Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials

Eva Laur,Evgueni Kirillov,Jean-François Carpentier,Aurélien Vantomme,Alexandre Welle,Jean-Michel Brusson

doi:10.3390/catal7120361

Abstract

The copolymerization of bio-renewable β-myrcene or β-farnesene with styrene was examined using an ansa-neodymocene catalyst, affording two series of copolymers with high styrene content and unprecedented syndioregularity of the polystyrene sequences. The incorporation of terpene in the copolymers ranged from 5.6 to 30.8 mol % (β-myrcene) and from 2.5 to 9.8 mol % (β-farnesene), respectively. NMR spectroscopy and DSC analyses suggested that the microstructure of the copolymers consists of 1,4- and 3,4-poly(terpene) units randomly distributed along syndiotactic polystyrene chains. The thermal properties of the copolymers are strongly dependent on the terpene content, which is easily controlled by the initial feed. The terpolymerization of styrene with β-myrcene in the presence of ethylene was also examined.

Highlights

The sustainability and possible eco-compatibility of bio-based polymers has raised much interest in finding inexpensive alternatives to petroleum-sourced materials
We reported new neutral allyl {Cp/Flu}-type neodymium and samarium complexes of the type {R2 C(C5 H4 )(R’R’Flu)}Ln(1,3-C3 H3 (SiMe3 )2 )(THF)x (Flu = 9-fluorenyl) that act as single-component catalysts for homo- and copolymerization of styrene with ethylene, featuring high syndioselectivity, good productivities and good control over the incorporated ethylene content [16]
We report on the copolymerization of styrene with β-myrcene or farnesene with such catalyst systems

Summary

Introduction

The sustainability and possible eco-compatibility of bio-based polymers has raised much interest in finding inexpensive alternatives to petroleum-sourced materials. Β-myrcene, or to a lesser extent β-farnesene, can polymerize via anionic or radical polymerization to form elastomeric materials [1]. Syndiotactic polystyrene (sPS) is a very attractive material due to its high melting point Its processability is limited by its high melting point and its brittleness. Syndioselective copolymerization of styrene with small amounts of a second monomer is one of the most common ways to tune the properties of sPS, and to improve its processability [9,10,11]. A few examples of styrene-myrcene polymers have already been reported, mostly via anionic or radical copolymerizations [12,13,14]. Only one paper has addressed the coordination copolymerization of styrene with β-myrcene (My) in the presence of the ternary system

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Conclusion