Steering polymer growth by molding nanochannels: 1,5-hexadiene polymerization in high silica mordenite

Marco Fabbiani (1, 2) , Giorgia Confalonieri (3) , Sara Morandi (1, 2) , Rossella Arletti (3) , Simona Quartieri (3) , Mario Santoro (4) , Francesco Di Renzo (5) , Julien Haines (5) , Riccardo Fantini (3) , Gloria Tabacchi (6) , Ettore Fois (6) , Giovanna Vezzalini (3) , Gabriele Ricchiardi (1, 2) , Gianmario Martra (1, 2)

1 University of Torino, Department of Chemistry
2 NIS - University of Torino, Interdepartmental Centre “Nanostructured Interfaces and Surfaces”
3 Department of Chemical and Geological Siences, University of Modena and Reggio-Emilia
4 National Institute of Optics (CNR-INO), National Research Council - Florence, Italy
5 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
6 Uninsubria - Universitá degli Studi dell’Insubria = University of Insubria [Varese]

Zeolites are known as scaffolds for the assembly of molecules via non-covalent interactions yielding organized supramolecular materials. Yet their potential in driving the growth of lowdimensional systems requiring covalent bond formation is still unexplored. We incorporated 1,5hexadiene in the channels of a high-silica mordenite and analyzed the material by infrared spectroscopy, X-ray powder diffraction, thermogravimetry and modeling techniques. Due to the few zeolite acid sites, 1,5-hexadiene experiences a slow conversion to a polymer mainly formed by cyclopentane units and featuring short side chains that are able to fit the channels. The shapedirecting abilities of zeolite frameworks play a twofold role, involving first the organization of the monomers inside the void-space and then the linear growth of the chain dictated by the channel geometry. These findings highlight the molding action of zeolites in directing transformations of covalent bonds under ambient conditions and may provide insights for obtaining confined polymers with intriguing prospective applications.

Domaines: Matériaux; Polymères

Marco Fabbiani, Giorgia Confalonieri, Sara Morandi, Rossella Arletti, Simona Quartieri, et al.. Steering polymer growth by molding nanochannels: 1,5-hexadiene polymerization in high silica mordenite. Microporous and Mesoporous Materials, 2021, 311, pp.110728. ⟨10.1016/j.micromeso.2020.110728⟩. ⟨hal-03002032⟩