Gel Permeation Chromatography Calibration. I. Use of Calibration Curves Based on Polystyrene in THF and Integral Distribution Curves of Elution Volume to Generate Calibration Curves for Polymers in 2,2,2-Trifluoroethanol

A general method is proposed for obtaining gel permeation chromato-graphic (GPC) molecular weight (MW) and hydrodynamic volume (HDV) calibration curves for polymer-solvent systems where primary polymer standards are unavailable. The method is demonstrated by using a HDV calibration curve based on polystyrene in tetrahydrofuran (THF), in conjunction with integral distribution curves of elution volume for poly(methyl methacrylate) (PMMA) in THF and in 2,2,2-tri-fluoroethanol (TFE) for the generation of a HDV calibration curve in TFE. Transformation methods for generating secondary MW calibration curves from HDV calibration curves are discussed and applied to PMMA in THF and TFE, and to poly(trimethylene oxide), poly(vinyl acetate), and certain polyamides in TFE. The utility and reliability of the secondary calibration curves are demonstrated by comparing MW average and intrinsic viscosites obtained by GPC and by the classical methods. Molecular structural differences among th polyamide samples associated with the distribution of short- and long-chain branches are discussed in relation to their secondary calibration curves.