Liquid chromatography under critical conditions: Practical applications in the analysis of amphiphilic polymers

Liquid chromatography under critical conditions (LCCC) allows the separation of block copolymers from the corresponding homopolymers as well as the separation of homopolymers according to their functionality. At the transition of exclusion and adsorption mode, the polymer chain becomes “chromatographically invisible,” and thus a separation according to other structural units can be achieved. In the case of block copolymers this situation can be utilized to detect and determine unwanted homopolymers. At critical conditions for the repeat unit, the other block may be eluted in the exclusion or the adsorption regime. In the first case, the block copolymer is eluted before the homopolymer, and its molar mass can be determined as in size-exclusion chromatography. In the second case, it is eluted later than the homopolymer, and the separation of the individual oligomers can be achieved. Advantages and limitations of different approaches in LCCC are discussed.