Sustainable Polymer Synthesis

Polymers are ubiquitous in our daily life and are an essential part of various technologies. To cope with further challenges concerning the polymer production, such as greenhouse gas emissions, environmental pollution and waste generation, innovative solutions are aimed for in polymer research. To contribute to this, we focus on the use of renewable resources, the use of less hazardous reaction conditions during the synthesis, such as in the development of non-isocyanate polyurethanes, the use of catalysts, and the use of atom-economic multi-component reactions.

Non-Isocyanate Polyurethanes

With polyurethanes representing an abundant polymer material with various applications e.g. in coatings, more sustainable synthesis routes without the need of hazardous phosgene and isocyanates are desirable. In our group, we investigate the access to non-isocyanate polyurethanes (NIPUs) by different approaches such as opening of cyclic carbonates or by rearrangement reactions. The resulting materials show promising properties for applications in polymer materials.

Working on this topic: Francesca Destaso, Nicollas Jaques, Celeste Libretti, Federico Mundo, Luca Narducci, Clara Scheelje

Recent publications

Scheelje, F. C. M.; Meier, M. A. R. (2023). Non-isocyanate polyurethanes synthesized from terpenes using thiourea organocatalysis and thiol-ene-chemistry. Communications Chemistry, 6 (1), Art.-Nr.: 239. doi:10.1038/s42004-023-01041-x

Scheelje, F. C. M.; Destaso, F. C. C.; Cramail, H.; Meier, M. A. R. (2022). Nitrogen‐Containing Polymers Derived from Terpenes: Possibilities and Limitations. Macromolecular Chemistry and Physics, 224 (3), Art.-Nr.: 2200403. doi:10.1002/macp.202200403

Kirchberg, A.; Khabazian Esfahani, M.; Röpert, M.-C.; Wilhelm, M.; Meier, M. A. R. (2022). Sustainable Synthesis of Non‐Isocyanate Polyurethanes Based on Renewable 2,3‐Butanediol. Macromolecular Chemistry and Physics, 223 (13), Art.-Nr.: 2200010. doi:10.1002/macp.202200010

Earlier fundamental contributions

Llevot, A.; Meier, M. (2019). Perspective: green polyurethane synthesis for coating applications. Polymer international, 68 (5), 826–831. doi:10.1002/pi.5655

Kreye, O.; Mutlu, H.; Meier, M. A. R. (2013). Sustainable routes to polyurethane precursors. Green Chemistry, 15 (6), 1431–1455. doi:10.1039/c3gc40440d

Sustainable Catalysis

The use of catalysts in chemical syntheses is of essential importance to develop more sustainable processes. As an example, small organic molecules can serve as homogeneous catalysts. In our group, we use thiourea catalysts obtained via a more sustainable synthesis approach to enable a selective functionalization of various materials. Also catalyst screening and optimization for specific tasks in the transformation of renewable substrate are performed.

Working on this topic: Andreas Ganzbuhl, Anja Kirchberg, Luis Santos Correa, Clara Scheelje

Recent publications

Kirchberg, A.; Wegelin, S.; Grutke, J.; Meier, M. A. R. (2024). Unexpected performance of iron( iii )chloride in the polymerization of renewable 2,3-butanediol and the depolymerization of poly(ethylene terephthalate). RSC Sustainability. doi:10.1039/D3SU00388D

Scheelje, F. C. M.; Meier, M. A. R. (2023). Non-isocyanate polyurethanes synthesized from terpenes using thiourea organocatalysis and thiol-ene-chemistry. Communications Chemistry, 6 (1), Art.-Nr.: 239. doi:10.1038/s42004-023-01041-x

Nickisch, R.; Gabrielsen, S. M.; Meier, M. A. R. (2020). Novel Access to Known and Unknown Thiourea Catalyst via a Multicomponent-Reaction Approach. ChemistrySelect, 5 (38), 11915–11920. doi:10.1002/slct.202003336

Multi-Component Reactions in Polymer Synthesis

In a multi-component reaction (MCR), three or more starting materials react in a one-pot reaction to a single product, incorporating most of the atoms. Due to their advantage in experimental simplicity, typically high yields, and simple purification protocols compared to conventional multistep synthesis, MCRs can be considered as ideal reactions. This way, highly complex architectures are accessible in a single reaction step, making MCRs powerful tools in organic chemistry, especially in combinatorial chemistry and drug discovery, and recently also in polymer chemistry. In our group, we focus on isocyanide-based MCRs (Passerini and Ugi reaction) or the Biginelli reaction to modify biopolymers, such as cellulose and starch, to build up sequence defined macromolecules, or renewable polymers. Furthermore, the use of elemental sulfur in MCRs offers the possibility to sustainably produce sulfur-containing building blocks and polymers.

Working on this topic: Philipp Bohn, Sandra Wegelin, Jiangling (Caitlyn) Liu

Recent publications

Wegelin, S.; Meier, M. A. R. (2023). Solution Self‐Assembly of Branched Macromolecules Obtained via Iterative OPE Synthesis and the Passerini Three‐Component Reaction. Macromolecular Chemistry and Physics. doi:10.1002/macp.202300337

Wolfs, J.; Ribca, I.; Meier, M. A. R.; Johansson, M. (2023). Polythionourethane Thermoset Synthesis via Activation of Elemental Sulfur in an Efficient Multicomponent Reaction Approach. ACS Sustainable Chemistry and Engineering, 11 (9), 3952–3962. doi:10.1021/acssuschemeng.3c00143

Windbiel, J. T.; Meier, M. A. R. (2022). RAFT Polymerization of a Renewable Ricinoleic Acid-Derived Monomer and Subsequent Post-Polymerization Modification via the Biginelli-3-Component Reaction. Macromolecular Chemistry and Physics, 223 (12), Art. Nr.: 2100360. doi:10.1002/macp.202100360

Nickisch, R.; Conen, P.; Meier, M. A. R. (2022). Polythiosemicarbazones by Condensation of Dithiosemicarbazides and Dialdehydes. Macromolecules, 55 (8), 3267–3275. doi:10.1021/acs.macromol.2c00409

Earlier fundamental contributions

Wolfs, J.; Nickisch, R.; Wanner, L.; Meier, M. A. R. (2021). Sustainable One-Pot Cellulose Dissolution and Derivatization via a Tandem Reaction in the DMSO/DBU/CO2 Switchable Solvent System. Journal of the American Chemical Society, 143 (44), 18693−18702. doi:10.1021/jacs.1c08783

Kreye, O.; Tóth, T.; Meier, M. A. R. (2011). Introducing Multicomponent Reactions to Polymer Science: Passerini Reactions of Renewable Monomers. Journal of the American Chemical Society, 133 (6), 1790–1792. doi:10.1021/ja1113003