Isoprene-styrene chain shuttling copolymerization mediated by a lanthanide half-sandwich complex and a lanthanidocene: straightforward access to a new type of thermoplastic elastomers

Andreia Valente; Gregory Stoclet; Fanny Bonnet; André Mortreux; Marc Visseaux; Philippe Zinck

doi:10.1002/anie.201311057

Isoprene-styrene chain shuttling copolymerization mediated by a lanthanide half-sandwich complex and a lanthanidocene: straightforward access to a new type of thermoplastic elastomers

Angew Chem Int Ed Engl. 2014 Apr 25;53(18):4638-41. doi: 10.1002/anie.201311057. Epub 2014 Mar 25.

Authors

Andreia Valente¹, Gregory Stoclet, Fanny Bonnet, André Mortreux, Marc Visseaux, Philippe Zinck

Affiliation

¹ Unité de Catalyse et Chemie du Solide, CNRS, University Lille 1, Science and Technology, 59655 Villeneuve d'Ascq (France).

PMID: 24668565
DOI: 10.1002/anie.201311057

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.

Keywords: block copolymers; chain shuttling; coordinative chain transfer polymerization; copolymerization; lanthanides.