A process of controlled radical polymerization, and products made therefrom is disclosed. The process includes performing controlled radical polymerization on a composition comprising a polymerizable compound, an initiator, a ligand, and a catalyst; permitting the controlled radical polymerization reaction to proceed until a desired level of conversion is attained, but prior to complete conversion to obtain an intermediate polymerization product; and further reacting the intermediate polymerization product with a reactant having a cluster of multiple reactive sites to provide a polymer reaction product having a cluster of pendent multiple reactive sites adjacent to said terminal ends of said polymer reaction product.