Isoprene–Styrene Chain Shuttling Copolymerization Mediated by a Lanthanide Half‐Sandwich Complex and a Lanthanidocene: Straightforward Access to a New Type of Thermoplastic Elastomers

Abstract

A lanthanide half-sandwich complex and a ansa lanthanidocene have been assessed for isoprene-styrene chain shuttling copolymerization with n-butylethylmagnesium (BEM). In the presence of 1 equiv BEM, a fully amorphous multiblock microstructure of soft and hard segments is achieved. The microstructure consists of poly(isoprene-co-styrene) blocks, with hard blocks rich in styrene and soft blocks rich in isoprene. The composition of the blocks and the resulting glass transition temperatures (Tg ) can be easily modified by changing the feed and/or the relative amount of the catalysts, highlighting a new class of thermoplastic elastomers (TPEs) with tunable transition temperatures. The materials self-organize into nanostructures in the solid state.