Z-RAFT star polymerization of styrene: Comprehensive characterization using size-exclusion chromatography

Reversible addition–fragmentation chain transfer (RAFT) polymerizations of styrene in bulk at 80 °C using tri-, tetra-, and hexafunctional trithiocarbonates, in which the active RAFT groups are linked to the core via the stabilizing Z-group, were studied in detail. These Z-RAFT star polymerizations of styrene showed excellent molecular weight control up to very high monomer conversions and star sizes of more than 200 kDa. The application of high pressure up to 2600 bar was found to significantly increase the relative amount of living star polymer. Not even at very high monomer conversions and for large star molecules, a shielding effect of growing arms hampering the RAFT process could be identified. Absolute molecular weights of star polymers using a conventionally calibrated SEC setup were determined with high precision by using a mixture of linear and star-shaped RAFT agents. When using phenylethyl as the leaving R-group, well-defined star polymers that perfectly match the theoretical predictions were formed. However, when using benzyl as the leaving group, a pronounced impact of monomer conversion on the star polymer topology was observed and pure star polymers with the expected number of arms could not be obtained.