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

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Journal ISSN
Volume Title
School of Chemical Technology | Doctoral thesis (article-based) | Defence date: 2016-11-18
Date
2016
Major/Subject
Mcode
Degree programme
Language
en
Pages
77 + app. 61
Series
Aalto University publication series DOCTORAL DISSERTATIONS, 216/2016
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

Kasvava tietoisuus ilmastonmuutoksesta sekƤ ehtyvƤt fossiiliset raaka-ainelƤhteet ovat kasvattaneet painetta korvata fossiilisista raaka-aineista perƤisin olevia materiaaleja uusiutuvilla vaihtoehdoilla. Biojalostamot tƤhtƤƤvƤt biomassan kokonaisvaltaiseen hyƶdyntƤmiseen, kuten perinteisessƤ ƶljynjalostamossa. Laajempia tuotevalikoimia on kehitetty jo olemassa olevista metsƤ- ja maatalouden sivuvirroista, mutta kuitenkaan ei biomassapohjaisten raaka-aineiden tƤyttƤ potentiaalia ole vielƤ pystytty hyƶdyntƤmƤƤn. TƤmƤn vƤitƶskirjan tavoitteena oli kehittƤƤ polymeerisiƤ tuotteita hyƶdyntƤmƤttƶmistƤ metsƤ- ja maatalouden sivuvirroista. Meso-galaktaarihappoa on mahdollista valmistaa bioteknisesti D-galakturonihaposta, jota on runsaasti saatavilla pektiinirikkaista sivutuotteista esim. omena- ja appelsiinimehun valmistuksessa. 2,3,4,5-tetra-O-asetyloitua galaktaarihappoa syntetisoitiin mesogalaktaarihaposta ja niistƤ polymeroitiin edelleen sarja kopolyanhydridejƤ yhdessƤ adipiinianhydridin kanssa. Galaktaarihappopohjaisen rakenneyksikƶn lisƤƤmisellƤ polyanhydridin rakenteeseen huomattiin olevan samankaltaisia vaikutuksia polymeerin termisiin ominaisuuksiin, kuin mitƤ aromaattisten rakenneyksikƶiden lisƤyksellƤ on. Glykolihappoa, maitohappoa sekƤ 2-hydroksibutyyrihappoa muodostuu merkittƤviƤ mƤƤriƤ sivutuotteina sellun valmistuksessa sulfaattimenetelmƤllƤ. Saadut tulokset indikoivat, ettƤ nƤitƤ yhdisteitƤ on mahdollista hyƶdyntƤƤ raaka-aineena kopolymeroinnissa ilman erillistƤ erottelua toisistaan. TƤmƤ valmistusreitti edesauttaa omalta osaltaan sulfaattiprosessin kehittƤmistƤ kohti kokonaisvaltaisempaa biojalostamoa. Kaksoissidosfunktionalisoituja kopolyestereitƤ syntetisoitiin maitohaposta, itakonihaposta sekƤ 1,4-butaanidiolista. Polymeerien ristisilloitusta radikaalireaktion kautta kehitettiin vastaamaan dispersiopƤƤllystysaplikaatioita, jossa jatkuvatoimisuuden takia silloitusnopeus on avainasemassa. TyƶssƤ kehitettiin syntetisoidusta kopolymeeristƤ vesipohjainen dispersio, jolla pƤƤllystettiin kartonkia pilot-mittakaavassa. KehitetyllƤ pƤƤllysteellƤ saavutettiin vesihƶyrynlƤpƤisevyys joka on alle 50 % teollisesta ekstruusiopƤƤllystetystƤ PLA-pƤƤllystetystƤ kartongista. Tulokset mahdollistavat maitohappopohjaisten polymeerien hyƶdyntƤmisen nykyistƤ laajemmin myƶs pakkausteollisuudessa. Saadut tulokset ovat tƤrkeƤ lisƤ jo olemassa olevien metsƤ- ja maatalouden prosessien sivuvirtojen hyƶdyntƤmiseksi mahdollistaen prosessien kehittƤmisen kohti entistƤ kattavampia biojalostamoita..
Description
Supervising professor
SeppƤlƤ, Jukka, Prof., Aalto University, Department of Biotechnology and Chemical Technology, Finland
Keywords
Biopolymer, Biorefinery, Polyester, Polyanhydride, Biopolymeerit, Biojalostamo, Polyesteri, Polyanhydridi
Other note
Parts
  • [Publication 1]: Mehtiƶ, Tuomas; Toivari, Mervi; Wiebe, Marilyn G.; Harlin, Ali; PenttilƤ, Merja; Koivula, Anu. 2016. Production and applications of carbohydrate-derived sugar acids as generic biobased chemicals. Critical Reviews in Biotechnology, volume 36, issue 5, pages 904-916.
    DOI: 10.3109/07388551.2015.1060189 View at publisher
  • [Publication 2]: Mehtiƶ, Tuomas; Nurmi, Leena; RƤmƶ, Virpi; Mikkonen, Mikkonen; Harlin, Ali. 2015. Synthesis and characterization of copolyanhydrides of carbohydratebased galactaric acid and adipic acid. Carbohydrate Research, volume 402, pages 102ā€“110.
    DOI: 10.1016/j.carres.2014.07.009 View at publisher
  • [Publication 3]: Mehtiƶ, Tuomas; Nurmi, Leena; RƤmƶ, Virpi; Harlin, Ali; Ropponen, Jarmo. 2012. Copolymerization of glycolic, D,L-lactic and D,L-2-hydroxybutyric acid mixtures present in kraft black liquors. European Polymer Journal, volume 48, issue 4, pages 774ā€“778.
    DOI: 10.1016/j.eurpolymj.2012.01.010 View at publisher
  • [Publication 4]: RƤmƶ, Virpi; Anghelescu-Hakala, Adina; Nurmi, Leena; Mehtiƶ, Tuomas; SalomƤki, Alina; HƤrkƶnen, Mika; Harlin, Ali. 2012. Preparation of aqueous crosslinked dispersions of functionalized poly(D,L-lactic acid) with a thermomechanical method. European Polymer Journal, volume 48, issue 8, pages 1495ā€“1503.
    DOI: 10.1016/j.eurpolymj.2012.06.005 View at publisher
  • [Publication 5]: Mehtiƶ, Tuomas; Anghelescu-Hakala, Adina; Hartman, Jonas; Kunnari, Vesa; Harlin, Ali. Crosslinkable PLA-based materials ā€“ Biomass-derived solution for barrier coatings. Journal of Applied Polymer Science.
    DOI: 10.1002/app.44326 View at publisher
Citation