High-light-color-fastness red dye containing bisazo structure as well as preparation method and application of high-light-color-fastness red dye

Abstract

The invention discloses a high-light-color-fastness red dye containing a bisazo structure and a preparation method and application thereof, the structural general formula of the high-light-color-fastness red dye containing the bisazo structure is shown as a formula III, and X is one or more of-F,-Cl or-CN. The preparation method comprises the following steps: carrying out cyclization reaction on an aromatic diamine derivative and thiocyanate under a catalytic condition to obtain an aminobenzothiazole series compound, carrying out diazotization pretreatment on the aminobenzothiazole series compound and naphthalene aminodisulfonate, coupling to obtain a material containing an azo structure, and connecting a hindered amine group to aromatic amine through ylide reaction to obtain the compound containing the azo structure. And reacting with trichlorocyanuric chloride, and reacting with a material containing an azo structure under an alkaline condition. The dye contains a benzothiazole group and a hindered amine group capable of absorbing ultraviolet light, has high stability to light and an oxidant or free radicals, contains hydroxyl capable of being coordinated with copper ions in molecules, further enhances the color fastness to light, and discovers that the red color of the dye has good color fastness to light through cloth dyeing experiments. # imgabs0 #

Description

Technical Field

[0001] The invention relates to a high light color fastness red dye containing a disazo structure and a preparation method and application thereof, belonging to the field of azo dyes. Background Art

[0002] Reactive dye ink is composed of high-purity reactive salt-free dye, co-solvent and deionized water, and is used for digital printing of fabrics such as cotton fiber, silk and wool. Most of the existing reactive dyes are based on the blue spectrum, and the light fastness of red spectrum reactive dyes is generally low. At present, only some azo groups have hydroxyl groups with coordination ability at the two ortho positions, which form a stable chelate ring with copper to improve light fastness. Generally speaking, the light fastness will increase with the increase of color depth. The main reason is that the larger the particles of dye aggregate on the fiber, the smaller the specific surface area of ​​dye particles exposed to the air, and the higher the light fastness. At present, the various series of reactive dye inks sold by Huntsman Company in Europe, DyStar Company in Germany and Epson Company in Japan are all representative and widely used reactive dye ink products. Although many domestic ink companies and scientific research institutions are also developing reactive dye inks, the quality of reactive dye inks developed in China is still far behind that of foreign countries. One of the more prominent problems is that red reactive dye ink has poor light fastness. When mixed with yellow and blue dye inks, red light is prone to fade first, causing color deviation of textiles. Therefore, it is urgent to develop a red dye with high light fastness. Summary of the invention

[0003] Purpose of the invention: The first purpose of the present invention is to provide a high light color fastness red dye containing a disazo structure, the second purpose of the present invention is to provide a preparation method of the high light color fastness red dye containing a disazo structure, and the third purpose of the present invention is to provide the use of the high light color fastness red dye containing a disazo structure in the preparation of polyester fiber textile materials or their blended fiber products.

[0004] Technical solution: The present invention discloses a red dye with high light fastness containing a disazo structure, and the general structural formula of the red dye with high light fastness containing a disazo structure is as shown in Formula III:

[0005]

[0006] Wherein, X is one or more of -F, -Cl or -CN.

[0007] Furthermore, the azo red dye compound is selected from any one of the following formulas III-1 to III-3:

[0008] The preparation method of the high light color fastness red dye containing a disazo structure of the present invention is synthesized according to the following route:

[0009]

[0010] Wherein, X is one or more of -F, -Cl or -CN.

[0011] Further, compound I is synthesized according to the following route:

[0012]

[0013] Furthermore, compound IX was synthesized according to the following route:

[0014]

[0015] Further, compound II is synthesized according to the following route:

[0016]

[0017] Wherein, X is one or more of -F, -Cl or -CN.

[0018] Furthermore, compound VI was synthesized according to the following route:

[0019]

[0020] Wherein, X is one or more of -F, -Cl or -CN.

[0021] Furthermore, Derived from any of the following compounds:

[0022]

[0023] The invention discloses an application of the high light color fastness red dye containing a disazo structure in the preparation of polyester fiber textile materials or blended fiber products thereof.

[0024] Furthermore, the polyester fiber textile material or its blended fiber products are used for dyeing and / or printing.

[0025] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0026] The molecular structure of the high light color fastness red dye containing a disazo structure in the present invention is a conjugated rigid structure as a whole, and the molecular size is large, which is easy to accumulate on the surface of the material, reducing the surface area exposed to the air, and has good light resistance. In addition, the compound structure contains a cyanobenzothiazole group that can absorb ultraviolet bands, and also has a hindered amine fragment, which further enhances its resistance to ultraviolet light oxidation. It has been verified by cloth dyeing experiments that it has good light color fastness. The synthesis method is simple, and it is easy to realize industrial production. It can be widely used in the dyeing and printing of polyester fiber textile materials and their blended fiber products, improving the wearing performance of textiles and promoting the development of downstream fabrics. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is the ultraviolet absorption spectrum diagram of the red disperse dye molecule prepared in Example 1 to Example 3. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further described below in conjunction with the accompanying drawings.

[0029] Example 1 Synthesis of Intermediate IX

[0030] The synthetic route is as follows:

[0031]

[0032] Under nitrogen protection, add 0.01 mol of 4-acetamidobenzyl bromide (raw material 5) and 2.0 mL of triethyl phosphite to a 50 mL single-necked flask, heat to 130 ° C and stir for 3 hours. After the reaction is complete, cool to room temperature to obtain a colorless oil, add 20 mL of tetrahydrofuran (THF) and stir to mix. Weigh 1.2 g of NaH (the molar ratio with raw material 5 is 5:1) and disperse it in 20 mL of THF, slowly drip the above solution, stir at room temperature for 30 minutes, and then add 10 mL of THF solution containing 0.01 mol of 2,2,6,6-tetramethyl-4-piperidone (raw material 4) dropwise. React at room temperature for 2 to 3 hours, and use TLC to detect the reaction until there is almost no raw material point. The reaction was quenched with ice water, filtered and dried directly. The product was recrystallized and purified with a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 3:1 to obtain a light yellow solid VII product with a yield of 92%. HPLC analysis of a sample of the VII product showed that the recrystallization purification reaction was completed when the content of piperidone was ≤1%.

[0033] Take 0.01 mol of compound VII and 0.02 mol of dichlorothionyl, 40 mL of methanol as solvent, stir and react at 40 ° C for 3 hours to obtain a deacetylated product VIII solution. After the raw material point almost disappears by TLC detection, unreacted dichlorothionyl and methanol solvent are removed by vacuum distillation. Add THF solution containing 0.012 mol of ethylene oxide to the system, add 0.001 mol of Sm(CF 3 SO 3 ) 3 As a catalyst, the reaction was stirred for 2 hours. After the raw material spot was almost disappeared by TLC detection, the unreacted reactants and solvent were evaporated under reduced pressure, and the reaction product was recrystallized with a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1:1 to obtain light yellow crystalline compound IX with a total yield of 90%. A sample of compound IX was taken for HPLC detection and analysis. If the deacetylated product VIII was ≤1%, the recrystallization purification reaction was completed.

[0034] The elemental analysis of compound IX showed the following results: Elemental analysis: (%) for C 18 H 28 N 2 O: Calculated: C 74.89; H 9.7; N 9.7, Found: C 74.91; H 9.64; N 9.68.

[0035] Compound IX was analyzed by H NMR spectrum, and the results were: 1 HNMR (500MHz, CDCl 3 ,TMS): d=9.55(br,1H),6.72~7.72(m,4H),6.15(s,1H),4.33(br,1H),3.5~3.61(m,4H),2.01(s,4H),1.27(s,12H),1.08(s,1H)ppm.

[0036] From the above analysis, it can be seen that the structure of compound IX is as follows:

[0037]

[0038] Example 2 Preparation of red disperse dye R1

[0039] The synthetic route is as follows:

[0040]

[0041]

[0042] 1. In a four-necked flask equipped with an electric stirrer, a reflux condenser, a thermometer and a feeding funnel, add 0.01 mol 2,5-difluoro-1,4-diphenylamine (Formula 3-1), 15 mL water, slowly add 0.02 mol concentrated sulfuric acid at a temperature below 50 ° C for reaction, then add 0.022 mol ammonium thiocyanate, gradually heat to 85 ° C for reaction for 5 hours, and then evaporate the water under reduced pressure to obtain the product shown in Formula IV-1. Add 50 mL chloroform to the four-necked flask, change the feeding funnel to a vent pipe, and place the four-necked flask in an ice-water bath. When the temperature drops to about 10 ° C, start to pass chlorine to the reaction system, control the chlorine introduction speed (5 ml / min), make the solution temperature in the reaction container at 10-15 ° C, and the chlorine introduction amount is 0.4-0.5 g. When the TLC chromatogram tracks that the raw material remains 4%-5%, stop passing chlorine, continue stirring at this temperature for 0.5 hours, and stop stirring. Add 30 mL of water and distill under normal pressure to remove all chloroform. At this time, the material is fully dissolved. Cool to room temperature and neutralize with 10% sodium hydroxide solution to pH 7-8. Cool to 15-20°C and filter. The filter cake is slurried twice with 40 mL of water and then filtered to obtain the benzothiazole derivative shown in formula V-1. 2 SO 4 The solution was adjusted to a pH between 1 and 2, stirred, and then cooled to 5 to 8 °C with ice, followed by slow dropwise addition of 0.022 mol NaNO 2 (mass concentration is 30%) aqueous solution, diazotization reaction for 2h to obtain solution 1 shown in formula VI-1. After dissolving 0.02mol 4-amino-5-hydroxy-2,7-naphthalene disulfonic acid (formula 2) in 30mL water, 30% sodium carbonate solution was added to adjust the pH of the solution to pH>6.5 to obtain solution 2, solution 1 was slowly added dropwise to solution 2, and the coupling reaction was carried out under the conditions of maintaining the temperature at 12-15°C and pH=6-7, and the red dye precursor solution 3 conforming to formula II-1 was obtained after stirring the reaction for 3h.

[0043] 2. Add 0.02 mol of cyanuric chloride (Formula 1) raw material to 30 g of ice / water mixture (mass ratio 1:1), add 5 drops of methyl silicone oil to assist ice grinding, and then carry out substitution reaction with 0.02 mol of aqueous solution of compound IX prepared in Example 1, control the temperature at 10-15°C, pH=2-3, stir the reaction for 3 hours to obtain solution 4 of the substitution product shown in Formula I, and directly carry out the next step reaction without separation.

[0044] 3. Add solution 3 dropwise into solution 4 for the second substitution reaction, maintain pH = 5-7, temperature at 30-50°C, stir the reaction for 3 hours, filter to remove insoluble impurities, and use a nanomembrane filtration system to remove most of the inorganic salts, water and a small amount of by-products to obtain the red dye represented by formula III-1 (denoted as R1), with a total yield of 78%.

[0045] The red dye compound R1 was analyzed by HPLC and had a purity of 96.7%.

[0046] The result of HPLC-MS analysis of red disperse dye R1 is [M+H] + 1718.2, [M+Na] + 1740.1.

[0047] The compound R1 was analyzed by nuclear magnetic hydrogen spectrum, and the result was: 1 HNMR (500MHz, CDCl 3 , TMS): d=8.5~9.01(br,8H),7.13~8.18(m,14H),6.15(s,2H),4.81(br,2H),3.25~3.61(m,8H),2.01(s,8H),1.27(s,24H),1.08(s,2H)ppm.

[0048] From the above analysis, it can be seen that the molecular structure of the red disperse dye R1 is shown in the following formula III-1:

[0049]

[0050] Example 3 Preparation of red disperse dye R2

[0051] The synthetic route is as follows:

[0052]

[0053]

[0054] The preparation process is the same as that of Example 2. The difference from Example 2 is that 0.01 mol of 2,5-dichloro-1,4-diphenylamine (Formula 3-2) is added in step 1 to replace Formula 3-1 in Example 2. The remaining raw materials and methods are the same as those in Example 1 and are not described here. The red disperse dye R2 is obtained with a yield of 80.1%. The red dye compound R2 is analyzed by HPLC, and the purity is 95.8%.

[0055] The result of HPLC-MS analysis of red disperse dye R2 is [M+H] + 1748.1, [M+Na]+ 1770.0.

[0056] The compound R2 was analyzed by nuclear magnetic hydrogen spectrum, and the result was: 1 HNMR (500MHz, CDCl 3 ,TMS): d=8.5~9.02(br,8H),7.13~8.19(m,14H),6.13(s,2H),4.80(br,2H),3.25~3.60(m,8H),2.02(s,8H),1.26(s,24H),1.07(s,2H)ppm.

[0057] From the above analysis, it can be seen that the molecular structure of the red disperse dye R2 is shown in the following formula III-2:

[0058]

[0059] Example 4 Preparation of red disperse dye R3

[0060] The synthetic route is as follows:

[0061]

[0062]

[0063] The preparation process is the same as that of Example 2, except that 0.01 mol of 2,5-diamino-p-terephthalonitrile (Formula 3-3) is added in step 1 to replace Formula 3-1 in Example 2, and the remaining raw materials and methods are the same as those of Example 1, which will not be described in detail. Red disperse dye R3 is obtained with a yield of 80.3%.

[0064] The red dye compound R3 was analyzed by HPLC and the purity was 94.8%.

[0065] The red dye compound R3 was subjected to HPLC-MS analysis to determine the red disperse dye R3, and the result was [M+H] + 1731.2, [M+Na] + 1753.1.

[0066] Compound R3 was analyzed by nuclear magnetic hydrogen spectrum, and the result was: 1 HNMR (500MHz, CDCl 3 ,TMS): d=8.5~9.01(br,8H),7.13~8.20(m,14H),6.14(s,2H),4.82(br,2H),3.25~3.62(m,8H),2.02(s,8H),1.27(s,24H),1.07(s,2H)ppm.

[0067] From the above analysis, it can be seen that the molecular structure of red disperse dye R3 is shown in the following formula III-3:

[0068]

[0069] The red disperse dye molecules prepared in Examples 1 to 3 were subjected to ultraviolet absorption spectroscopy analysis, and the results were as follows: Figure 1 As shown. Figure 1 It can be seen that R-1~R-3 all showed strong absorption at 510nm~560nm, corresponding to the blue-green band of visible light, showing red characteristics. In addition, due to the introduction of hindered amine fragments that can absorb ultraviolet light, the dye produced strong absorption in the ultraviolet region, indicating that the introduction of hindered amine fragments can enhance the absorption of dye molecules in the ultraviolet region that affects stability.

[0070] Example 5

[0071] 10 g of each red disperse dye obtained from R1 to R3 prepared in Examples 1 to 3 and comparative examples CI Reactive Red 1, CI Reactive Red 24 and CI Reactive Red 24:1 were dispersed and ground with a sand mill together with 12 g of dispersant MF, 3 g of sodium lignin sulfonate and 37.5 g of water. After the dispersion and grinding treatment, they were spray-dried. The spray-dried red dye was dispersed in 500 mL of water to form a dye suspension. 25 mL of the suspension was absorbed and mixed with 25 mL of water. The pH value of the dye bath was adjusted to 4 with acetic acid, the temperature was raised to 60° C., and 2.5 g of polyester fiber cloth were respectively put in. The temperature was raised to 130° C. in 30 min, kept warm for 50 min, cooled, thoroughly washed with water, and dried.

[0072] The dyed fabric samples were post-dyed according to the national standards GB / 3921-2008 "Textiles - Tests for Color Fastness - Color Fastness to Soaping", GB / 3920-2008 "Textiles - Tests for Color Fastness - Color Fastness to Rubbing", GB / T 8427-2009 "Textiles - Tests for Color Fastness to Artificial Light: Xenon Arc", and their color fastness to water, dry / wet rubbing, light fastness and sublimation were obtained. The test results are shown in Table 1.

[0073] Table 1 Performance data of dyes R1 to R3 prepared in Example 1 to Example 3 and color fastness of cotton fabrics printed with existing dye pastes

[0074]

[0075] As can be seen from Table 1 above, the red disperse R1 to R3 dyes prepared in Examples 1 to 3 have good water fastness, perspiration fastness, sunlight fastness and sublimation color fastness, and have comprehensive fastness performance. However, the dyes of comparative examples CI Reactive Red 1, CI Reactive Red 24, and CI Reactive Red 24:1 have poor sunlight fastness and sublimation fastness, and their overall fastness is worse than that of the red disperse R1 to R3 dyes prepared in Examples 1 to 3.

[0076] Finally, it should be noted that the above examples are only some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and there are many variations. All variations that can be directly derived or associated with the content disclosed by a person skilled in the art should be considered as the protection scope of the present invention.

Claims

1. A red dye with high light fastness containing a disazo structure, characterized in that: The general structural formula of the high light fastness red dye containing a disazo structure is shown in Formula III: Wherein, X is one or more of -F, -Cl or -CN.

2. The high light fastness red dye containing a disazo structure according to claim 1, characterized in that: The azo red dye compound is selected from any one of the following formulas III-1 to III-3:

3. The method for preparing the high light fastness red dye containing a disazo structure according to claim 1 or 2, characterized in that: Synthesized according to the following route: Wherein, X is one or more of -F, -Cl or -CN.

4. The preparation method according to claim 3, characterized in that: Compound I was synthesized according to the following route:

5. The preparation method according to claim 4, characterized in that: Compound IX was synthesized according to the following route:

6. The preparation method according to claim 3, characterized in that: Compound II was synthesized according to the following route: Wherein, X is one or more of -F, -Cl or -CN.

7. The preparation method according to claim 5, characterized in that: Compound VI was synthesized according to the following route: Wherein, X is one or more of -F, -Cl or -CN.

8. The preparation method according to claim 7, characterized in that: Derived from any of the following compounds:

9. Use of the high light color fastness red dye containing a disazo structure as claimed in claim 1 or 2 in the preparation of polyester fiber textile materials or their blended fiber products.

10. The use according to claim 9, characterized in that: It is used for dyeing and / or printing when preparing polyester fiber textile materials or their blended fiber products.

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