Well-defined amphiphilic copolymers of styrene and poly(ethylene glycol) methyl ether methacrylate (PEGMA) were successfully synthesized using reverse atom transfer radical polymerization (RATRP). The initial feed ratio of the macromonomer, PEGMA has a significant effect on the copolymer yield. Copolymer yield decreased with increasing the monomer feed ratio of PEGMA, but number average molecular weight followed the opposite trend. The resultant copolymers were characterized by nuclear magnetic resonance (NMR) spectroscopy to confirm their structures and comonomer compositions. The macromonomer content in the copolymer has a significant effect on the thermal and mechanical properties.

Atom transfer radical polymerization (ATRP) is one of the most promising approaches for controlled radical polymerization.^[1] ATRP can be used in two different initiating systems: (a) an alkyl halide and transition- metal compound in its lower oxidation state of CuBr complexed by two molecules of ligand for example 4,4Õ›-di(alkyl)-2,2Õ›- bipyridine or one molecule of N,N,NÕ›,Nʺ,Nʺ-pentamethyldiethylenetriamine (b) a conventional radical initiator such as azobis(isobutyronitrile) (AIBN) with the transition-metal compound in its higher oxidation state of CuBr₂ complexed by an appropriate ligand. 

The latter approach has been named reverse atom transfer radical polymerization (RATRP) and was successfully used for copper-based heterogeneous and homogeneous systems in solution and in emulsion as well as for iron complexes.  These systems successfully used to prepare polymers with predetermined molecular weights, low polydispersity (PDI), and precise end functionalities as well as a variety of copolymers with controlled topologies and compositions.

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