“Monomer Carbonization for Polymer Decarbonization”

The utilization of CO₂ as a monomer feedstock is a strategy for valorizing carbon capture, reducing polymer feedstock costs, and introducing new function into polymer materials. However, the activation of CO₂ with high-energy comonomers often merely moves the emissions around and the pursuit of ‘carbon-negative’ materials remains elusive through these strategies (1). Recently, the telomerization of CO₂ and butadiene has emerged as a potential carbon-negative, low-cost, and highly reactive monomer (2). This talk will describe our discoveries into the polymerization and divergent mechanisms in these unsaturated lactones towards useful polymeric materials (3,4). Armed with the mechanistic understanding, we can now control the pathways for tuning thermomechanical properties. When appropriately controlled this monomer feedstock can afford low T_g (-40 °C) elastomers, high strength thermosets (stress at break = 40 MPa), recyclable carbonfiber composites (flexural modulus = 40 GPa), and biodegradable plastics (5). 

1.  M. Bachmann, C. Zibunas, J. Hartmann, V. Tulus, S. Suh, G. Guillén-Gosálbez, A. Bardow, Towards Circular Plastics Within Planetary Boundaries. Nat. Sustain. 2023, 6, 599–610.

2.  S. Tang, B. Lin, I. Tonks, J. M. Eagan, X. Ni, K. Nozaki. Sustainable Copolymer Synthesis from Carbon Dioxide and Butadiene. Chem. Rev. 2024, doi.org/10.1021/acs.chemrev.3c00847.

3.  J. M. Eagan. The Divergent Reactivity of Lactones Derived from Butadiene and Carbon Dioxide in Macromolecular Synthesis. Macromol. Rapid. Commun. 2022, doi.org/10.1002/marc.202200348.

4.  B. J. Crawford, C. Bochenek, L. D. Garcia Espinosa, A. R. Keating, K. Williams-Pavlantos, C. Wesdemiotis, J. M. Eagan. Anionic Conjugate Addition Oligomerization of Carbon Dioxide/Butadiene Derived Lactones. ACS Macro Lett., 2024, 13, 658–663.

5.  J. M. Eagan, L. D. Garcia Espinosa. Degradable polymer structures from carbon dioxide and olefin and corresponding method. US20220073675A1