Synthesis of New Macromolecular Architectures Based on Ring Opening Metathesis Polymerisation and Atom Transfer Radical Polymerisation

Thanks to recent advances in the chemistry of preparing polymers, an increasing number of tools are at our disposal for the design of polymer materials. The design level ranges from monomer synthesis, controlled stepwise or chainwise polymerisation, block copolymer synthesis, branching and crosslinking reactions. Depending on the structure of the individual polymer chains formed, these will be organised in the bulk to give specific properties. Hence, this gives us two architectural levels: the structure of individual macromolecules and the microstructure of the material produced. The synthesis of properly tailored macromolecular architectures [1] can be achieved by using living/controlled polymerisation processes such as anionic [2], cationic [3], radical [4] or group transfer polymerisation [5], ring-opening polymerisation of lactones and lactides [6], ring-opening metathesis polymerisation (ROMP) of cyclic olefins [7-9], and co-ordination polymerisation [10]. Of particular interest today is the combination of two of these processes. The present chapter aims at reviewing the synthetic routes developed recently for building up novel (co)polymer structures based on ROMP and atom transfer radical polymerisation (ATRP), with a special emphasis on the combination of two living/controlled polymerisation techniques.