Transition-Metal Complex Macroinitiators

Research on the synthesis of polypeptide hybrid diblock copolymers began in the mid-1970s (Yamashita et al., 1975). Advances in polymer synthesis, culminating in the development of controlled/living polymerization techniques and click chemistry (Sumerlin and Vogt, 2010), in combination with the living ROP of NCAs, allowed for the preparation not only of simple diblock but also of a wide variety of multiblock Chimeras. In this section we will describe the materials synthesized according to the macroinitiators used for the ROP of the NCAs amino-and transition-metal complexes. 

Hydroxy-terminated PEG is readily transformed into ATRP macroinitiators by conversion of the hydroxyl groups to terminal halide units followed by reaction with a transition metal/ligand complex, and used to form diblocks with several monomers, including the sodium salt of methacrylic acid. 

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