Substituent Effects on RAFT Polymerization with Benzyl Aryl Trithiocarbonates

The RAFT polymerization of styrene in the presence of benzyl aryl trithiocarbonate RAFT agents (Z′SC(=S)SR) has been studied. The values of the apparent transfer constants of the benzyl aryl trithiocarbonates (0.029 M) in bulk styrene polymerization at 110 °C fall within the range 10–25 depending on substituents on the aryl ring (Z′) and are higher than that of benzyl dodecyl trithiocarbonate 1 for which was determined to be 9.4. There is a trend for higher transfer constant, lower dispersity product and better control over polymerization with more electron‐withdrawing substituents with the most active in the series studied being the 3,5‐bis(trifluoromethyl)phenyl derivative. magnified image