지시약 적정법 및 분광광도법에 의한 양이온 고분자 전해질의 전해밀도 정량

Abstract

Polyelectrolyte titration, which was called colloid titration is based on the stoichiometric reaction between oppositely charged polyelectrolytes, This can be used, for instance, to determine the charge density of a cationic polyelectrolyte, using an anionic polyelectrolyte of known charge density, such as potassium polyvinyl sulfate (PPVS). The technique requires a suitable method of end-point detection and there are several possibilities. In this work, two methods have been investigated: visual titrimetry based on the color change of a cationic dye (o-toluidine blue, o-Tb) and spectrophotometry based on the absorbance change corresponding to the color change of the same dye. These have been applied to several cationic polyelectrolytes with different charge density and molecular weight. In all cases, the cationic charge was due to quaternary nitrogen groups. In the case of cationic dye, it was shown that the sharpness depends on the charge density of cationic polyelectrolyte. With the polyelectrolytes of lower charge density, the binding to PPVS is weaker and binding of the dye to PPVS can occur before all of the polyelectrolyte charge has been neutralized. However, by carrying out titrations at several polyelectrolyte concentrations, good linear relationships were found, from which reliable charge density values could be derived. Effects of pH and ionic strength were also briefly investigated. For cationic polyelectrolytes (copolymers of acrylamide and dimethylaminoethy] acrylate), there was some loss of charge at higher pH values, probably as a result of hydrolysis. Increasing ionic strength causes a less distinct color change of o-Tb, as a result of weaker electrostatic interactions.