Fundamental Study on the Parameters in Order to Quantify Solvent Effects in Solvent Dyeing

对有机溶剂和二元混合溶剂中的溶剂效应进行了定量研究。Taft和他的同事们提出了线性溶剂化能关系(LSER)参数来量化溶剂效应：溶剂极性的PI*标度，氢键供体的α标度，氢键受体的β标度。通过对溶剂变色指示剂4-硝基苯胺、N，N-二甲基-4-硝基苯胺和偶氮染料的光谱测量，提出了一种评价pi*、α、β标度的常规方法，并观察了这些染料在非极性和极性溶剂中的溶致变色性。采用选择性溶剂化模型，分析了这些染料的最大波数随混合溶剂组成的变化。研究了具有较大负溶剂变色性的偶氮染料[A(o-OH)，B(p-OH)和C(Me-p-OH)]与环糊精包合物的形成和吸收光谱。染料A(OH)和A(O^-)不被α-、β-、伽马-环糊精通过O-位氧的空间位阻所包覆。α-环糊精可以包括B(O^-)和C(O^-)，但不包括B(OH)和C(HO)。而β-环糊精和伽马-环糊精得到(1：1)包裹体B(OH)、B(O^-)、C(OH)和C(O^-)。根据包裹体的结构推测了包裹体的结构，研究了负致变色性表面活性剂增溶的吸收光谱。解离染料A、B、C可被阴离子、阳离子和非离子表面活性剂增溶。根据它们的光谱结果表明，染料是在阴离子表面活性剂的胶束外增溶，而在阳离子和非离子表面活性剂的胶束内则是水增溶。

This work has been undertaken to quantify solvent effects in organic solvent and binary mixture solvent. Taft and his co-workers proposed Linear Solvation Energy Relationships ( LSER ) parameters in order to quntify solvent effect : pi*scale of solvent polarity, alpha scale of hydrogen bond donor, beta scale of hydrogen bond acceptor. A conventional method for evaluation of pi*, alpha, beta, scales scales were proposed based on spectroscopic measurements using solavatochromic indicators, 4-nitroaniline, N, Ndimethy-4-nitroaniline and azoniabetain dyes.The solvtochromism of these dyes was observed in nonpolar and polar solvents. The shifts of maximum wave numbers of these dyes by composition of binary mixture of solvents were analyzed by assuming the selective solvation model. The results obtained indicate that the solvation model of dyes is almost explained by the selective model.Formation and absorption spectra of inclusion between cyclodextrin and azoniabetain dyes [ A(o-OH),B(p-OH) and C(Me-p-OH) ] having large negative solvatochromism were investigated. The dyes A(OH) and A(O^-) were not included by alpha-, beta-, gamma-ciclodextrin by steric hindrance of oxygen at o-position of the dyes. Alpha-cyclodextrin can include B(O^-) and C(O^-), but not B(OH) and C(HO). While beta- and gamma- cyclodextrins gave (1 : 1) inclusions B(OH), B(O^-), C(OH) and C(O^-). Structures of inclusions were suggested on basis of their spectra.Absorption spectra of solubilization by surfactants having negative solvatochromism were investigated. Dissociatived dyes of A, B and C could be solubilized by anionic, cationic and nonionic surfactants. The results on basis of their spectra were suggested that dyes were solubilized at outside of micel of anionic surfactant and water included in inner micell of cationic and nonionic surfactants.