Diheterocyclic yellow azo disperse dye as well as synthesis method and application thereof

Abstract

The invention relates to the technical field of disperse dye synthesis, in particular to a diheterocyclic yellow azo disperse dye as well as a synthesis method and application thereof. The structure of the diheterocyclic yellow azo disperse dye is shown in a formula (1). When the dye is used for dyeing polyester fibers, the dye uptake reaches more than 80.0%, the dry and wet rubbing color fastness reaches more than level 4, and the light fastness reaches more than level 5.

Description

Technical Field

[0001] The invention relates to the technical field of disperse dye synthesis, and in particular to a diheterocyclic yellow azo disperse dye and a synthesis method and application thereof. Background Art

[0002] As a special dye for polyester fiber dyeing, disperse dyes have been increasingly valued over the past few decades as the polyester textile market continues to expand. Today, with the full popularization of polyester textile products in the market, disperse dyes have become an indispensable part of commercial dyes. However, the common commercial disperse dyes for polyester dyeing often have the following disadvantages:

[0003] 1. Insufficient color depth: The parent structure of most commercial disperse dyes is the traditional aniline structure. These disperse dyes often introduce chain structures such as acid esters and cyano groups, or use halogen atoms such as bromine atoms and chlorine atoms to modify the aniline parent structure to achieve the effect of color enhancement or color adjustment. However, these common methods are often not effective in enhancing the color of some disperse dyes with aniline parent structures, especially yellow dyes, resulting in insufficient actual color depth and lighter color.

[0004] 2. Insufficient color fastness: The π-π stacking between disperse dye molecules and polyester fiber macromolecules is an important basis for increasing the interaction between dye molecules and fiber macromolecules, thereby improving the color fastness of disperse dye dyeing. However, in the current market, a considerable number of disperse dye structures often have a large proportion of chain structures and a small proportion of aromatic structures. As a result, the overall planarity of the dye molecules is poor, the contact area with the polyester fiber macromolecule chain becomes smaller, the π-π stacking is reduced, and the van der Waals force is reduced, which directly leads to a lower dyeing rate of disperse dyes on polyester fibers and insufficient color fastness.

[0005] 3. Insufficient light fastness: Light stability is an important property of disperse dyes in actual dyeing applications. However, the currently common disperse dyes with aniline matrix structure often have weak light stability of aniline chromophores, and photo-oxidation or photo-reduction reactions occur after long-term exposure to ultraviolet or visible light, resulting in fading of the dyes and insufficient light fastness.

[0006] In summary, among the many commercial disperse dyes that are widely used at present, there are still a considerable number of dyes that have problems such as light color, low color fastness, and insufficient light fastness due to reasons such as single color development structure, low molecular coplanarity, and poor structural light stability.

[0007] As an important branch of disperse dyes, heterocyclic disperse dyes have gradually attracted attention in the field of synthesis research and dye production in recent years due to their excellent properties. For example, the Chinese invention patent with announcement number CN115612309B discloses a method for preparing heterocyclic diester-based azo disperse dyes, which attempts to improve the fastness of the dyes through the synergistic effect of quinoline heterocyclic structure and acid ester structure. The prepared disperse dyes are safe and environmentally friendly, with high color fastness, high dispersibility, high dyeing rate and other characteristics, but there is still room for improvement in light fastness. Summary of the invention

[0008] The technical problem to be solved by the present invention is to provide a diheterocyclic yellow azo disperse dye with high dyeing rate, color fastness and light fastness, and a synthesis method and application thereof.

[0009] In order to solve the above technical problems, the technical solution adopted by the present invention is: a diheterocyclic yellow azo disperse dye, the structure of which is shown in formula (1):

[0010]

[0011] Wherein, R is methyl or ethyl.

[0012] Another technical solution adopted by the present invention is: the synthesis method of the above-mentioned biheterocyclic yellow azo disperse dye comprises the following steps:

[0013] S1: adding a catalyst and a compound of formula (2) to an alcohol, stirring to carry out an esterification reaction, and purifying after the reaction to obtain a compound of formula (3); adding a compound of formula (4) to a concentrated acid solution to dissolve it, cooling it in an ice-water bath, adding nitrosyl sulfuric acid, stirring to carry out a diazotization reaction, and then adding aminosulfonic acid to neutralize excess nitrosyl sulfuric acid to obtain a solution of a compound of formula (5);

[0014] S2: dispersing the compound of formula (3) in ice water, beating the mixture in an ice water bath to obtain a dispersed aqueous solution of the compound of formula (3); dripping a solution of the compound of formula (5) into the dispersed aqueous solution of the compound of formula (3), then adjusting the pH of the solution to 6.5-7.0 to perform a diazo coupling reaction, filtering the reaction solution and retaining the filter residue for purification to obtain a biheterocyclic yellow azo disperse dye;

[0015]

[0016] Wherein, R is methyl or ethyl.

[0017] Another technical solution adopted by the present invention is: use of the above-mentioned biheterocyclic yellow azo disperse dye in the preparation of commercial dyes.

[0018] The beneficial effect of the present invention is that the present invention uses the planarity, light stability and color depth of heterocyclic structures, namely benzothiazole and pyrazolone, to design and synthesize a yellow disperse dye with a high dye uptake rate for polyester. The dye is used to dye polyester fibers, and the dye uptake rate reaches more than 80.0%, the color fastness to dry and wet friction reaches more than level 4, and the light fastness reaches more than level 5. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The target dye I of Example 1 of the present invention is shown in FIG. 1 H NMR test pattern;

[0020] Figure 2 The target dye II of Example 2 of the present invention is shown. 1 H NMR test pattern;

[0021] Figure 3 Shown are the UV-visible light absorption spectra of the target dye I and the target dye II of the present invention;

[0022] Figure 4 The above is a graph showing the change in dyeing temperature according to the ninth embodiment of the present invention. DETAILED DESCRIPTION

[0023] In order to explain the technical content, achieved objectives and effects of the present invention in detail, the following is an explanation in combination with the implementation modes and the accompanying drawings.

[0024] A diheterocyclic yellow azo disperse dye, the structure of which is shown in formula (1):

[0025]

[0026] Wherein, R is methyl or ethyl.

[0027] As can be seen from the above description, the beneficial effects of the present invention are: in order to solve the problems of insufficient color depth, low color fastness and low light fastness of some current disperse dyes, the present invention introduces a double heterocyclic structure into the disperse dye structure to improve the planarity of the dye chemical structure, thereby increasing the contact area between the dye molecule and the polyester fiber macromolecule and the π-π stacking degree, and enhancing the dye-fiber interaction force. At the same time, due to the stability of the double heterocyclic structure-benzothiazole and pyrazolone to photochemical reactions, their introduction greatly improves the light fastness of the disperse dye, and the light fastness grade of the polyester fabric dyed with the synthesized dye is 6 or above. Adding an ester group of a chain structure to the dye structure can increase the contact area between the dye and the polyester fiber, increase the intermolecular interaction force between the dye and the fiber, and finally achieve the effect of improving the dye uptake rate.

[0028] Therefore, the biheterocyclic yellow azo disperse dye of the present invention has excellent dye uptake and color fastness, effectively saving the amount of dye and related resources. At the same time, the dye also has good light fastness, can effectively ensure the durability of dyed fabrics, and can be widely used in the industrial production of polyester fabrics.

[0029] Another technical solution adopted by the present invention is: the synthesis method of the above-mentioned biheterocyclic yellow azo disperse dye comprises the following steps:

[0030] S1: adding a catalyst and a compound of formula (2) to an alcohol, stirring to carry out an esterification reaction, and purifying after the reaction to obtain a compound of formula (3); adding a compound of formula (4) to a concentrated acid solution to dissolve it, cooling it in an ice-water bath, adding nitrosyl sulfuric acid, stirring to carry out a diazotization reaction, and after judging the completion of the reaction by the ring method, adding aminosulfonic acid to neutralize excess nitrosyl sulfuric acid to obtain a solution of a compound of formula (5);

[0031] S2: dispersing the compound of formula (3) in ice water, beating in an ice water bath to obtain a dispersed aqueous solution of the compound of formula (3); dripping a solution of the compound of formula (5) into the dispersed aqueous solution of the compound of formula (3), and then adjusting the pH of the solution to 6.5-7.0 to carry out a diazo coupling reaction. After judging that the reaction is completed by the ring penetration method, filtering the reaction solution and retaining the filter residue for purification to obtain a biheterocyclic yellow azo disperse dye;

[0032]

[0033] Wherein, R is methyl or ethyl.

[0034] As can be seen from the above description, the synthesis process of the present invention is as follows:

[0035]

[0036] The present invention is to completely dissolve the compound of formula (4) in a concentrated acid solution and then drop nitrosyl sulfuric acid to carry out a diazotization reaction. This method allows the compound of formula (4) and nitrosyl sulfuric acid to undergo a fully effective contact reaction in the form of a solution, thereby reducing the amount of acid used and the hydrolysis of the generated diazonium salt.

[0037] The compound of formula (3) of the present invention contains an ester group. When the pH value of the diazo coupling reaction is adjusted to 6.5-7.0, the hydrolysis of the ester structure can be prevented, the generation of dye byproducts can be reduced, and the pyrazolone ester can be prevented from being sensitive to pH changes, and the occurrence of tautomerism can be avoided to affect the reaction activity. The compound of formula (3) is a coupling component, and the compound of formula (5) is a diazo component. Aminosulfonic acid is added to remove excess nitrosyl sulfuric acid.

[0038] Furthermore, the purification in S1 includes the steps of extraction, water removal, filtration, rotary evaporation and drying performed in sequence.

[0039] Furthermore, the solvent used for extraction in S1 is ethyl acetate, and the pH is adjusted to 4.5-7.0 during extraction.

[0040] From the above description, it can be seen that the extraction is weakly acidic, the operation is simpler, and there is no obvious difference in the extraction effect within this acidity range.

[0041] Furthermore, anhydrous magnesium sulfate powder is added during water removal.

[0042] Furthermore, the purification in S2 includes recrystallization, filtration and drying steps performed sequentially.

[0043] Furthermore, the solvent used for recrystallization is anhydrous ethanol.

[0044] Furthermore, the catalyst is concentrated sulfuric acid.

[0045] Furthermore, the molar ratio of the alcohol to the compound of formula (2) in S1 is 4 to 6:1.

[0046] Preferably, the molar ratio of the alcohol to the compound of formula (2) in S1 is 4.5-5.5:1.

[0047] Furthermore, the reaction temperature of the esterification reaction in S1 is 110-120° C., and the reaction time is 3-4 h.

[0048] From the above description, it can be seen that the esterification reaction requires high temperature conditions to occur and sufficient time to complete the reaction.

[0049] Furthermore, the molar ratio of the compound of formula (4) to nitrosyl sulfuric acid in S1 is 1:1.05-1.1.

[0050] From the above description, it can be seen that the amount of nitrosyl sulfuric acid added is too much to ensure that the compound of formula (4) reacts completely. If the amount of nitrosyl sulfuric acid added is too large, more aminosulfonic acid is needed to neutralize the excess nitrosyl sulfuric acid, resulting in increased costs and waste.

[0051] Furthermore, the reaction temperature of the diazotization reaction in S1 is 0-5°C, and the reaction time is 0.5-1h.

[0052] Furthermore, the reaction temperature in the diazo coupling reaction in S2 is 0-5°C, and the reaction time is 4-8h.

[0053] From the above description, it can be seen that both the diazotization reaction and the diazo coupling reaction need to be controlled at a low temperature of 0 to 5°C to avoid the decomposition of the diazonium salt and the problem of low reaction activity. For the diazotization reaction, too short a reaction time may lead to incomplete reaction, and too long a reaction time may lead to decomposition of unstable diazonium salts. For the diazo coupling reaction, due to the stability of the reaction product, too long a reaction time will not lead to the generation of side reactions, but too short a reaction time may lead to incomplete reaction.

[0054] Furthermore, the molar ratio of the compound of formula (5) in the solution of the compound of formula (3) and the compound of formula (5) in S2 is 1:1.2-1.3.

[0055] From the above description, it can be seen that the amount of the compound of formula (5) added is relatively large to ensure that the compound of formula (3) reacts completely.

[0056] Furthermore, the compound of formula (3) is methyl pyrazolone formate or ethyl pyrazolone formate.

[0057] Another technical solution adopted by the present invention is: the use of the above-mentioned biheterocyclic yellow azo disperse dye in the preparation of commercial dyes, that is, a method for preparing a dye paste.

[0058] Furthermore, the method comprises the following steps: mixing and pre-dispersing the diheterocyclic yellow azo disperse dye, a dispersant, zirconium oxide beads and deionized water, and then grinding to obtain a commercial dye.

[0059] Furthermore, the grinding time is 6 to 8 hours, and the grinding speed is 450 revolutions per minute.

[0060] Furthermore, the mass ratio of the diheterocyclic yellow azo disperse dye, the dispersant, the zirconium oxide beads, and the deionized water is 0.1:0.1 to 0.3:30:20.

[0061] Furthermore, the diameter of the zirconia beads is 0.3 to 0.4 mm.

[0062] Furthermore, the dispersant includes any one of dispersant NNO, dispersant MF and sodium lignin sulfonate.

[0063] From the above description, it can be seen that these three types of dispersants are currently widely available in the market, are inexpensive, have good effects, and have low costs of use.

[0064] Another technical scheme adopted by the present invention is: the polyester dyeing method using the above commercial dye comprises the following steps: the commercial dye is used to prepare a dye liquor with a pH value of 4.5 to 5.5, the mass ratio of the polyester fabric to the diheterocyclic yellow azo disperse dye in the dye liquor is 50:1, and the bath ratio of the polyester fabric to the dye liquor is 1:40; during dyeing, the dyeing temperature is heated to 70°C at a heating rate of 2°C / min, kept warm for 10 minutes, then heated to 130°C at a rate of 2°C / min, kept warm for 30 to 45 minutes, and then cooled to room temperature; after taking the dyed polyester fabric out of the dye liquor, washing, reduction cleaning and drying are carried out in sequence to complete the dyeing.

[0065] From the above description, it can be seen that the beneficial effects of the present invention are: the dye of the present invention is used to dye polyester fibers, the dyeing rate reaches more than 80.0%, the dry and wet friction color fastness reaches more than level 4, the sunlight fastness reaches more than level 5, and the polyester fiber fabric after dyeing obtains a darker yellow color.

[0066] Embodiment 1 of the present invention is: a biheterocyclic yellow azo disperse dye, the structure of which is shown in formula (6), named as target dye I:

[0067]

[0068] Wherein, R is a methyl group.

[0069] The target dye I 1 H NMR test (600MHz, Chloroform-d (deuterated chloroform)) and UV-Vis absorption spectrum test, the test results are shown in Figure 1 and Figure 3 .

[0070] Embodiment 2 of the present invention is: a biheterocyclic yellow azo disperse dye, the structure of which is shown in formula (7), named as target dye II:

[0071]

[0072] Wherein, R is ethyl.

[0073] Target dye II 1 H NMR test (600MHz, Chloroform-d (deuterated chloroform)) and UV-Vis absorption spectrum test, the test results are shown in Figure 2 and Figure 3 .

[0074] Embodiment 3 of the present invention is: the synthesis method of the diheterocyclic yellow azo disperse dye in Embodiment 1, the steps are as follows:

[0075] S1: 2.18 g (10 mmol) of the compound of formula (2) (1-(4-carboxyphenyl)-3-methyl-5-pyrazolone), 1.60 g (50 mmol) of anhydrous methanol, and 0.1 mL of concentrated sulfuric acid were added to a 100 mL round-bottom flask in sequence, and the mixture was stirred and evenly mixed. Under the condition of an external condensation water device, the mixture was heated and stirred under reflux at 120°C for 4 h. After the reaction was completed, 10 wt% Na 2 CO 3 solution, adjusting the pH of the solution to 4.5-7.0, adding ethyl acetate for extraction; then taking the upper ethyl acetate oil phase, adding anhydrous magnesium sulfate powder to the extracted ethyl acetate, standing for 5 hours, then filtering, rotary evaporating, and drying to obtain the compound of formula (8) (1-(4-methylformylphenyl)-3-methyl-5-pyrazolone);

[0076] In a 50 mL three-necked flask, add 1 mL of 98% (m / m) concentrated sulfuric acid, 3 mL of 85% (m / m) concentrated phosphoric acid, and 0.923 g (5 mmol) of the compound of formula (4) (aminobenzothiazole). Stir thoroughly until all components are completely dissolved, and then cool to 0-5°C in an ice-water bath. Slowly drop 0.362 g of NaNO 2 With 2mL HO 2 SO 4 The prepared nitrosyl sulfuric acid solution is reacted at 0-5°C for 1 hour; after the reaction is completed, a small amount of aminosulfonic acid (the molar amount of aminosulfonic acid is the molar amount difference between nitrosyl sulfuric acid and aminobenzothiazole) is added to obtain a solution of the compound of formula (5) (diazonium salt of aminobenzothiazole);

[0077] S2: ultrasonically disperse 5 mmol of the compound of formula (8) in a small amount of ice water, cool the dispersion to below 5°C in an ice water bath, and slurry the dispersion to obtain a dispersion aqueous solution of the compound of formula (8); drip 6 mmol of the solution of the compound of formula (5) into the dispersion aqueous solution of the compound of formula (8) while adding crushed ice, and after the dripping is completed, drip 20 wt% of Na 2 CO 3 solution, adjusting the solution pH to 6.5-7.0; then continuing to stir and react at 0-5°C for 4 hours, and continuing to stir at room temperature for 4 hours; after the reaction is completed, using 20wt% Na 2 CO 3 The solution was adjusted to a neutral pH, and the residue was filtered under reduced pressure to be retained, and then recrystallized in anhydrous ethanol, and then filtered and dried to obtain the target dye I in the form of an orange-yellow solid powder;

[0078]

[0079] Embodiment 4 of the present invention is:

[0080] The only difference between Example 4 and Example 3 is that anhydrous methanol is replaced by an equal molar amount of anhydrous ethanol, the esterification product is a compound of formula (9) (1-(4-ethylformylphenyl)-3-methyl-5-pyrazolone), and the final product is the target dye II;

[0081]

[0082] Embodiment 5 of the present invention is: the synthesis method of the diheterocyclic yellow azo disperse dye in Embodiment 1, the steps are as follows:

[0083] S1: 2.18 g (10 mmol) of the compound of formula (2), 1.28 g (40 mmol) of anhydrous methanol, and 0.1 mL of concentrated sulfuric acid were added to a 100 mL round-bottom flask in sequence, and the mixture was stirred and shaken thoroughly. Under the condition of an external condensation water device, the mixture was heated and stirred under reflux at 110 ° C for 3.5 h. After the reaction was completed, 10 wt% Na 2 CO 3 solution, adjusting the pH of the solution to 4.5-7.0, adding ethyl acetate for extraction; then taking the upper ethyl acetate oil phase, adding anhydrous magnesium sulfate powder to the extracted ethyl acetate, standing for 4 hours, and then filtering, rotary evaporating, and drying to obtain a compound of formula (8);

[0084] In a 50 mL three-necked flask, add 1 mL of 98% (m / m) concentrated sulfuric acid, 3 mL of 85% (m / m) concentrated phosphoric acid, and 0.923 g (5 mmol) of the compound of formula (4). Stir thoroughly until all components are completely dissolved, and then cool to 0-5°C in an ice-water bath. Slowly drop 0.35 g of NaNO 2 With 2mL HO 2 SO 4 The prepared nitrosyl sulfuric acid solution is reacted at 0-5°C for 0.8h; after the reaction is completed, a small amount of aminosulfonic acid (the molar amount of aminosulfonic acid is the molar amount difference between nitrosyl sulfuric acid and aminobenzothiazole) is added to obtain a solution of the compound of formula (5);

[0085] S2: ultrasonically disperse 5 mmol of the compound of formula (8) in a small amount of ice water, cool the dispersion to below 5°C in an ice water bath, and slurry the dispersion to obtain a dispersion aqueous solution of the compound of formula (8); drip 6.5 mmol of the solution of the compound of formula (5) into the dispersion aqueous solution of the compound of formula (8) while adding crushed ice, and after the dripping is completed, drip 20 wt% of Na 2 CO 3 solution, adjusting the solution pH to 6.5-7.0; then continuing to stir and react at 0-5°C for 5 hours, and continuing to stir at room temperature for 4 hours; after the reaction is completed, using 20wt% Na 2CO 3 The pH of the solution was adjusted to neutral, and the residue was retained by filtration under reduced pressure, which was recrystallized in anhydrous ethanol. The target dye I was obtained as an orange-yellow solid powder after filtration and drying.

[0086] Embodiment 6 of the present invention is: a method for synthesizing the diheterocyclic yellow azo disperse dye in Embodiment 1, comprising the following steps:

[0087] S1: 2.18 g (10 mmol) of the compound of formula (2), 1.92 g (60 mmol) of anhydrous methanol, and 0.1 mL of concentrated sulfuric acid were added to a 100 mL round-bottom flask in sequence, and the mixture was stirred and evenly mixed. Under the condition of an external condensation water device, the mixture was heated and stirred under reflux at 115 ° C for 3 h. After the reaction was completed, 10 wt% Na 2 CO 3 solution, adjusting the pH of the solution to 4.5-7.0, adding ethyl acetate for extraction; then taking the upper ethyl acetate oil phase, adding anhydrous magnesium sulfate powder to the extracted ethyl acetate, standing for 6 hours, then filtering, rotary evaporating, and drying to obtain a compound of formula (8);

[0088] In a 50 mL three-necked flask, add 1 mL of 98% (m / m) concentrated sulfuric acid, 3 mL of 85% (m / m) concentrated phosphoric acid, and 0.923 g (5 mmol) of the compound of formula (4). Stir thoroughly until all components are completely dissolved, and then cool to 0-5°C in an ice-water bath. Slowly drop 0.37 g of NaNO 2 With 2mL HO 2 SO 4 The prepared nitrosyl sulfuric acid solution is reacted at 0-5°C for 0.5h; after the reaction is completed, a small amount of aminosulfonic acid (the molar amount of aminosulfonic acid is the molar amount difference between nitrosyl sulfuric acid and aminobenzothiazole) is added to obtain a solution of the compound of formula (5);

[0089] S2: ultrasonically disperse 5 mmol of the compound of formula (8) in a small amount of ice water, cool the dispersion to below 5°C in an ice water bath, and slurry the dispersion to obtain a dispersion aqueous solution of the compound of formula (8); drip 6 mmol of the solution of the compound of formula (5) into the dispersion aqueous solution of the compound of formula (8) while adding crushed ice, and after the dripping is completed, drip 20 wt% of Na 2 CO 3 solution, adjusting the solution pH to 6.5-7.0; then continuing to stir and react at 0-5°C for 8h, and continuing to stir at room temperature for 4h; after the reaction is completed, using 20wt% Na 2 CO 3 The pH of the solution was adjusted to neutral, and the residue was retained by filtration under reduced pressure, which was recrystallized in anhydrous ethanol. The target dye I was obtained as an orange-yellow solid powder after filtration and drying.

[0090] Embodiment 7 of the present invention is: a method for preparing a dye paste from target dye I, the steps are as follows:

[0091] 0.1 g of target dye, 0.1 g of dispersant NNO, 20 g of zirconia beads with a diameter of 0.3-0.4 mm and 20 mL of deionized water were added into a sand mill and mechanically ground at a speed of 450 rpm for 6 h. After grinding, the mixture was filtered and the filtrate was added to a 50 mL volumetric flask with clean water to make up to volume to obtain dye paste I.

[0092] Embodiment 8 of the present invention is: a method for preparing a dye paste from target dye II, the steps are as follows:

[0093] 0.1 g of the target dye, 0.3 g of sodium lignin sulfonate, 20 g of zirconium oxide beads with a diameter of 0.3-0.4 mm and 20 mL of deionized water were added into a sand mill and mechanically ground at a speed of 450 rpm for 8 h. After grinding, the mixture was filtered and the filtrate was added to a 50 mL volumetric flask with clean water to make up to volume to obtain dye paste II.

[0094] Embodiment 9 of the present invention is: dyeing polyester fabric with dye paste I and dye paste II respectively, and the dyeing method is as follows: after removing the dye paste according to the chromaticity requirement of 2% owf, adding water at a dye bath ratio of 1:20 and transferring it to a dyeing cup; then, slowly dripping 3g / L glacial acetic acid solution into the dyeing cup to adjust the pH of the dyeing solution to 4.5-5.5, adding the wetted polyester fabric to the dyeing cup, the mass ratio of the polyester fabric to the biheterocyclic yellow azo disperse dye in the dyeing solution is 50:1; putting it into a high temperature and high pressure infrared dyeing machine, heating it to 70°C at 2°C / min, keeping it warm for 10min, and then heating it to 130°C at 2°C / min, keeping it warm for 45min and then cooling it to room temperature (see Figure 4 ), take out the dyed fabric sample, wash it with clean water, perform reduction washing, and dry it to obtain the dyed fabric sample, and calculate the dye uptake rate, dry friction resistance grade, wet friction resistance grade, and sunlight resistance grade of the dyed fabric sample.

[0095] (1) The dye uptake rate was determined by taking 0.1 ml of the fully dispersed dye solution before and after dyeing into a 10 ml volumetric flask, adding acetone to the volume, and using a UV-visible spectrophotometer to measure the maximum absorption wavelength (λ max ) to measure the absorbance, and calculate the dyeing rate according to the following formula:

[0096] E(%)=(1-A 1 ) / A 0 ×100%

[0097] Among them, A 0 is the absorbance of the dye solution before staining, A 1is the absorbance of the residual solution after staining.

[0098] (2) The test methods for color fastness to dry abrasion, wet abrasion and sunlight exposure are as follows: after the dyed fabric samples are treated with reduction cleaning according to the treatment method of the national standard "Test method for color shade and intensity of disperse dyes" (GB / T 2394□2013), their color fastness to dry abrasion, wet abrasion and sunlight exposure are measured according to the national standards "Textiles - Tests for color fastness - Color fastness to rubbing" (GB / T 3920-2008) and "Textiles - Tests for color fastness - Color fastness to artificial light: Xenon arc fading lamp" (GB / T8427-2019). The test results are shown in the following table:

[0099] dye Dyeing rate (%) Dry friction grade Wet friction grade Sun resistance level Dye Paste Ⅰ 92.5 4 4～5 6 Dye Paste Ⅱ 94.1 4～5 4～5 7

[0100] In summary, the biheterocyclic yellow azo disperse dye provided by the present invention and its synthesis method and application have the following advantages:

[0101] 1. The introduction of double heterocyclic structures - benzothiazole and pyrazolone into the disperse dye structure enhances the dye-fiber interaction, solves the current problems of insufficient color depth and low color fastness of some disperse dyes, and greatly improves the sunlight fastness of disperse dyes.

[0102] 2. After the compound of formula (4) is completely dissolved in a concentrated acid solution, nitrosylsulfuric acid is added dropwise to carry out a diazotization reaction, thereby reducing the amount of acid used and the hydrolysis of the generated diazonium salt.

[0103] 3. Adjusting the solution pH to 6.5-7.0 or weak acidity can prevent the hydrolysis of the ester structure and reduce the formation of dye by-products.

[0104] 4. The dye uptake rate of the dye of the present invention on polyester fiber reaches more than 80.0%, the color fastness to dry and wet friction reaches more than level 4, and the light fastness reaches more than level 5. After dyeing, the polyester fiber fabric obtains a darker yellow color.

[0105] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention's specification and drawings, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A diheterocyclic yellow azo disperse dye, characterized in that: The structure of the diheterocyclic yellow azo disperse dye is shown in formula (1): Wherein, R is methyl or ethyl.

2. The method for synthesizing a diheterocyclic yellow azo disperse dye according to claim 1, wherein: The following steps are involved: S1: adding a catalyst and a compound of formula (2) to an alcohol, stirring to carry out an esterification reaction, and purifying after the reaction to obtain a compound of formula (3); adding a compound of formula (4) to a concentrated acid solution to dissolve it, cooling it in an ice-water bath, adding nitrosyl sulfuric acid, stirring to carry out a diazotization reaction, and then adding aminosulfonic acid to neutralize excess nitrosyl sulfuric acid to obtain a solution of a compound of formula (5); S2: dispersing the compound of formula (3) in ice water, beating the mixture in an ice water bath to obtain a dispersed aqueous solution of the compound of formula (3); dripping a solution of the compound of formula (5) into the dispersed aqueous solution of the compound of formula (3), then adjusting the pH of the solution to 6.5-7.0 to perform a diazo coupling reaction, filtering the reaction solution and retaining the filter residue for purification to obtain a biheterocyclic yellow azo disperse dye; Wherein, R is methyl or ethyl.

3. The synthetic method of the diheterocyclic yellow azo disperse dye according to claim 2, characterized in that, The molar ratio of the alcohol to the compound of formula (2) in S1 is 4 to 6:

1.

4. The method for synthesizing a diheterocyclic yellow azo disperse dye according to claim 2, wherein: The reaction temperature of the esterification reaction in S1 is 110-120° C., and the reaction time is 3-4 hours.

5. The method for synthesizing a diheterocyclic yellow azo disperse dye according to claim 2, characterized in that: The molar ratio of the compound of formula (4) in S1 to nitrosyl sulfuric acid is 1:1.05-1.

1.

6. The method for synthesizing a diheterocyclic yellow azo disperse dye according to claim 2, characterized in that: The reaction temperature of the diazotization reaction in S1 is 0-5°C, and the reaction time is 0.5-1h.

7. The method for synthesizing a diheterocyclic yellow azo disperse dye according to claim 2, characterized in that: The reaction temperature in the diazo coupling reaction in S2 is 0-5°C, and the reaction time is 4-8h.

8. The method for synthesizing a diheterocyclic yellow azo disperse dye according to claim 2, characterized in that: The molar ratio of the compound of formula (5) in the solution of the compound of formula (3) and the compound of formula (5) in S2 is 1:1.2-1.

3.

9. Use of the diheterocyclic yellow azo disperse dye as claimed in claim 1 in making commercial dyes.

10. The use according to claim 9, characterized in that: The method comprises the following steps: mixing and pre-dispersing a diheterocyclic yellow azo disperse dye, a dispersant, zirconium oxide beads and deionized water, and then grinding to obtain a commercial dye.

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