Furfuryl alcohol polymerization in H-Y confined spaces: reaction mechanism and structure of carbocationic intermediates.

The acid-catalyzed polymerization and resinification, in the 300-673 K interval, of furfuryl alcohol adsorbed in the framework of a protonic Y zeolite is studied by means of FTIR, Raman, and UV-vis spectroscopies. The idea is that restricted spaces can impose a constraint to the growth of the oligomeric chains, therefore moderating the formation of conjugated sequences responsible for the color of the products and allowing their observation by means of spectroscopic techniques. The detailed study of the evolution of UV-vis, FTIR, and Raman spectra upon dosed amount, contact time, and temperature has allowed the spectroscopic features of some of the single species, either neutral and positively charged (carbocationic intermediates), to be singled out and assigned to understand the mechanism of initiation. The vibrational assignments have been confirmed by computer simulations on model compounds and compared with the results of the mechanistic description of the reaction mechanism made in the past (Choura, et al. Macromolecules 1996, 29, 3839-3850). The spectroscopic methods have been applied in a large temperature range in order to follow also the formation of more complex products into the pores, associated with longer conjugated sequences, gradually filling the open spaces of the zeolite. For samples contacted with furfuryl alcohol at 673 K, this methodology gives information also on the incipient carbonization process, leading to the formation of a carbonaceous replica phase inside the internal porosity of the zeolite.