Evaluating the Effect of Termination by Chain–Chain Coupling in Living Free-Radical Polymerizations

A novel approach based on the reaction of multifunctional star polymers with chromophore-labelled linear polymers is presented for evaluating the extent of termination by chain–chain coupling during living free-radical polymerizations. A mixed initiating system consisting of an unlabelled, multifunctional initiator and an excess of a monofunctional alkoxyamine initiator containing a chromophore, such as pyrene, is used to initiate the living polymerization of vinyl monomers leading to a mixture of star and linear polymers. The occurrence of chain–chain coupling is readily identified and quantified by isolating the star polymer that is obtained and elucidating the level of incorporation of pyrene units by UV/vis spectroscopy. This allows the level of chain–chain coupling to be determined since the inclusion of pyrene into the star structure is a direct result of termination by radical coupling.