Synthesis of block copolymer by integrated living anionic polymerization-atom transfer radical polymerization (ATRP)

Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) a nd poly-(styrene-b-butadiene) oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synth esized by living anionic polymeri-zation using n-butyllithium as initiator. Then the PS-CH2CH2OCOCCl3 (PS-Cl-3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl-3) was used as the macroinitiator in the polymerization of(meth)acrylates in t he presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepare d by the integrated living anionic polymerization (LAP)-atom transfer radic al polymerization (ATRP). The structures of the PSB-Cl-3 and the P(S-b-MMA) were identified by FTIR and H-1-NMR spectrum, respectively. A new way to d esign block copolymers (the combination of LAP and ATRP) was developed.