技术领域Technical field
本发明属于染料领域，具体涉及一种羧酸丁二酰亚胺酯染料及其反应性染色方法。The invention belongs to the field of dyes, and specifically relates to a carboxylic acid succinimide ester dye and a reactive dyeing method thereof.
背景技术Background technique
酸性染料和活性染料是蚕丝染色的两种常用染料。酸性染料在上染蚕丝纤维时能够使纤维获得鲜艳的颜色，染料与蚕丝织物之间通过离子键、范德华力和氢键结合，故而其耐湿处理牢度较差。活性染料在蚕丝纤维染色过程中，染料分子中的活性基团与蚕丝氨基酸残基中的一些基团(氨基、羟基)发生化学反应，形成共价键结合，能够解决蚕丝织物耐湿处理牢度问题。但是，由于活性染料的结构特征，其反应性基团容易水解，并且需要在碱性、高温条件下才能实现反应固色，该方法染色不仅需要较高的能耗，并且容易损伤蚕丝纤维，影响蚕丝品质，同时由于反应性基团的水解使染料失去反应活性，造成染料利用率下降，染色废水中色度增加，污染环境。Acid dyes and reactive dyes are two commonly used dyes for silk dyeing. When dyeing silk fibers, acid dyes can make the fibers obtain bright colors. The dyes and silk fabrics are bonded through ionic bonds, van der Waals forces and hydrogen bonds, so their fastness to moisture treatment is poor. During the dyeing process of silk fiber with reactive dyes, the reactive groups in the dye molecules react chemically with some groups (amino groups, hydroxyl groups) in the amino acid residues of silk to form covalent bonds, which can solve the problem of the fastness of silk fabrics to moisture treatment . However, due to the structural characteristics of reactive dyes, their reactive groups are easily hydrolyzed and require alkaline and high-temperature conditions to achieve reaction and color fixation. This dyeing method not only requires high energy consumption, but also easily damages the silk fiber, affecting the At the same time, due to the hydrolysis of the reactive groups, the dye loses its reactivity, resulting in a decrease in dye utilization, an increase in chroma in dyeing wastewater, and environmental pollution.
酸性染料和活性染料与其相对应的染色方法均无法满足当下印染企业节能减排的需求。因此，开发一种既能使染料与蚕丝纤维形成牢固共价键结合并且节能减排的新型染料染色方法，对蚕丝制品染整行业的发展具有积极意义。Acid dyes, reactive dyes and their corresponding dyeing methods cannot meet the current needs of energy conservation and emission reduction of printing and dyeing enterprises. Therefore, the development of a new dye dyeing method that can form a strong covalent bond between dyes and silk fibers and save energy and reduce emissions is of positive significance to the development of the silk products dyeing and finishing industry.
发明内容Contents of the invention
本发明要解决的技术问题是提供一种羧酸丁二酰亚胺酯染料及其反应性染色方法。The technical problem to be solved by the present invention is to provide a carboxylic acid succinimide ester dye and a reactive dyeing method thereof.
为解决上述技术问题，本发明提供一种羧酸丁二酰亚胺酯染料，其结构通式为：In order to solve the above technical problems, the present invention provides a carboxylic acid succinimide ester dye, the general structural formula of which is:
结构通式中的羧酸丁二酰亚胺酯活性基的数量至少为1个。The number of carboxylic acid succinimide ester active groups in the general structural formula is at least one.
作为本发明的羧酸丁二酰亚胺酯染料的改进，为以下任一结构式：As an improvement of the carboxylic acid succinimide ester dye of the present invention, it is any of the following structural formulas:
染料Y-1：Dye Y-1:
染料R-1：Dye R-1:
染料B-1：Dye B-1:
说明：上述3只染料均仅含有一个羧酸丁二酰亚胺酯活性基。Note: The above three dyes all contain only one carboxylic acid succinimide ester active group.
本发明还同时提供了上述羧酸丁二酰亚胺酯染料的制备方法，包括以下步骤：The invention also provides a preparation method for the above-mentioned carboxylic acid succinimide ester dye, which includes the following steps:
步骤一、含羧酸基染料的制备：Step 1. Preparation of carboxylic acid group-containing dyes:
为以下任一方式：Either of the following ways:
方式1、含羧酸基偶氮染料的制备：Method 1. Preparation of carboxylic acid group-containing azo dyes:
1.1)、重氮化反应：1.1), diazotization reaction:
在盐酸水溶液中，重氮组分与亚硝酸钠进行重氮化反应，反应温度0～5℃，反应时间30±5min；制备获得重氮盐溶液，即，制备获得作为中间产物的重氮盐；In the hydrochloric acid aqueous solution, the diazo component and sodium nitrite undergo a diazotization reaction at a reaction temperature of 0 to 5°C and a reaction time of 30 ± 5 minutes; a diazonium salt solution is prepared, that is, a diazonium salt as an intermediate product is prepared. ;
所述重氮组分为间氨基苯甲酸；The diazo component is m-aminobenzoic acid;
重氮组分：亚硝酸钠＝1:1～1.05的摩尔比；Diazo component: sodium nitrite = molar ratio of 1:1 to 1.05;
1.2)偶合反应：1.2) Coupling reaction:
将步骤1.1)所得的重氮盐溶液与吡唑啉酮衍生物或乙酰化H酸进行偶合反应，反应温度为0～5℃，反应时间2±0.2h；得偶合产物——含羧酸基偶氮染料；Couple the diazonium salt solution obtained in step 1.1) with a pyrazolone derivative or acetylated H acid. The reaction temperature is 0~5°C and the reaction time is 2±0.2h; a coupling product containing a carboxylic acid group is obtained. Azo dyes;
吡唑啉酮衍生物或乙酰化H酸：步骤1.1)的重氮组分＝1:1的摩尔比；Pyrazolone derivative or acetylated H acid: diazo component of step 1.1) = molar ratio of 1:1;
吡唑啉酮衍生物为1-(4-磺酸苯基)-3-甲基-5-吡唑啉酮；The pyrazolone derivative is 1-(4-sulfophenyl)-3-methyl-5-pyrazolone;
方式二、含羧酸基蒽醌染料的制备：Method 2. Preparation of carboxylic acid-containing anthraquinone dyes:
乌尔曼缩合反应：将溴氨酸、间氨基苯甲酸、氯化亚锡和硫酸铜共热，反应温度90±10℃，反应时间为8±1h；生成缩合物——含羧酸基蒽醌染料，Ullmann condensation reaction: Heat bromine, meta-aminobenzoic acid, stannous chloride and copper sulfate together, the reaction temperature is 90±10℃, the reaction time is 8±1h; the condensation product-carboxylic acid-containing anthracene is generated quinone dyes,
所述溴氨酸为4-溴-1-氨基蒽醌-2-磺酸，The bromoamino acid is 4-bromo-1-aminoanthraquinone-2-sulfonic acid,
溴氨酸：间氨基苯甲酸＝1:1；Bromine: meta-aminobenzoic acid = 1:1;
每0.01mol的溴氨酸配用0.5±0.05g硫酸铜以及0.5±0.05g氯化亚锡；For every 0.01 mol of bromine, 0.5±0.05g copper sulfate and 0.5±0.05g stannous chloride are used;
步骤二、酯化反应Step 2. Esterification reaction
于溶剂中，在催化剂和脱水剂作用下，步骤一所得的含羧酸基偶氮染料或含羧酸基蒽醌染料与N-羟基丁二酰亚胺(NHS)发生酯化反应；反应温度为室温，反应时间为12±1h；制得作为目标产物的羧酸丁二酰亚胺酯染料；In a solvent, under the action of a catalyst and a dehydrating agent, the carboxylic acid group-containing azo dye or carboxylic acid group-containing anthraquinone dye obtained in step 1 undergoes an esterification reaction with N-hydroxysuccinimide (NHS); reaction temperature At room temperature, the reaction time is 12±1h; the carboxylic acid succinimide ester dye as the target product is obtained;
含羧酸基偶氮染料/含羧酸基蒽醌染料：NHS＝1:2的摩尔比；The molar ratio of carboxylic acid-containing azo dye/carboxylic acid-containing anthraquinone dye: NHS=1:2;
含羧酸基偶氮染料/含羧酸基蒽醌染料：脱水剂＝1:2的摩尔比；Carboxylic acid group-containing azo dye/carboxylic acid group-containing anthraquinone dye: dehydrating agent = molar ratio of 1:2;
含羧酸基偶氮染料/含羧酸基蒽醌染料：催化剂＝1:0.05的摩尔比。The molar ratio of carboxylic acid group-containing azo dye/carboxylic acid group-containing anthraquinone dye:catalyst=1:0.05.
作为本发明的羧酸丁二酰亚胺酯染料的制备方法的改进：As an improvement on the preparation method of the carboxylic acid succinimide ester dye of the present invention:
脱水剂为二环己基碳二亚胺(DCC)；The dehydrating agent is dicyclohexylcarbodiimide (DCC);
催化剂为4-二甲氨基吡啶(DMAP)；The catalyst is 4-dimethylaminopyridine (DMAP);
溶剂为N,N-二甲基甲酰胺(DMF)。The solvent is N,N-dimethylformamide (DMF).
作为本发明的羧酸丁二酰亚胺酯染料的制备方法的改进：As an improvement of the preparation method of the carboxylic acid succinimide ester dye of the present invention:
所述方式一的步骤1.1)中：In step 1.1) of the first method:
重氮组分和水混合后，先于0～5℃加入盐酸调节pH至5±0.2；再加入亚硝酸钠水溶液进行重氮化反应；亚硝酸钠水溶液的加入方式为滴加，滴加时间约为1min；After the diazo component and water are mixed, hydrochloric acid is first added at 0-5°C to adjust the pH to 5±0.2; then a sodium nitrite aqueous solution is added to carry out a diazotization reaction; the sodium nitrite aqueous solution is added dropwise for about 1 minute;
所述方式一的步骤1.2)中：吡唑啉酮衍生物与水混合后，先调节pH至9～10，而后冷却到0～5℃，再滴加步骤1.1)所得的重氮盐溶液形成反应体系，重氮盐溶液的滴加过程中控制反应体系pH值为9～10及温度为0～5℃。In step 1.2) of the first method: after the pyrazolone derivative is mixed with water, the pH is first adjusted to 9-10, then cooled to 0-5°C, and then the diazonium salt solution obtained in step 1.1) is added dropwise to form In the reaction system, during the dripping process of the diazonium salt solution, the pH value of the reaction system is controlled to be 9-10 and the temperature is 0-5°C.
本发明还提供了利用上述羧酸丁二酰亚胺酯染料进行的蚕丝反应性染色方法：羧酸丁二酰亚胺酯染料与蚕丝(蛋白质)中的氨基反应，生成稳定的羧酰胺共价键，从而实现对蚕丝的反应性染色。The present invention also provides a reactive silk dyeing method using the above-mentioned carboxylic acid succinimide ester dye: the carboxylic acid succinimide ester dye reacts with the amino group in silk (protein) to generate stable carboxamide covalent bond, thereby achieving reactive dyeing of silk.
作为本发明的蚕丝反应性染色方法的改进：As an improvement of the silk reactive dyeing method of the present invention:
所述羧酸丁二酰亚胺酯染料与蚕丝的质量比为0.01～0.05:1；染色浴比1:15～80，始染pH值在3.5～4.5范围内，染色温度为室温，保温1～2小时，再加碱调节pH至8～9，续染1～2小时，染色结束后，将染料浮色从蚕丝上洗涤干净，晾干(10～25℃的室温下晾至恒重)。The mass ratio of the carboxylic acid succinimide ester dye to silk is 0.01~0.05:1; the dyeing bath ratio is 1:15~80, the initial dyeing pH value is in the range of 3.5~4.5, the dyeing temperature is room temperature, and the insulation is 1 ~2 hours, add alkali to adjust the pH to 8~9, and continue dyeing for 1~2 hours. After the dyeing is completed, wash the dye floating color from the silk and dry it (dry it at room temperature of 10~25℃ until it reaches constant weight) .
备注说明：用醋酸-醋酸钠的缓冲溶液来调节上述pH值，此为常规技术。Remarks: Use acetic acid-sodium acetate buffer solution to adjust the above pH value. This is a conventional technique.
本发明的反应化学式如下：The reaction chemical formula of the present invention is as follows:
染料Y-1的合成：Synthesis of dye Y-1:
染料R-1的合成：Synthesis of dye R-1:
染料B-1的合成：Synthesis of dye B-1:
本发明中，含有苯甲酸结构的染料母体与N-羟基丁二酰亚胺(NHS)发生酯化反应生成羧酸丁二酰亚胺酯染料。羧酸丁二酰亚胺酯染料与蛋白质中的氨基残基发生共价键结合，从而实现蚕丝的反应性染色。In the present invention, an esterification reaction occurs between a dye parent containing a benzoic acid structure and N-hydroxysuccinimide (NHS) to generate a carboxylic acid succinimide ester dye. Carboxylic acid succinimide ester dyes covalently bond with amino residues in proteins to achieve reactive dyeing of silk.
在本发明中，对蚕丝无特殊要求，桑蚕丝与柞蚕丝均可。考虑到蚕丝纤维中端氨基与残基氨基含量较高，本发明根据羧酸丁二酰亚胺酯衍生物与氨基发生反应的机理，提供一种羧酸丁二酰亚胺酯染料及其与蚕丝纤维通过酰胺键牢固结合的反应性染色方法。该反应染色方法不需要加盐促染，在室温下即可染色，染浴为先弱酸后弱碱，对纤维损伤较小。相比活性染料与弱酸性染料对蚕丝的染色，本发明中的羧酸丁二酰亚胺酯染料与蚕丝氨基在室温下即可发生，染色温度低，染色湿处理牢度高，染色过程不需要加其他主助剂，废液更加清洁，能耗更小，环保性更高。In the present invention, there is no special requirement for silk, and both mulberry silk and tussah silk can be used. Taking into account the high content of terminal amino groups and residual amino groups in silk fibers, the present invention provides a carboxylic acid succinimide ester dye and its dye based on the reaction mechanism between carboxylic acid succinimide ester derivatives and amino groups. A reactive dyeing method in which silk fibers are firmly bonded through amide bonds. This reaction dyeing method does not require the addition of salt to promote dyeing, and can be dyed at room temperature. The dye bath is first weakly acidic and then weakly alkali, which causes less damage to the fibers. Compared with the dyeing of silk with reactive dyes and weak acidic dyes, the carboxylic acid succinimide ester dye and silk amino group in the present invention can be produced at room temperature, the dyeing temperature is low, the dyeing wet treatment fastness is high, and the dyeing process is simple. It is necessary to add other main additives to make the waste liquid cleaner, consume less energy and be more environmentally friendly.
本发明将羧酸丁二酰亚胺酯染料与蚕丝蛋白中的氨基通过形成酰胺键结合染色方法的反应机理如下所示：The reaction mechanism of the dyeing method of combining carboxylic acid succinimide ester dye with amino groups in silk protein by forming amide bonds is as follows:
本发明所提供的适用于蚕丝的反应性染色方法具有如下优势：The reactive dyeing method suitable for silk provided by the present invention has the following advantages:
(1)染色温度为室温染色，能耗低；(1) The dyeing temperature is room temperature and the energy consumption is low;
(2)室温弱碱性条件染色，对纤维损伤小；(2) Dyeing under weakly alkaline conditions at room temperature will cause little damage to fibers;
(3)为反应性染色，所染织物湿处理牢度高。(3) It is reactive dyeing and the dyed fabric has high wet fastness.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此：The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto:
本发明中的盐酸是指36％-38％的浓盐酸。Hydrochloric acid in the present invention refers to 36%-38% concentrated hydrochloric acid.
1-(4-磺酸苯基)-3-甲基-5-吡唑啉酮(CAS:89-36-1)；1-(4-phenylsulfonate)-3-methyl-5-pyrazolone (CAS:89-36-1);
乙酰H酸(CAS:134-34-9)；Acetyl hydrogen acid (CAS:134-34-9);
溴氨酸：4-溴-1-氨基蒽醌-2-磺酸(CAS:116-81-4)。Bromoamic acid: 4-bromo-1-aminoanthraquinone-2-sulfonic acid (CAS: 116-81-4).
实施例1、一种羧酸丁二酰亚胺酯染料的制备方法，依次进行以下步骤：Example 1. A method for preparing a carboxylic acid succinimide ester dye. The following steps are performed in sequence:
(1)重氮化反应(1) Diazotization reaction
在烧杯中加入10ml水及1.37g间氨基苯甲酸(0.01mol)，搅拌使间氨基苯甲酸溶解后，倒入至100ml三口烧瓶中，用冰水浴使其温度在0～5℃之间。在不断搅拌下，向三口烧瓶中滴加适量的盐酸使溶液的pH为5。另溶0.73g(0.0105mol)NaNO2于5ml水中，缓慢滴加入上述三口烧瓶中；滴加时间约1min，滴加完成后用淀粉--碘化钾试纸检验(微变蓝，表明已生成亚硝酸)，再于冰水浴中反应30min。Add 10 ml of water and 1.37 g of m-aminobenzoic acid (0.01 mol) into the beaker, stir to dissolve the m-aminobenzoic acid, then pour it into a 100 ml three-necked flask, and use an ice water bath to keep the temperature between 0 and 5°C. While stirring continuously, add an appropriate amount of hydrochloric acid dropwise into the three-necked flask to make the pH of the solution 5. Dissolve 0.73g (0.0105mol) NaNO2 in 5ml water, and slowly add it dropwise into the above three-necked flask; the dropping time is about 1 minute. After the dropwise addition is completed, use a starch-potassium iodide test paper to test (it turns slightly blue, indicating that nitrous acid has been generated) , and then react in an ice water bath for 30 minutes.
反应结束后，加入0.6g(0.01mol)的尿素从而除去未反应的亚硝酸(即，除去过量的亚硝酸)；所得的重氮盐溶液留置于冰水中备用。After the reaction is completed, 0.6 g (0.01 mol) of urea is added to remove unreacted nitrous acid (ie, excess nitrous acid is removed); the resulting diazonium salt solution is left in ice water for later use.
重氮盐为：Diazonium salt is:
(2)偶合反应(2) Coupling reaction
称取2.54g(0.01mol)1-(4-磺酸苯基)-3-甲基-5-吡唑啉酮放入250ml烧杯中，加入20ml冰水打浆，用碳酸钠水溶液调节pH至9～10，用冰水浴冷却到0～5℃。将步骤(1)所得的全部的重氮盐溶液缓慢滴加到上述吡唑啉酮溶液中(控制体系温度为0～5℃)，同时滴加碳酸钠水溶液调节反应pH值在9～10(重氮盐溶液缓慢滴加过程中始终控制pH在9～10)，重氮盐滴加完成后，继续在0～5℃下搅拌2小时进行偶合反应；用渗圈法检验反应终点。Weigh 2.54g (0.01mol) 1-(4-sulfophenyl)-3-methyl-5-pyrazolone into a 250ml beaker, add 20ml ice water to make a slurry, and adjust the pH to 9 with sodium carbonate aqueous solution ~10, cool to 0~5℃ in an ice water bath. Slowly add all the diazonium salt solution obtained in step (1) dropwise into the above-mentioned pyrazolone solution (control the system temperature to 0-5°C), and at the same time, add sodium carbonate aqueous solution dropwise to adjust the reaction pH to 9-10 ( During the slow dripping of the diazonium salt solution, always control the pH at 9 to 10). After the dripping of the diazonium salt is completed, continue stirring at 0 to 5°C for 2 hours to perform the coupling reaction; use the percolation circle method to check the reaction end point.
偶合反应完成后，滴加酸(质量浓度为38％的盐酸)至产物大量析出，过滤，收集滤饼，60℃烘箱干燥至恒重，得到黄色含羧酸基偶氮染料。After the coupling reaction is completed, add acid (hydrochloric acid with a mass concentration of 38%) dropwise until a large amount of product precipitates, filter, collect the filter cake, and dry it in a 60°C oven to constant weight to obtain a yellow carboxylic acid group-containing azo dye.
黄色含羧酸基偶氮染料为：Yellow carboxylic acid group-containing azo dyes are:
(3)酯化反应(3)Esterification reaction
称取步骤(2)所得的含羧酸基偶氮染料0.405g(0.001mol)于100ml的三口烧瓶中，加入40ml DMF使其充分溶解，冰水浴条件下冷却到0-5℃；加入0.230g(0.002mol)NHS，搅拌20min后，加入0.412g(0.002mol)二环己基碳二亚胺(DCC)与0.0061g(0.00005mol)4-二甲氨基吡啶(DMAP)，搅拌溶解后升温至室温，反应12小时。反应结束后，抽滤，向滤液中加入乙酸乙酯(约150ml)使产物析出，抽滤，取滤饼，真空冷冻干燥(-40℃)至恒重，得到黄色羧酸丁二酰亚胺酯染料Y-1。Weigh 0.405g (0.001mol) of the carboxylic acid group-containing azo dye obtained in step (2) into a 100ml three-necked flask, add 40ml DMF to fully dissolve it, cool to 0-5°C in an ice-water bath; add 0.230g (0.002mol) NHS, stir for 20 minutes, add 0.412g (0.002mol) dicyclohexylcarbodiimide (DCC) and 0.0061g (0.00005mol) 4-dimethylaminopyridine (DMAP), stir to dissolve and then warm to room temperature , react for 12 hours. After the reaction is completed, filter with suction, add ethyl acetate (about 150 ml) to the filtrate to precipitate the product, filter with suction, take the filter cake, and vacuum freeze-dry (-40°C) to constant weight to obtain yellow carboxylic acid succinimide. Ester dye Y-1.
染料Y-1的结构式如下：The structural formula of dye Y-1 is as follows:
1H NMR(400MHz,DMSO-d6)：δ13.24(s,1H),8.20(s,1H),8.12(d,1H),7.85(d,2H),7.77(t,1H),7.74(d,2H),7.68(d,1H),2.64(t,4H),2.31(s,3H).ESI-MS(m/z,％):498.06([M-Na]-,,100).1 H NMR (400MHz, DMSO-d6): δ13.24(s,1H),8.20(s,1H),8.12(d,1H),7.85(d,2H),7.77(t,1H),7.74( d,2H),7.68(d,1H),2.64(t,4H),2.31(s,3H).ESI-MS(m/z,%):498.06([M-Na]- ,,100).
实施例2、一种羧酸丁二酰亚胺酯染料的制备方法：Example 2. Preparation method of carboxylic acid succinimide ester dye:
将实施例1步骤(2)中的0.01mol的1-(4-磺酸苯基)-3-甲基-5-吡唑啉酮改成乙酰H酸；其余等同于实施例1；Change 0.01 mol of 1-(4-sulfophenyl)-3-methyl-5-pyrazolinone in step (2) of Example 1 into acetyl H acid; the rest is equivalent to Example 1;
最终获得红色羧酸丁二酰亚胺酯染料R-1。Finally, a red carboxylic acid succinimide ester dye R-1 was obtained.
步骤(1)所得的重氮盐为：The diazonium salt obtained in step (1) is:
步骤(2)所得的红色含羧酸基偶氮染料为：The red carboxylic acid group-containing azo dye obtained in step (2) is:
染料R-1的结构如下：The structure of dye R-1 is as follows:
1H NMR(400MHz,DMSO-d6)：δ9.85(s,1H),9.01(s,1H),8.48(s,1H),8.39(s,1H),8.35(d,1H),8.25(d,1H),7.86(t,1H),7.75(s,1H),7.72(s,1H),2.64(t,4H),2.18(s,3H).ESI-MS(m/z,,％):302.00([M-2Na]2-/2,100).1 H NMR (400MHz, DMSO-d6): δ9.85(s,1H),9.01(s,1H),8.48(s,1H),8.39(s,1H),8.35(d,1H),8.25( d,1H),7.86(t,1H),7.75(s,1H),7.72(s,1H),2.64(t,4H),2.18(s,3H).ESI-MS(m/z,,% ):302.00([M-2Na]2- /2,100).
实施例3、一种羧酸丁二酰亚胺酯染料的制备方法：Example 3. Preparation method of carboxylic acid succinimide ester dye:
(1)乌尔曼缩合反应(1) Ullmann condensation reaction
称取4.18g(0.01mol)溴氨酸，6.3g碳酸钠于三口烧瓶中，加入50ml水，充分搅拌使溴氨酸溶解，加入1.37g(0.01mol)间氨基苯甲酸，充分搅拌并升温至80℃，一小时后加入0.25g硫酸铜和0.25g氯化亚锡的固体混合物并将反应升温至90℃，一小时后加入第二份0.25g硫酸铜和0.25g氯化亚锡的固体混合物，90℃保温继续反应7小时。此时利用点板来判断反应程度，不出现红色点便证明反应结束。Weigh 4.18g (0.01mol) of bromoamic acid and 6.3g of sodium carbonate in a three-necked flask, add 50ml of water, stir well to dissolve the bromoamic acid, add 1.37g (0.01mol) of m-aminobenzoic acid, stir well and heat to 80°C, add a solid mixture of 0.25g of copper sulfate and 0.25g of stannous chloride one hour later and heat the reaction to 90°C, add a second portion of a solid mixture of 0.25g of copper sulfate and 0.25g of stannous chloride one hour later, keep warm at 90°C and continue the reaction for 7 hours. At this time, use a dot plate to judge the degree of reaction, and the absence of red dots indicates that the reaction is over.
反应结束后，滴加酸(质量浓度为38％的盐酸)至产物大量析出，过滤，收集滤饼，60℃烘箱干燥至恒重，得到缩合物蓝色含羧酸基蒽醌染料。After the reaction is completed, add acid (hydrochloric acid with a mass concentration of 38%) dropwise until a large amount of product precipitates, filter, collect the filter cake, and dry it in a 60°C oven to constant weight to obtain a condensate blue anthraquinone dye containing carboxylic acid groups.
溴氨酸为4-溴-1-氨基蒽醌-2-磺酸。Bromoacid is 4-bromo-1-aminoanthraquinone-2-sulfonic acid.
步骤(1)所得的蓝色含羧酸基蒽醌染料为：The blue carboxylic acid group-containing anthraquinone dye obtained in step (1) is:
(2)酯化反应(2)Esterification reaction
称取步骤(1)所得的蓝色含羧酸基蒽醌染料0.460g(0.001mol)于100ml的三口烧瓶中，加入40ml DMF使其充分溶解，冰水浴条件下冷却到0-5℃。加入0.230g(0.002mol)NHS，搅拌20min后，加入0.412g(0.002mol)二环己基碳二亚胺(DCC)与0.0061g(0.00005mol)4-二甲氨基吡啶(DMAP)，搅拌溶解后升温至室温，反应12小时。反应结束后，抽滤，向滤液中加入乙酸乙酯(约150ml)使产物析出，抽滤，取滤饼，真空冷冻干燥(-40℃)至恒重，得到蓝色羧酸丁二酰亚胺酯染料B-1。Weigh 0.460g (0.001mol) of the blue carboxylated anthraquinone dye obtained in step (1) into a 100ml three-necked flask, add 40ml of DMF to fully dissolve it, and cool to 0-5°C in an ice-water bath. Add 0.230g (0.002mol) NHS, stir for 20 minutes, add 0.412g (0.002mol) dicyclohexylcarbodiimide (DCC) and 0.0061g (0.00005mol) 4-dimethylaminopyridine (DMAP), stir and dissolve The temperature was raised to room temperature and the reaction was carried out for 12 hours. After the reaction is completed, suction filtrate, add ethyl acetate (about 150 ml) to the filtrate to precipitate the product, suction filtrate, take the filter cake, and vacuum freeze-dry (-40°C) to constant weight to obtain blue carboxylic acid succinimidyl. Urethane dye B-1.
染料B-1的结构如下：The structure of dye B-1 is as follows:
1H NMR(400MHz,DMSO-d6)：δ12.27(s,1H),8.29(t,2H),7.97(d,,1H),7.88(s,1H),7.85(d,2H),7.81(d,1H),7.70(s,1H),7.43(t,1H),4.82(s,2H),2.64(t,4H).ESI-MS(m/z,,％):534.05([M-Na]-,100).1 H NMR (400MHz, DMSO-d6): δ12.27(s,1H),8.29(t,2H),7.97(d,,1H),7.88(s,1H),7.85(d,2H),7.81 (d,1H),7.70(s,1H),7.43(t,1H),4.82(s,2H),2.64(t,4H).ESI-MS(m/z,,%):534.05([M -Na]- ,100).
下面通过实验来说明本发明的羧酸丁二酰亚胺酯结构染料在蚕丝织物染色中的应用。The application of the carboxylic acid succinimide ester structural dye of the present invention in silk fabric dyeing will be explained through experiments below.
实验1Experiment 1
染料Y-1、染料R-1或染料B-1加入水配制成染液。Add dye Y-1, dye R-1 or dye B-1 to water to prepare a dye solution.
羧酸丁二酰亚胺酯染料染色工艺：染色所用蚕丝织物1.0g(±0.02g)，染料与蚕丝的质量比为0.03:1，即染料用量3％(owf)、浴比1:50，用醋酸和醋酸钠缓冲溶液调节pH值至4，染色温度为室温(约20℃)，90min后加入约0.8g左右的无水碳酸钠，调节pH至8-9，在室温下继续染色1.5h，染色结束后，取出染色布样，洗涤(洗涤用的水量为100mL)，合并染色残液及洗涤液，用250ml容量瓶定容测吸光度，设计空白对比染浴进行相同操作，利用朗伯-比尔定律求出染料的上染率。根据染色布样剥色前后的色深K/S值来计算固色率，其主要方法如下：将染色的蚕丝织物浸入300mL DMF中，并在95℃下萃取30min。30min后将织物取出，用水洗涤并在室温下干燥。利用公式(1)计算羧酸丁二酰亚胺酯染料对蚕丝的上染率：Carboxylic acid succinimide ester dyeing process: 1.0g (±0.02g) of silk fabric used for dyeing, the mass ratio of dye to silk is 0.03:1, that is, the amount of dye is 3% (owf), the bath ratio is 1:50, the pH value is adjusted to 4 with acetic acid and sodium acetate buffer solution, the dyeing temperature is room temperature (about 20°C), about 0.8g of anhydrous sodium carbonate is added after 90min, the pH is adjusted to 8-9, and dyeing is continued at room temperature for 1.5h. After dyeing, the dyed fabric sample is taken out, washed (the amount of water used for washing is 100mL), the dyeing residual liquid and the washing liquid are combined, and the absorbance is measured by constant volume with a 250ml volumetric flask, and a blank comparative dye bath is designed to perform the same operation, and the dye uptake rate of the dye is calculated using the Lambert-Beer law. The color fixation rate is calculated according to the color depth K/S value before and after the dyed fabric sample is stripped. The main method is as follows: the dyed silk fabric is immersed in 300mL DMF and extracted at 95°C for 30min. After 30 minutes, the fabric was taken out, washed with water and dried at room temperature. The dyeing rate of carboxylic acid succinimide ester dye on silk was calculated using formula (1):
在公式(1)中％E为染料的上染百分率，A1是染色残液的吸光度，V1是染色残液稀释后的体积，A0是空白染浴的吸光度，V0是空白染浴稀释后的体积。In formula (1), %E is the dye uptake percentage,A1 is the absorbance of the dyeing residual solution,V1 is the volume of the dyeing residual solution after dilution,A0 is the absorbance of the blank dye bath, andV0 is the volume of the blank dye bath after dilution.
利用公式(2)计算羧酸丁二酰亚胺酯染料对蚕丝的相对固色率：Use formula (2) to calculate the relative fixation rate of carboxylic acid succinimide ester dye on silk:
％F＝(K/S)i/(K/S)0 公式(2)%F＝(K/S)i /(K/S)0 formula (2)
在公式(2)中，％F是基于在蚕丝织物上的染料的最大吸收波长下测得的K/S值计算的。(K/S)0和(K/S)1分别是DMF剥色前后蚕丝织物最大吸收波长下测定的K/S值。并依据ISO 105-X12:2001、ISO 105-F06:2000分别测定上述染色布样的耐皂洗变色牢度、耐湿摩擦牢度。In formula (2), %F is calculated based on the K/S value measured at the maximum absorption wavelength of the dye on silk fabric. (K/S)0 and (K/S)1 are the K/S values measured at the maximum absorption wavelength of the silk fabric before and after DMF stripping, respectively. And according to ISO 105-X12:2001 and ISO 105-F06:2000, the color fastness to soaping and wet rubbing fastness of the above dyed cloth samples were measured.
表1Table 1
对比例1：将实验1中的染料分别改为含吡唑啉酮结构的商品酸性染料C.I.酸性黄11和含有H酸结构的商品酸性染料C.I.酸性红1。Comparative Example 1: The dyes in Experiment 1 were changed to commercial acid dye C.I. Acid Yellow 11 containing pyrazolone structure and commercial acid dye C.I. Acid Red 1 containing H acid structure.
酸性染料染色工艺：染色所用蚕丝织物1.0g(±0.02g)，染料与蚕丝的质量比为0.03:1，即染料用量3％(owf)、浴比1:50，元明粉10g/L，用醋酸和醋酸钠缓冲溶液调节pH值至4，染色起始温度为50℃，升温至90℃，升温速率约1℃/min，在90℃下保温1h，降温30min，降至温度30℃，降温速率约2℃/min，染色结束后，取出染色布样，洗涤(洗涤用的水量为200mL)，其余测试条件同实验1。Acid dye dyeing process: the silk fabric used for dyeing is 1.0g (±0.02g), the mass ratio of dye to silk is 0.03:1, that is, the dye dosage is 3% (owf), the bath ratio is 1:50, and Yuanming powder is 10g/L. Use acetic acid and sodium acetate buffer solutions to adjust the pH value to 4. The starting temperature of dyeing is 50°C, and the temperature is raised to 90°C. The heating rate is about 1°C/min. Incubate at 90°C for 1 hour, cool down for 30 minutes, and then drop to the temperature of 30°C. The cooling rate is about 2°C/min. After dyeing, take out the dyed cloth sample and wash it (the amount of water used for washing is 200mL). The other test conditions are the same as Experiment 1.
染料结构式如下：The dye structural formula is as follows:
所得结果如表1所述。The results obtained are shown in Table 1.
对比例2：将实验1中的染料换成商品活性染料C.I.活性红24或C.I.活性黄3，加入水配置成染液。Comparative Example 2: The dye in Experiment 1 was replaced with commercial reactive dyes C.I. Reactive Red 24 or C.I. Reactive Yellow 3, and water was added to prepare a dye liquor.
活性染料染色工艺：染色所用蚕丝织物1.0g(±0.02g)，染料用量3％(owf)、浴比1:50，元明粉30g/L，染色起始温度为50℃，30min后升温至90℃，升温速率约2℃/min，同时加入碳酸钠调节pH至11(碱剂浓度为10g/L)，在90℃下保温60min，降温30min，降至温度30℃，降温速率约2℃/min，染色结束后，取出染色布样，洗涤(洗涤用的水量为200mL)。其余测试条件同实验1。Reactive dye dyeing process: 1.0g silk fabric used for dyeing (±0.02g), dye dosage 3% (owf), liquor ratio 1:50, Yuanming powder 30g/L, dyeing starting temperature is 50℃, and the temperature is raised to 30min after 30min. 90℃, the heating rate is about 2℃/min, and sodium carbonate is added to adjust the pH to 11 (alkali concentration is 10g/L). Keep it at 90℃ for 60min, cool down for 30min, then drop to the temperature of 30℃, the cooling rate is about 2℃. /min, after dyeing is completed, take out the dyed cloth sample and wash (the amount of water used for washing is 200mL). The remaining test conditions are the same as Experiment 1.
染料结构式如下：The dye structural formula is as follows:
织物相对强力测试：根据GB/T3923.1-2013测定织物强力。织物相对强力保留率(％)为织物染色后强力和织物染色前断裂强力的比值。Fabric relative strength test: Fabric strength is measured according to GB/T3923.1-2013. Fabric relative strength retention rate (%) is the ratio of fabric strength after dyeing to fabric breaking strength before dyeing.
所得结果如表2所示。The results are shown in Table 2.
表2Table 2
根据表1可知：羧酸丁二酰亚胺酯染料与酸性染料的上染率相当，这两种染料都含有酸性基团，当染浴以pH在蚕丝等电点以下时染料可以通过离子间引力吸附到纤维上。但羧酸丁二酰亚胺酯染料的固色率要远大于商品酸性染料，酸性染料染色织物固色率仅5.3％，经过DMF剥色后蚕丝上颜色基本褪去，而羧酸丁二酰亚胺酯染色织物固色率可高达97.7％，经过DMF剥色后蚕丝织物几乎没有褪色，这是因为酸性染料与蛋白质纤维之间是离子键结合，在剥色的过程中，离子键断裂，染料被萃取进入DMF溶液中，并且由于染料和纤维是离子键结合，也导致了酸性染料的湿处理牢度不佳；而羧酸丁二酰亚胺酯染料和蚕丝纤维是共价键结合，在剥色的过程中，只是洗掉了未与纤维结合的极少量染料浮色，绝大部分染料与纤维共价键结合，因此剥色后蚕丝上仍然有较深的颜色，并且牢固的羧酰胺共价键结合使羧酸丁二酰亚胺酯染后的织物湿处理牢度较好。According to Table 1, it can be seen that the dyeing rates of carboxylic acid succinimide ester dyes and acid dyes are equivalent. Both dyes contain acidic groups. When the pH of the dye bath is below the isoelectric point of silk, the dye can pass through the ion space. Gravity adsorbs to the fibers. However, the fixation rate of carboxylic acid succinimide ester dyes is much greater than that of commercial acid dyes. The fixation rate of fabrics dyed with acid dyes is only 5.3%. After DMF stripping, the color on the silk basically fades, while carboxylic acid succinimide ester dyes have a fixation rate of only 5.3%. The fixation rate of urethane dyed fabrics can be as high as 97.7%. Silk fabrics almost do not fade after DMF stripping. This is because the acid dyes and protein fibers are ionically bonded. During the stripping process, the ionic bonds are broken and the dye It is extracted into the DMF solution, and because the dye and fiber are ionically bonded, it also leads to poor wet processing fastness of acid dyes; while carboxylic acid succinimide ester dye and silk fiber are covalently bonded, and in During the stripping process, only a very small amount of dye floating color that is not combined with the fiber is washed away. Most of the dye is covalently bonded with the fiber. Therefore, after stripping, the silk still has a darker color and a strong carboxamide Covalent bonding makes fabrics dyed with carboxylic acid succinimide ester have better wet treatment fastness.
根据表2可知：羧酸丁二酰亚胺酯染料和活性染料都是反应型染料，二者都需要在碱性条件下与纤维发生亲核取代反应，蚕丝纤维耐弱酸不耐碱，活性染料在碱性高温的条件下染固色，对纤维的损伤更重，造成蚕丝纤维强力下降更多。此外，活性染料在高温下水解加快，最终上染到纤维上的染料量少，导致上染率和固色率均较低。本发明中的羧酸丁二酰亚胺酯染料在室温弱酸条件下上染纤维，染料大量吸附上纤维后在室温弱碱性条件下固着到纤维上，对纤维损伤小，使蚕丝在染色后仍能保持较高的纤维强力和较好的物理机械性能，且上染率和固色率均高于活性染料。According to Table 2, carboxylic acid succinimide ester dyes and reactive dyes are both reactive dyes, and both need to undergo nucleophilic substitution reactions with fibers under alkaline conditions. Silk fibers are weakly acid-resistant but not alkali-resistant. Reactive dyes dye and fix under alkaline and high temperature conditions, which causes more serious damage to the fibers, resulting in a greater decrease in silk fiber strength. In addition, reactive dyes are hydrolyzed faster at high temperatures, and the amount of dye finally dyed on the fibers is small, resulting in lower dye uptake and fixation rates. Carboxylic acid succinimide ester dyes in the present invention dye fibers under weak acid conditions at room temperature, and dyes are fixed to fibers under weak alkaline conditions at room temperature after being adsorbed on the fibers in large quantities, causing little damage to the fibers, so that silk can still maintain higher fiber strength and better physical and mechanical properties after dyeing, and dye uptake and fixation rates are higher than reactive dyes.
综上所述，本发明中含羧酸丁二酰亚胺酯型结构的染料，由于结构中存在羧酸丁二酰亚胺酯活性基团，能够和蚕丝形成羧酰胺键共价结合。与普通的酸性染料相比，染料的固色率获得显著提升，其耐皂洗变色牢度和耐湿摩擦牢度同样提升明显。与活性染料相比，对蚕丝纤维损伤更小，上染率和固色率更高。上述优点能够提高染料对蚕丝纤维的染色效率，降低能耗，减少废水中染料含量，满足工业生产需求。To sum up, the dye containing carboxylic acid succinimide ester type structure in the present invention can covalently bond with silk to form a carboxamide bond due to the presence of carboxylic acid succinimide ester active groups in the structure. Compared with ordinary acid dyes, the fixation rate of the dye is significantly improved, and its color fastness to soaping and wet rubbing fastness are also significantly improved. Compared with reactive dyes, it causes less damage to silk fibers and has higher dye uptake and color fixation rates. The above advantages can improve the dyeing efficiency of silk fibers, reduce energy consumption, reduce the dye content in wastewater, and meet the needs of industrial production.
最后，还需要注意的是，以上列举的仅是本发明的若干个具体实施例。显然，本发明不限于以上实施例，还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。Finally, it should also be noted that the above enumerations are only several specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and many modifications are possible. All modifications that a person of ordinary skill in the art can directly derive or associate from the disclosure of the present invention should be considered to be within the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310600645.8ACN116790136B (en) | 2023-05-25 | 2023-05-25 | Carboxylic acid succinimide ester dye and reactive dyeing method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310600645.8ACN116790136B (en) | 2023-05-25 | 2023-05-25 | Carboxylic acid succinimide ester dye and reactive dyeing method thereof |
| Publication Number | Publication Date |
|---|---|
| CN116790136A CN116790136A (en) | 2023-09-22 |
| CN116790136Btrue CN116790136B (en) | 2024-04-02 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310600645.8AActiveCN116790136B (en) | 2023-05-25 | 2023-05-25 | Carboxylic acid succinimide ester dye and reactive dyeing method thereof |
| Country | Link |
|---|---|
| CN (1) | CN116790136B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118727475B (en)* | 2024-07-12 | 2025-04-29 | 绍兴劲草化工有限公司 | Room temperature salt-free rapid reactive dyeing and recycling method suitable for cellulose fibers |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3805318A1 (en)* | 1988-02-20 | 1989-08-31 | Hoechst Ag | Chemiluminescent 9-sulphonyl-aminocarbonyl-acridinium salts |
| CN101643436A (en)* | 2009-05-27 | 2010-02-10 | 北京维德维康生物技术有限公司 | Sudan hapten and antigen as well as preparation method and application thereof |
| CN104507902A (en)* | 2012-07-10 | 2015-04-08 | 佐治亚州立大学研究基金会公司 | Anthraquinone analogues and methods for their preparation and use |
| WO2015191735A1 (en)* | 2014-06-11 | 2015-12-17 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Water-soluble triazabutadienes |
| CN105949281A (en)* | 2016-05-04 | 2016-09-21 | 新乡医学院 | Fluorescence resonance energy transfer probe, preparation method and application thereof |
| CN111393872A (en)* | 2020-03-18 | 2020-07-10 | 宝天生物科技（上海）有限公司 | Ultraviolet light excited fluorescent dye and application thereof |
| CN113049557A (en)* | 2021-03-12 | 2021-06-29 | 广州江元医疗科技有限公司 | Multiple fluorescent staining solution for genital secretion and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3805318A1 (en)* | 1988-02-20 | 1989-08-31 | Hoechst Ag | Chemiluminescent 9-sulphonyl-aminocarbonyl-acridinium salts |
| CN101643436A (en)* | 2009-05-27 | 2010-02-10 | 北京维德维康生物技术有限公司 | Sudan hapten and antigen as well as preparation method and application thereof |
| CN104507902A (en)* | 2012-07-10 | 2015-04-08 | 佐治亚州立大学研究基金会公司 | Anthraquinone analogues and methods for their preparation and use |
| WO2015191735A1 (en)* | 2014-06-11 | 2015-12-17 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Water-soluble triazabutadienes |
| CN105949281A (en)* | 2016-05-04 | 2016-09-21 | 新乡医学院 | Fluorescence resonance energy transfer probe, preparation method and application thereof |
| CN111393872A (en)* | 2020-03-18 | 2020-07-10 | 宝天生物科技（上海）有限公司 | Ultraviolet light excited fluorescent dye and application thereof |
| CN113049557A (en)* | 2021-03-12 | 2021-06-29 | 广州江元医疗科技有限公司 | Multiple fluorescent staining solution for genital secretion and preparation method and application thereof |
| Publication number | Publication date |
|---|---|
| CN116790136A (en) | 2023-09-22 |
| Publication | Publication Date | Title |
|---|---|---|
| CN102964870B (en) | Active black dye composition | |
| CN101307186A (en) | A kind of red disazo dye compound, preparation method and composition thereof | |
| CN116790136B (en) | Carboxylic acid succinimide ester dye and reactive dyeing method thereof | |
| CN117306277A (en) | Suitable for aromatic modification of cellulose fibers and their dyeing methods | |
| CN102504585A (en) | Blue active dye, preparation method and application thereof | |
| CN108530944A (en) | A kind of orange active dye compound and its preparation method and application | |
| CN111484753B (en) | Sun-proof easy-to-wash red azo disperse dye and preparation method thereof | |
| CN111484751B (en) | Alkali washable sun-proof orange azo disperse dye and preparation method thereof | |
| CN111303654A (en) | Diarylamine acid dye containing β -naphthylamine structure and preparation method thereof | |
| CN116218254B (en) | A kind of brilliant red reactive dye and preparation method thereof | |
| CN109338747B (en) | Dyeing method for reducing dye thiourea dioxide at low temperature | |
| CN104672160B (en) | A kind of compound in triazine class and its application as dye additive | |
| CN111205670B (en) | Double-aromatic primary amine acid dye containing H acid structure and preparation method thereof | |
| CN115746578B (en) | Cyclic imine dye and reactive dyeing method thereof | |
| CN105176139A (en) | Brown polyazo reactive dye compound, and preparation method and application thereof | |
| CN116876243A (en) | Modified dyeing methods of cotton fabrics and modifiers used | |
| CN105038312B (en) | A kind of red reactive dyes compound and its preparation and application | |
| JPS5940852B2 (en) | Improved method for producing C.I. Acid Red 42 | |
| CN102268195B (en) | A kind of alkali-proof active dye | |
| CN116445003B (en) | Isolated primary aromatic amine azo dye and preparation method thereof | |
| CN118727475B (en) | Room temperature salt-free rapid reactive dyeing and recycling method suitable for cellulose fibers | |
| CN111978202A (en) | Recovery method of alkaline washable disperse dye hydrolysate | |
| CN109679367B (en) | Blue acid dye and preparation method thereof | |
| CN102433027A (en) | Azo type blue reactive dye and preparation method thereof | |
| CN115725189B (en) | A disazo disperse dye and its synthesis method and application |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |