Bifunctional Carbanionic Synthesis of Fully Bio-Based Triblock Structures Derived from β-Farnesene and ll-Dilactide: Thermoplastic Elastomers

Angew Chem Int Ed Engl. 2023 Oct 16;62(42):e202310519. doi: 10.1002/anie.202310519. Epub 2023 Sep 11.

Abstract

Current environmental challenges and the shrinking fossil-fuel feedstock are important criteria for the next generation of polymer materials. In this context, we present a fully bio-based material, which shows promise as a thermoplastic elastomer (TPE). Due to the use of β-farnesene and L-lactide as monomers, bio-based feedstocks, namely sugar cane and corn, can be used. A bifunctional initiator for the carbanionic polymerization was employed, to permit an efficient synthesis of ABA-type block structures. In addition, the "green" solvent MTBE (methyl tert-butyl ether) was used for the anionic polymerisation, enabling excellent solubility of the bifunctional anionic initiator. This afforded low dispersity (Đ=1.07 to 1.10) and telechelic polyfarnesene macroinitiators. These were employed for lactide polymerization to obtain H-shaped triblock copolymers. TEM and SAXS revealed clearly phase-separated morphologies, and tensile tests demonstrated elastic mechanical properties. The materials featured two glass transition temperatures, at - 66 °C and 51 °C as well as gyroid or cylindrical morphologies, resulting in soft elastic materials at room temperature.

Keywords: Anionic Polymerization; Bifunctional; Phase Separation; Polyfarnesene; Thermoplastic Elastomer.