Bottle-grade polyethylene furanoate from ring-opening polymerisation of cyclic oligomers

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Abstract

<jats:title>Abstract</jats:title><jats:p>Polyethylene furanoate (PEF) represents a promising renewable resource-based bioplastic as replacement for fossil-based polyethylene terephthalate (PET) with improved material properties. However, the synthesis of PEF through conventional polycondensation remains challenging, since the time-intensive reaction leads to degradation and undesired discolouration of the product. Here we show the successful rapid synthesis of bottle-grade PEF via ring-opening polymerisation (ROP) from cyclic PEF oligomers within minutes, thereby avoiding degradation and discolouration. The melting point of such mixture of cyclic oligomers lies around 370 °C, well above the degradation temperature of PEF (~329 °C). This challenge can be overcome, exploiting the self-plasticising effect of the forming polymer itself (which melts around 220 °C) by initiation in the presence of a high boiling, yet removable, and inert liquid plasticiser. This concept yields polymer grades required for bottle applications (<jats:italic>M</jats:italic><jats:sub>n</jats:sub> > 30 kg mol<jats:sup>−1</jats:sup>, conversion > 95%, colour-free products), and can be extended to other diffusion-limited polymer systems.</jats:p>

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