Isoprene–Styrene Chain Shuttling Copolymerization Mediated by a Lanthanide Half‐Sandwich Complex and a Lanthanidocene: Straightforward Access to a New Type of Thermoplastic Elastomers1. Issue 18 (25th March 2014)

• Record Type: Journal Article
• Authors: Valente, Andreia; Stoclet, Gregory; Bonnet, Fanny; Mortreux, André; Visseaux, Marc; Zinck, Philippe
• Is Part Of: Angewandte Chemie international edition. Volume 53:Issue 18(2014)
• Page Start: 4638
• Page End: 4641
• Publication Date: 2014-03-25
• Subjects: block copolymers -- chain shuttling -- coordinative chain transfer polymerization -- copolymerization -- lanthanides; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201311057
• Languages: English
• ISSNs: 1433-7851

Abstract

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 ( T g ) 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. Abstract : Chain shuttling copolymerization of isoprene and styrene using a borohydrido lanthane half‐sandwich complex, a borohydrido ansa ‐neodymocene, and a magnesium dialkyl affords direct access to new amorphous thermoplastic elastomers. The resulting multiblock microstructure of soft and hard statistical copolymeric segments self‐assembles at the nanoscale.