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

本文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。为了量化溶剂效应，Taft和他的同事提出了线性溶剂化能量关系（LSER）参数：溶剂极性的pi*尺度，氢键给体的alpha尺度，氢键受体的beta尺度。采用日光致变色指示剂、4-硝基苯胺、N， ndimethy -4-硝基苯胺和偶氮氮染料，提出了一种基于光谱测量的pi*、α、β、标度的常规评价方法。在非极性溶剂和极性溶剂中观察了染料的溶剂致色性。假设选择性溶剂化模型，分析了二元溶剂混合对染料最大波数的影响。结果表明，染料的溶剂化模型几乎可以用选择性模型来解释。研究了环糊精与大负溶剂变色偶氮黄染料[A（o-OH）、B（p-OH）和C(Me-p-OH)]包合物的形成和吸收光谱。染料A（OH）和A（O^-）由于氧在O位的空间位阻而不被α -、β -、γ -环糊精吸收。α -环糊精可以包括B（O^-）和C(O^-)，但不包括B（OH）和C（HO）。-环糊精和-环糊精的包合物为（1:1）包合物B（OH）、B（O^-）、C（OH）和C（O^-）。根据其光谱推测了夹杂物的结构。研究了负溶剂变色表面活性剂增溶作用的吸收光谱。A、B和C的解离染料可被阴离子、阳离子和非离子表面活性剂溶解。光谱分析结果表明，染料在阴离子表面活性剂胶束外溶解，而在阳离子和非离子表面活性剂胶束内含有水。

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.