Pyrimidine acid observation blue active dye and preparation method and application thereof

Abstract

The application relates to the dye technology field, and particularly discloses a pyrimidine acid observation blue active dye, a preparation method and application thereof. A trichloropyrimidine is introduced as an active group on the basis of the observation blue structure, the reactivity of the trichloropyrimidine is lower than that of the cyanuric chloride structure, the pyrimidine acid observation blue active dye is more stable after being combined with cellulose fibers, is not easy to hydrolyze, the acid and alkali resistance of a 'dye-fiber' covalent bond is better, and the dyeing performance is more superior; in addition, water-soluble groups such as sulfonic acid groups and carboxyl groups are introduced to improve the water solubility of the pyrimidine acid observation blue active dye. Furthermore, the pyrimidine acid observation blue active dye prepared by the application has good dyeing effects on acrylic fibers, spandex and other chemical fiber fabrics and blended fiber fabrics, further improves the adaptability of the observation blue, the dyeing is stable, the color is deep, the fixation effect is good, meanwhile, the acid and alkali resistance of the fabric is improved, and the application prospect is wide.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of dyes, in particular to a pyrimidine acid indigoid reactive dye, a preparation method and application thereof. BACKGROUND

[0002] Indigoidine is a kind of bacterial natural product with antioxidant and antibacterial activity, which is stable in nature, environmentally friendly, and has broad application prospects as a deep blue natural pigment. Indigoidine is a non-water-soluble blue pigment with poor solubility in solvents, only having a small solubility in DMF and DMSO. Therefore, it is necessary to modify the structure of indigoidine to improve the solubility of the dye and produce a dye with practical value.

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

[0004] In view of the shortcomings of indigoidine dyeing, a variety of indigoidine reactive dyes have been reported to be synthesized. The application with application number 2018106072177 is prepared by reacting indigoidine dye with a condensate of cyanuric chloride and aminobenzene sulfonic acid. The prepared reactive dye can achieve efficient dyeing of cotton fabric in water system. The application with application number 2018105729317 discloses a reactive dye mainly applied to dyeing of polyester fiber, which is difficult to dye other fabrics to deep color, and the color fastness to sublimation of the dyed fabric is also low. The application with application number 201911369938 discloses a reactive dye which improves the affinity of the dye to hydrophobic nylon fiber and improves the dyeing depth and color fixation rate of the dye to nylon fiber. However, this type of dye uses cyanuric chloride as the active group, and has the disadvantages of poor hydrolytic stability and poor acid and alkali resistance of the "dye-fiber" covalent bond, resulting in low dyeing rate and color fixation rate of acrylic fiber, spandex fiber and their blended fabrics. SUMMARY

[0005] The present application aims to overcome the shortcomings of the prior art and provide a pyrimidine acid indigoid reactive dye, a preparation method and application thereof. The pyrimidine acid indigoid reactive dye of the present application is not easily hydrolyzed, has deep color, has stronger acid and alkali stability of dyed fabric, and can achieve efficient dyeing of various chemical fibers and blended fiber fabrics in water system with high dyeing rate and color fixation rate. The preparation process is simple and has strong operability.

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

[0007] The application provides a pyrimidine acid cyanine active dye, a structural general formula of the pyrimidine acid cyanine active dye is shown as formula (I).

[0008]

[0009] The R1 includes one of -NH-SO3M, -NH-Ar-SO3M and -NH-Ar-COOM.

[0010] The M includes one of H, Na, K and Li.

[0011] The R2 includes

[0012]

[0013] As a preferred embodiment of the pyrimidine acid cyanine active dye, a structural general formula of the pyrimidine acid cyanine active dye is shown as formula (II) or formula (III).

[0014]

[0015] The R1 includes one of -NH-SO3M, -NH-Ar-SO3M and -NH-Ar-COOM.

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

[0017] As a preferred embodiment of the pyrimidine acid cyanine active dye, the R1 is selected from one of -NH-SO3M, -NH-Ar-SO3M and -NH-Ar-COOM.

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

[0019] By adopting the technical scheme, the trichloropyrimidine is used as an active group, the electron cloud density on the carbon atom is increased after the pyrimidine acid cyanine active dye synthesized by adopting the technical scheme is combined with the fiber, good C-O bond stability is obtained, the dyeing performance is more superior, and the color fixation rate and the dyeing fastness are effectively improved.

[0020] As a preferred embodiment of the pyrimidine acid cyanine active dye, the pyrimidine acid cyanine active dye has any one of the following structures.

[0021]

[0022]

[0023] The pyrimidine acid cyanine active dye with the above structural formula is adopted, and the dyeing effect is more excellent.

[0024] The application also provides a preparation method of the pyrimidine acid observation blue active dye, comprising the following steps:

[0025] S1, mixing observation blue, trichloropyrimidine and ethanol, then adding an acid binding agent, and then performing a condensation reaction to obtain intermediate 1 or intermediate 2;

[0026] S2, adding an amino coupling agent to the intermediate 1 or the intermediate 2, and then adding an acid binding agent to perform a reaction to obtain a reaction solution;

[0027] S3, purifying the reaction solution, collecting and drying the solid to obtain the pyrimidine acid observation blue active dye.

[0028] As a preferred embodiment of the preparation method of the pyrimidine acid observation blue active dye, the structure of the intermediate 1 or the intermediate 2 is as follows:

[0029] The intermediate 1 is N-dichloropyrimidine observation blue;

[0030] The intermediate 2 is N,N'-bis-dichloropyrimidine observation blue;

[0031]

[0032] As a preferred embodiment of the preparation method of the pyrimidine acid observation blue active dye, in the step S1, when the intermediate 1 is synthesized, the reaction temperature is 5-15℃, the reaction time is 3-5h, and the molar ratio of observation blue: trichloropyrimidine: acid binding agent is 1:(1.0-1.2):(1.0-1.2).

[0033] When the intermediate 1 is synthesized under the above low temperature condition, the reactivity of observation blue and trichloropyrimidine is reduced, observation blue only reacts with one molecule of trichloropyrimidine in the reaction system to generate a single-sided structure of pyrimidine observation blue structure, which can effectively reduce the generation of the intermediate 2.

[0034] As a preferred embodiment of the preparation method of the pyrimidine acid observation blue active dye, in the step S1, when the intermediate 2 is synthesized, the reaction temperature is 25-40℃, the reaction time is 3-5h, and the molar ratio of observation blue: trichloropyrimidine: acid binding agent is 1:(2.0-2.2):(2.0-2.2).

[0035] The reaction temperature for synthesizing the intermediate 2 is increased, and the molar ratio of trichloropyrimidine and acid binding agent to observation blue is also increased, which promotes the reaction of observation blue with two molecules of trichloropyrimidine to generate observation blue with double-sided pyrimidine structure.

[0036] As a preferred embodiment of the preparation method of the pyrimidine acid cyanine active dye, the purification comprises: extracting the reaction liquid obtained by the condensation reaction to obtain a solid precipitate, washing the precipitate with 3-5 times the mass of pure water, then washing the precipitate with 3-5 times the mass of ethyl acetate, and drying at room temperature to obtain the intermediate 1 or the intermediate 2.

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

[0038] The cyanine with a single pyrimidine structure is more likely to react with the amino coupling agent, and the reaction can be promoted at 50-60 ℃.

[0039] As a preferred embodiment of the preparation method of the pyrimidine acid cyanine active dye, in the step S2, the temperature of the reaction is 80-100 ℃, the time of the reaction is 4-6 h, and the molar ratio of the intermediate 2, the amino coupling agent, and the acid-binding agent is 1:(2.0-2.2):(2.0-2.2).

[0040]

[0041] Since the intermediate 2 has two pyrimidine structures, the reactivity is low, and a higher temperature (80-100 ℃) is required to promote the reaction in the present application, which effectively promotes the production of the product.

[0042] As a preferred embodiment of the preparation method of the pyrimidine acid cyanine active dye, the acid-binding agent comprises sodium bicarbonate.

[0043] As a preferred embodiment of the preparation method of the pyrimidine acid cyanine active dye, the acid-binding agent comprises sodium bicarbonate, and the amino coupling agent comprises at least one of sodium sulfamate, sodium p-aminobenzenesulfonate, and sodium p-aminobenzoate.

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

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

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

[0047] Preferably, the chemical fibers comprise acrylic or / and spandex. ​

[0048] The reactive dyes of the application have good dyeing and fixing effects on acrylic fiber, spandex fiber and their blended fabrics, and the acid and alkali resistance of the dyed fabrics is better.

[0049] As a preferred embodiment of the application, the mass concentration of the reactive dyes of the application is 0.5-10% (o.w.f) when applied.

[0050] The reactive dyes of the application prepared in the application can be well combined with chemical fiber and blended fiber textiles, and can effectively improve the color fixing rate and dyeing fastness.

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

[0052] The application provides a reactive dye of the acid observation blue type and a preparation method and application thereof. The trichloropyrimidine is introduced into the structure of the acid observation blue as an active group in the application, the reactivity of the active group with the cyanuric chloride structure is lower, the reactive dye of the acid observation blue type is more stable after being combined with cellulose fiber and is not easy to hydrolyze, the acid and alkali resistance of the covalent bond of “dye-fiber” is better, and the dyeing performance is more superior. In addition, the water-soluble groups such as sulfonic acid groups and carboxyl groups are introduced to improve the water solubility of the reactive dye of the acid observation blue type. Moreover, the preparation method of the reactive dye of the acid observation blue type in the application is simple in operation and can be industrially produced, the prepared reactive dye of the acid observation blue type has excellent comprehensive performance, the reactive dye of the acid observation blue type prepared in the application has good dyeing effects on acrylic fiber, spandex fiber and their blended fiber fabrics, and the adaptability of the acid observation blue is further improved. The dye has stable dyeing, deep color, good fixing effect, improves the acid and alkali resistance of the fabric, increases the applicability of the acid observation blue dye, and has a wide application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0053] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the reactive dye of the acid observation blue type I-1 of Example 3 is shown in the figure;

[0054] Figure 2 The nuclear magnetic resonance hydrogen spectrum of the reactive dye of the acid observation blue type I-2 of Example 4 is shown in the figure;

[0055] Figure 3 The nuclear magnetic resonance hydrogen spectrum of the reactive dye of the acid observation blue type I-3 of Example 5 is shown in the figure;

[0056] Figure 4 The nuclear magnetic resonance hydrogen spectrum of the reactive dye of the acid observation blue type II-1 of Example 6 is shown in the figure;

[0057] Figure 5 The nuclear magnetic resonance hydrogen spectrum of the reactive dye of the acid observation blue type II-2 of Example 7 is shown in the figure;

[0058] Figure 6 NMR spectrum of the pyrimidine acid observation blue reactive dye II-3 of Example 8;

[0059] Figure 7 Staining result chart of the experimental example. DETAILED DESCRIPTION

[0060] For the purpose of better illustrating the purpose, technical scheme and advantages of the present application, the present application will be further described in the following with reference to the drawings and specific examples.

[0061] In the following examples and comparative examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are commercially available unless otherwise specified.

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

[0063] The NMR hydrogen spectrum test of the synthesized pyrimidine acid observation blue reactive dye was detected by NMR spectrometer Avance II (400 MHz) and AVANCE III (500); the mass spectrum test was detected by matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF.

[0064] Preparation method of Example 1, intermediate 1

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

[0066] 1) The observation blue dye was ground through a 100-mesh sieve, 0.01 mol was taken and loaded into a three-necked flask with a stirrer and a thermometer, 100 mL of ethanol was added, and a dye suspension was formed by stirring at room temperature, and was ready for use;

[0067] 2) 0.011 mol of trichloropyrimidine was mixed and dissolved in 50 mL of ethanol, and then added to the above dye dispersion, followed by the addition of 0.011 mol of sodium bicarbonate, and reacted at 5°C for 4 h; after the reaction was completed, a mixed solution containing a large amount of intermediate 1 and a small amount of intermediate 2 was obtained.

[0068] 3) The above reaction mixture was washed with 3 times the mass of pure water for 2 times, and 3 times the mass of ethyl acetate for 2 times, and then dried to obtain the solid of intermediate 1 (N-dichloropyrimidine observation blue), and the trace amount of intermediate 2 was negligible.

[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] Preparation method of Example 2, intermediate 2

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

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

[0077] 2), mix and dissolve 0.022 mol of trichloropyrimidine (which is double the amount added in Example 1) with 50 mL of ethanol, then add it to the above dye dispersion, followed by adding 0.022 mol of sodium bicarbonate, and react at 15°C for 5h (increasing the temperature for reaction can promote the combination of two molecules of trichloropyrimidine with one molecule of observation blue); after the reaction is completed, a mixed solution containing a large amount of intermediate 2 and a small amount of intermediate 1 is obtained.

[0078] 3), wash the above reaction mixture with 3 times the mass of pure water twice, and 3 times the mass of ethyl acetate twice, and dry to obtain the solid of intermediate 2 (N,N'-bisdichloropyrimidine observation 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] Preparation method and structural identification of a pyrimidine acid observation blue active dye I-1

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

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

[0087] 2) After the reaction is complete, the ethanol is removed by rotary evaporation at 50°C, and the product is dried at room temperature to obtain a pyrimidine acid blue reactive dye containing the structure shown below.

[0088] The synthetic route for step 1) is as follows:

[0089]

[0090] The structural formula of the pyrimidine acid blue reactive dye I-1 is as follows:

[0091]

[0092] like 1 As shown in the H-NMR spectrum (e.g.) Figure 1 ), 1 H NMR (400MHz, 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).

[0093] ESI-MS m / z: 454.01 [MH] - .

[0094] Analysis of the proton NMR data revealed two sets of proton signals for the amides at δ9.93 (s, 1H) and δ9.77 (s, 1H) in the low field region. The isolated singlet at δ9.75 (s, 1H) was deduced to be a proton signal from the active hydrosulfonic acid group. Based on their chemical shift values ​​and the structural characteristics of the blue core, the peaks at δ7.77 (d, 1H) and δ7.67 (d, 1H) were inferred to be olefinic proton signals from the core ring. The isolated singlet at δ7.08 (s, 1H) was identified as an olefinic proton signal from the dichloropyrimidine ring. The peaks at δ5.46 (s, 1H) and 5.36 (s, 1H) suggested the presence of an amino group in the molecule. Combined with the molecular weight calculated from the mass spectrometry, the structure of the reactive dye I-1 was determined to be the target product.

[0095] Example 4: Preparation method and structural identification of a pyrimidine acid blue reactive dye I-2

[0096] This embodiment provides a method for preparing pyrimidine acid blue reactive dye I-2, which is carried out according to the following steps:

[0097] 1) Take 0.02 mol of solid powder containing the above-prepared intermediate 1, add 0.022 mol of sodium p-aminobenzenesulfonate and sodium bicarbonate, and stir at 55°C for 5 h.

[0098] 2) After the reaction is completed, the ethanol is removed by rotary evaporation at 50°C and dried at room temperature to obtain a pyrimidine acid blue reactive dye containing the structure shown below.

[0099] The synthetic route of step 1) is the same as step 1) of Example 3.

[0100] The structural formula of the pyrimidine acid observation blue active dye I-2 is as follows:

[0101]

[0102] As 1 H-NMR spectrum (as Figure 2 ), 1 H 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).

[0103] ESI-MS m / z: 530.04 [M-H] - .

[0104] Analyzing the hydrogen spectrum data, according to the chemical shift values of the low field region δ 9.96 (s, 1H), 9.93 (s, 1H) and the structural characteristics of the parent nucleus, it is inferred that the imine proton signal in the heterocyclic parent nucleus is δ 9.77 (s, 1H), and it is inferred that the proton at δ 9.77 (s, 1H) is the signal of the imine condensed with observation blue from dichloropyrimidine, and δ 7.00-8.00 is the peak region of olefinic hydrogen protons, which gives seven olefinic hydrogen proton information of 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 is consistent with the target structure, and δ 5.46 (s, 1H), 5.36 (s, 1H) is also the amino proton signal in the observation blue parent nucleus, and the structure of the active dye I-2 is determined as the target product in combination with the molecular weight in the mass spectrum.

[0105] Example 5, a preparation method and structural identification of a pyrimidine acid observation blue active dye I-3

[0106] This example provides a preparation method of a pyrimidine acid observation blue active dye I-3, which is prepared according to the following steps:

[0107] 1) Take 0.02 mol of the solid powder containing the above prepared intermediate 1, add 0.024 mol of sodium p-aminobenzoate and sodium bicarbonate, and stir at 50°C for 6h;

[0108] 2), after the reaction, 50 ℃ rotary evaporation to remove ethanol, drying at room temperature to obtain a pyrimidine acid observation blue active dye containing the structure shown below.

[0109] The synthetic route of step 1) is the same as step 1) of Example 3.

[0110] The structural formula of the pyrimidine acid observation blue active dye I-3 is as follows:

[0111]

[0112] As 1 H-NMR spectrum (as Figure 3 ), 1 H 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).

[0113] ESI-MS m / z: 494.07 [M-H] - .

[0114] Analyzing the hydrogen spectrum data, the active dye I-3 has similar spectral characteristics to the active dye I-2, wherein the low field region δ 9.96 (s, 1H), 9.93 (s, 1H), 9.77 (s, 1H), 9.24 (s, 1H) is inferred to be the proton signal of the four imines in the molecule according to the chemical shift value and the peak type of the multiplet peak, δ 7.95-7.02 also gives seven ene hydrogen proton signals, combined with δ 5.46 (s, 1H), 5.36 (s, 1H) gives the amino proton signal, and the calculated molecular weight in the mass spectrum, determines the structure of the active dye I-3 as the target product.

[0115] Example 6, a preparation method and structural identification of a pyrimidine acid observation blue active dye II-1

[0116] This example provides a preparation method of a pyrimidine acid observation blue active dye II-1, which is prepared according to the following steps:

[0117] 1), take 0.02 mol of the solid powder containing the above prepared intermediate 2, add 0.044 mol of sodium sulfamate and sodium bicarbonate, stir at 100 ℃ for 4 h;

[0118] 2), after the reaction, 50 ℃ rotary evaporation to remove ethanol, drying at room temperature to obtain a pyrimidine acid observation blue active dye containing the structure shown below.

[0119] The synthetic route of step 1) is as follows:

[0120]

[0121] The structural formula of the pyrimidine acid observation blue active dye II-1 is as follows:

[0122]

[0123] As shown in the H-NMR spectrum (as shown in 1 H-NMR spectrum (as shown in Figure 4 ), 1 H NMR (400 MHz, DMSO-d6): δ 9.77 (s, 1H), 9.75 (s, 1H), 7.77 (s, 1H), 7.08 (s, 1H).

[0124] ESI-MS m / z: 660.96 [M-H] - .

[0125] The analysis of the hydrogen spectrum data gives four groups of proton signals, and it is speculated that the molecule is a symmetrical structure. The low field region gives two groups of proton signals δ 9.77 (s, 1H), δ 9.75 (s, 1H), and the chemical shift value and the structure characteristics of the parent nucleus are combined. Two groups of signals correspond to four imine groups in the molecule. The peak region of the olefinic hydrogen proton δ 7.77 (s, 1H), 7.08 (s, 1H) corresponds to two pairs of olefinic hydrogen protons in the parent nucleus and dichloropyrimidine in the molecule. The molecular weight calculated by mass spectrum verifies the structure of the molecule, and it is determined that the structure of II-1 is the target product.

[0126] Example 7, a preparation method and structural identification of a pyrimidine acid observation blue active dye II-2

[0127] The present embodiment provides a preparation method of a pyrimidine acid observation blue active dye II-2, which is prepared according to the following steps:

[0128] 1) Take 0.02 mol of solid powder containing the above prepared intermediate 2, add 0.04 mol of sodium p-aminobenzenesulfonate and sodium bicarbonate, and stir at 90°C for 5h;

[0129] 2) After the reaction is completed, the ethanol is removed by rotary evaporation at 50°C and dried at room temperature to obtain a pyrimidine acid observation blue active dye containing the following structure.

[0130] The synthetic route of step 1) is as in step 1) of Example 6.

[0131] The structural formula of the pyrimidine acid observation blue active dye II-2 is as follows:

[0132]

[0133] As 1 H-NMR spectrum shows (as Figure 5 ), 1 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).

[0134] ESI-MS m / z: 813.02 [M-H] - .

[0135] The analysis of hydrogen spectrum data in the low field region δ 9.96 (s, 1H), 9.77 (s, 1H), 9.30 (s, 1H) gives three groups of proton signals, respectively corresponding to three groups of imines in the molecule, δ 7.77-7.02 gives six groups of proton signals, corresponding to the peak area of the olefinic hydrogen proton signal, indicating that there are six groups of double bonds in the molecule, which is consistent with the expected product structure, combined with the calculated molecular weight in the mass spectrum, the structure of the reactive dye II-2 is determined as the target product.

[0136] Example 8, a preparation method and structural identification of a pyrimidine acid observation blue reactive dye II-3

[0137] This example provides a preparation method of a pyrimidine acid observation blue reactive dye II-3, which is prepared according to the following steps:

[0138] 1) Take 0.02 mol of the solid powder containing the above prepared intermediate 2, add 0.042 mol of sodium p-aminobenzoate and sodium bicarbonate, and stir at 80°C for 6h;

[0139] 2) After the reaction is completed, remove ethanol at 50°C by rotary evaporation, and dry at room temperature to obtain a pyrimidine acid observation blue reactive dye containing the following structure.

[0140] The synthetic route of step 1) is the same as step 1) of example 6.

[0141] The structural formula of the pyrimidine acid observation blue reactive dye II-3 is as follows:

[0142]

[0143] As 1 H-NMR spectrum shows (as Figure 6 ), 1H 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).

[0144] ESI-MS m / z: 741.08 [M-H] - .

[0145] Analyzing the hydrogen spectrum data, the low field region δ 9.96 (s, 1H), 9.77 (s, 1H), 9.24 (s, 1H) gave three groups of single peak signals corresponding to the imine protons in the molecule respectively, and in the olefin hydrogen proton peak region, six signals of 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), 7.02 (s, 1H) were given, indicating that there were six olefin hydrogen protons in the molecule, combined with the structure characteristics of the mother nucleus and the intermediate and the symmetry of the molecule, and combined with the calculated molecular weight in the mass spectrum, the structure of the active dye II-3 was determined as the target product.

[0146] Experimental example, application of pyrimidine acid observation blue active dye in dyeing

[0147] The pyrimidine acid observation blue active dye synthesized in the above examples and the unmodified observation blue dye were used to dye acrylic, cotton and spandex blended fabric according to the following process.

[0148] Dyeing process: pyrimidine acid observation blue active dye or observation blue 2% (o.w.f), peregal 2g / L, NaCl 25g / L, dyeing temperature 60℃, time 30min; alkali agent Na2CO3 10g / L, fixing temperature 90℃, fixing time 30min; bath ratio 1:50.

[0149] And, the blue water-soluble active dye (A) was applied to acrylic and spandex fabric dyeing as Comparative Example 1 according to the above dyeing process, and the blue water-soluble active dye (A) was prepared by the method provided in the patent with application number 2018106072177.7;

[0150] The blue water-soluble active dye (B) was applied to acrylic and spandex fabric dyeing as Comparative Example 2 according to the above dyeing process, and the blue water-soluble active dye (B) was prepared by the method provided in the patent with application number 201911369938.X;

[0151] The acid dye (C) is applied to acrylic and spandex fabric dyeing as Comparative Example 3 according to the acid dye dyeing process, and the acid dye (C) is prepared by the method provided in the patent with the application number 201811221115.8. The acid dye dyeing process also refers to the patent with the application number 201811221115.8.

[0152]

[0153] After dyeing, the dyed fabric sample is taken out, washed, and the dyeing residue and the washing liquid are combined, and the absorbance is measured after constant volume. The dye uptake and fixation rate are calculated by using the Lambert-Beer law.

[0154] The dyed fabric sample is subjected to dyeing after-treatment according to the national standard "Method for Determining Color Shade and Intensity of Reactive Dyeing" (GB / T 2387-1980). The performance of the dye is tested according to the following standards, and the test results are recorded in Table 1 below.

[0155] The alkali spot color fastness is tested according to GB / T 5716-2013; the acid spot color fastness is tested according to GB / T 5715-2013; the water color fastness is tested according to GB / T 5713-2013; the soaping color fastness is tested according to GB / T 3921-2008; and the rubbing color fastness is tested according to GB / T 3920-2008.

[0156] Table 1

[0157]

[0158] The trichloropyrimidine is introduced as the reactive group on the observation blue structure in the present application, which is less reactive than the tricyanopyrimidine structure, so that the pyrimidine acid observation blue reactive dye is more stable after being combined with cellulose fiber and is not easy to hydrolyze. The "dye-fiber" covalent bond has better acid and alkali stability, and the dyeing performance is more superior. In addition, the water-soluble groups such as sulfonic acid groups and carboxyl groups are introduced to improve the water solubility of the pyrimidine acid observation blue reactive dye.

[0159] When the pyrimidine acid observation blue reactive dyes of Examples 3-8 are applied to acrylic dyeing, the dyeing rate is 95-98.5%, and the fixation rate is 83.6-89.5%. The water washing color fastness, alkali spot color fastness, soaping color fastness, and wet rubbing color fastness are all ≥4 levels.

[0160] When the pyrimidine acid observation blue reactive dyes of Examples 3-8 are applied to cotton and spandex dyeing, the dyeing rate is 93-97.6%, and the fixation rate is 80-88.7%. The water washing color fastness, alkali spot color fastness, soaping color fastness, and wet rubbing color fastness are all ≥4 levels.

[0161] Compared with the present application, the unmodified observation blue has poor dyeing rate, fixation rate, color fastness to washing, color fastness to alkali stain, color fastness to soaping, and color fastness to wet rubbing when applied to cotton spandex dyeing under the dyeing conditions of the present patent. It shows that pyrimidine acid observation blue reactive dyes can achieve efficient dyeing of various chemical fibers and their blended fiber fabrics in water system, with the advantages of high dyeing rate and fixation rate.

[0162] Compared with the present application, the blue water-soluble reactive dye (A) uses s-triazine structure as the reactive group, and has poor acid and alkali resistance. The color fastness to alkali stain, color fastness to acid stain, and color fastness to soaping after dyeing are all lower than the pyrimidine acid observation blue reactive dyes of the present application.

[0163] Compared with the present application, the blue water-soluble reactive dye (B) has good water solubility and becomes a hydrophobic dye during the alkali fixation process, with high affinity to hydrophobic fibers. However, the covalent bond formation ability between the dye and the fiber is lower than that of the dyes of the present application, and the dye has poor acid and alkali resistance, resulting in low color fastness to alkali stain and color fastness to acid stain of the dyed fabric.

[0164] Compared with the present application, the acid dye (C) has good dyeing and adsorption capacity for spandex, and high color depth after dyeing. However, since the dye does not form covalent bond with the fiber, it is only combined with spandex fiber through ion bond, weak van der Waals force, and hydrogen bond, which are easily affected by water. Therefore, the dye has poor acid and alkali resistance, resulting in low wet treatment fastness, poor color fastness to acid stain and alkali stain of the dyed fabric.

[0165] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and do not limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced equivalently without departing from the spirit and scope 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 dyes is shown in formula (I); Formula (I); Wherein, R1 includes one of -NH-SO3M, -NH-Ar-SO3M, and -NH-Ar-COOM; M includes one of H, Na, K, or Li; R2 includes Or H.

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

3. The pyrimidine acid blue reactive dye as described in claim 1, characterized in that, The pyrimidine acid blue reactive dye has any of the following structures: Formula I-1; Formula I-2; Formula I-3; Formula II-1; Formula II-2; Formula II-3.

4. A method for preparing a pyrimidine acid blue reactive dye as described in any one of claims 1 to 3, characterized in that, Includes the following steps: S1. Mix styrax, trichloropyrimidine and ethanol, then add an acid-binding agent, and carry out a condensation reaction to obtain intermediate 1 or intermediate 2. S2. Add the amino coupling agent to intermediate 1 or intermediate 2, then add the acid-binding agent to react and obtain the reaction solution; S3. Purify the reaction solution, collect the solid and dry it to obtain pyrimidine acid blue reactive dyes; When synthesizing intermediate 1, the reaction temperature in step S1 is 5~15℃, the reaction time is 3~5 h, and the molar ratio of lanthanum:trichloropyrimidine:acid-binding agent is 1:(1.0~1.2):(1.0~1.2); in step S2, the reaction temperature is 50~60℃, the reaction time is 4~6 h, and the molar ratio of intermediate 1:amino coupling agent:acid-binding agent is 1:(1.0~1.2):(1.0~1.2). When synthesizing intermediate 2, the reaction temperature in step S1 is 25~40℃, the reaction time is 3~5 h, and the molar ratio of lanthanum:trichloropyrimidine:acid-binding agent is 1:(2.0~2.2):(2.0~2.2); in step S2, the reaction temperature is 80~100℃, the reaction time is 4~6 h, and the molar ratio of intermediate 2:amino coupling agent:acid-binding agent is 1:(2.0~2.2):(2.0~2.2). The structure of intermediate 1 or intermediate 2 is as follows: 。 5. The method for preparing pyrimidine acid blue reactive dyes as described in claim 4, characterized in that, 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.

6. The application of pyrimidine acid blue reactive dyes as described in any one of claims 1 to 3 in dyeing.

7. The application as described in claim 6, characterized in that, The application is the use of pyrimidine blue reactive dyes in the dyeing of chemical fibers.

8. The application as described in claim 6, characterized in that, The mass concentration of the pyrimidine acid blue reactive dye is 0.5~10% (owf) when used.

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