Control agents that have a nitrogen-nitrogen bond covalently bonded to a
thiocarbonyl moiety are provided for living-type free radical
polymerization of a wide variety of monomers. These control agents provide
superior properties for control of the polymerization and/or the
properties of the polymers obtained and/or the monomers that may be
polymerized. In some embodiments, a bulky group is pendant off the
activated thiocarbonyl portion of the control agents. Multifunctional
control agents provide the opportunity for a variety of structurally
unique polymers, including block copolymers, stars and hyper-branched
polymers.
