Design of a green chemoenzymatic cascade for scalable synthesis of bio-based styrene alternatives

authored by

Philipp Petermeier, Jan Philipp Bittner, Simon Müller, Emil Byström, Selin Kara

Abstract

As renewable lignin building blocks, hydroxystyrenes are particularly appealing as either a replacement or addition to styrene-based polymer chemistry. These monomers are obtained by decarboxylation of phenolic acids and often subjected to chemical modifications of their phenolic hydroxy groups to improve polymerization behaviour. Despite efforts, a simple, scalable, and purely (chemo)catalytic synthesis of acetylated hydroxystyrenes remains elusive. We thus propose a custom-made chemoenzymatic route that utilizes a phenolic acid decarboxylase (PAD). Our process development strategy encompasses a computational solvent assessment informing about solubilities and viable reactor operation modes, experimental solvent screening, cascade engineering, heterogenization of biocatalyst, tailoring of acetylation conditions, and reaction upscale in a rotating bed reactor. By this means, we established a clean one-pot two-step process that uses the renewable solvent CPME, bio-based phenolic acid educts and reusable immobilised PAD. The overall chemoenzymatic reaction cascade was demonstrated on a 1 L scale to yield 18.3 g 4-acetoxy-3-methoxystyrene in 96% isolated yield.

Organisation(s)

Institute of Technical Chemistry

External Organisation(s)

Hamburg University of Technology (TUHH)
Aarhus University
SpinChem AB

Type

Article

Journal

Green chemistry

Volume

24

Pages

6889-6899

No. of pages

11

ISSN

1463-9262

Publication date

08.08.2022

Publication status

Published

Peer reviewed

Yes

Sustainable Development Goals

SDG 7 - Affordable and Clean Energy

Electronic version(s)

https://doi.org/10.1039/d2gc01629j (Access: Open)