Rare Earth Metal-Mediated Group-Transfer Polymerization: From Defined Polymer Microstructures to High-Precision Nano-Scaled Objects

Poly­(2-isopropenyl-2-oxazoline) (PIPOx) and poly­(2-vinylpyridine) (P2VP) have been efficiently synthesized using bis­(cyclopentadienyl)­methylytterbium (Cp₂YbMe) as catalyst. The polymerizations of 2-isopropenyl-2-oxazoline (IPOx) and 2-vinylpyridine (2VP) follow a living group-transfer polymerization (GTP) mechanism, allowing a precise molecular-weight control of both polymers with very narrow molecular-weight distribution. The GTP of IPOx and 2VP occurs via N coordination at the rare earth metal center, which has rarely been reported previously. The relative coordination strength of different monomers at the ytterbium center is determined by copolymerization investigations to be in the order of DEVP > MMA > IPOx > 2VP. In combination with living cationic ring-opening polymerization, PIPOx is converted to molecular brushes with defined backbone and poly­(2-oxazoline) side chains using the <i>grafting-from</i> method