CN116496636A - A kind of synthetic technology of acid yellow - Google Patents

A kind of synthetic technology of acid yellow Download PDF

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CN116496636A
CN116496636A CN202310457247.5A CN202310457247A CN116496636A CN 116496636 A CN116496636 A CN 116496636A CN 202310457247 A CN202310457247 A CN 202310457247A CN 116496636 A CN116496636 A CN 116496636A
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acid
ice
acid yellow
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minutes
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丁永
毛佳乐
李凯
马成龙
季孝文
季平
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Ningxia Baolong Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00Monoazo dyes prepared by diazotising and coupling
    • C09B29/34Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3665Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms
    • C09B29/3669Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms from a pyrimidine ring
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0072Preparations with anionic dyes or reactive dyes

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a synthesis process of acid yellow, which comprises the following steps: s1: diazo reaction: dissolving 2.5-dichloroaniline in hydrochloric acid at a certain ratio, adding emulsifier, adding sodium nitrite solution, and detecting potassium iodide (oxidizing I 2 ) When congo red is blue, sodium nitrite is eliminated by sulfamic acid to obtain diazonium solution; s2: the coupling component is dissolved: mixing 2-dibutylamino-4- (4' -sulfonic acid) phenethylamino-6-methylpyrimidine, an organic solvent and water, regulating pH to 10-11.5 with liquid alkali, stirring until the mixture is fully dissolved, and adding sodium carbonate and ice for later use; s3: adding diazonium solution into the solution for coupling reaction, adjusting pH to 6-6.5 with hydrochloric acid after the reaction is completed, heating up to evaporate butanone, adding salt, stirring at high temperature for 20-40 min, and suction filtering to obtain acid yellow. The invention aims to improve dyeing performance of the dye, improve dyeing fastness, ensure more complete raw material reaction, realize high yield and reduce raw material consumption.

Description

一种酸性黄的合成工艺A kind of synthetic technology of acid yellow

技术领域technical field

本发明属于化工染料的制造领域,具体涉及一种酸性黄的合成工艺。The invention belongs to the field of manufacturing chemical dyes, and in particular relates to a synthesis process of acid yellow.

技术背景technical background

酸性黄是印染行业和色素着色领域得到广泛使用的染料。它是一种新型杂环偶氮分散染料,能溶于甲醇、二氯甲烷等,在偶合组分中引入了二丁胺基,使其具有色光鲜艳,吸光系数大,高温分散稳定性和耐碱性好,牢度和强度性能优越等优点。主要用于涤纶及其混纺织物的染色和印花。Acid yellow is a dye widely used in the printing and dyeing industry and in the field of pigment coloring. It is a new type of heterocyclic azo disperse dye, which can be dissolved in methanol, dichloromethane, etc., and dibutylamine group is introduced into the coupling component to make it have bright color, large absorption coefficient, high temperature dispersion stability and resistance Good alkalinity, superior fastness and strength properties, etc. Mainly used for dyeing and printing of polyester and its blended fabrics.

目前,公开的酸性黄的制备方法有以下几种,申请号为202010993593.1的专利,公开一种C.I.酸性黄23染料及其清洁化生产工艺,利用2-乙酰基-丁二酸二甲酯和对氨基苯磺酸重氮盐偶合,闭环,再与对氨基苯磺酸重氮盐再次偶合,水解,使用混合盐盐析,分离回收混合盐,即得C.I.酸性黄23染料。申请号为201610210566.6的专利,将联苯胺类化合物和酸性试剂通入反应器中,搅拌混匀;向反应器中加入亚硝酸盐搅拌反应得到重氮盐;配制含5-吡唑啉酮的碱性溶液并加入到反应器中与重氮盐反应得到偶氮中间体Ⅰ;配制相同浓度的5-吡唑啉酮的碱性溶液加入到反应器中与偶氮中间体Ⅰ反应得到偶氮中间体Ⅱ;经过盐析、过滤和烘干得到酸性黄N-R粉末。At present, there are the following methods for preparing Acid Yellow, the patent application number is 202010993593.1, which discloses a C.I. Acid Yellow 23 dye and its clean production process, using 2-acetyl-succinic acid dimethyl ester and p- The diazonium salt of aminobenzenesulfonic acid is coupled, the ring is closed, and then coupled with the diazonium salt of p-aminobenzenesulfonic acid, hydrolyzed, salted out with a mixed salt, and the mixed salt is separated and recovered to obtain C.I. Acid Yellow 23 dye. The patent application number is 201610210566.6. The benzidine compound and the acidic reagent are passed into the reactor, stirred and mixed; the nitrite is added to the reactor and stirred to react to obtain the diazonium salt; the base containing 5-pyrazolone is prepared and add it into the reactor to react with the diazonium salt to obtain the azo intermediate Ⅰ; prepare an alkaline solution of the same concentration of 5-pyrazolone and add it to the reactor to react with the azo intermediate Ⅰ to obtain the azo intermediate Body II; acid yellow N-R powder was obtained after salting out, filtering and drying.

随着酸性黄产品的应用不断被开发和挖掘,具有较好的发展前景,因此,迫切的需要开发出低能耗、操作简单、安全、环保的清洁化生产工艺。As the application of acid yellow products is continuously developed and excavated, it has a good development prospect. Therefore, it is urgent to develop a clean production process with low energy consumption, simple operation, safety and environmental protection.

发明内容Contents of the invention

针对现有技术的不足之处,本发明的目的在于提高染料改善染色性能,提高染色牢度,制备出的产品不经纯化就能满足应用要求,大大降低生产成本,适合规模化清洁生产的需要。Aiming at the deficiencies of the prior art, the purpose of the present invention is to improve the dyeing performance, improve the color fastness, and the prepared product can meet the application requirements without purification, greatly reduce the production cost, and is suitable for the needs of large-scale clean production .

本发明的技术方案概述如下:Technical scheme of the present invention is summarized as follows:

一种酸性黄的制备方法,包括以下步骤:A preparation method of acid yellow, comprising the following steps:

S1:重氮反应:将2,5-二氯苯胺溶于盐酸中,在40~70℃保温1.5~4.5小时后,加入乳化剂降温至25~30℃,在8~12分钟内加冰降温约至0~5℃后,加入亚硝酸钠和2~3滴碘化钾和刚果红溶液,缓慢升温后,用冰控制温度在15~20℃保温40~80分钟,当碘化钾和刚果红都显蓝色时,得到重氮盐,继续加1~2mol冰后用氨基磺酸消剩余亚硝酸钠得到重氮液;S1: Diazo reaction: Dissolve 2,5-dichloroaniline in hydrochloric acid, keep warm at 40-70°C for 1.5-4.5 hours, add emulsifier to cool down to 25-30°C, add ice to cool down within 8-12 minutes After about 0-5°C, add sodium nitrite and 2-3 drops of potassium iodide and Congo red solution, after slowly heating up, use ice to control the temperature at 15-20°C for 40-80 minutes, when potassium iodide and Congo red both appear blue When the color changes, the diazonium salt is obtained, continue to add 1 to 2 mol of ice, and then use sulfamic acid to eliminate the remaining sodium nitrite to obtain the diazonium solution;

S2:偶合组分溶解:将2-二丁胺基-4-(4’-磺酸)苯乙胺基-6-甲基嘧啶、有机溶剂和水混合,并用液碱调节pH=10~11.5后搅拌至全溶,再加入纯碱、冰备用;S2: Coupling component dissolution: mix 2-dibutylamino-4-(4'-sulfonic acid) phenethylamino-6-methylpyrimidine, organic solvent and water, and adjust pH=10~11.5 with liquid caustic Finally, stir until it is completely dissolved, then add soda ash and ice for later use;

S3:偶合反应:将重氮液加入S2所得溶液中进行偶合反应,滴加2~3滴间苯二酚搅拌20~55分钟,中后期用冰将温度控制在3~10℃,当pH值降到8.5~9时停止加冰并搅拌5分钟后,继续用液碱调pH=10~10.5,继续偶合,其中在3~10℃保温1~3小时,保温后升温至15~45℃继续保温0.5~1.5小时直到偶合结束;到达终点后用盐酸缓慢回调pH至6~6.5,调好后升温至95~100℃蒸丁酮,蒸好微降温至90~95℃,加入盐高温搅拌20~40分钟,得到颗粒状产物,降温后抽滤后得到酸性黄。S3: Coupling reaction: add diazonium solution to the solution obtained in S2 for coupling reaction, add 2 to 3 drops of resorcinol dropwise and stir for 20 to 55 minutes. When it drops to 8.5-9, stop adding ice and stir for 5 minutes, then continue to adjust the pH to 10-10.5 with liquid caustic soda, and continue the coupling, in which the temperature is kept at 3-10°C for 1-3 hours, and then the temperature is raised to 15-45°C to continue Keep warm for 0.5-1.5 hours until the coupling is completed; after reaching the end point, use hydrochloric acid to slowly adjust the pH to 6-6.5, after adjustment, heat up to 95-100°C to steam butanone, after steaming, cool down slightly to 90-95°C, add salt and stir at high temperature for 20 After ~40 minutes, a granular product was obtained, and acid yellow was obtained after suction filtration after cooling down.

优选的是,所述步骤S1中2,5-二氯苯胺、盐酸、亚硝酸钠、氨基磺酸、乳化剂的用量比为(0.04-0.06)mol:(0.1-0.2)mol:(0.05-0.07)mol:(0.002-0.005)mol:(1-3)g。Preferably, the amount ratio of 2,5-dichloroaniline, hydrochloric acid, sodium nitrite, sulfamic acid and emulsifier in the step S1 is (0.04-0.06) mol:(0.1-0.2) mol:(0.05- 0.07) mol: (0.002-0.005) mol: (1-3) g.

优选的是,所述步骤S1中2,5-二氯苯胺、盐酸用量之比为1:3.3。Preferably, the ratio of 2,5-dichloroaniline to hydrochloric acid in the step S1 is 1:3.3.

优选的是,所述乳化剂为T-80或脂肪酸甲酯乙氧基化物。Preferably, the emulsifier is T-80 or fatty acid methyl ester ethoxylate.

优选的呢是,所述步骤S2中2-二丁胺基-4-(4’-磺酸)苯乙胺基-6-甲基嘧啶、丁酮、液碱、纯碱的用量比为(0.04-0.06)mol:(1.5-2.5mol):(0.01-0.03)mol:(3-5)g。Preferably, the amount ratio of 2-dibutylamino-4-(4'-sulfonic acid) phenethylamino-6-methylpyrimidine, butanone, liquid caustic soda and soda ash in the step S2 is (0.04 -0.06) mol: (1.5-2.5 mol): (0.01-0.03) mol: (3-5) g.

优选的是,所述步骤S2中有机溶剂为丁酮或者丙酮。Preferably, the organic solvent in the step S2 is butanone or acetone.

优选的是,所述步骤S2中有机溶剂用量为0.5~1.5mol。Preferably, the amount of organic solvent used in the step S2 is 0.5-1.5 mol.

优选的是,所述步骤S3中盐包括氯化钠、氯化钾、硫酸钠中的一种或多种。Preferably, the salt in step S3 includes one or more of sodium chloride, potassium chloride, and sodium sulfate.

优选的是,所述盐的用量为6~12%体积。Preferably, the salt is used in an amount of 6-12% by volume.

优选的是,所述步骤S3中降温抽滤的温度为25-30℃。Preferably, the temperature of the cooling suction filtration in the step S3 is 25-30°C.

优选的是,所述步骤S3中反应终点为当间苯二酚与料的润圈交界处不显黄色时到达反应终点。Preferably, the end point of the reaction in step S3 is reached when the junction of resorcinol and the wet circle of the material does not show yellow.

本发明的有益效果:Beneficial effects of the present invention:

本发明中,用2.5-二氯苯胺进行重氮反应制备重氮盐、与2-二丁胺基-4-(4’-磺酸)苯乙胺基-6-甲基嘧啶进行偶合反应优点在于,生产的酸性黄染料耐日晒、升华、磨擦,遮盖性好;原料反应更完全,收率高,降低了原料消耗,节省了生产成本,解决了常规偶合收率不高,产生纯度低的难题,产物不经纯化能够满足应用要求,极大的降低了生产成本,为该偶氮染料的合成提供了一种新的制备方法。In the present invention, use 2.5-dichloroaniline to carry out diazo reaction to prepare diazonium salt, and carry out coupling reaction with 2-dibutylamino-4-(4'-sulfonic acid) phenethylamino-6-methylpyrimidine. Advantages The acid yellow dye produced is resistant to sunlight, sublimation and friction, and has good covering properties; the reaction of raw materials is more complete, the yield is high, the consumption of raw materials is reduced, the production cost is saved, and the conventional coupling yield is not high, resulting in low purity. The problem is that the product can meet the application requirements without purification, which greatly reduces the production cost, and provides a new preparation method for the synthesis of the azo dye.

附图说明Description of drawings

图1为本发明酸性黄的制备方法流程图;Fig. 1 is the preparation method flowchart of acid yellow of the present invention;

具体实施方式Detailed ways

下面结合实施例对本发明做进一步的详细说明,以令本领域技术人员参照说明书文字能够据以实施。The present invention will be further described in detail below in conjunction with the embodiments, so that those skilled in the art can implement it with reference to the description.

该实施例的酸性黄的制备方法,包括以下步骤:The preparation method of the acid yellow of this embodiment may further comprise the steps:

S1:重氮反应:将2,5-二氯苯胺溶于盐酸中,在40~70℃保温1.5~4.5小时后,加入乳化剂降温至25~30℃,在8~12分钟内加冰降温约至0~5℃后,加入亚硝酸钠和2~3滴碘化钾和刚果红溶液,缓慢升温后,用冰控制温度在15~20℃保温60分钟,当碘化钾和刚果红都显蓝色时,得到重氮盐,继续加1~2mol冰后用氨基磺酸消剩余亚硝酸钠得到重氮液。所述2,5-二氯苯胺、盐酸、亚硝酸钠、氨基磺酸、乳化剂的用量比为(0.04-0.06)mol:(0.1-0.2)mol:(0.05-0.07)mol:(0.002-0.005)mol:(1-3)g。S1: Diazo reaction: Dissolve 2,5-dichloroaniline in hydrochloric acid, keep warm at 40-70°C for 1.5-4.5 hours, add emulsifier to cool down to 25-30°C, add ice to cool down within 8-12 minutes After about 0-5°C, add sodium nitrite and 2-3 drops of potassium iodide and Congo red solution, after slowly heating up, use ice to control the temperature at 15-20°C for 60 minutes, when potassium iodide and Congo red are both blue , to obtain diazonium salt, continue to add 1 to 2 mol of ice, and then use sulfamic acid to eliminate the remaining sodium nitrite to obtain diazonium solution. The consumption ratio of described 2,5-dichloroaniline, hydrochloric acid, sodium nitrite, sulfamic acid, emulsifier is (0.04-0.06) mol: (0.1-0.2) mol: (0.05-0.07) mol: (0.002- 0.005) mol: (1-3) g.

S2:偶合组分溶解:将2-二丁胺基-4-(4’-磺酸)苯乙胺基-6-甲基嘧啶、有机溶剂和水混合,并用液碱调节pH=10~11.5后搅拌至全溶,再加入纯碱、冰备用;所述2-二丁胺基-4-(4’-磺酸)苯乙胺基-6-甲基嘧啶、丁酮、液碱、纯碱的用量比为(0.04-0.06)mol:(1.5-2.5mol):(0.01-0.03)mol:(3-5)g;所述有机溶剂为0.5~1.5mol的丁酮或者丙酮。S2: Coupling component dissolution: mix 2-dibutylamino-4-(4'-sulfonic acid) phenethylamino-6-methylpyrimidine, organic solvent and water, and adjust pH=10~11.5 with liquid caustic Afterwards, stir until completely dissolved, then add soda ash and ice for later use; The dosage ratio is (0.04-0.06) mol:(1.5-2.5 mol):(0.01-0.03) mol:(3-5) g; the organic solvent is 0.5-1.5 mol of butanone or acetone.

S3:偶合反应:将重氮液加入S2所得溶液中进行偶合反应,滴加2~3滴间苯二酚搅拌20~55分钟,中后期用冰将温度控制在3~10℃,当pH值降到8.5~9时停止加冰并搅拌5分钟后,继续用液碱调pH=10~10.5,继续偶合,其中在3~10℃保温1~3小时,保温后升温至15~45℃继续保温0.5~1.5小时直到偶合结束;到达终点后用盐酸缓慢回调pH至6~6.5,调好后升温至95~100℃蒸丁酮,蒸好微降温至90~95℃,加入6~12%体积的盐高温搅拌20~40分钟,得到颗粒状产物,降温后抽滤后得到酸性黄。所述盐包括氯化钠、氯化钾、硫酸钠中的一种或多种。S3: Coupling reaction: Add diazonium solution to the solution obtained in S2 for coupling reaction, add 2 to 3 drops of resorcinol dropwise and stir for 20 to 55 minutes. When it drops to 8.5-9, stop adding ice and stir for 5 minutes, then continue to adjust the pH to 10-10.5 with liquid caustic soda, and continue the coupling, in which the temperature is kept at 3-10°C for 1-3 hours, and then the temperature is raised to 15-45°C to continue Keep warm for 0.5-1.5 hours until the coupling is completed; after reaching the end point, use hydrochloric acid to slowly adjust the pH to 6-6.5, after adjustment, heat up to 95-100°C to steam methyl ethyl ketone, cool down to 90-95°C after steaming, add 6-12% The volume of salt was stirred at high temperature for 20 to 40 minutes to obtain a granular product, which was cooled and filtered to obtain acid yellow. The salt includes one or more of sodium chloride, potassium chloride, and sodium sulfate.

实施例1Example 1

一种实施例的酸性黄的制备方法,包括以下步骤:The preparation method of the acid yellow of a kind of embodiment, comprises the following steps:

S1:重氮反应:将20g盐酸、8.1g折百2.5-二氯苯胺、50g水混合,开加热升温到50℃保温2小时至没有片状的原料后,加入2gT-80后降到25~30℃,在8~12分钟内加冰30g降温约至0~5℃后,加入3.7g亚硝酸钠、10g水和2~3滴碘化钾和刚果红溶液,缓慢升温后,用冰控制温度在15~20℃保温60分钟,当碘化钾和刚果红都显蓝色时,得到重氮盐,继续加20g冰后用0.4g氨基磺酸消剩余亚硝酸钠得到重氮液;S1: Diazo reaction: mix 20g of hydrochloric acid, 8.1g of 2.5-dichloroaniline, and 50g of water, heat it up to 50°C and keep it warm for 2 hours until there is no flaky raw material, then add 2g of T-80 and drop it to 25~ 30°C, add 30g of ice within 8-12 minutes to cool down to about 0-5°C, add 3.7g of sodium nitrite, 10g of water and 2-3 drops of potassium iodide and Congo red solution, after slowly heating up, use ice to control the temperature at Incubate at 15-20°C for 60 minutes. When both potassium iodide and Congo red appear blue, a diazonium salt is obtained. After adding 20 g of ice, use 0.4 g of sulfamic acid to eliminate the remaining sodium nitrite to obtain a diazonium solution;

S2:偶合组分溶解:将21g折百2-二丁胺基-4-(4’-磺酸)苯乙胺基-6-甲基嘧啶、70g丁酮和30g水混合,并用9g液碱调节pH=10~11.5后搅拌至全溶,再加入4g纯碱、90g冰备用;S2: Coupling component dissolution: mix 21g of 2-dibutylamino-4-(4'-sulfonic acid)phenethylamino-6-methylpyrimidine, 70g of methyl ethyl ketone and 30g of water, and mix with 9g of liquid caustic soda Adjust the pH to 10-11.5 and stir until completely dissolved, then add 4g of soda ash and 90g of ice for later use;

S3:偶合反应:将S1所得重氮液加入S2所得溶液中进行偶合反应,滴加2~3滴间苯二酚搅拌40min分钟,中后期用冰将温度控制在5~8℃,当pH值降到8.5~9时停止加冰并搅拌5分钟,继续用液碱调pH至10~10.5进行偶合,其中在5~8℃保温2小时,保温后升温至25~30℃继续保温1小时直到偶合结束;当间苯二酚与料的润圈交界处不显黄色时到达反应终点,用盐酸缓慢回调pH至6~6.5,调好后升温至95~100℃蒸丁酮,蒸好微降温至90~95℃,加入35g的氯化钠高温搅拌30分钟,有晶型,降温至25-30℃,没有晶型继续加8g氯化钠得到颗粒状产物,降温至25-30℃后抽滤后得到黄色晶体30.02g,收率98.1%,液相色谱含量98.31%,不经纯化即满足应用要求。S3: Coupling reaction: add the diazo solution obtained in S1 to the solution obtained in S2 for coupling reaction, add 2 to 3 drops of resorcinol dropwise and stir for 40 minutes, use ice to control the temperature at 5 to 8°C in the middle and later stages, when the pH value When the temperature drops to 8.5-9, stop adding ice and stir for 5 minutes, continue to adjust the pH to 10-10.5 with liquid caustic soda for coupling, and keep warm at 5-8°C for 2 hours, then raise the temperature to 25-30°C and continue to keep warm for 1 hour until Coupling is completed; when the junction of resorcinol and the wet circle of the material does not show yellow, reach the end of the reaction, slowly adjust the pH to 6-6.5 with hydrochloric acid, after adjustment, heat up to 95-100°C to steam methyl ethyl ketone, and cool down slightly after steaming To 90-95°C, add 35g of sodium chloride and stir at high temperature for 30 minutes, if there is a crystal form, cool down to 25-30°C, if there is no crystal form, continue to add 8g of sodium chloride to obtain a granular product, cool down to 25-30°C and pump After filtration, 30.02 g of yellow crystals were obtained, with a yield of 98.1%, and a liquid chromatography content of 98.31%, which met the application requirements without purification.

实施例2Example 2

S1:重氮反应:将21g盐酸、6.5g折百2.5-二氯苯胺、50g水混合,开加热升温到40℃保温1小时至没有片状的原料后,加入1.5gT-80后降到25~30℃,在8~12分钟内加冰30g降温约至0~5℃后,加入2.9g亚硝酸钠、10g水和2~3滴碘化钾和刚果红溶液,缓慢升温后,用冰控制温度在15~20℃保温60分钟,当碘化钾和刚果红都显蓝色时,得到重氮盐,继续加20g冰后用0.4g氨基磺酸消剩余亚硝酸钠得到重氮液;S1: Diazo reaction: Mix 21g of hydrochloric acid, 6.5g of 2.5-dichloroaniline, and 50g of water, heat up to 40°C and keep it warm for 1 hour until there are no flaky raw materials, then add 1.5g of T-80 and drop to 25 ~30°C, add 30g of ice within 8~12 minutes to cool down to about 0~5°C, add 2.9g of sodium nitrite, 10g of water and 2~3 drops of potassium iodide and Congo red solution, after slowly heating up, use ice to control the temperature Incubate at 15-20°C for 60 minutes. When both potassium iodide and Congo red are blue, the diazonium salt is obtained. After adding 20 g of ice, use 0.4 g of sulfamic acid to eliminate the remaining sodium nitrite to obtain the diazonium solution;

S2:偶合组分溶解:将17g折百2-二丁胺基-4-(4’-磺酸)苯乙胺基-6-甲基嘧啶、65g丁酮和30g水混合,并用7.6g液碱调节pH=10~11.5后搅拌至全溶,再加入4g纯碱、90g冰备用;S2: Dissolution of coupling components: 17g of 2-dibutylamino-4-(4'-sulfonic acid)phenethylamino-6-methylpyrimidine, 65g of butanone and 30g of water were mixed, and mixed with 7.6g of liquid Adjust the pH to 10-11.5 with alkali and stir until completely dissolved, then add 4g of soda ash and 90g of ice for later use;

S3:偶合反应:将S1所得重氮液加入S2所得溶液中进行偶合反应,滴加2~3滴间苯二酚搅拌30min分钟,中后期用冰将温度控制在4~6℃,当pH值降到8.5~9时停止加冰并搅拌5分钟,继续用液碱调pH至10~10.5进行偶合,其中在4~6℃保温1小时,保温后升温至15~20℃继续保温1小时直到偶合结束;当间苯二酚与料的润圈交界处不显黄色时到达反应终点,用盐酸缓慢回调pH至6~6.5,调好后升温至95~100℃蒸丁酮,蒸好微降温至90~95℃,加入35g的氯化钠高温搅拌30分钟,有晶型,降温至25-30℃,没有晶型继续加8g氯化钠得到颗粒状产物,降温至25-30℃后抽滤后得到黄色晶体24.98g,收率97.4%,液相色谱含量99.24%,不经纯化即满足应用要求。S3: Coupling reaction: add the diazonium solution obtained in S1 to the solution obtained in S2 for coupling reaction, add 2 to 3 drops of resorcinol dropwise and stir for 30 minutes, and use ice to control the temperature at 4 to 6°C in the middle and later stages, when the pH value When the temperature drops to 8.5-9, stop adding ice and stir for 5 minutes, continue to adjust the pH to 10-10.5 with liquid caustic soda for coupling, and keep warm at 4-6°C for 1 hour, then raise the temperature to 15-20°C and continue to keep warm for 1 hour until Coupling is completed; when the junction of resorcinol and material does not show yellow, the end point of the reaction is reached, and the pH is slowly adjusted to 6-6.5 with hydrochloric acid. After adjustment, the temperature is raised to 95-100°C to steam butanone, and the temperature is slightly lowered after steaming. To 90-95°C, add 35g of sodium chloride and stir at high temperature for 30 minutes, if there is a crystal form, cool down to 25-30°C, if there is no crystal form, continue to add 8g of sodium chloride to obtain a granular product, cool down to 25-30°C and pump After filtration, 24.98 g of yellow crystals were obtained, with a yield of 97.4%, and a liquid chromatography content of 99.24%, which met the application requirements without purification.

实施例3Example 3

S1:重氮反应:将30g盐酸、9.7g折百2.5-二氯苯胺、50g水混合,开加热升温到60℃保温3小时至没有片状的原料后,加入2.5gT-80后降到25~30℃,在8~12分钟内加冰30g降温约至0~5℃后,加入4.2g亚硝酸钠、10g水和2~3滴碘化钾和刚果红溶液,缓慢升温后,用冰控制温度在15~20℃保温60分钟,当碘化钾和刚果红都显蓝色时,得到重氮盐,继续加20g冰后用0.4g氨基磺酸消剩余亚硝酸钠得到重氮液;S1: Diazo reaction: Mix 30g of hydrochloric acid, 9.7g of 2.5-dichloroaniline, and 50g of water, heat up to 60°C for 3 hours until there is no flaky raw material, then add 2.5g of T-80 and drop to 25 ~30°C, add 30g of ice within 8~12 minutes to cool down to about 0~5°C, add 4.2g of sodium nitrite, 10g of water and 2~3 drops of potassium iodide and Congo red solution, after slowly heating up, use ice to control the temperature Incubate at 15-20°C for 60 minutes. When both potassium iodide and Congo red are blue, the diazonium salt is obtained. After adding 20 g of ice, use 0.4 g of sulfamic acid to eliminate the remaining sodium nitrite to obtain the diazonium solution;

S2:偶合组分溶解:将25g折百2-二丁胺基-4-(4’-磺酸)苯乙胺基-6-甲基嘧啶、75g丁酮和30g水混合,并用12g液碱调节pH=10~11.5后搅拌至全溶,再加入4g纯碱、90g冰备用;S2: Dissolution of coupling components: Mix 25g of 2-dibutylamino-4-(4'-sulfonic acid)phenethylamino-6-methylpyrimidine, 75g of methyl ethyl ketone and 30g of water, and mix with 12g of liquid caustic soda Adjust the pH to 10-11.5 and stir until completely dissolved, then add 4g of soda ash and 90g of ice for later use;

S3:偶合反应:将S1所得重氮液加入S2所得溶液中进行偶合反应,滴加2~3滴间苯二酚搅拌50min分钟,中后期用冰将温度控制在8~10℃,当pH值降到8.5~9时停止加冰并搅拌5分钟,继续用液碱调pH至10~10.5进行偶合,其中在8~10℃保温1小时,保温后升温至40~45℃继续保温1小时直到偶合结束;当间苯二酚与料的润圈交界处不显黄色时到达反应终点,用盐酸缓慢回调pH至6~6.5,调好后升温至95~100℃蒸丁酮,蒸好微降温至90~95℃,加入35g的氯化钠高温搅拌30分钟,有晶型,降温至25-30℃,没有晶型继续加8g氯化钠得到颗粒状产物,降温至25-30℃后抽滤后得到黄色晶体35.38g,收率95.8%,液相色谱含量97.32%,不经纯化即满足应用要求。S3: Coupling reaction: Add the diazo solution obtained in S1 to the solution obtained in S2 for coupling reaction, add 2 to 3 drops of resorcinol dropwise and stir for 50 minutes, use ice to control the temperature at 8 to 10°C in the middle and later stages, when the pH value When the temperature drops to 8.5-9, stop adding ice and stir for 5 minutes, continue to adjust the pH to 10-10.5 with liquid caustic soda for coupling, and keep warm at 8-10°C for 1 hour, then raise the temperature to 40-45°C and continue to keep warm for 1 hour until Coupling is completed; when the junction of resorcinol and the wet circle of the material does not show yellow, reach the end of the reaction, slowly adjust the pH to 6-6.5 with hydrochloric acid, after adjustment, heat up to 95-100°C to steam methyl ethyl ketone, and cool down slightly after steaming To 90-95°C, add 35g of sodium chloride and stir at high temperature for 30 minutes, if there is a crystal form, cool down to 25-30°C, if there is no crystal form, continue to add 8g of sodium chloride to obtain a granular product, cool down to 25-30°C and pump After filtration, 35.38 g of yellow crystals were obtained, with a yield of 95.8%, and a liquid chromatography content of 97.32%, which met the application requirements without purification.

本发明的制备的酸性黄具有收率高,产物纯度高,反应温度低节约能耗等优点,特别适合工业化生产The acid yellow prepared by the present invention has the advantages of high yield, high product purity, low reaction temperature and energy saving, and is especially suitable for industrial production

上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.

Claims (9)

1. A method for preparing acid yellow, which is characterized by comprising the following steps:
s1: diazo reaction: dissolving 2, 5-dichloroaniline in hydrochloric acid, preserving heat for 1.5-4.5 hours at 40-70 ℃, adding an emulsifying agent, cooling to 25-30 ℃, adding ice for cooling to about 0-5 ℃ within 8-12 minutes, adding sodium nitrite and 2-3 drops of potassium iodide and Congo red solution, slowly heating, controlling the temperature at 15-20 ℃ by ice, preserving heat for 40-80 minutes to obtain diazonium salt, and removing residual sodium nitrite by sulfamic acid after adding ice to obtain diazonium solution;
s2: the coupling component is dissolved: mixing 2-dibutylamino-4- (4' -sulfonic acid) phenethylamino-6-methylpyrimidine, an organic solvent and water, regulating pH to 10-11.5 with liquid alkali, stirring until the mixture is fully dissolved, and adding sodium carbonate and ice for later use;
s3: coupling reaction: adding diazonium solution into the solution obtained by S2 for coupling reaction, dropwise adding 2-3 drops of resorcinol, stirring for 20-55 minutes, controlling the temperature at 3-10 ℃ by using ice in the middle and later stages, stopping adding ice when the pH value is reduced to 8.5-9, stirring for 5 minutes, continuously adjusting the pH value to be 10-10.5 by using liquid alkali, and continuously reacting, wherein the solution is kept at 3-10 ℃ for 1-3 hours, and then heated to 15-45 ℃ for continuously keeping the temperature for 0.5-1.5 hours until coupling is finished; and slowly adjusting the pH value to 6-6.5 by using hydrochloric acid after reaching the end point, heating to 95-100 ℃ after adjusting, steaming butanone, cooling to 90-95 ℃ after steaming, adding salt, stirring at high temperature for 20-40 minutes to obtain a granular product, and filtering after reducing to a certain temperature to obtain acid yellow.
2. The method for synthesizing acid yellow according to claim 1, wherein the amount ratio of 2, 5-dichloroaniline, hydrochloric acid, sodium nitrite, sulfamic acid and emulsifier in the step S1 is (0.04-0.06) mol, (0.1-0.2) mol, (0.05-0.07) mol, (0.002-0.005) mol, (1-3) g.
3. The method according to claim 1, wherein the emulsifier in the step S1 is T-80 or fatty acid methyl ester ethoxylate.
4. The method for synthesizing acid yellow according to claim 1, wherein the dosage ratio of 2-dibutyl amino-4- (4' -sulfonic acid) phenethyl amino-6-methyl pyrimidine, butanone, liquid caustic soda and sodium carbonate in the step S2 is (0.04-0.06) mol (0.01-0.03) mol (3-5) g.
5. The method for synthesizing acid yellow according to claim 1, wherein the organic solvent in the step S2 is butanone or acetone.
6. The method for synthesizing acid yellow according to claim 5, wherein the amount of the organic solvent is 0.5 to 1.5mol.
7. The method for synthesizing acid yellow according to claim 1, wherein the salt in the step S3 comprises one or more of sodium chloride, potassium chloride and sodium sulfate.
8. The method for synthesizing acid yellow according to claim 7, wherein the salt is used in an amount of 6 to 12% by volume.
9. The method for synthesizing acid yellow according to claim 1, wherein the temperature of the suction filtration after the step S3 is reduced to a certain temperature is 25-30 ℃.
CN202310457247.5A 2023-04-25 2023-04-25 A kind of synthetic technology of acid yellow Pending CN116496636A (en)

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CN110128849A (en) * 2019-05-18 2019-08-16 上海雅运纺织化工股份有限公司 A kind of Yellow acid dye composition and its tint applications on fiber
CN110878175A (en) * 2019-05-19 2020-03-13 金华双宏化工有限公司 Acid dye for dyeing nylon fiber and preparation method thereof
CN112111171A (en) * 2020-09-21 2020-12-22 恒升化工有限公司 C.I. acid yellow 23 dye and clean production process thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1479771A (en) * 2000-12-05 2004-03-03 �����ﰲ�ز���(Bvi)���޹�˾ Trichromatic dyeing process
CN104479406A (en) * 2014-12-10 2015-04-01 嘉兴科隆化工有限公司 Industrial production method of transparent high-gloss pigment red 146 applied to solvent ink
CN109385115A (en) * 2018-11-20 2019-02-26 宣城英特颜料有限公司 A kind of preparation method of permanent bordeaux F5RK pigment
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