Molecular structure characterization of linear and branched polystyrene blends by size exclusion chromatography coupled with viscometry

Owing to their low polydispersity and their well controlled molecular architecture, 3-arms stars polystyrenes made by anionic synthesis are suitable models to study the solution properties of long chain branched polymers. A fine characterization of such polymers by size exclusion chromatography–viscometry has shown that they often contain unwanted linear chains, leading to chromatograms presenting overlapping peaks. A mathematical procedure has been developed in order to deconvolute these chromatograms and has been validated, thanks to blends of polystyrene standards. It allows one to calculate the purity of the sample as well as the intrinsic viscosity and molar mass distribution of each component. For stars with three arms of the same length, branching parameters have also been calculated and a viscosity law has been established.