海藻酸纤维染色性能的研究李赵义专用染料及助剂对海藻酸纤维染色性能的研究

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1、 摘要摘 要海藻酸纤维作为一种新型的“绿色”生物质型合成纤维,具有可再生、可降解、各项性能优良的特点,但由于其难以进行染色,限制了该类型纤维在纺织服装领域的应用。本文针对海藻酸纤维的结构特点和性能,提出采用羧酸型染料对其进行“络合染色”来提升纤维的染色性能。海藻酸纤维内部含有或引入的金属离子,能够分别与羧酸型染料以及纤维之间以络合键的形式结合在一起,从而实现染料在纤维上的吸附和固着。本文采用多羧酸型大分子染料PMA-D1、PMA-D2以及分子量相对较小的羧酸型小分子染料D1D10对海藻酸纤维进行染色研究,探究染料的染色机理和性能,并考察其最佳染色工艺和条件。采用“两浴两步法”的染色工艺,对PM

2、A-D1、PMA-D2两种染料进行染色工艺研究。通过单因素法确定了其最佳染色工艺:预处理工艺中加入的Al3+的量为海藻酸纤维上钙离子含量的15%(mol%),预处理pH为6,预处理温度40,预处理时间60 min,染色色度2% o.w.f,浴比1:30,染色温度70 ,时间60 min。染色结果说明,染料能够与纤维形成牢固的络合键结合,从而有效提高其上染率及染色牢度。在最佳的染色条件下,两种染料的上染率达到了75%以上,断裂强力损失小于7%,染色牢度达到3级以上。通过SEM测试表明纤维表面的形貌保存较完整。以对硝基苯胺、苯胺、2,4-二硝基苯胺、对氨基苯磺酸等为原料合成染料的重氮组分;以苯胺、

3、氯乙酸、丙烯酸等为原料合成含有羧基的染料中间体并作为偶合组分,通过重氮偶合反应合成了偶氮结构羧酸型染料D1D9。以2-氨基蒽醌、溴乙酸乙酯等为原料通过取代反应合成了蒽醌结构羧酸型染料D10。通过NMR等对10支染料的结构进行了表征。通过紫外-可见吸收光谱测试确定了10支染料的最大吸收波长。采用“两浴两步法”的染色工艺,对10支多羧酸型小分子染料在海藻酸纤维上的染色行为和机理进行了研究。选取D1、D2、D6、D10考察该类型染料在海藻酸纤维的染色性能,并确定了最佳染色工艺:预处理染液中的Al3+的含量为2g/L,染色色度2% o.w.f,染色pH为6,浴比1:20,染色温度80, 染色时间70m

4、in。在最佳染色条件下,偶氮型的含双羧甲基及双羧乙基的D2、D6染料的上染率能够达到85%以上,蒽醌型双羧甲基D10染料的上染率能够达到60%以上。结果表明,羧酸型小分子染料可以通过“络合染色”的方式达到对纤维上染的目的。相比于多羧酸型大分子染料,小分子染料由于溶解度更高,更加容易渗透进纤维内部,络合效果提升,染料的染色性能更加突出。染色后纤维的强力损失在5%以内,SEM测试亦表明纤维表面的形貌保存完整。通过对两类染料的构效关系及染色性能的研究,表明两类含多羧酸型结构的染料均能够较好的实现对海藻酸纤维的染色,各项性能优良,具有很好地应用前景。关键词:海藻酸纤维;络合;羧酸型染料;染色性能;合成

5、II*硕士学位论文 AbstractAbstractAs a new type of green biomass synthetic fiber, alginate fiber is renewable, degradable and has excellent properties. However, it is subject to the problem of low dyeability, which seriously restricts it from becoming an promising textile fiber. Based on the structure and p

6、roperties of alginate fibers, we propose that the carboxylic acid dyes shoud be suitable to the coloration of such fibers. The metal ions existed in alginate fiber can form covalent bonding with both carboxyl dyes and fiber, and thus, resulted in firmly adsorption and fixation of dyes on alginate fi

7、ber. In this paper, polycarboxylic acid (PMA) type macromolecular dyes (PMA-D1, PMA-D2) and small molecular dyes D1D10 which also contains carboxylic acid type were prepared to study their dyeing properties and mechanism on alginate fibers.Two dyes, PMA-D1 and PMA-D2, were prepared by grafting diffe

8、rent chromophorets on PMA with polymaleic anhydride (PMA) as the backbone. The optimal dyeing process was determined by single factor method using a “two-bath and two step” dyeing process: Al3+ content added was 15%, pretreatment pH was 6, pretreatment temperature 40, pretreatment time 60min, 2% (o.

9、w.f), bath ratio 1:30, dyeing temperature 70, dyeing time 60min. The dyeing results suggest that these dyes can be fixed on alginate fiber by the formation of coordination bonding between carboxyl groups in dyes and metal ions fedded in fiber. Under the dyeing conditions, the dyeing adsorption of th

10、e two dyes reached more than 75%, the strength loss of dyed fiber was less than 7%. The morphology of the fiber surface was maintained well according to the test of SEM.To get azo-dyes containing carboxyl groups, p-nitroaniline, aniline, 2,4-dinitroaniline, p-aminobenzenesulfonic acid were used to g

11、et diazo components, and the coupling components containing carboxyl groups were synthesized from aniline, chloroacetic acid, acrylic acid, etc. The anthraquinone dye D10 containing carboxylic groups was synthesized by substitution reaction of 2-amino-anthraquinone and ethyl bromoacetate. The struct

12、ure of 10 dyes was characterized by NMR. The maximum absorption wavelength of ten dyes was determined by ultraviolet - visible absorption spectroscopy.The dyeing properties and mechanism on alginate fibers of small molecular dyes D1D10 which contains carboxylic acid type were studied by “two-bath an

13、d two step” dyeing process. Four dyes, D1, D2, D6 and D10 were selected to determine the optimal dyeing process: Al3+ content was 2g/L, 2% (o.w.f), bath ratio 1:20, dyeing temperature 80, dyeing time 70min. Under the dyeing conditions, the dyeing adsorption of D2, D6 reached more than 85%, the dyein

14、g adsorption of D10 reached more than 60%. The results show that the small molecular dyes which contains carboxylic acid type can form covalent bonding with fiber. Due to the higher solubility, compared to PMA-D1 and PMA-D2, the small molecular dyes permeated into the fiber easier. The complexation

15、and dyeing properties of small molecular dyes were also improved. The strength loss of dyed fiber was less than 7%. The morphology of the fiber surface was maintained well according to the test of SEM.The dyeing behaviour and results of these two types of dyes containing carboxyl groups showed that these dyes can give excellent dyeing performance and fastness properties, thus have a good application prospect in the future. Keywords: alginate fiber; complexation; carboxylic acid dyes; dyeing properties; synthesisVI*硕士学位论文

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