Taking advantage of the structural diversity of different biomass resources, recent efforts were directed towards the synthesis of renewable monomers and polymers, either for the substitution of petroleum-based resources or for the design of novel polymers. Not only the use of biomass, but also the development of sustainable chemical approaches is a crucial aspect for the production of sustainable materials. This review discusses the recent examples of chemical modifications and polymerizations of abundant biomass resources with a clear focus on the sustainability of the described processes. Topics such as synthetic methodology, catalysis, and development of new solvent systems or greener alternative reagents are addressed. The chemistry of vegetable oil derivatives, terpenes, lignin, carbohydrates, and sugar-based platform chemicals was selected to highlight the trends in the active field of a sustainable use of renewable resources.

A novel strategy is demonstrated to obtain polyamides with finely tunable structure using the Ugi fourcomponent reaction (Ugi-4CR). By the use of two bifunctional and two monofunctional components, six different combinations for the synthesis of polyamides via the Ugi-4CR are possible and were investigated in detail within this contribution. In contrast to conventional polyamide synthesis, this approach proceeds under very mild reaction conditions and without the use of a catalyst in a one-pot reaction. General applicability is shown by variation of the components, leading to finely tuned macromolecular structures (i.e., side groups and repeat units can be engineered). Finally, a facile introduction of clickable alkyne moieties is demonstrated, which was used for post-polymerization modification in an azide−alkyne cycloaddition, in order to demonstrate the high versatility of this approach.

Aliphatic long‐chain polyesters are a common class of renewable polymers and can be obtained by various synthetic routes, most notably from renewable fatty acids. In contrast, for aliphatic long chain polyethers only a few examples are known. Recently, the GaBr3‐catalyzed reduction of esters to ethers has been introduced as convenient post‐polymerization modification to obtain polyethers directly from polyesters. Here, this reduction is applied to synthesize fatty acid–based ω,ω′‐unsaturated diene diether monomers, which are polymerized afterward by thiol‐ene or acyclic diene metathesis (ADMET) polymerizations in the “green” solvents methyl‐THF (2‐methyltetrahydrofuran) and polarclean. After polymerization, the thiol‐ene or ADMET polymers are modified by either oxidation or hydrogenation, respectively.

Herein, a novel approach is reported for the synthesis of medium- and long-chain aliphatic polyethers 2 based on the GaBr -catalysed reduction of polyesters 1 with TMDS as the reducing agent. Thus, various linear and branched aliphatic polyesters 1 were prepared and systematically investigated for this reduction strategy, demonstrating the applicability and versatility of this new polyether synthesis protocol. Medium- and long-chain chain polyethers were obtained from the respective polyesters without or with minor chain degradation, whereas short-chain polyesters, such as poly-l-lactide 1 i and poly[(R)-3-hydroxybutanoate] 1 j, showed major chain degradation. In this way, previously unavailable and uncommon polyethers were obtained and studied.

Efficient synthesis of valuable platform chemicals from renewable feedstock is a challenging, yet essential strategy for developing technologies that are both economical and sustainable. In the present study, we investigated the synthesis of 2,5-furandicarboxylic acid (FDCA) in a two-step catalytic process starting from sucrose as largely available biomass feedstock. In the first step, 5-(hydroxymethyl)furfural (HMF) was synthesized by hydrolysis and dehydration of sucrose using sulfuric acid in a continuous reactor in 34% yield. In a second step, the resulting reaction solution was directly oxidized to FDCA without further purification over a Au/ZrO2 catalyst with 84% yield (87% selectivity, batch process), corresponding to 29% overall yield with respect to sucrose. This two-step process could afford the production of pure FDCA after the respective extraction/crystallization despite the impure intermediate HMF solution. To demonstrate the direct application of the biomass-derived FDCA as monomer, the isolated product was used for Ugi-multicomponent polymerizations, establishing a new application possibility for FDCA. In the future, this efficient two-step process strategy toward FDCA should be extended to further renewable feedstock.