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  • 1.
    Stamm, Arne
    et al.
    KTH Royal Institute of Technology, Sweden.
    Oehlin, Johannes
    KTH Royal Institute of Technology, Sweden.
    Mosbech, Caroline
    KTH Royal Institute of Technology, Sweden.
    Olsen, Peter
    KTH Royal Institute of Technology, Sweden.
    Guo, Boyang
    KTH Royal Institute of Technology, Sweden.
    Söderberg, Elisabeth
    KTH Royal Institute of Technology, Sweden.
    Biundo, Antonino
    KTH Royal Institute of Technology, Sweden.
    Fogelström, Linda
    KTH Royal Institute of Technology, Sweden.
    Bhattacharyya, Shubhankar
    RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.
    Bornscheuer, Uwe T.
    University of Greifswald, Germany.
    Malmström, Eva
    KTH Royal Institute of Technology, Sweden.
    Syren, Per-Olof
    KTH Royal Institute of Technology, Sweden.
    Pinene-based oxidative synthetic toolbox for scalable polyester synthesis2021In: JACS Au, E-ISSN 2691-3704, Vol. 1, no 11, p. 1949-1960Article in journal (Refereed)
    Abstract [en]

    Generation of renewable polymers is a long-standing goal toward reaching a more sustainable society . Herein we show how conceptually simple oxidative transformations can be used to unlock the inherent reactivity of terpene synthons in generating polyesters by two different mechanisms starting from the same α-pinene substrate. In the first pathway, α-pinene was oxidized into the bicyclic verbanone based lactone (VaL) and subsequently polymerized into star-shaped polymers via ring-opening polymerization, resulting in a biobased semicrystalline polyester with tunable glass transition and melting temperatures In a second pathway, polyesters were synthesized via polycondensation, utilizing the diol (1-(1'-hydroxyethyl)-3-(2'-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC)) synthesized by oxidative cleavage of the double bond of α-pinene, together with unsaturated biobased diesters such as di-Me maleate (DMM) and di-Me itaconate (DMI), resp. The resulting families of terpene-based polyesters were thereafter successfully crosslinked by either transetherification, utilizing the terminal hydroxyl groups of the synthesized verbanone-based materials, or by UV-irradiation, utilizing the unsaturation provided by the DMM or DMI moieties within the HHDC-based copolymers. This work highlights the potential to apply an oxidative toolbox to valorize inert terpene metabolites enabling generation of bio sourced polyesters and coatings thereof by complementary mechanisms.

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