含聚醚链段阳离子活性染料与纤维素纤维的作用机理和行为调控

Reactive dyes are one of the most widely used dyes in cellulose fiber dyeing. Because of the Coulomb repulsion effect between sulfonic acid groups of reactive dyes and hydroxyl anions of cellulose, a great amount of electrolyte is necessitated to promote exhaustion rate during cellulose dyeing process with reactive dyes. Now the effect mechanism between cationic reactive dyes and cellulose fiber is not revealed. Existing cationic reactive dyes are not suitable for salt-free dyeing of cellulose fiber, because the only existent quaternary ammonium in dyes structure is not dissoluble enough and results in dyes aggregation easily. In this project, we launch the investigation from dyes structure and design cationic reactive dyes through introducing polyether segments and quaternary ammonium groups into dye chromophores. The effect mechanism between these polyether containing cationic reactive dyes and cellulose fiber, relationship between dyes structure and dyeing behavior will be studied. In the end, the dyeing behavior of these cationic reactive dyes can be regulated by changing polymerization degree of polyether segments and structure of quaternary ammonium groups. The effect between these polyether containing cationic reactive dyes and cellulose fiber does not only contain covalent bonds, but also contains some supramolecular interactions, such as Coulomb attraction, resulted by quaternary ammonium cationic groups and hydroxyl anions of cellulose, hydrogen bonds and van der Waals forces between polyether segments and cellulose. All of these intermolecular forces exist synchronously and change with dyes structure alteration. So dyeing behavior can be regulated by changing the structure of dyes.

活性染料是纤维素纤维染色的主要染料之一。但由于活性染料结构中磺酸根离子同纤维素羟基阴离子之间的斥力作用，其在用于纤维素纤维染色时常需要加入大量的电解质进行促染。目前阳离子活性染料对棉织物的作用机理尚不明确，已有的几种阳离子活性染料又因结构中仅含季铵盐基团，导致溶解性不够，容易聚集，难以用于棉织物的无盐染色。本课题从染料分子结构入手，向染料发色体中引入聚醚链段和季铵盐结构来设计阳离子活性染料，并研究此含聚醚链段阳离子活性染料同纤维素纤维之间的作用机理，染料结构与染色行为之间的关系，最终通过改变染料中聚醚链段大小和季铵盐结构来对染色行为进行调控。此含聚醚链段阳离子活性染料与纤维的作用，不仅有共价键结合，还有季铵盐正电荷与纤维羟基负离子之间的库仑引力，聚醚链段与纤维之间的氢键和范德华力等超分子作用，这些分子间力同时存在，其大小随染料的结构而有异。因此可以通过改变染料的结构来调控染色行为。

纤维素纤维在使用传统活性染料进行染色时，为了提高染料的上染率，常常需要加入电解质进行促染。这种工艺成本高，废水处理难度大。常用的棉织物无盐染色工艺是棉织物的阳离子改性法，但是这种方法增加了织物加工工艺，且最终染色效果依赖于织物的阳离子工艺。.利用阳离子活性染料来实现纤维素纤维的无盐染色是一种较好的思路。但是，单纯的阳离子活性染料，采用季铵盐水溶性基团取代传统的活性染料的磺酸基，其水溶性不够，限制了阳离子活性染料的应用。本课题利用聚醚链段来给阳离子活性染料提供足够的水溶性，利用季铵盐结构来赋予阳离子活性染料正电性，制备出了一系列含聚醚链段的阳离子活性染料，并研究了此类阳离子活性染料的染色物理与化学问题。.利用聚醚胺化合物与环氧丙基三甲基氯化铵反应，再与三聚氯氰及氨基蒽醌发色体反应，制备处了一系列蒽醌发色体含聚醚链段的阳离子活性染料，利用元素分析和核磁共振图谱确认了产物结构，经无盐染色试验发现，此类阳离子活性染料对棉织物的最佳染色pH值是6，无盐染色上染率达到96%以上，不同于传统的活性染料的Freundlich型吸附等温线，阳离子活性染料属于langmiur型染色等温线，且染色织物具有较好的匀染性。经检测，用含聚醚结构阳离子活性染料染色后的织物，其日晒牢度达5-6级，水洗、汗渍和干磨牢度达4级，湿摩擦牢度达3-4级。.为了进一步丰富阳离子活性染料的色谱，本项目研究人员还合成出了一系列含偶氮结构发色体的阳离子活性染料。其制备路线是，首先，选择具有羟基或胺基的偶氮分散染料，在有机溶剂中与三聚氯氰反应，制备偶氮染料取代三聚氯氰衍生物；然后，用二甲胺与环氧丙基聚氧乙烯醚反应，制备（3-聚氧乙烯基-2-羟基）丙基二甲基胺；最后，将偶氮染料取代三聚氯氰衍生物与（3-聚氧乙烯基-2-羟基）丙基二甲基胺产物混合加热至30-45℃反应，制备出含聚醚链段的偶氮结构阳离子活性染料。经染色试验检测，此类偶氮结构阳离子活性染料可以用于棉织物的无盐染色，且染色性能良好。

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