CN116496636A - A kind of synthetic technology of acid yellow - Google Patents
A kind of synthetic technology of acid yellow Download PDFInfo
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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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- FPVGTPBMTFTMRT-UHFFFAOYSA-L disodium;2-amino-5-[(4-sulfonatophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 235000019233 fast yellow AB Nutrition 0.000 title claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 36
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000005859 coupling reaction Methods 0.000 claims abstract description 34
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000012954 diazonium Substances 0.000 claims abstract description 23
- 230000008878 coupling Effects 0.000 claims abstract description 20
- 238000010168 coupling process Methods 0.000 claims abstract description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 10
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 phenethylamino-6-methylpyrimidine Chemical compound 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract 2
- 230000001105 regulatory effect Effects 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- 235000002639 sodium chloride Nutrition 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 150000001989 diazonium salts Chemical class 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- 230000001276 controlling effect Effects 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004043 dyeing Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 239000013078 crystal Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 2
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical group CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 1
- XREKLQOUFWBSFH-UHFFFAOYSA-N dimethyl 2-acetylbutanedioate Chemical compound COC(=O)CC(C(C)=O)C(=O)OC XREKLQOUFWBSFH-UHFFFAOYSA-N 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3665—Monoazo 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
- C09B29/3669—Monoazo 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing 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
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
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.
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