.67 (d, 1H), 7.65 (d, 1H), 7.02 (s, 1H), 5.46 (s, 1H), 5.36 (s, 1H).

[0114] ESI-MS m / z: 494.07 [M-H] - .

[0115] Analyzing the 1H NMR data, the active dye I-3 has spectral characteristics similar to those of the active dye I-2. Among them, in the low-field region, δ 9.96 (s, 1H), 9.93 (s, 1H), 9.77 (s, 1H), 9.24 (s, 1H) are inferred to be the proton signals of four imines in the molecule according to the chemical shift values and the peak shapes of the multiplets. δ 7.95 - 7.02 also gives seven vinylic proton signals. Combining the amino proton signals given by δ 5.46 (s, 1H), 5.36 (s, 1H), and the molecular weight calculated in the mass spectrum, the structure of the active dye I-3 is determined to be the target product.

[0116] Example 6. Preparation method and structure identification of a pyrimidine acid cyan blue active dye II-1

[0117] This example provides a preparation method of a pyrimidine acid cyan blue active dye II-1, which is prepared according to the following steps:

[0118] 1), Take 0.02 mol of the solid powder of the intermediate 2 prepared above, add 0.044 mol of sodium sulfamate and sodium bicarbonate, and stir and react at 100 °C for 4 h;

[0119] 2), After the reaction, ethanol was removed by rotary evaporation at 50 °C, and after drying at room temperature, a pyrimidine acid phthalocyanine-based reactive dye having the following structure was obtained.

[0120] The synthesis route of step 1) is as follows:

[0121]

[0123] The structural formula of the pyrimidine acid phthalocyanine-based reactive dye II-1 is as follows:

[0124]

[0125] As 1 shown in the 1H-NMR spectrum (as Figure 4 ), 1 1H NMR (400 MHz, DMSO-d6): δ 9.77 (s, 1H), 9.75 (s, 1H), 7.77 (s, 1H), 7.08 (s, 1H).

[0126] ESI-MS m / z: 660.96 [M-H] - .

[0127] Analyzing the 1H NMR data, a total of four sets of proton signals were given. It was speculated that the molecule had a symmetric structure. Among them, two sets of proton signals, δ 9.77 (s, 1H) and δ 9.75 (s, 1H), were given in the low-field region. Combining the chemical shift values and the structural characteristics of the parent nucleus, the two sets of signals corresponded to four sets of imines in the molecule respectively. The two sets of signals at δ 7.77 (s, 1H) and 7.08 (s, 1H) in the peak region of vinylic hydrogen protons corresponded to two pairs of vinylic hydrogen protons in the parent nucleus and dichloropyrimidine in the molecule respectively. The molecular structure was verified by calculating the molecular weight through mass spectrometry, and the structure of II-1 was determined to be the target product.

[0128] Example 7, Preparation method and structure identification of a pyrimidine acid phthalocyanine-based reactive dye II-2

[0129] This example provides a preparation method of a pyrimidine acid phthalocyanine-based reactive dye II-2, which is prepared according to the following steps:

[0130] 1), Take 0.02 mol of the solid powder of the intermediate 2 prepared above, add 0.04 mol of sodium sulfanilate and sodium bicarbonate, and stir and react at 90 °C for 5 h;

[0131] 2), After the reaction, ethanol was removed by rotary evaporation at 50 °C and dried at room temperature to obtain a pyrimidine acid phthalocyanine-based reactive dye having the following structure.

[0132] The synthesis route of step 1) is the same as that of step 1) in Example 6.

[0133] The structural formula of the pyrimidine acid phthalocyanine-like reactive dye II-2 is as follows:

[0134]

[0135] As 1 shown in the Figure 5 H-NMR spectrum (as 1 shown in

[0136] ), - H NMR(400 MHz, DMSO-d6): δ 9.96 (s, 1H), 9.77 (s, 1H), 9.30 (s, 1H), 7.77 (s, 1H), 7.71 (d, 1H), 7.70 (d, 1H), 7.52 (d, 1H), 7.51 (d, 1H), 7.02 (s, 1H).

[0137] Analysis of the low-field region of the hydrogen spectrum data, δ 9.96 (s, 1H), 9.77 (s, 1H), 9.30 (s, 1H), gives three sets of proton signals, corresponding to three sets of imines in the molecule. The region from δ 7.77 to 7.02 gives a total of six sets of proton signals, corresponding to the peak region of the vinylic hydrogen proton signals, indicating that there are six sets of double bonds in the molecule, which is consistent with the structure of the expected product. Combining with the calculated molecular weight in the mass spectrum, the structure of the reactive dye II-2 was determined to be the target product.

[0138] Example 8, Preparation method and structure identification of a pyrimidine acid phthalocyanine-like reactive dye II-3

[0139] This example provides a preparation method of a pyrimidine acid phthalocyanine-like reactive dye II-3, which is prepared according to the following steps:

[0140] 1), Take 0.02 mol of the solid powder of the intermediate 2 prepared above, add 0.042 mol of sodium p-aminobenzoate and sodium bicarbonate, and stir and react at 80 °C for 6 h;

[0141] 2), After the reaction is completed, rotate and evaporate to remove ethanol at 50 °C, and dry at room temperature to obtain the pyrimidine acid phthalocyanine-like reactive dye with the following structure shown.

[0142] The synthesis route of step 1) is the same as that of step 1) in Example 6.

[0143] The structural formula of the pyrimidine acid phthalocyanine-like reactive dye II-3 is as follows:

[0144]

[0145] As 1 shown in the Figure 6 H-NMR spectrum (as 11H NMR (400 MHz, DMSO-d6): δ 9.96 (s, 1H), 9.77 (s, 1H), 9.24 (s, 1H), 7.94 - 7.95 (m, 1H), 7.93 - 7.94 (m, 1H), 7.77 (s, 1H), 7.66 - 7.67 (m, 1H), 7.64 - 7.65 (m, 1H), 7.02 (s, 1H).

[0146] ESI-MS m / z: 741.08 [M-H] - 。

[0147] Analysis of the 1H NMR data showed that in the low-field region, δ 9.96 (s, 1H), 9.77 (s, 1H), and 9.24 (s, 1H) gave three sets of singlet signals, which respectively corresponded to the imine protons in the molecule. In the region where the vinylic protons appeared, a total of six sets of signals, δ 7.94 - 7.95 (m, 1H), 7.93 - 7.94 (m, 1H), 7.77 (s, 1H), 7.66 - 7.67 (m, 1H), 7.64 - 7.65 (m, 1H), and 7.02 (s, 1H), were given, indicating the presence of six vinylic protons in the molecule. Combining the structural characteristics of the parent nucleus and the intermediate, as well as the molecular symmetry, and also combining the calculated molecular weight in the mass spectrum, the structure of the reactive dye II-3 was determined to be the target product.

[0148] Experimental Example: Application of Pyrimidine Acid Blue Reactive Dyes in Dyeing

[0149] Take the pyrimidine acid blue reactive dyes synthesized in the above examples and the unmodified blue dyes to dye acrylic, cotton and spandex blended fabrics according to the following process.

[0150] Dyeing process: Pyrimidine acid blue reactive dyes or blue dyes 2% (o.w.f), Peregal 2 g / L, NaCl 25 g / L, dyeing temperature 60 °C, time 30 min; alkali agent Na2CO3 10 g / L, fixing temperature 90 °C, fixing time 30 min; bath ratio 1:50.

[0151] And, apply the blue water-soluble reactive dye (A) to dye acrylic and spandex fabrics according to the above dyeing process as Comparative Example 1. The blue water-soluble reactive dye (A) was prepared by the method provided in the patent with the application number

[0152] 2018106072177.7;

[0153] Apply the blue water-semi-soluble reactive dye (B) to dye acrylic and spandex fabrics according to the above dyeing process as Comparative Example 2. The blue water-semi-soluble reactive dye (B) was prepared by the method provided in the patent with the application number 201911369938.X;

[0154] The acid dye (C) was applied to the dyeing of acrylic and spandex fabrics according to the acid dyeing process as Comparative Example 3. The acid dye (C) was prepared by the method provided in the patent with the application number 201811221115.8. The acid dyeing process also referred to the patent with the application number 201811221115.8.

[0155]

[0156] After the dyeing was completed, the dyed fabric samples were taken out, washed, and the dyebath residues and washing solutions were combined and made up to a fixed volume to measure their absorbance. The dye uptake rate and fixation rate were calculated using the Lambert-Beer law.

[0157] The above dyed fabric samples were post-treated according to the national standard "Determination Method for Shade and Strength of Reactive Dyes" (GB / T 2387-1980). The various properties of the dyes were tested according to the following standards, and the test results were recorded in Table 1 below.

[0158] The alkali spot color fastness was tested according to GB / T 5716-2013; the acid spot color fastness was tested according to GB / T 5715-2013; the water color fastness was tested according to GB / T 5713-2013; the soaping color fastness was tested according to GB / T 3921-2008; the rubbing color fastness was tested according to GB / T 3920-2008.

[0159] Table 1

[0160]

[0161] In this application, trichloropyrimidine was introduced as an active group into the indigo structure, which has lower reactivity than the active group of cyanuric chloride structure. This makes the pyrimidine acid indigo-based reactive dye more stable after binding to cellulose fibers, less prone to hydrolysis, and has better acid and alkali stability for the "dye-fiber" covalent bond, and better dyeing performance. In addition, the introduction of water-soluble groups such as sulfonic acid groups and carboxyl groups improves the water solubility of the pyrimidine acid indigo-based reactive dyes.

[0162] When the pyrimidine acid indigo-based reactive dyes of Examples 3-8 were applied to acrylic dyeing, the color uptake rate was 95-98.5%, and the fixation rate was 83.6-89.5%; the water wash color fastness, alkali spot color fastness, soaping color fastness, and wet rubbing color fastness were ≥4 grades.

[0163] When the pyrimidine acid indigo-based reactive dyes of Examples 3-8 were applied to cotton-spandex dyeing, the color uptake rate was 93-97.6%, and the fixation rate was 80-88.7%; the water wash color fastness, alkali spot color fastness, soaping color fastness, and wet rubbing color fastness were ≥4 grades.

[0164] Compared with the present application, when unmodified indigo blue is applied to the dyeing of cotton spandex under the dyeing conditions of this patent, the color uptake rate, color fixation rate, color fastness to washing, color fastness to alkali spots, color fastness to soaping, and color fastness to wet rubbing are all poor. It shows that the pyrimidine acid indigo blue type reactive dyes can achieve efficient dyeing of various chemical fibers and their blended fiber fabrics in an aqueous system, with the advantages of high dye uptake rate and color fixation rate.

[0165] Compared with the present application, the blue water-soluble reactive dye (A) uses a sym-triazine structure as the reactive group, and its acid and alkali stability is poor. After dyeing, the color fastness to alkali spots, color fastness to acid spots, and color fastness to soaping are all lower than those of the pyrimidine acid indigo blue type reactive dyes of the present application.

[0166] Compared with the present application, the blue water temporarily soluble reactive dye (B) has good water solubility and becomes a hydrophobic dye during the alkali fixation treatment, with a relatively high affinity for hydrophobic fibers. However, the covalent bond binding ability formed between this dye and the fiber is lower than that of the dye of the present application, and the acid and alkali resistance of the dye is poor. After dyeing, the color fastness to alkali spots and color fastness to acid spots of the fabric are relatively low.

[0167] Compared with the present application, the acid dye (C) has a good dye uptake and adsorption ability for spandex, and the color depth is relatively high after dyeing. However, since no covalent bond is formed between this dye and the fiber, the dye and spandex fiber are only combined by ionic bond forces, weak van der Waals forces, and hydrogen bond forces that are easily affected by water, and it is not resistant to acids and alkalis, resulting in low color fastness to wet treatment and poor color fastness to acid and alkali spots after dyeing.

[0168] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application rather than to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A pyrimidine acid blue reactive dye, characterized in that: The general structural formula of the pyrimidine acid blue reactive dye is shown in formula (I); Wherein, the R1 includes one of -NH-SO3M, -NH-Ar-SO3M, and -NH-Ar-COOM; M includes one of H, Na, K or Li; The R2 includes or H.

2. The pyrimidine acid blue reactive dye according to claim 1, characterized in that: The general structural formula of the pyrimidine acid blue reactive dye is shown in formula (II) or formula (III); wherein R1 includes one of -NH-SO3M, -NH-Ar-SO3M, and -NH-Ar-COOM; M includes one of H, Na, K or Li.

3. The pyrimidine acid blue reactive dye according to claim 1 or 2, characterized in that: The R1 is selected from one of -NH-SO3M, -NH-Ar-SO3M, and -NH-Ar-COOM; M is one of H, Na, K or Li.

4. The pyrimidine acid blue reactive dye according to claim 1, characterized in that: The R2 is or H.

5. The pyrimidine acid blue reactive dye according to claim 1 or 2, characterized in that: The pyrimidine acid blue reactive dye is any one of the following structures:

6. A method for preparing a pyrimidine acid blue reactive dye according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1, mixing indigo plant, trichloropyrimidine and ethanol, then adding an acid binding agent, and then performing a condensation reaction, and purifying to obtain an intermediate 1 or an intermediate 2; S2, adding an amino coupling agent to the intermediate 1 or the intermediate 2, and then adding an acid binding agent to react to obtain a reaction solution; S3, purifying the reaction solution, collecting the solid and drying it to obtain a pyrimidine acid blue active dye.

7. The method for preparing the pyrimidine acid blue reactive dye according to claim 6, wherein: The structure of the intermediate 1 or intermediate 2 is as follows:

8. The method for preparing the pyrimidine acid blue reactive dye according to claim 6, wherein: In the step S1, the reaction temperature is 5-15° C. when synthesizing the intermediate 1, the reaction time is 3-5 h, and the molar ratio of the indigo plant: trichloropyrimidine: acid-binding agent is 1:(1.0-1.2):(1.0-1.2).

9. The method for preparing a pyrimidine acid blue reactive dye according to claim 6, wherein: In the step S1, the reaction temperature when synthesizing the intermediate 2 is 25-40° C., the reaction time is 3-5 hours, and the molar ratio of the indigo plant: trichloropyrimidine: acid binding agent is 1:(2.0-2.2):(2.0-2.2).

10. The method for preparing the pyrimidine acid blue reactive dye according to claim 6, wherein: In the step S2, the reaction temperature is 50-60°C, the reaction time is 4-6 hours, and the molar ratio of the intermediate 1: amino coupling agent: acid binding agent is 1: (1.0-1.2): (1.0-1.2).

11. The method for preparing the pyrimidine acid blue reactive dye according to claim 6, wherein: In the step S2, the reaction temperature is 80-100°C, the reaction time is 4-6 hours, and the molar ratio of the intermediate 2: amino coupling agent: acid binding agent is 1: (2.0-2.2): (2.0-2.2).

12. The method for preparing the pyrimidine acid blue reactive dye according to claim 6, wherein: The acid binding agent includes sodium bicarbonate; the amino coupling agent includes at least one of sodium aminosulfonate, sodium p-aminobenzenesulfonate, and sodium p-aminobenzoate.

13. Use of the pyrimidine acid blue reactive dye according to any one of claims 1 to 5 in dyeing.

14. The use according to claim 13, characterized in that The application is the application of pyrimidine blue reactive dyes in dyeing chemical fibers and blended fibers.

15. The use according to claim 13, characterized in that The mass concentration of the pyrimidine acid blue active dye when used is 0.5-10% (owf).

Images