New AB or ABA type block copolymers: atom transfer radical polymerization (ATRP) of methyl methacrylate using iodine-terminated PVDFs as (macro)initiators

PMMA homopolymer with CF3(CF2)(2)CF2- end group was prepared by the ATRP of MMA using CF3(CF2)(2)CF2-I as an initiator and copper(I) salts/bipy catalysts. This indicated the production of perfluorobutyl radicals by ATRP mechanism and successful polymerization by them. Di- and triblock copolymers were also prepared by the ATRP of MMA using iodine-terminated PVDF as (macro)initiators. The kinetic plots (In[M](o)/[M] vs. time) showed nearly first-order with respect to monomer concentration and the M-n,(NMR) Of block copolymers increased linearly with conversion. However, iodine-terminated PVDF showed low initiator efficiency because propagating rate was much faster than initiating rate.