Transition metal-based homopolymerisation of macromonomers

Abstract

Since their first utilisation in 1958 for the synthesis of graft copolymers, macromonomers have raised increasing interest because of their ability to provide an easy access to a large number of (co)polymers of different chemical natures and various controlled topologies (comb-like, bottlebrush, star-like, graft copolymers...) exhibiting very different solution or solid-state properties compared to their linear homologues. During the first decades, the (co)polymerisation of macromonomers was based on poorly controlled free radical polymerisations. Therefore, it was difficult to obtain polymers in a controlled manner. With the appearance of Ring Opening Metathesis Polymerisation (ROMP) or of new free radical processes such as Atom Transfer Radical Polymerisation (ATRP) that allow control of molar masses, and of Ziegler–Natta-type polymerisation that allows control of the tacticity of the polymacromonomer backbone, these processes have been increasingly utilised for macromonomer (co)polymerisations. In this paper, a review of the results published in the literature regarding the homopolymerisation of macromonomers in the presence of transition metal is presented.