【作者】 张维；

【导师】 杜建功；

【作者基本信息】 河北科技大学 ， 纺织化学与染整工程， 2009， 硕士

【摘要】 柠檬酸作为具有广阔发展前景的多元羧酸类无甲醛整理剂,其自身的优势十分明显,价廉、无毒性、不含甲醛,但整理后织物也存在着一些缺点,如泛黄、强力损失严重、回复角不高、耐洗牢度差等。本论文从柠檬酸的化学结构出发,寻求改善其抗皱整理效果的方法。按照多元酸先脱水形成环状酸酐然后交联成酯的机理,柠檬酸作为一个三元酸,只有一半的可能与纤维素交联,这就是其抗皱效果不如四元酸的原因。针对这一问题,我们应用两种手段改变柠檬酸单一的小分子化学结构,增加其与纤维素进行交联反应的基团,实质就是增加可形成环状酸酐的羧基数量,以提高酯化结合的程度,从而达到改善抗皱整理效果的目的。课题的研究内容主要有以下两个方面:首先,运用化学方法改变柠檬酸的三羧基结构,增加新的羧基,使其生成类似于BTCA具有四个羧基的化合物,这样就能够提高与纤维素上羟基的交联程度。这种方法是根据相关化学理论提出的一种探索性研究。其次,在柠檬酸里加入乙二醇和丙三醇,多元醇不再是作为简单的添加剂,而是使其先与柠檬酸进行一定程度的酯化反应,生成具有网状结构的大分子化合物,再配制成整理液对棉织物进行抗皱整理。多元醇的多个羟基可能和多元羧酸的羧基和纤维素大分子上的羟基发生反应,增加交联的平均长度和支化度,从而提高交联网络的弹性,使整理品在使用中能够均匀的承担外力,从而提高织物的强力和柔韧性,而在纤维无定型区引入一定数量的羟基,增加了氢键数量,以弥补因酯化而失去的氢键,从而增加了分子间的作用力。另外,通过柠檬酸与乙二醇的酯化有可能使柠檬酸的羟基发生醚化,从而降低织物的泛黄。通过实验得出如下结论:(1)运用化学改性的方法增加柠檬酸与纤维素的交联程度,效果一般,需在氧化剂的选择以及工艺条件控制上进一步研究;(2)乙二醇与柠檬酸酯化交联的最佳工艺条件为:摩尔比为1∶2,反应时间0.5h;(3)丙三醇与柠檬酸酯化交联的最佳工艺条件为:摩尔比为1∶3,反应时间1h;(4)在柠檬酸抗皱整理中,加入的多元醇的羟基数量越多,抗皱整理效果越好;(5)催化剂次磷酸钠在反应中不仅起催化作用而且参与了反应。更多还原

【Abstract】 Citric acid as a polycarboxylic acid formaldehyde-free crease-resistant finishing agent has broad prospects for development. Its own advantages are clear, inexpensive, non-toxic, non-formaldehyde.But there are also some shortcomings with the finished fabrics, yellowing, severe strength loss, recovery angle not high, and poor washing fastness. In this paper, starting from the chemical structure of citric acid, seeking to improve its anti-crease finishing effectiveness.In accordance with the formation of cyclic polycarboxylic acid anhydride, dehydrated and then cross-linked into the mechanism of ester, citric acid as a triple acid, only half of the possible cross-linked with cellulose, which is not as good as its anti-wrinkle effects of quaternary acid causes. In response to this problem, we apply two kinds of changes by means of a single small molecule of citric acid chemical structure to increase its cross-linking reaction with the cellulose to the base group, can be formed in real terms is to increase the amount of cyclic anhydride of the carboxyl group to enhance the esterification with the extent so as to achieve the purpose of improving the anti-crease finishing results. Using chemical methods to change the three-carboxyl group of citric acid structure, adding a new carboxyl group to generate similar BTCA has four carboxylic compounds, so that can improve with the cellulose hydroxyl on the extent of cross-linking.The main two tasks and conclusions are show as below:First of all, using chemical methods to change the three-carboxyl group of citric acid structure, adding a new carboxyl group to generate similar BTCA has four carboxylic compounds, so that can improve with the cellulose hydroxyl on the extent of cross-linking. This method is based on a related chemical theory to explore research. Second, ethylene glycol and citric acid have added glycerin, polyol additive is no longer as simple, but so that it first be a certain degree of esterification reaction of macromolecular compounds with a mesh structure, adding made finishing agent for cotton fabric is wrinkle resistant finish. Polyols may be a number of multi-hydroxy acids on the carboxyl and hydroxyl cellulose molecules react, increasing the average length of cross-linking degree of branching, thereby enhancing cross-linked network of flexibility so that the finishing materials in use can be commitment to uniform force, thereby enhancing the fabric strength and flexibility, while the amorphous zone in the fibers to introduce a certain amount of hydroxyl, an increase of the number of hydrogen bonds, to compensate for the loss of hydrogen bonds esterification, thereby increasing the role of intermolecular force. In addition, through the esterification of citric acid and ethylene glycol has the potential to occur etherification of hydroxy citric acid, thereby reducing the fabric yellowing.Through the experiments, we can reach the following conclusions:(1) the ways of using chemical modifications to increase citric acid and cellulose cross-linking degree, the effect is general , need to carefully studying on the choice of oxidant and process conditions controlling; (2) the optimum conditions of ethylene glycol and citric acid esterification and crosslinking is: molar ratio of 1:2, the reaction time 0.5h; (3) the optimum conditions of glycerol and citric acid esterification and crosslinking is: the molar ratio of 1:3, the reaction time 1h; (4)in citric acid anti-crease finish,adding the polyols-the more number of alcohol-OH, the anti-wrinkle finishing the better;(5) the catalyst sodium hypophosphite in the reaction not only to play a catalytic role bust also involve in the reaction.更多还原