DS0204 - Conversion des ressources primaires en carburants et molécules plateforme, chimie du carbone

Carbon Dioxide Activation to produce monomers and carboxylated molecules – CaDiAc

Submission summary

Syntheses of lactones and acrylates from carbon dioxide and alkenes allow access to sustainable monomers that can be further polymerized into high-tonnage and/or biodegradable materials. Featuring tunable mechanical properties, these plastics yield materials used in numerous applications. A new iron-based catalysis allows for the use of carbon dioxide CO2 as raw material, and alkenes as reactive counterparts. CO2 has never been copolymerized with alkenes. Yet it is far more attractive than carbon monoxide–used to synthesize polyketones with alkenes. The activation of CO2 at the iron catalyst triggers an oxidative coupling with an alkene partner. The formation of a metalla-lactone ensues. The corresponding irona-lactone can be further derivatized into acrylic acid or cyclic ester derivatives. An extension to the carboxylation of complex molecules is foreseen. Sustainability is at the center of CaDiAc. We believe that this iron-catalyzed carboxylation method will find an industrial application.
The bottleneck of the copolymerization of CO2 and olefins and/or dienes is the unfavorable thermodynamics that hamper its implementation. In the CaDiAc project, we propose to circumvent this issue by rather proposing the synthesis of easily polymerizable monomers composed exclusively of CO2 and olefins and/or dienes. In the case of CO2 and ethylene for instance, we will synthesize acrylic acid (as a carboxylate salt to render the DeltarG<<0), whereas for CO2 and butadiene, we target 5- and 6- membered lactones (potentially involving 2 diene molecules for 1 of CO2). Both these classes of monomers are readily polymerized by industrial techniques, notably conventional radical polymerization.
The CaDiAc project aims at answering the need for new technologies valorizing carbon dioxide, an ever-growing waste though potential raw material. In order to address this societal challenge, we propose an atom-economical method involving catalysis, and utilizing carbon dioxide directly as a resource without altering the oxidation state at the carbon center. This strategy will allow us to minimize chemical transformations, thus overall energetic costs. The envisioned catalysis also abides the sustainability principle, revolving around iron as a key metal. Moreover, the synthetic targets are high-tonnage classes of monomers (and synthetic intermediates) that provide access to extremely ubiquitous polymers (polyacrylics and polyesters), with in the case of unsaturated polyesters a potential for biodegradability and/or bioassimilation.
The interest of the CaDiAc project is therefore twofold. Firstly, it will provide a new straightforward access to a wide range of high-tonnage chemicals. Secondly, it will contribute to the development of iron catalysis and its application to synthetic methodology.
The C2P2 laboratory (UMR 5265) possesses all the equipment and expertise necessary for the realization of this ANR JC project which will be undertaken during the course of a PhD. The gathered team of researchers will proceed according 4 main tasks: 1) synthesis and characterization of iron complexes; 2) development of catalysis; 3) production and use of synthesized monomers; 4) development of carboxylation methodology. All work packages and deliverables are further discussed into the corresponding scientific document.

Project coordination

Jean RAYNAUD (Laboratoire Chimie Catalyse Procédés Polymerisation)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

C2P2 - LCPP - UMR5265 - CNRS - Univ. Lyon 1 - CPE Lyon Laboratoire Chimie Catalyse Procédés Polymerisation

Help of the ANR 224,120 euros
Beginning and duration of the scientific project: September 2015 - 42 Months

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