Gradient high-performance liquid chromatography of statistical and block copolymers of styrene and t-butyl methacrylate

Copolymers of styrene (S) and tert-butyl methacrylate (TBMA) containing 24–92 mass % of the latter monomer were investigated using a silica column with isooctane/tetrahydrofuran (THF) gradients and on a phenyl bonded-phase column by methanol (MeOH)/THF gradients using UV detection. In both cases, retention decreased with increasing TBMA content of the sample. This is in contrast to the behavior of copolymers of S and methyl methacrylate (MMA) whose retention in gradient elution on silica columns increases with MMA content due to the polarity of this unit. The inversion of elution order is a result of the bulky TBMA residues shielding the polar groups of the ester units. For copolymers of va…