The Mechanics Ruling Polymerizations for a Greener Sustainable Future

Here we summarize theoretical investigations on the mechanisms of polymerization of monomers presenting a polar group promoted by metal-based and metal-free catalysts (Figure 1). The monomers that will be considered will span from methacrylates,^1,2 to methlyene butyrolactones,^3,4 to lactones, to epoxides.⁵ Attention will be focused on the formation of the active species, as well as on the mechanism of chain initiation, growth and termination. The origin of selectivity in the stereoselective polymerization of monomers of the methacrylate family and of epoxides will be also explained. The metal-based catalysts that will be considered include zirconocenes^1,2 and lanthanides,^4,7,9 while the metal-free catalysts used in the organopolymerization include N-heterocyclic carbenes^3,8,10 and N-heterocyclic olefins.⁶

Figure 1. Monomers that will be considered in this presentation.

References

[1] X. Chen, L. Caporaso, L. Cavallo, E. X.-Y. Chen, J. Am. Chem. Soc. 2012, 134, 7278.

[2] F. Vidal, L. Falivene, L. Caporaso, L. Cavallo, E. X.-Y. Chen, J. Am. Chem. Soc. 2016, 138, 9533.

[3] M. Hong, H. Tang, L. Falivene, L. Caporaso, L. Cavallo, E.Y.-X. Chen, J. Am. Chem. Soc. 2016, 138, 2021.

[4] Tang, X.; Hong, M.; Falivene, L.; Caporaso, L.; Cavallo, L.; Chen, E. Y.-X. J. Am. Chem. Soc. 2016, 138, 14326.

[5] Ahmed, S. M.; Poater, A.; Childers, M. I.; Widger, P. C. B.; LaPointe, A. M.; Lobkovsky, E. B.; Coates, G. W.; Cavallo, L. J. Am. Chem. Soc. 2013, 135, 18901.

[6] Naumann, S.; Mundsinger, K.; Cavallo, L.; Falivene, L. Polym. Chem. 2017, 8, 5803.

[7] Tang, X.; Westlie, A. H.; Caporaso, L.; Cavallo, L.; Falivene, L.; Chen, E. Y.-X. Angew. Chem. 2020, 59, 7881-7890.

[8] Shi, C.; McGraw, M. L.; Li,Z. C.; Cavallo, L.; Falivene, L.; Chen, E. YT.-X. Sci. Adv. 2020, 6, eabc0495

[9] Shi, C.; Li, Z. C.; Caporaso, L.; Cavallo, L.; Falivene, L.; Chen, E. Y.-X. Chem 2021, 7, 670-685

[10] McGraw, M. L.; Reilly, L. T.; Clarke, R. W.; Cavallo, L.; Falivene, L.; Chen, E. Y.-X. Angew. Chem. Int. Ed. 2022, 61, e202116303

Speakers

Luigi Cavallo

KAUST

KAUST Research Centers

KCC Research Groups