Characterization of poly(methyl methacrylate)-graft-poly(styrene)s using various chromatographic techniques

•Heterogeneities of two differently synthesized PMMA-g-PS samples were analyzed.•Information from multidetector SEC, gradient chromatography and 2D-LC were compared.•One sample contained h-PS, h-PMMA and highly grafted product.•The second sample contained, h-PS and graft product of lower grafting density.•2D-LC yielded separation by composition and molecular size.

Two graft copolymer samples of identical average composition were synthesized by grafting living polystyrene anions onto a broadly distributed PMMA backbone. Size exclusion chromatography (SEC) with only RI-detection, SEC with viscometry and light scattering detection, SEC with UV and RI dual detection, gradient chromatography and 2-dimensional chromatography were applied to compare the information that can be obtained by the different techniques. While only limited information was retrieved by conventional SEC or SEC with molar mass sensitive detection, SEC with UV and RI revealed different chemical heterogeneity of the samples. Using gradient chromatography and 2-dimensional chromatography it was possible to identify non-grafted side chains and unreacted parent PMMA besides the actual graft copolymer molecules. While in one sample a heavily grafted product was formed besides non-grafted PMMA, the second sample did not contain ungrafted PMMA but a graft product of lower grafting density. The different product distributions were explained by the different synthetic procedures.