α-(三氟甲基)苯基重氮酯型染料与合成纤维的反应机制  

Reaction mechanism betweenα-trifluoromethyl phenyl diazo ester dye and synthetic fiber

作　　者：解晓康 江华[1] 王也 石璐璐 XIE Xiaokang;JIANG Hua;WANG Ye;SHI Lulu(Engineering Research Center for Eco-Dyeing&Finishing of Textiles,Ministry of Education,Zhejiang Sci-Tech University,Hangzhou,Zhejiang 310018,China)

机构地区：[1]浙江理工大学生态染整技术教育部工程研究中心,浙江杭州310018

出　　处：《纺织学报》2025年第2期145-152,共8页Journal of Textile Research

基　　金：国家自然科学基金项目(22278377);浙江省自然科学基金项目(LY22B060005);浙江理工大学基本科研业务费项目(24202101-Y)。

摘　　要：为解决分散染料染色纤维中染料分子与纤维亲和力不足的问题,在C.I.分散红13结构中引入α-(三氟甲基)苯基重氮酯结构,设计合成新型卡宾型染料,将该染料应用于涤纶、丙纶、氨纶和锦纶的染色,测试了固色率、染料移染率和色牢度,并通过模拟反应以及理论计算推测了染料与纤维的反应机制。结果表明:使用所合成染料染色的4种合成纤维均有固色效果,固色率分别达到73%(涤纶)、48%(丙纶)、85%(氨纶)和53%(锦纶),染料移染率为12%~14%,色牢度达到4级及以上。与C—H键插入反应相比,染料在高温下形成的卡宾中间体更易与N—H键发生反应,脂肪链C—H键的插入反应是染色涤纶或丙纶的主要固色反应类型,N—H键插入反应则是染色氨纶或锦纶的主要固色反应类型。Objective The carbene-type dye that emerged in recent years could achieve strong covalent bonding between dyes and fibers,which is expected to solve the thermal migration problem of conventional disperse dyes.To date,the carbene dyes are still not widely available,and the reaction mechanism between dyes and fibers is yet to be fully understood.This research developed a novel carbene-type dye based on the structure ofα-(trifluoromethyl)phenyl diazo ester,which was used for dyeing and fixing various synthetic fibers.This paper article aims to reveal the reaction mechanism between dyes and fibers by further simulation experiments and theoretical calculations.Method Dye D1 was synthesized through a two-step post-modification of an azo dye containing one hydroxyl group.The absorption and thermal properties of dye D1 were studied.Then,dye D1 was applied to dyeing polyester,polypropylene,polyurethane and polyamide fibers.The color firmness was confirmed by testing fixation,dye migration and fastness properties.Simulation reactions between D1 and small molecule analogues,such as benzene,dioxane,cyclohexane,and piperidine,were used to clarify the reaction site on fibers.Theoretical calculations of reactions between 4-(trifluoromethyl)phenyldiazoacetic acid methyl ester and methane or methylamine were performed.Based on the above,the reaction mechanism between the dye and fiber was speculated.Results Dye D1 with an overall yield of 79%was obtained through the two-step post-modification of azo dye.The color of dye D1 was red and its maximum absorption wavelength in UV-vis absorption spectrum located at 492 nm,with a molar extinction coefficient of 35300 L/(mol•cm).The thermogravimetric curve of dye D1 showed a weight loss of 5.6%at 100-200℃,with a quickest weight loss temperature of 152℃.The weight loss at this stage was related to the dissociation of the diazo group by releasing nitrogen gas.The DSC curve indicated one endothermic peak with the temperature of 141℃,and one exothermic peak corresponding to a tempera

关 键 词：重氮化合物 分散染料 合成纤维 染色性能 反应机制 

分 类 号：TQ613.1[化学工程—精细化工]