Two‐dimensional liquid chromatography with active solvent modulation for studying monomer incorporation in copolymer dispersants

A pseudo‐comprehensive two‐dimensional liquid chromatography approach with size exclusion chromatography in the first dimension and gradient reversed‐phase liquid chromatography in the second dimension was successfully developed for the characterization of vinyl acetate/acrylic acid copolymers and vinyl acetate/itaconic acid/acrylic acid terpolymers. Active solvent modulation was exploited to prevent the polymer breakthrough in the second dimension separation caused by the strong solvent used in the first dimension. The conditions of the active solvent modulation valve were optimized to achieve sufficient on‐line dilution and to completely prevent polymer breakthrough without adding excessive time to the modulation cycle. Using this approach, copolymers made with different monomer ratios and processes were studied. Heterogeneous composition distribution due to insufficient monomer incorporation was detected in some of the copolymer samples. We demonstrated that with active solvent modulation, the two‐dimensional liquid chromatography approach is no longer limited to water‐soluble polymers and can be used for a broader range of polymers and copolymers.