DETERMINATION OF FUNCTIONALITY AND MOLAR-MASS DISTRIBUTION OF ALIPHATIC POLYESTERS BY ORTHOGONAL LIQUID-CHROMATOGRAPHY .1. OFF-LINE INVESTIGATION OF POLY(1,6-HEXANEDIOL ADIPATES)

During polycondensation of polyesters products are formed distributed in molar mass and functionality (end groups). Especially in polyuretha ne chemistry the knowledge of the distribution of terminal groups is n ecessary for correlating material properties containing different spec ies in raw materials. The characterization of polyesters by ''Liquid A dsorption Chromatography at Critical Conditions'' (LACCC) is a new pow erful tool for kinetics and modelling. Separation of polyesters accord ing to their terminal groups independently of their molar mass is feas ible at the critical conditions determined by the chromatographic syst em silica/acetone/hexane. Owing to side reactions, the number of combi nations of COOH- and OH terminal groups identified was higher than exp ected. Cyclic species, hexanediol ether structures and alkyl-terminate d homologues were identified. Model substances for all structures were synthesized. For orthogonal separation LACCC was combined off-line wi th SEC. With the help of preparative separation enough material was ob tained to identify the species by spectroscopic methods (NMR, MALDI-TO F-MS) and to calibrate both the detector response and SEC. Finally, an algorithm is proposed for the characterization of end-group distribut ed reactive polymers by orthogonal liquid chromatographic methods.