Biobased chiral semi-crystalline or amorphous high-performance polyamides and their scalable stereoselective synthesis

• Published in: Nature communications 2020-01, Vol.11 (1), p.509-509, Article 509
• Main Authors: Stockmann, Paul N., Van Opdenbosch, Daniel, Poethig, Alexander, Pastoetter, Dominik L., Hoehenberger, Moritz, Lessig, Sebastian, Raab, Johannes, Woelbing, Marion, Falcke, Claudia, Winnacker, Malte, Zollfrank, Cordt, Strittmatter, Harald, Sieber, Volker
• Format: Article
• Language: English
• Subjects: 3-Carene; 639/638/403/935; 639/638/455/953; 639/638/455/958; 639/638/549/941; Caprolactam; Catalysis; Cellulose; Chemical synthesis; Chromatography, Gel; Conversion; Crystal structure; Crystallinity; Crystallization; Crystallography, X-Ray; Green chemistry; Humanities and Social Sciences; Lactams - chemistry; Macromolecules; Magnetic Resonance Spectroscopy; Molecular Conformation; multidisciplinary; Nylons - chemical synthesis; Nylons - chemistry; Organic chemistry; Oxidation; Polyamide resins; Polyamides; Polymerization; Polymers; Production costs; Science; Science (multidisciplinary); Stereoisomerism; Stereoselectivity; Temperature; Thermal properties; Thermodynamic properties
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-020-14361-6

The use of renewable feedstock is one of the twelve key principles of sustainable chemistry. Unfortunately, bio-based compounds often suffer from high production cost and low performance. To fully tap the potential of natural compounds it is important to utilize their functionalities that could make them superior compared to fossil-based resources. Here we show the conversion of (+)-3-carene, a by-product of the cellulose industry into ε-lactams from which polyamides. The lactams are selectively prepared in two diastereomeric configurations, leading to semi-crystalline or amorphous, transparent polymers that can compete with the thermal properties of commercial high-performance polyamides. Copolyamides with caprolactam and laurolactam exhibit an increased glass transition and amorphicity compared to the homopolyamides, potentially broadening the scope of standard polyamides. A four-step one-vessel monomer synthesis, applying chemo-enzymatic catalysis for the initial oxidation step, is established. The great potential of the polyamides is outlined. Bio‐based compounds often suffer from high production cost and low performance when used to synthesise macromolecules. Here the authors show the conversion of (+)‐3‐ carene, a by‐product of the cellulose industry, into its ε‐lactams and then to polyamides with high‐performance thermal properties.