Constructing functional polyolefins through an iron catalyzed one-pot POLYmerization FUNctionalization strategy

Projektinformationen

POLYFUN

ID Finanzhilfevereinbarung: 101062863

DOI

10.3030/101062863

Projekt abgeschlossen

EK-Unterschriftsdatum 15 Juni 2022

Startdatum 1 Februar 2023

Enddatum 31 Dezember 2025

Finanziert unter

• Marie Skłodowska-Curie Actions (MSCA)

Gesamtkosten

Keine Daten

EU-Beitrag

€ 233 151,83

Koordiniert durch

CONSIGLIO NAZIONALE DELLE RICERCHE
Italy

Periodic Reporting for period 1 - POLYFUN (Constructing functional polyolefins through an iron catalyzed one-pot POLYmerization FUNctionalization strategy)

Berichtszeitraum: 2023-02-01 bis 2025-12-31

Zusammenfassung vom Kontext und den Gesamtzielen des Projekts

The modern chemical industry is facing a dual challenge: the urgent need to transition from fossil-based resources to renewable feedstocks and the requirement for more sustainable, cost-effective catalytic processes. Most current industrial plastic production and chemical transformations rely on expensive, and often toxic, noble metal catalysts. This project was born from the necessity to replace these systems with earth-abundant, non-toxic, and inexpensive transition metals, specifically focusing on iron-based catalysis.
The primary objective of the research was to develop a versatile chemical "toolbox" based on iron complexes to transform both traditional olefins and bio-derived molecules into high value functional materials. By using natural terpenes, such as beta-myrcene, which can be extracted from plants, the project aimed to create a new generation of bio based polymers. This approach directly addresses the European strategic priority of the Circular Bioeconomy, which seeks to reduce carbon footprints by substituting petroleum-derived components with sustainable alternatives.
The project pathway to impact was designed to bridge the gap between fundamental organometallic chemistry and practical materials science. The motivation was not only to synthesize new polymers but to understand how changing the metal center could radically alter the internal structure and properties of a polymer. This level of control is crucial for designing materials with specific mechanical and thermal characteristics for industrial applications, ranging from high-performance elastomers to sustainable coatings.

Arbeit, die ab Beginn des Projekts bis zum Ende des durch den Bericht erfassten Berichtszeitraums geleistet wurde, und die wichtigsten bis dahin erzielten Ergebnisse

The project successfully established a sustainable catalytic platform based on iron, neodymium, and copper complexes stabilized by imino-pyridine ligands. The research initially focused on the molecular design and structural characterization of these catalysts, which were then applied to the polymerization of bio-based monomers like beta-myrcene. A major scientific achievement was the discovery of a metal-dependent stereoselectivity: while neodymium catalysts produced highly regular cis-1,4 polymers, the iron and copper analogues led to an unprecedented alternating cis-1,4-alt-3,4 microstructure. These results, which demonstrate the high degree of structural control achievable with non-precious metals, were published in Polymer Chemistry (2024).When technical barriers arose during the post-polymerization functionalization phase, the project was strategically redirected toward a novel Iron-Mediated Hydrogen Atom Transfer (MHAT) polymerization strategy. Using a commercially available catalyst, I successfully demonstrated that radicals could be generated from electron-poor olefins. This innovative methodology allowed for the efficient polymerization of acrylates and was published in Polymer Chemistry (2025) with the fellow as corresponding author. Finally, a comprehensive study of the polymers thermal and mechanical properties established a clear correlation between molecular weight and material performance, specifically in terms of tensile strength and elasticity, proving the potential of these sustainable catalytic systems for industrial applications.

Fortschritte, die über den aktuellen Stand der Technik hinausgehen und voraussichtliche potenzielle Auswirkungen (einschließlich der bis dato erzielten sozioökonomischen Auswirkungen und weiter gefassten gesellschaftlichen Auswirkungen des Projekts)

not applicable