Combination of Atom Transfer Radical Polymerization (ATRP) and Atom Transfer Radical Cross Coupling (ATRCC) processes as a route to prepare telechelic polymers was described. The concept is based on the activation of the dormant species at the chain ends of polystyrene (Br-PS-Br or PS-Br) prepared by ATRP and functional ATRP initiator (F-R-Br) in the absence of a monomer. Depending on the type of polystyrene used in the system, cross coupling of these active species gives α,ω-polystyrene and ω-polystyrene telechelics. Detailed investigations using a model system revealed that the efficiency of functionalization was not very high because of the self-coupling of the species derived from the polymer and functional initiator. However, the highest functionalization (Xf=0.85) was achieved by introducing a small amount of styrene in the ATRCC.
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