CN109054438B - 超临界co2流体中天然纤维无水染色专用偶氮染料及其制备方法 - Google Patents

超临界co2流体中天然纤维无水染色专用偶氮染料及其制备方法 Download PDF

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CN109054438B
CN109054438B CN201811019400.1A CN201811019400A CN109054438B CN 109054438 B CN109054438 B CN 109054438B CN 201811019400 A CN201811019400 A CN 201811019400A CN 109054438 B CN109054438 B CN 109054438B
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龙家杰
闫凯
徐导
俞金林
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Jiangsu Danmao Textile Co ltd
Suzhou University
Nantong Textile and Silk Industrial Technology Research Institute
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Suzhou University
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Abstract

本发明公开了一种超临界CO2流体中天然纤维无水染色专用活性分散染料及其中间体。该活性分散染料的染料发色母体与活性基团之间具有较长的烷烃链桥基，能够有效促进共轭体系电子云的供‑吸效应，增强深色效应，同时有效降低活性基团本身及其反应对染料发色体系的影响，并提高染料色泽耐酸碱稳定性；此外，也有利于提高该染料与超临界流体的相容性及对天然纤维的染色性能。本发明还公开了所述活性分散染料中间体及活性分散染料的制备方法。

Description

超临界CO2流体中天然纤维无水染色专用偶氮染料及其制备 方法
技术领域
本发明涉及活性分散染料技术领域，尤其涉及一种超临界CO2流体中天然纤维无水染色专用偶氮染料及其制备方法。
背景技术
超临界CO2流体加工技术作为一种对环境友好的工艺方法，在纺织染整领域已经被广泛的关注，超临界CO2流体不仅具有低粘度、高扩散性、无毒无害、绿色环保等特点，同时可实现二氧化碳流体和染整加工助剂的回收利用，可有效的解决传统染整加工中用水多、排污多的问题(参考文献：Synthesis and Measurement of Solubilities ofReactive Disperse Dyes for Dyeing Cotton Fabrics in Supercritical CarbonDioxide[J].Industrial and Engineering Chemistry Research,2014, 53(36):13862-13870；超临界CO2染色[J].印染助剂,2006,23(4):10-13；Dyeing of Textiles inSupercritical Carbon Dioxide[J].Textile Research Journal,1993, 63(3):135-142.)。
由于超临界CO2流体自身的特点，因此在合成纤维无水染整加工中的应用较为成熟。然而，超临界CO2流体应用于天然纤维的染色加工依然存在一定的局限性，由于天然纤维与合成纤维本身不同的结构特点及染整加工原理，使得超临界CO2流体对合成纤维的染色加工工艺不能完全应用于天然纤维的加工处理。解决这一局限性的方法可从两个方面着手，其一：对天然纤维的改性处理；其二：制备能够实现在超临界CO2流体中完成对天然纤维染色的特殊型染料(参考文献：Dyeing of cotton fabric with reactive disperse dyecontain acyl fluoride group in supercritical carbon dioxide[J].Dyes andPigments,2017,139:566-574；Dyeing of natural and synthetic textiles insupercritical carbon dioxide with disperse reactive dyes[J].Journal ofSupercritical Fluids,2007,40(3):470-476.)。
活性分散染料是一种能够在非极性的超临界CO2流体中溶解，并能与天然纤维中活性基团反应的特殊型结构染料，通常以分散染料母体中接入活性基团制备，该类型染料不仅能够适用于超临界CO2对天然纤维的染色加工，同时可避免纤维改性造成的纤维原有性能的破坏(参考文献：Dyeing and fastness properties of a reactive disperse dyeon PET,nylon,silk and N/P fabrics[J].Fibers and Polymers,2006,7(2):174-179；Dyeing process,DE3906724[P].1990.)。
伴随着超临界CO2流体技术在天然纤维加工中的应用发展，活性分散染料的研究同样被人们逐渐关注，其研究成果不断增加。《超临界CO2流体专用活性分散染料的合成及表征》(魏晓晨，苏州大学硕士学位论文，公开日期2015 年12月3日)公开了一种超临界CO2染色专用活性分散染料的中间体及活性分散染料，该染料具有如式(Ⅳ)所示的结构通式。该活性分散染料发色强度高、色谱齐全、色泽艳丽，能够适用于超临界CO2对天然纤维的染色。但是该活性分散染料的结构较为简单,在结构上也存在偶合组分对共轭体系电子云供-吸效应不够理想，活性基团易于对染料母体电子云密度产生影响等不足。
Figure BDA0001786939090000021
发明内容
本发明要解决的技术问题是提供一种能够有效减小活性基团本身及其反应对染料发色体系影响的活性分散染料及其中间体。
为了解决上述技术问题，本发明提供了一种活性分散染料中间体，具有式 (Ⅰ)所示的结构通式，
Figure BDA0001786939090000031
其中，R1为Cl或Br；
偶合组分的取代侧链中，n的取值范围为1≤n≤6，例如：n＝1时取代基为乙基、n＝2时为丙基、n＝3时为丁基、n＝4时为戊基等；m的取值范围为1 ≤m≤6，例如m＝1时取代基为1-氨甲基、m＝2时为2-氨乙基、m＝3时为3-氨丙基、m＝4时为4-氨丁基等。
优选的，R1为Cl；n＝1，即取代基为乙基；m＝2，即取代基为2-氨乙基。
本发明还提供了一种活性分散染料，由前述的染料中间体直接制备而成，其具有式(Ⅱ)所示的结构通式，
Figure BDA0001786939090000032
其中，R1为Cl或Br；
偶合组分的取代侧链中，n的取值范围为1≤n≤6，例如：n＝1时取代基为乙基、n＝2时为丙基、n＝3时为丁基、n＝4时为戊基等；m的取值范围为1 ≤m≤6，例如m＝1时取代基为1-氨甲基、m＝2时为2-氨乙基、m＝3时为3-氨丙基、m＝4时为4-氨丁基等。
优选的，R1为Cl；n＝1，即取代基为乙基；m＝2，即取代基为2-氨乙基。
此外，本发明还提供了前述的活性分散染料中间体的一种制备方法，包括以下步骤：
1)在酸性条件下，将2-氯-4-硝基苯胺或2-溴-4-硝基苯胺重氮化；
2)将得到的重氮化产物在pH为5～7的条件下与偶合组分进行偶合反应，得到式(Ⅰ)所示染料中间体；其中，所述偶合组分具有式(Ⅲ)所示的结构通式
Figure BDA0001786939090000041
其中，偶合组分的取代侧链中，m，n的取值范围为1≤m≤6，1≤n≤6。
在本发明的一种优选的实施方式中，步骤1)具体包括：将2-氯-4-硝基苯胺或2-溴-4-硝基苯胺溶于溶剂中，加入浓盐酸控制得到的溶液为酸性，再与亚硝酸钠发生重氮化反应。
本发明步骤1)中，可采用浓盐酸、浓硫酸或醋酸调节反应介质为酸性，优选的采用浓盐酸。
在本发明的一种优选的实施方式中，步骤1)中，所述溶剂包括有机溶剂和水，溶剂中包含水，是因为该反应中需要水溶性原料的参与。所述有机溶剂为N,N-二甲基甲酰胺、二氧六环和醋酸中的一种或多种。
在本发明的一种优选的实施方式中，步骤1)中，所述有机溶剂与水的体积比为15～10:5～10，更优选的为5～10:5～10。如果有机溶剂比例过少，原料不能充分溶解；如果比例过多，后期产物分离难度增加。
在本发明的一种优选的实施方式中，步骤1)中，重氮化反应的时间为2～4 小时。
在本发明的一种优选的实施方式中，步骤2)中，还包括在偶合反应发生前加入尿素水溶液去除过量的亚硝酸钠的步骤，以防止亚硝酸钠影响偶合反应的进行。
在发明的步骤2)中，pH为5～7的有利于偶合反应的进行，更优选的pH 为6，此在pH条件下，偶合反应的效果最好。优选的，采用氢氧化钠溶液调节反应介质的pH。
在本发明的一种优选的实施方式中，步骤2)中，偶合反应的温度为0～5℃，时间为3～5小时。
在本发明的一种优选的实施方式中，还包括采用硅胶色谱柱纯化得到的染料中间体的步骤，其中，纯化时所用的硅胶粉为200～300目，洗脱剂为石油醚、二氯甲烷和丙酮，且石油醚与二氯甲烷的体积比为0～3:1～4，丙酮与二氯甲烷的体积比为0～4:1～4。
此外，本发明还提供了前述的活性分散染料的一种制备方法，包括：将式 (I)所示的染料中间体与三聚氯氰在缚酸剂存在的条件下于溶剂中进行反应，得到如式(Ⅱ)所示的活性分散染料。其中，所述溶剂包括有机溶剂和水，所述有机溶剂为N,N-二甲基甲酰胺、二氧六环和醋酸中的一种或多种。
在本发明的一种优选的实施方式中，所述缚酸剂为碳酸钠和/或碳酸氢钠。缚酸剂在反应中能够中和反应中生成的非染料产物，从而使反应生成更多的目标染料，提高染料的产率。
在本发明的一种优选的实施方式中，还包括采用硅胶色谱柱纯化得到的活性分散染料的步骤，其中，纯化时所用的硅胶粉为200～300目，洗脱剂为石油醚、二氯甲烷和丙酮，且石油醚与二氯甲烷的体积比为0～3:1～4，丙酮与二氯甲烷的体积比为0～4:1～4。
在本发明的一种优选的实施方式中，在染料中间体和染料的制备过程中，芳伯胺、浓盐酸、亚硝酸钠、偶合组分、缚酸剂、三聚氯氰的摩尔比为1:10～15: 1.1～1.5:1.1～1.5:1～2:1～1.5。
本发明的有益效果在于：
本发明的活性分散染料，其染料发色母体与三聚氯氰活性基团之间具有较长的烷烃链桥基，能够有效促进共轭体系电子云的供-吸效应，增强深色效应，同时有效降低活性基团本身及其反应对染料发色体系的影响，并提高染料色泽耐酸碱稳定性；且也有利于提高该染料与超临界流体的相容性及对天然纤维的染色性能。
本发明的活性分散染料，不仅可适用于水浴染色加工，同时为超临界CO2染色天然纤维提供了一种理想的染料。
本发明所采用的制备工艺条件较为温和，反应可控性较高，操作安全性强，降低了生产成本。
附图说明
图1为本发明实施例的活性分散染料中间体提纯产物的傅里叶红外转换红外光谱图；
图2为本发明实施例的活性分散染料提纯产物的傅里叶红外转换红外光谱图；
图3为本发明实施例的染料中间体和活性分散染料的紫外-可见吸收光谱图。
具体实施方式
下面通过具体实施例对本发明的方法进行说明，以使本发明技术方案更易于理解、掌握，但本发明并不局限于此。下述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1
制备染料中间体：
(1)称取0.5mmol 2-氯-4-硝基苯胺，并置于100ml三口烧瓶中，加入10ml N,N-二甲基甲酰胺和5ml去离子水超声分散溶解，将三口烧瓶放置于低温磁力搅拌器中，控制温度为0～5℃匀速搅拌，再向体系中加入5mmol浓盐酸，待反应体系达到预定温度范围后，向体系中缓慢滴加5ml 0.11mmol/ml亚硝酸钠水溶液，控制反应2h后，加入5ml 0.01mmol/mL尿素溶液，充分反应10min。通过TLC对反应产物进行追踪。
(2)采用氢氧化钠溶液调节步骤(1)重氮盐反应体系pH约为6，移取 0.55mmol N-(2-氨乙基)-N-乙基间甲苯胺溶液，并用5ml N,N-二甲基甲酰胺进行溶解，然后缓慢滴加到上述重氮盐溶液中，保持0～5℃反应3h，TLC追踪反应历程。反应结束，用去离子水稀释反应体系，抽滤、洗涤，滤液采用二氯甲烷萃取、旋蒸浓缩，并与抽滤产物混合，混合产物采用硅胶色谱柱分离提纯，得染料中间体，提纯产率93.58％，产物纯度为99％。
实施例2
制备染料中间体：
(1)称取0.5mmol 2-氯-4-硝基苯胺，并置于100ml三口烧瓶中，加入10ml 二氧六环和5ml去离子水超声分散溶解，将三口烧瓶放置于低温磁力搅拌器中，控制温度为0～5℃匀速搅拌，再向体系中加入5mmol浓盐酸，待反应体系达到预定温度范围后，向体系中缓慢滴加5ml 0.11mmol/ml亚硝酸钠水溶液，控制反应2h后，加入5ml 0.01mmol/mL尿素溶液，充分反应10min。通过TLC对反应产物进行追踪。
(2)采用氢氧化钠溶液调节步骤(1)重氮盐反应体系pH约为6，移取 0.55mmol N-(2-氨乙基)-N-乙基间甲苯胺溶液，并用5ml二氧六环进行溶解，然后缓慢滴加到上述重氮盐溶液中，保持0～5℃反应3h，TLC追踪反应历程。反应结束，用去离子水稀释反应体系，抽滤、洗涤，滤液采用二氯甲烷萃取、旋蒸浓缩，并与抽滤产物混合，混合产物采用硅胶色谱柱分离提纯，得染料中间体，提纯产率94.19％，产物纯度为98％。
实施例3
制备活性分散染料：
(1)称取目标染料中间体提纯产物0.05g(0.138mmol)，在100ml三口烧瓶中，用5ml二氧六环和5ml去离子水超声分散溶解，将三口烧瓶放置于低温磁力搅拌器中，控制温度为0～5℃，匀速搅拌。称取0.207mmol三聚氯氰和 0.276mmol碳酸钠分别采用5ml二氧六环和5ml去离子水溶解，然后同时缓慢滴加到三口烧瓶中，保持反应2h。反应结束，用去离子水稀释反应体系，抽滤、洗涤，滤液采用二氯甲烷萃取、旋蒸浓缩，并与抽滤产物混合，混合产物采用硅胶色谱柱分离提纯，得最终活性分散染料产率71.56％，产物纯度为99％。
实施例4
制备活性分散染料：
(1)称取目标染料中间体提纯产物0.05g(0.138mmol)，在100ml三口烧瓶中，用5ml二氧六环和5ml去离子水超声分散溶解，将三口烧瓶放置于低温磁力搅拌器中，控制温度为0～5℃，匀速搅拌。称取0.207mmol三聚氯氰和 0.276mmol碳酸氢钠分别采用5ml二氧六环和5ml去离子水溶解，然后同时缓慢滴加到三口烧瓶中，保持反应2h。反应结束，用去离子水稀释反应体系，抽滤、洗涤，滤液采用二氯甲烷萃取、旋蒸浓缩，并与抽滤产物混合，混合产物采用硅胶色谱柱分离提纯，得最终活性分散染料产率74.40％，产物纯度为99％。
实施例5
表征与性能检测：
利用傅里叶转换红外光谱和紫外-可见吸收光谱对实施例1-4的染料中间体体和活性分散染料的提纯产物进行结构表征，结果如图1、2、3所示。
图1中染料中间体的傅里叶转换红外光谱测试结果显示，在3444.37cm-1和3421.78cm-1处分别-NH2的反对称伸缩振动和对称伸缩振动吸收峰，3099.35cm-1为芳环上C-H键的伸缩振动，2969.31cm-1和2923.82cm-1分别为烷烃C-H键的反对称伸缩振动和对称伸缩振动吸收峰，1601.11cm-1处为N＝N的伸缩振动吸收峰，1512.70cm-1处及1338.05cm-1处分别为Ar-NO2的反对称伸缩振动和对称伸缩振动的吸收峰，1104.40cm-1为芳环上C-Cl键的伸缩振动吸收峰。
图2中活性分散染料的傅里叶转换红外光谱测试结果显示，在3419.87cm-1为N-H的伸缩振动吸收峰，3259.67cm-1为芳环上C-H键的伸缩振动，2963.82cm-1和2926.19cm-1分别为烷烃C-H键的反对称伸缩振动和对称伸缩振动吸收峰， 1597.90cm-1为N＝N的伸缩振动吸收峰，1551.99cm-1为C＝N伸缩振动吸收峰， 1512.98cm-1及1333.58cm-1分别为Ar-NO2的反对称伸缩振动和对称伸缩振动的吸收峰，1101.15cm-1为芳环上C-Cl键的伸缩振动吸收峰，798.76cm-1为三嗪环上C-Cl的伸缩振动吸收峰。
对比图1和图2的测试结果表明，三聚氯氰活性基团成功引入本发明所制备的活性分散染料的母体结构中。
图3为染料中间体和活性分散染料在二氯甲烷溶液中的紫外-可见吸收光谱，其中曲线a为染料中间体(最大吸收波长为496nm，对应摩尔吸光系数εmax＝8.86×103L/(mol·cm)，曲线b为活性分散染料(最大吸收波长为505nm，对应摩尔吸光系数εmax＝5.91×103L/(mol·cm)。由曲线a、b可知，本发明实施例的活性分散染料和染料中间体之间的最大吸收波长的改变量△λmax＝505-496＝9 nm，远小于《超临界CO2流体专用活性分散染料的合成及表征》中记载的最大吸收波长的改变量△λmax＝395-326＝69nm。以上结果表明，活性基团与染料母体之间的烷烃桥基连接使得三聚氯氰活性基团的引入对染料母体发色结构的影响显著降低，避免三聚氯氰活性基团造成染料主色调发生较大改变。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (9)

1.一种活性分散染料，其特征在于，具有式(Ⅰ)所示的结构通式：
Figure FDA0002358392680000011
其中，R1为Cl或Br；1≤m≤6，1≤n≤6。
2.如权利要求1所述的活性分散染料，其特征在于，R1为Cl；m＝2；n＝1。
3.一种如权利要求1或2所述的活性分散染料的制备方法，其特征在于，包括：将式(Ⅱ)所示的染料中间体与三聚氯氰在缚酸剂存在的条件下在溶剂中进行反应，得到式(Ⅰ)所示的活性分散染料，
Figure FDA0002358392680000012
其中，R1为Cl或Br；1≤m≤6，1≤n≤6。
4.如权利要求3所述的活性分散染料的制备方法，其特征在于，所述缚酸剂为碳酸钠和/或碳酸氢钠。
5.如权利要求3所述的活性分散染料的制备方法，其特征在于，所述染料中间体的制备方法包括以下步骤：
1)在酸性条件下，将2-氯-4-硝基苯胺或2-溴-4-硝基苯胺重氮化；
2)将得到的重氮化产物在pH为5～7的条件下与偶合组分进行偶合反应，得到式(Ⅱ)所示染料中间体；所述偶合组分具有式(Ⅲ)所示的结构通式：
Figure FDA0002358392680000021
其中，1≤m≤6，1≤n≤6。
6.如权利要求5所述的活性分散染料的制备方法，其特征在于，步骤1)具体包括：将2-氯-4-硝基苯胺或2-溴-4-硝基苯胺溶于有机溶剂与水的混合溶剂中，加入浓盐酸，控制得到的溶液为酸性，再加入亚硝酸钠进行重氮化反应，得到重氮化产物。
7.如权利要求6所述的活性分散染料的制备方法，其特征在于，所述有机溶剂为N,N-二甲基甲酰胺、二氧六环和醋酸中的一种或多种。
8.如权利要求5所述的活性分散染料的制备方法，其特征在于，步骤2)中，还包括在偶合反应发生前向反应液中加入尿素水溶液去除过量的亚硝酸钠的步骤。
9.如权利要求5所述的活性分散染料的制备方法，其特征在于，步骤2)中还包括采用硅胶色谱柱纯化所述染料中间体的步骤，其中，洗脱剂为石油醚、二氯甲烷和丙酮，石油醚与二氯甲烷的体积比为0～3:1～4，丙酮与二氯甲烷的体积比为0～4:1～4。
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