【作者】 党喃燕；

【导师】 张淑芬；

【作者基本信息】 大连理工大学 ， 应用化学， 2010， 博士

【摘要】 交联染料通过交联剂和染色纤维实现共价结合,因此交联染料不仅可使染色纤维有很好的湿处理牢度,还克服了活性染料存在的活性基团水解问题,大大提高染料利用率。本文首先研究了多胺型可交联染料的溶解特性、分子大小和渗透性能,通过软件模拟和纤维切片的方式证实了染料可以对纤维达到透染的目的。研究了染液pH值、染色温度、染色时间以及染料结构等对染色性能影响。发现不含磺酸基的多乙烯多胺可交联染料适合浸染染色蛋白质纤维,其中交联染料PAD1在丝绸和羊毛上的竭染率最高,分别为99.8%和95.5%,不含磺酸基的聚乙烯胺可交联染料对蛋白质和纤维素纤维都可采用浸染染色的方式,竭染率最高的是交联染料PVD4,在棉和丝绸上可分别达到97.6%和99.3%；而含有磺酸基的两类多胺型可交联染料更适合轧染染色工艺。分别以交联染料PAD1和PVD4为例,研究了多乙烯多胺可交联染料在丝绸和羊毛上以及聚乙烯胺可交联染料在棉纤维上的吸附动力学和吸附平衡模型。研究显示多乙烯多胺可交联染料和聚乙烯胺可交联染料在蛋白质纤维上的吸附过程遵循准二级动力学方程,以化学吸附为主,吸附平衡模型为Langmuir型,吸附过程是自发进行的：而聚乙烯胺可交联染料在棉纤维上的吸附过程遵循准一级动力学方程,以物理吸附为主,吸附平衡为Freundlich型,吸附过程是自发吸热的过程。本文研究了固色pH值、交联剂用量、交联反应温度和反应时间等条件对交联固色性能影响,得出最佳固色条件,测定了染料的各项色牢度。结果表明不含磺酸基的多胺型可交联染料在棉、丝绸和羊毛纤维上都可得到近100%的交联反应率和优良的色牢度,耐洗牢度可达4-5级,耐摩擦牢度可达4级。采用色牢度法、DMF剥色法、红外差谱等方法,证明了多胺型可交联染料经交联剂固色后染料和纤维间共价键的存在。通过对交联剂水解速率、交联剂放置时间和交联剂循环使用次数对交联反应率影响的研究,发现本文所用的交联剂M不仅交联固色性能优良,而且稳定性良好。通过测量染色织物折皱回复角的方法研究了两类可交联染料染色纤维的折皱回复性能,当交联染料用量为丝绸染色0.67g／L,棉纤维染色1g/L,交联剂用量20g/L时,与未染色纤维相比,多胺交联染色丝绸纤维的折皱回复性能与丁烷四酸整理的丝绸相当,交联染色棉纤维的折皱回复性能也有了较明显提高。交联染色纤维的抗皱性能还可随交联剂用量和交联染料用量的提高而提高,而且交联染料的交联固色性能、织物手感和强力性质不受影响。更多还原

【Abstract】 Crosslinking dyes can form covalent bonds with dyed fibers by crosslinking agent. The advantages of crosslinking dye are avoiding the hydrolysis of reactive dyes and at same time keeping good fastness properties, which can improve the dye utilization obviously.The solubility, molecule size and penetrability of polyamine crosslinking dyes were studied in the paper. The methods of software simulation and fiber slice validated that crosslinking dyes could obtain good dye penetrability. The effect of pH value, dyeing temperature, dyeing time and structure of dyes on dyeing properties was investigated in detail. We found that polyethylene polyamine crosslinking dyes without sulphonic groups suited exhaustion dyeing manner on protein fibers, and Exhaustion of PAD1 were 99.8% and 95.5% on silk and wool respectively; polyvinylamine crosslinking dyes without sulphonic groups suited exhaustion dyeing manner on cotton and silk fibers, and Exhaustion of PVD4 were 97.6% and 99.3% on cotton and silk, respectively. Padding method was more suitable for two kinds of crosslinking dyes with sulphonic groups.Take PAD1 and PVD4 for examples, the model of adsorption kinetics and adsorption equilibrium of polyethylene polyamine and polyvinylamine crosslinking dyes on silk, wool and cotton were discussed respectively. The results showed that the adsorption of polyethylene polyamine and polyvinylamine crosslinking dyes on silk and wool which followed pseudo second-order kinetics equation gave priority to chemisorption and adsorption equilibrium was Langmuir type. The adsorption process of polyvinylamine crosslinking dyes on cotton which belongs to pseudo first-order kinetics equation and Freundlich model is spontaneous, endothermic and dominated by physical adsorption.Effect of pH value, amount of crosslinker, crosslinking reaction temperature and reaction time on crosslinking fixation of crosslinker was studied. The color fastness and fixing condition were discussed. The results indicated that approximately 100% crosslinking ratio and good fastness could be obtained. The washfastness, dry rubfastness reached 4-5 grade and 4 grade, respectively. The type of intermolecular force between crosslinking dyes and dyed fibers was investigated by colorfastness, DMF color stripping, dyeing of polypropene fiber and IR. spectra. The formation of covalent bonds between fibers and the crosslinking dyes was comfirmed. The hydrolysis ratio of crosslinking agent was calculated and the effect of storage time and recycle application of crosslinker M on crosslinking ratio was discussed. It was found that crosslinker M with excellent reactivity was stable. Crease resistance of dyed fibers was investigated by measuring wrinkle recovery angles in this paper. When the concentration of the crosslinking dyes was 0.67 g/L on silk,1 g/L on cotton and that of the crosslinker was 20 g/L, the crease resistance of the dyed silk fabrics was comparable to that obtained from that finished with BTCA and that of the dyed cotton fabrics also was improved evidently. With the increase of the concentrations of both the crosslinking dyes and the crosslinker, the wrinkle resistance of the dyed fabrics was further improved. Furthermore, under those conditions, crosslinking fixation properties, the handle and tensile strength of the silk fabrics were still satisfactory.更多还原