Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction

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Abstract

Six-membered cyclic carbonates with hydroxyl and methoxycarbonyloxy functional groups were prepared by transesterification of trimethylolpropane (TMP) with dimethylcarbonate (DMC) by solvent-free lipase-mediated flow reaction followed by thermal cyclization. The flow reaction efficiency was evaluated using different configurations of reactor consisting of packed beds of Novozym 435 (immobilized Candida antarctica lipase B—CalB—a.k.a. N435) and molecular sieves, flow rate, and biocatalyst loads. The mixed column of the bio-catalyst and molecular sieves, allowing rapid and efficient removal of the by-product—methanol—was the most efficient setup. Higher conversion (81.6%) in the flow reaction com-pared to batch process (72%) was obtained using same amount of N435 (20% (w/w)N435:TMP) at 12 h, and the undesirable dimer and oligomer formation were suppressed.Moreover, the product was recovered easily without extra separation steps, and the biocatalyst and the molecular sieves remained intact for subsequent regeneration and recycling.The reaction of CalB with DMC and the primary transesterification product, monocarbonated TMP, respectively, as acyl donors was evaluated by in silico modeling and empirically to determine the role of the enzyme in the formation of cyclic carbonates and other side products. DMC was shown to be the preferred acyl donor, suggesting that TMP and its carbonated derivatives serve only as acyl acceptors in the lipase-catalyzed reaction. Subsequent cyclization to cyclic carbonate is catalyzed at increased temperature and not by the enzyme.

Detaljer

Författare
Enheter & grupper
Externa organisationer
  • Helwan University
  • Lund University
Forskningsområden

Ämnesklassifikation (UKÄ) – OBLIGATORISK

  • Industriell bioteknik
Originalspråkengelska
Sidor (från-till)375-382
Antal sidor8
TidskriftBiotechnology Progress
Volym33
Utgivningsnummer2
StatusPublished - 2017
PublikationskategoriForskning
Peer review utfördJa