Azo red dye compound as well as preparation method and application thereof

Abstract

The invention discloses an azo red dye compound as well as a preparation method and application thereof. The structural general formula of the compound is shown as a formula III. A cyano aromatic amine derivative and thiocyanate are subjected to a cyclization reaction under the catalytic condition, and 2-aminobenzothiazole series compounds 1 are obtained. Naphthalene aminodisulfonate is used as a parent structure of the red dye to react with trichlorocyanuric chloride, and then the product and a compound 1 are subjected to diazotization pretreatment and then coupled to obtain a product 2. And connecting a hindered amine group to aromatic amine through ylide reaction to obtain a product 3. And reacting the product 3 with the product 2 under an alkaline condition to obtain the target dye compound. The red dye compound contains the benzothiazole group and the hindered amine group which can absorb ultraviolet light, so that the red dye compound has relatively high stability to light and an oxidizing agent or free radicals, and the molecules contain cyano groups capable of generating strong hydrogen-bond interaction and hydroxyl groups capable of being coordinated with copper ions, so that the light color fastness of the red dye compound can be enhanced. # imgabs0 #

Description

Technical Field

[0001] The invention relates to an azo red dye compound and a preparation method and application thereof, belonging to the field of azo dyes. Background Art

[0002] my country's national standards have long stipulated the light fastness of reactive dyes. For example, GB / T411-93 cotton printing and dyeing standard stipulates that the light fastness of reactive dye dyed cloth is 4 to 5. Among the existing reactive dyes, more than 75% of the parent structure is azo type, and the rest are anthraquinone type, phthalocyanine type and formazan type, mostly in blue color spectrum. Azo dyes have poor light fastness because the azo bond is easily photooxidized, while anthraquinone type, phthalocyanine type and formazan type dyes have relatively good light fastness. The light fading effect of dyes is very complicated. It is not only related to the chemical structure of the dye, but also to the aggregation state of the dye, the properties of the dyed fiber material, human sweat, temperature and other factors. Among them, the sunlight fastness of red spectrum reactive dyes is generally low. At present, only some azo groups have hydroxyl groups with coordination ability at the two adjacent positions, which form a stable chelate ring with copper to improve sunlight fastness.

[0003] Through the design, synthesis and structure-activity analysis of the molecular structure, some functional groups, UV absorption fragments or hindered amine photostabilization fragments that can strengthen intermolecular hydrogen bonds are introduced to inhibit the photooxidation or photoreduction reactions of azo dyes, which can improve the light fastness of the dyes to a certain extent and solve the problem of poor light fastness of existing red dyes on cotton fabrics and textiles. Summary of the invention

[0004] Purpose of the invention: The first purpose of the present invention is to provide an azo red dye compound that can improve light fastness. The second purpose of the present invention is to provide a method for preparing the azo red dye compound. The third purpose of the present invention is to provide an application of the azo red dye compound in the preparation of polyester fiber textile materials or their blended fiber products.

[0005] Technical solution: The azo red dye compound described in the present invention has a general structural formula as shown in Formula III:

[0006]

[0007] Wherein, X is a halogen.

[0008] Furthermore, X is preferably F or Cl.

[0009] Furthermore, the azo red dye compound is selected from any one of the following formulas III-1 to III-6:

[0010]

[0011] The preparation method of the azo red dye compound of the present invention is synthesized according to the following route:

[0012]

[0013] Wherein, compound I reacts with a benzothiazole diazonium salt derivative to obtain compound II, and compound II reacts with a hydroxyethyl aryl secondary amine to obtain the target compound III.

[0014] Furthermore, the raw materials for preparing compound I also include:

[0015]

[0016] Furthermore, the benzothiazole diazonium salt derivative is synthesized according to the following reaction route:

[0017]

[0018] Furthermore, Derived from one of the following compounds:

[0019]

[0020] Further, the hydroxyethyl aryl secondary amine is synthesized according to the following reaction route:

[0021]

[0022] The invention discloses an application of the azo red dye compound in the preparation of polyester fiber textile materials or blended fiber products thereof.

[0023] Furthermore, the polyester fiber textile material or its blended fiber products are used for dyeing and / or printing.

[0024] The azo red dye compound synthesized by the invention contains an ultraviolet absorption segment and a light stabilization segment.

[0025] The present invention selects cyano-substituted benzothiazole as an ultraviolet absorption fragment, adopts tetramethylpiperidinamine as a hindered amine light stabilization fragment, and prepares a red azo reactive dye with good light color fastness through a suitable synthesis route. The synthesized azo red dye compound contains an ultraviolet absorption fragment and a light stabilization fragment. CI Reactive Red 24:1, a mainstream red ink dye with a similar structure to CI Reactive Red, is used as a reference, and the light color fastness, the soaping color fastness of the dyed fabric, and the rubbing color fastness of the dyed fabric are tested according to national standards. The test data are comprehensively evaluated in terms of color fixation rate, light fading rate and color fastness, and it is found that the performance of the azo red dye in the present invention is better than CI Reactive Red 24:1.

[0026] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0027] The azo red dye compound of the present invention has a simple synthesis method and is easy to realize industrial production. The compound structure contains a cyanobenzothiazole group that can absorb ultraviolet waves and a hindered amine segment. The compound has good light color fastness as verified by cloth dyeing experiments. The compound can be widely used in dyeing and printing of polyester fiber textile materials and blended fiber products thereof, improves the wearing performance of textiles, and promotes the development of downstream fabrics. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The ultraviolet absorption spectra of the red disperse dye molecules RL-1 to RL-6 prepared in Examples 2 to 7 are shown. DETAILED DESCRIPTION

[0029] The technical solution of the present invention is further described below in conjunction with the accompanying drawings.

[0030] Example 1 Synthesis of Intermediate IX

[0031] The preparation route is as follows:

[0032]

[0033] Under nitrogen protection, add 0.01mol of acetamidobenzyl bromide (raw material 5) and 2.0mL of triethyl phosphite to a 50mL single-necked flask, heat to 130℃ and stir for 3h. After the reaction is complete, cool to room temperature to obtain a colorless oil, add 20mL of tetrahydrofuran (THF) and stir to mix. Weigh 1.2gNaH (the molar ratio with raw material 5 is 5:1) and disperse it in 20mL THF, slowly drip the above solution, stir at room temperature for 30min, and then add 10mL of THF solution containing 0.01mol 2,2,6,6-tetramethyl-4-piperidone (raw material 4) dropwise. React at room temperature for 2-3h, 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%.

[0034] Take 0.01mol of compound VII and 0.02mol of thionyl chloride, 40mL of methanol as solvent, stir and react at 40°C for 3h to obtain a deacetylated product VIII solution. After the reaction raw material point almost disappears by TLC chromatography, unreacted thionyl chloride and methanol solvent are removed by reduced pressure distillation. Add THF solution containing 0.012mol of ethylene oxide to the system, add 0.001mol of Sm(CF3SO3)3 as a catalyst, stir and react for 2h, after the reaction raw material point almost disappears by TLC chromatography, unreacted reactants and THF solvent are removed by reduced pressure distillation, and the reaction product is recrystallized with a mixed solvent of ethyl acetate and petroleum ether with a volume ratio of 1:1 to obtain a light yellow crystalline compound IX, with a total yield of 90%. Take a sample of compound IX and HPLC to detect and analyze the deacetylated product VIII ≤1%, and the recrystallization purification reaction is completed.

[0035] The elemental analysis of compound IX showed the following results: Elemental analysis: (%) for C 18 H 28 N2O: calculated: C 74.89; H 9.7; N 9.7, found: C 74.91; H 9.64; N 9.68.

[0036] Compound IX was analyzed by H NMR spectrum, and the results were: 1 HNMR (500MHz, CDCl3, 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.

[0037] From the above analysis, it can be seen that the structure of compound IX is as follows:

[0038]

[0039] Example 2

[0040] The preparation route is as follows:

[0041]

[0042] 1. In a four-necked flask equipped with an electric stirrer, a reflux condenser, a thermometer and a charging funnel, add 0.01 mol of 2-amino-6-fluorobenzonitrile (Formula 3-1) and 12 mL of water, slowly drop 0.005 mol of concentrated sulfuric acid at a temperature below 50°C for reaction, then add 0.011 mol of 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 of chloroform to the four-necked flask, change the charging funnel to a vent, place the four-necked flask in an ice-water bath, wait until the temperature drops to about 10°C, start passing chlorine into the reaction system, control the chlorine introduction rate (5 ml / min), keep the solution temperature in the reaction vessel at 10-15°C, and the chlorine introduction amount is 0.2-0.3 g. TLC chromatogram tracking stops passing chlorine when the raw material remains 4%-5%, continue stirring at this temperature for 0.5 hours, and stop stirring. Add 30mL of water, distill under normal pressure, and evaporate all the chloroform. At this time, the material is in a fully dissolved state. Cool to room temperature, neutralize with 10% sodium hydroxide solution to a pH between 7 and 8, cool to 15-20°C and filter. The filter cake is pulped twice with 40mL of water and then filtered to obtain a benzothiazole derivative as shown in Formula V-1. The solution is adjusted to a pH between 1 and 2 with 0.1mol / LH2SO4 solution, stirred, and then cooled to 5-8°C with ice, followed by slowly dropping 0.011mol NaNO2 (mass concentration of 30%) aqueous solution, and diazotization reaction is performed for 2h to obtain a solution 1 shown in Formula VI-1.

[0043] 2. Add 0.01 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 add 0.01 mol of raw material 4-amino-5-hydroxy-2,7-naphthalene disulfonic acid (Formula 2) aqueous solution to carry out substitution reaction, control the temperature at 10-15° C., pH=2-3, stir the reaction for 3 hours to obtain solution 2 of the substitution product shown in Formula I, and directly carry out the next step of reaction without separation.

[0044] 3. Add 30% sodium carbonate solution to adjust the pH of solution 2 to pH>6.5, slowly add solution 1 dropwise to solution 2, and carry out coupling reaction under the conditions of maintaining the temperature at 12-15°C and pH=6-7. After stirring the reaction for 3 hours, a red dye precursor solution 3 of formula II-1 is obtained.

[0045] 4. Finally, solution 3 was subjected to a second substitution reaction with 0.01 mol of compound IX prepared in Example 1, maintaining pH = 5-7 and temperature at 30-50°C. After stirring the reaction for 3 hours, the insoluble impurities were removed by suction. Most of the inorganic salts, water and a small amount of by-products were removed using a nanomembrane filtration system to obtain a red dye compound represented by formula III-1 (denoted as RL-1), with a total yield of 81%.

[0046] The red dye compound RL-1 was analyzed by HPLC and its purity was 96.5%.

[0047] The red dye compound RL-1 was subjected to LC-MS analysis. The result of LC-MS determination of red disperse dye RL-1 was [M+H] + 923.2, [M+Na] + 945.1.

[0048] The compound RL-1 was analyzed by H NMR spectrum, and the results were: 1 HNMR (500MHz, d 6 -DMSO, TMS): d=8.5~9.5(br,4H),7.10~8.20(m,9H),6.13(s,1H),4.80(br,1H),3.25~3.60(m,4H),1.98(s,4H),1.27(s,12H),1.08(s,1H)ppm.

[0049] From the above analysis, it can be seen that the molecular structure of the red disperse dye compound RL-1 is shown in the following formula III-1:

[0050]

[0051] Example 3

[0052] The preparation route is as follows:

[0053]

[0054]

[0055] The preparation process is the same as that of Example 2, except that 0.01 mol of 2-amino-6-chlorobenzonitrile (Formula 3-2) is added in step 1 instead of Formula 3-1 in Example 2, and the remaining raw materials and methods are the same as those in Example 2, which will not be described again. The red disperse dye compound RL-2 is obtained with a yield of 82.3%.

[0056] The red dye compound RL-2 was analyzed by HPLC and its purity was 95.5%.

[0057] The red dye compound RL-2 was subjected to LC-MS analysis. The result of LC-MS determination of red disperse dye RL-2 was [M+H] + 939.1, [M+Na] + 961.0.

[0058] The compound RL-2 was analyzed by nuclear magnetic hydrogen spectrum, and the results were: 1 HNMR (500MHz, d6 -DMSO, TMS): d=8.4~9.4(br,4H),7.10~8.15(m,9H),6.12(s,1H),4.80(br,1H),3.24~3.60(m,4H),1.98(s,4H),1.26(s,12H),1.07(s,1H)ppm.

[0059] From the above analysis, it can be seen that the molecular structure of the red disperse dye compound RL-2 is shown in the following formula III-2:

[0060]

[0061] Example 4

[0062] The preparation route is as follows:

[0063]

[0064] The preparation process is the same as that of Example 2, except that 0.01 mol of 2-amino-5-fluorobenzonitrile (Formula 3-3) is added in step 1 instead of Formula 3-1 in Example 2, and the remaining raw materials and methods are the same as those in Example 2, which will not be described again. The red disperse dye compound RL-3 is obtained with a yield of 84.2%.

[0065] The red dye compound RL-3 was analyzed by HPLC and the purity was 96.1%.

[0066] The red dye compound RL-3 was subjected to LC-MS analysis. The result of LC-MS determination of red disperse dye RL-3 was [M+H] + 923.2, [M+Na] + 945.1.

[0067] The compound RL-3 was analyzed by nuclear magnetic hydrogen spectrum, and the results were: 1 HNMR (500MHz, d 6 -DMSO, TMS): d=8.5~9.5(br,4H),7.12~8.3(m,9H),6.13(s,1H),4.81(br,1H),3.25~3.58(m,4H),1.96(s,4H),1.27(s,12H),1.07(s,1H)ppm.

[0068] From the above analysis, it can be seen that the molecular structure of the red disperse dye compound RL-3 is shown in the following formula III-3:

[0069]

[0070] Example 5

[0071] The preparation route is as follows:

[0072]

[0073] The preparation process is the same as that of Example 2, except that 0.01 mol of 2-amino-4-chlorobenzonitrile (Formula 3-4) is added in step 1 instead of Formula 3-1 in Example 2, and the remaining raw materials and methods are the same as those of Example 2, which will not be described in detail. The red disperse dye compound RL-4 is obtained with a yield of 84.5%.

[0074] The red dye compound RL-4 was analyzed by HPLC and the purity was 94.8%.

[0075] The red dye compound RL-4 was subjected to LC-MS analysis. The result of LC-MS determination of red disperse dye RL-4 was [M+H] + 939.1, [M+Na] + 961.0.

[0076] The compound RL-4 was analyzed by nuclear magnetic hydrogen spectrum, and the results were: 1 HNMR (500MHz, d 6 -DMSO, TMS): d=8.46~9.45(br,4H),7.13~8.41(m,9H),6.13(s,1H),4.81(br,1H),3.25~3.58(m,4H),1.96(s,4H),1.27(s,12H),1.07(s,1H)ppm.

[0077] From the above analysis, it can be seen that the molecular structure of red disperse dye RL-4 is shown in the following formula III-4:

[0078]

[0079] Example 6

[0080] The preparation route is as follows:

[0081]

[0082] The preparation process is the same as that of Example 2, except that 0.01 mol of 2-amino-4-fluorobenzonitrile (Formula 3-5) is added in step 1 instead of Formula 3-1 in Example 2, and the remaining raw materials and methods are the same as those in Example 2, which will not be described again. The red disperse dye compound RL-5 is obtained with a yield of 82.3%.

[0083] The red dye compound RL-5 was analyzed by HPLC and the purity was 95.1%.

[0084] The red dye compound RL-5 was subjected to LC-MS analysis. The result of LC-MS determination of red disperse dye RL-5 was [M+H] + 923.2, [M+Na] + 945.1.

[0085] The compound RL-5 was analyzed by nuclear magnetic hydrogen spectrum, and the results were: 1 HNMR (500MHz, d 6 -DMSO, TMS): d=8.47~9.43(br,4H),7.13~8.18(m,9H),6.12(s,1H),4.80(br,1H),3.24~3.59(m,4H),1.96(s,4H),1.27(s,12H),1.07(s,1H)ppm.

[0086] From the above analysis, it can be seen that the molecular structure of red disperse dye RL-5 is shown in the following formula III-5:

[0087]

[0088] Example 7

[0089] The preparation route is as follows:

[0090]

[0091] The preparation process is the same as that of Example 2, except that 0.01 mol of 2-amino-4-chlorobenzonitrile (Formula 3-6) is added in step 1 instead of 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 again. The red disperse dye compound RL-6 is obtained with a yield of 82.8%.

[0092] The red dye compound RL-6 was analyzed by HPLC and the purity was 96.2%.

[0093] The red dye compound RL-6 was subjected to LC-MS analysis. The result of LC-MS determination of red disperse dye RL-6 was [M+H] + 939.1, [M+Na] + 961.0.

[0094] The compound RL-6 was analyzed by nuclear magnetic hydrogen spectrum, and the results were: 1 HNMR (500MHz, d 6-DMSO, TMS): d=8.5~9.44(br,4H),7.13~8.18(m,9H),6.13(s,1H),4.81(br,1H),3.26~3.57(m,4H),1.96(s,4H),1.26(s,12H),1.06(s,1H)ppm.

[0095] From the above analysis, it can be seen that the molecular structure of red disperse dye RL-6 is shown in the following formula III-6:

[0096]

[0097] The red disperse dye molecules RL-1 to RL-6 prepared in Examples 2 to 7 were subjected to ultraviolet absorption spectrum analysis. The results are as follows: Figure 1 As shown. Figure 1 It can be seen that RL-1 to RL-6 all exhibited a wide absorption at 500nm to 550nm, 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 compounds obtained in Examples 2 to 7 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.

[0098] Example 8

[0099] RL-1 to RL-6 prepared in Examples 2 to 7 and CI Reactive Red 1, CI Reactive Red 24, and a mixture of CI Reactive Red 1 and CI Reactive Red 24 in a mass ratio of 24:1 (CI Reactive Red 24:1) were used as comparisons. 10 g of the foregoing substances were respectively used as red disperse dyes and dispersed and ground with 12 g of dispersant MF, 3 g of sodium lignin sulfonate, and 37.5 g of water using a sand mill. 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 dye suspension was 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., 2.5 g of polyester fiber cloth were respectively put in, the temperature was raised to 130° C. within 30 min, the temperature was kept for 50 min, the temperature was lowered, the mixture was thoroughly washed with water, and the mixture was dried.

[0100] 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.

[0101] Table 1 Performance data of dyes of Examples R1 to R6 and color fastness of printed cotton fabrics with existing dye pastes

[0102]

[0103]

[0104] As can be seen from Table 1 above, the red disperse dyes RL-1 to RL-6 of the present invention 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 disperse dyes RL-1 to RL-6 prepared in Examples 2 to 7.

[0105] 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. An azo red dye compound, characterized in that: The general structural formula of the azo red dye compound is shown in Formula III: Wherein, X is a halogen.

2. The azo red dye compound according to claim 1, characterized in that: X is F or Cl.

3. The azo red dye compound 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-6:

4. The method for preparing the azo red dye compound according to any one of claims 1 to 3, characterized in that: Synthesized according to the following route: Wherein, compound I reacts with a benzothiazole diazonium salt derivative to obtain compound II, and compound II reacts with a hydroxyethyl aryl secondary amine to obtain the target compound III.

5. The preparation method according to claim 4, characterized in that: The raw materials for preparing compound I also include:

6. The preparation method according to claim 4, characterized in that: The benzothiazole diazonium salt derivative is synthesized according to the following reaction route:

7. The preparation method according to claim 6, characterized in that: Derived from one of the following compounds:

8. The preparation method according to claim 4, characterized in that: Hydroxyethyl aryl secondary amine is synthesized according to the following reaction route:

9. Use of the azo red dye compound according to any one of claims 1 to 3 in the preparation of polyester fiber textile materials or blended fiber products thereof.

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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