Synthesis of novel polymeric materials based on aliphatic polyesters by combination of different controlled polymerization methods

Combination of the living ring‐opening polymerization (ROP) of ε‐CL and lactides with the “controlled” free radical polymerization of styrene and methacrylic monomers is a versatile strategy for the synthesis of well‐defined block and graft copolymers. In this respect, the dual “living” polymerization strategy in which two different functional groups on a single molecule used to initiate the two controlled mechanisms is particularly efficient. Combination of ROP and step‐growth polymerization is another versatile methodology for the preparation of a large variety of new materials, e.g. polyimide nanofoams, polyester/silica hybrid materials and star and branched polyesters by dendritic initiation.