Synthetic polymers from building block chemicals produced by biorefineries - PLA-based polyesters and galactaric acid-based polyanhydrides

Tuomas Mehtiö

    Research output: ThesisDoctoral ThesisCollection of Articles

    Abstract

    Increasing environmental concerns as well as diminishing fossil fuel resources have increased the pressure to replace fossil fuel derived materials with renewable alternatives. Biorefineries target in comprehensive utilization of all components of biomass with similar principles than conventional petroleum refinery. Improved product portfolios have started to emerge from already existing side-streams of agriculture and forest industries. However, full commercial potentiality of biomass-derived building blocks has not yet materialized. This thesis targeted in developing polymeric products from under-utilized side-streams of forest industry and agriculture. Meso-galactaric acid can be produced biotechnologically from D-galacturonic acid, a major component of pectin-rich industrial side-streams from e.g. sugar beet processing and apple and orange juice production. 2,3,4,5-Tetra-O-acetylated galactaric acid was synthesized from meso-galactaric acid and utilized in the polymerization of copolyanhydrides with adipic anhydride. Incorporation of 2,3,4,5-Tetra-O-acetylgalactaric acid moieties in the polymer structure were found to have similar effects on thermal properties of the polymer as incorporation of aromatic moieties. Glycolic acid (GA), DL-lactic acid (DL-LA) and D,L-2-hydroxybutyric acid (DL-2HBA), present in kraft black liquors, are major side-products of kraft pulp process. Obtained results indicate that these monomer mixtures could be applied as monomers for polymerization without additional separation from each other. This utilization route for the hydroxy acid mixture would partly help developing kraft pulp process towards more comprehensive biorefinery. Double bond functionalized copolyesters (PLABDIA) were synthesized from DL-LA, itaconic acid and 1,4-butanediol. Radical crosslinking reaction of the polymers was developed to be efficient and rapid enough for various dispersion-based applications, e.g. roll-to-roll coating. The aqueous dispersion of PLABDIA was prepared and coated onto boxboard on a pilot-scale line coater. Achieved WVTR were less than 50 % of that corresponding to the commercial extruded PLA coating. Improvements are significant in terms of making PLA-based materials more suitable for wider range of packaging applications. Obtained results provide valuable data and utilization routes for already existing side-streams of of forest industry and agriculture targeting in developing these processes towards more comprehensive biorefinery approach
    Translated title of the contributionSynteettiset polymeerit biojalostamoista saatavista raaka-aineista: PLA-pohjaiset polyesteritsekä galaktaarihappopohjaiset polyanhydridit
    Original languageEnglish
    QualificationDoctor's degree
    Awarding Institution
    • Aalto University
    Supervisors/Advisors
    • Seppälä, Jukka, Supervising Professor
    Publisher
    Print ISBNs978-952-60-7082-7
    Electronic ISBNs978-952-60-7081-0
    Publication statusPublished - 2016
    MoE publication typeG5 Doctoral dissertation (article)

    Keywords

    • Biopolymer
    • Biorefinery
    • Polyester
    • Polyanhydride

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