A polymerization process comprising initiating a first polymerization of
monomers using an initiator functionalized with an ATRP initiating site,
wherein the first polymerization is selected from the group of cationic
polymerization, anionic polymerization, conventional free radical
polymerization, metathesis, ring opening polymerization, cationic ring
opening polymerization, and coordination polymerization to form a
macroinitiator comprising an ATRP initiating site and further initiating
an ATRP polymerization of radically polymerizable monomers using the
macroinitiator comprising an ATRP initiating site. Novel block copolymers
may be formed by the disclosed method.