Steering polymer growth by molding nanochannels: 1,5-hexadiene polymerization in high silica mordenite
Authors: Fabbiani M., Confalonieri G., Morandi S., Arletti R., Quartieri S., Santoro M., Di Renzo F., Haines J., Fantini R., Tabacchi G., Fois E., Vezzalini G., Ricchiardi G., Martra G.
Autors Affiliation: Department of Chemistry, University of Torino, Via Pietro Giuria 7, Torino, 10125, Italy; Interdepartmental Centre “Nanostructured Interfaces and Surfaces” – NIS, University of Torino, Via Pietro Giuria 7, Torino, 10125, Italy; Department of Chemical and Geological Sciences, University of Modena e Reggio Emilia, Via Campi 103, Modena, 41125, Italy; National Institute of Optics CNR-INO and European Laboratory for Non Linear Spectroscopy LENS, Via Nello Carrara 1, Sesto Fiorentino, 50019, Italy; ICGM, University of Montpellier, CNRS, ENSCM, Place Eugine Bataillon, Montpellier, 34095, France; Department of Science and High Technology and INSTM, University of Insubria, Via Valleggio 9, Como, 22100, Italy
Abstract: 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 low-dimensional systems requiring covalent bond formation is still unexplored. We incorporated 1,5-hexadiene 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 shape-directing abilities of zeolite frameworks play a two-fold 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.
Journal/Review: MICROPOROUS AND MESOPOROUS MATERIALS
Volume: 311 Pages from: 110728-1 to: 110728-8
More Information: This work was carried out in the framework of the PRIN project ZAPPING (PRIN2015 Prot.2015HK93L7) funded by the Italian MIUR. FAR2018 Uninsubria is acknowledged for funding.KeyWords: Zeolite; Polymerization; Nanostructure; Density functional calculation; X-ray diffractionDOI: 10.1016/j.micromeso.2020.110728