Influence of pore size on the separation of random and block copolymers by interactive liquid chromatography

Stationary phase materials with small pore diameters are often used for the separation of copolymers according to their chemical composition. The rationale for such a column selection is to minimize the influence of the molecular weight on the separation. In this paper, we describe a detailed study of the influence of the pore size on the retention and separation of poly(methylmethacrylate) (PMMA)–poly(butylmethacrylate) copolymers. We used normal-phase (NP) and reversed-phase (RP) columns with various pore diameters, as well as non-porous columns and a monolithic column. The pore size was found to affect the separation, especially for (co-)polymer molecules with characteristic diameters that roughly correspond to the exclusion limit of the column. Also possibilities to separate block copolymers according to block length are strictly investigated. The making of one block in a di-block (DB) copolymer “invisible” can only be fulfilled if the “invisible” block does not play any role in the separation.