Temperature-programmed packed capillary liquid chromatography with UV detec
tion has been used for the separation of a wide range of polystyrenes. The
low thermal mass of the reversed phase packed capillary columns (0.32-mm in
ternal diameter) allowed rapid temperature programming for retention contro
l. By the use of temperature gradients as steep as 40 degreesC.min(-1), rap
id separations (11 minutes) of polystyrene standards (2000-400000) could be
achieved. Furthermore, the oligomers of the polystyrene 1000 standard were
resolved using temperature programming. When replacing tetrahydrofurane wi
th acetonitrile as mobile phase component, peak splitting within the oligom
er peaks was observed, revealing some information about the tacticity of th
e polystyrene 1000 sample.