异双官能团型活性染料在羊毛/蚕丝上的染色性能研究
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摘要
活性染料色泽鲜艳、色牢度高,在羊毛和蚕丝上的染色应用逐渐广泛。羊毛和蚕丝同属蛋白质纤维,其物理和化学结构的差异导致活性染料在羊毛和蚕丝上的染色性能差异,由此引起羊毛/蚕丝多组分纤维的活性染料染色加工中一系列的问题。本论文系统研究了异双官能团型活性染料对羊毛和蚕丝的反应性能和染色性能差异,旨在对开发科学合理的羊毛/蚕丝染色工艺和技术提供理论指导。
论文应用高效液相色谱分析比较了活性深蓝M-2GE在羊毛和蚕丝染浴中的水解特性;采用模拟反应法研究了活性深蓝M-2GE分别与羊毛和蚕丝上的不同亲核基团的反应性能和反应条件;结合异双官能团型活性染料在羊毛和蚕丝上的实际染色结果揭示异双官能团型活性染料与羊毛、蚕丝的染色性能差异及其本质所在。最后,利用高效液相色谱分析中性盐硫酸钠在活性染料水解过程及其与羊毛和蚕丝模拟反应过程中对染料的水解和反应性能的影响。主要研究结果如下:
在弱碱性下,活性深蓝M-2GE在蚕丝染浴中染料的乙烯砜基水解产物含量低于羊毛染浴中;活性深蓝M-2GE与醇羟基反应速率较慢,温度和pH增加醇羟基与水的竞争反应能力增加;染料在弱碱性下与氨基和酚羟基反应速度都较快,氨基与活性深蓝M-2GE上乙烯砜基上的反应速率大于一氯均三嗪基而酚羟基则相反;在pH=4-10值范围内活性深蓝M-2GE与巯基的反应速度都较快,巯基在弱酸性下主要与一氯均三嗪基反应而在弱碱性条件下与乙烯砜基反应。从该一系列研究结果推断:在羊毛染色时,羊毛上的巯基和氨基在与异双官能团型活性染料的反应中起了主导作用,在酸性条件下巯基与染料反应活性可能是活性染料在酸性下在羊毛上有较高固着率的主要原因;蚕丝染色时,异双官能团型活性染料上的一氯均三嗪基和乙烯砜型基分别与蚕丝上的酚羟基和氨基反应,染料与蚕丝可能形成了交联的模式。此外,在羊毛和蚕丝染色中,加入过量的硫酸钠不利于异双官能团型活性染料对羊毛和蚕丝的染色,一方面由于盐可使染料发生聚集或促进染料分解,另一方面盐对染料与纤维的反应存在一定的抑制作用。
Reactive dyes have bright color, high color fastness, and are widely used in wool and silk fiber. Although wool and silk are protein fibers, they have large differences both in physical structure and chemical composition. However, reactive dyes show great differences when dyeing with wool and silk, which brings a series of problems when dyeing with wool/silk multi-component fibers. By studying the reaction differences and dyeing difference of reactive dyes on silk and wool, this paper is to provide theoretical guidance on designing and developing new dyeing technology on wool/silk.
This paper applied high performance liquid chromatography (HPLC) to analyse the hydrolysis characteristics of mixed bifunctional reactive dyes M-2GE on wool and silk and used simulation reaction experiment to study the nucleophilic reaction and reaction conditions of reactive dyes with nucleophilic group in wool and silk. Combined with the actual dyeing results of the mixed bifunctional reactive dyes on wool and silk, the differences and essence of dyeing performance between wool and silk were analyzed. Finally, use HPLC to analyze influence of sodium sulfate on reactive dyes hydrolysis and nucleophilic reaction between wool and silk. The main results showed that:
When wool and silk were dyed by mixed bifunctional reactive dyes at low alkalescence condition, the relative content of hydrolysis product in wool bath was more than that in silk bath. Mixed bifunctional reactive dyes M-2GE reacted slowly with alcohol-hydroxyl groups, and the competition reaction with alcohol and water reaction was increased by pH value and temperature. Mixed bifunctional reactive dyes M-2GE reacted quickly with amino groups and phenol groups, the reaction rate of VS with amino groups was quicker than MCT. The reaction of mixed bifunctional reactive dyes M-2GE with amino groups was different from with phenol groups and MCT reacted quickly with phenol groups. The mixed bifunctional reactive dyes and hydrosulfide group had strong reactivity with dyes in the range of pH 4-10, and had different products at different pH. In weak acidic condition, hydrosulfide groups mainly reacted with MCT; in weak alkali conditions, hydrosulfide groups mainly reacted with VS. It could be concluded that: when wool dyed with mixed bifunctional reactive dyes, hydrosulfide group and amino groups on wool played a principal role. The reactivity between hydrosulfide and dyes in acidic condition might explain why reactive dyes had high fixation ratio on wool in acid bath. When silk dyed with mixed bifunctional reactive dyes firstly, MCT in mixed bifunctional reactive dyes reacted with a large of phenolic group on silk surface. Meanwhie, VS in mixed bifunctional reactive dyes also could react with amino groups on silk, in addition, and reactive dyes and silk might form a cross-linking mode. In addition, when wool and silk were dyed with reactive dyes, excess sodium sulfate made against dying, this could be attributed to dyes aggregation and the inhibition on the reaction with dye and fiber.
论文应用高效液相色谱分析比较了活性深蓝M-2GE在羊毛和蚕丝染浴中的水解特性;采用模拟反应法研究了活性深蓝M-2GE分别与羊毛和蚕丝上的不同亲核基团的反应性能和反应条件;结合异双官能团型活性染料在羊毛和蚕丝上的实际染色结果揭示异双官能团型活性染料与羊毛、蚕丝的染色性能差异及其本质所在。最后,利用高效液相色谱分析中性盐硫酸钠在活性染料水解过程及其与羊毛和蚕丝模拟反应过程中对染料的水解和反应性能的影响。主要研究结果如下:
在弱碱性下,活性深蓝M-2GE在蚕丝染浴中染料的乙烯砜基水解产物含量低于羊毛染浴中;活性深蓝M-2GE与醇羟基反应速率较慢,温度和pH增加醇羟基与水的竞争反应能力增加;染料在弱碱性下与氨基和酚羟基反应速度都较快,氨基与活性深蓝M-2GE上乙烯砜基上的反应速率大于一氯均三嗪基而酚羟基则相反;在pH=4-10值范围内活性深蓝M-2GE与巯基的反应速度都较快,巯基在弱酸性下主要与一氯均三嗪基反应而在弱碱性条件下与乙烯砜基反应。从该一系列研究结果推断:在羊毛染色时,羊毛上的巯基和氨基在与异双官能团型活性染料的反应中起了主导作用,在酸性条件下巯基与染料反应活性可能是活性染料在酸性下在羊毛上有较高固着率的主要原因;蚕丝染色时,异双官能团型活性染料上的一氯均三嗪基和乙烯砜型基分别与蚕丝上的酚羟基和氨基反应,染料与蚕丝可能形成了交联的模式。此外,在羊毛和蚕丝染色中,加入过量的硫酸钠不利于异双官能团型活性染料对羊毛和蚕丝的染色,一方面由于盐可使染料发生聚集或促进染料分解,另一方面盐对染料与纤维的反应存在一定的抑制作用。
Reactive dyes have bright color, high color fastness, and are widely used in wool and silk fiber. Although wool and silk are protein fibers, they have large differences both in physical structure and chemical composition. However, reactive dyes show great differences when dyeing with wool and silk, which brings a series of problems when dyeing with wool/silk multi-component fibers. By studying the reaction differences and dyeing difference of reactive dyes on silk and wool, this paper is to provide theoretical guidance on designing and developing new dyeing technology on wool/silk.
This paper applied high performance liquid chromatography (HPLC) to analyse the hydrolysis characteristics of mixed bifunctional reactive dyes M-2GE on wool and silk and used simulation reaction experiment to study the nucleophilic reaction and reaction conditions of reactive dyes with nucleophilic group in wool and silk. Combined with the actual dyeing results of the mixed bifunctional reactive dyes on wool and silk, the differences and essence of dyeing performance between wool and silk were analyzed. Finally, use HPLC to analyze influence of sodium sulfate on reactive dyes hydrolysis and nucleophilic reaction between wool and silk. The main results showed that:
When wool and silk were dyed by mixed bifunctional reactive dyes at low alkalescence condition, the relative content of hydrolysis product in wool bath was more than that in silk bath. Mixed bifunctional reactive dyes M-2GE reacted slowly with alcohol-hydroxyl groups, and the competition reaction with alcohol and water reaction was increased by pH value and temperature. Mixed bifunctional reactive dyes M-2GE reacted quickly with amino groups and phenol groups, the reaction rate of VS with amino groups was quicker than MCT. The reaction of mixed bifunctional reactive dyes M-2GE with amino groups was different from with phenol groups and MCT reacted quickly with phenol groups. The mixed bifunctional reactive dyes and hydrosulfide group had strong reactivity with dyes in the range of pH 4-10, and had different products at different pH. In weak acidic condition, hydrosulfide groups mainly reacted with MCT; in weak alkali conditions, hydrosulfide groups mainly reacted with VS. It could be concluded that: when wool dyed with mixed bifunctional reactive dyes, hydrosulfide group and amino groups on wool played a principal role. The reactivity between hydrosulfide and dyes in acidic condition might explain why reactive dyes had high fixation ratio on wool in acid bath. When silk dyed with mixed bifunctional reactive dyes firstly, MCT in mixed bifunctional reactive dyes reacted with a large of phenolic group on silk surface. Meanwhie, VS in mixed bifunctional reactive dyes also could react with amino groups on silk, in addition, and reactive dyes and silk might form a cross-linking mode. In addition, when wool and silk were dyed with reactive dyes, excess sodium sulfate made against dying, this could be attributed to dyes aggregation and the inhibition on the reaction with dye and fiber.
引文
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