Fabrication of Thermoplastic Poly(ether-ester) Elastomers with High Melting Temperature and Elasticity from Bio-based 2,5-Furandicarboxylic Acid

Abstract

Even though current research on bio-based poly(ester-ether) elastomers (TPEEs) has expanded to include applications, only odd TPEEs with outstanding melting temperatures have been reported thus far. This is due to certain features, like desirable elastic properties and high melting temperature, which are still challenging to obtain without the utilization of petroleum-based monomers. In order to prepare bio-based TPEE with both high thermal resistance and elastic recovery, furan-based poly(1,4-cyclohexanedimethylene furandicarboxylate)-poly(tetramethylene glycol) multiblock copolymers (PCFTMG^2k) were synthesized in this work. These copolymers had weight fractions of soft segments PTMG (ω_PTMG) ranging from 30 to 80% while maintaining M_n of the soft segments at 2 kg/mol. Indeed, while PTMG segments are found to delay substantially the crystallization of the PCF within the copolymers, the results show that TPEEs with both elastic properties and high melting temperatures can be successfully prepared by introducing soft segments with relatively good crystallization ability and controlling the content of soft segments. Moreover, the crystallization behavior of the copolymers was investigated, from which it was found that the copolymers transformed from a non-cocrystallization state to an isodimorphic state as the content of soft segments increased. More importantly, PCFTMG^2k-80, containing 80 wt % of the PTMG segment, showed a shape recovery rate as high as 84.9% during the first cyclic test at 200% strain and T_m up to 198°C at a high PTMG concentration, which is higher than those of almost all the TPA-based TPEEs. This PCFTMG^2k bio-based TPEE will occupy an important position in the future market of high melting temperature thermoplastic elastomers.