醛基型三苯二噁嗪活性染料的合成与应用

Synthesis and application of triphenodioxazine reactive dye with aldehyde as reactive group

将2,5-二氨基苯磺酸通过缩合反应连接到四氯苯醌的2,5位碳原子上,得到染料中间体Ⅰ;然后在微波条件下氧化闭环,得到中间体Ⅱ(染料母体);中间体Ⅱ与戊二醛前体的溴代物缩合、水解,得到目标产物。采用正交试验获得微波条件下氧化闭环反应的最佳工艺参数为:微波功率120W,辐射时间15min,浓硫酸用量为中间体Ⅰ的22倍,在此条件下中间体Ⅱ的产率为86%。通过质谱(ESI-MS)、红外(FT-IR)和紫外(UV-vis)对目标产物进行表征,并进行了皮革染色试验。结果表明:目标产物的各项色牢度均达到4级以上,具备了活性染料的特征。

Triphenodioxazine reactive dye with aldehyde as reactive group was achieved by four procedures. An in- termediate I was generated by condensation reaction between 2,5-diaminobenzene-2-sulphonic acid and tetrachloro -p-benzoquinone. Under microwave condition, an intermediate Ⅱ was obtained via oxidative cyclisation reaction. The pre-dye was synthesized by intermediate Ⅱ condensing with bromide pre-glutaraldehyde compound. The pre- dye was hydrolyzed to produce the target product. The optimized condition of oxidative cyclisation reaction under mi- crowave were investigated by orthogonal experiment method and the results are as follows： microwave power 120 W, irradiation time 15min, the dosage of sulfuric acid is 22 times of the mass of intermediate Ⅰ. At this condition, the yield of intermediate Ⅱ is 86%. Electrospray ionization mass spectrometry （ESI- MS ） , Fourier transformation infrared spectrometry （FT-IR） and ultraviolet visible （UV-vis） were applied to identify the synthetic products. Practicing test for the target product was undertaking to leather dyeing. The fastness properties of dyed leather indi- cates that the target product has satisfied fastness, and each color fastness index is above grade 4.