Surface Modifications: from Heterogeneous Catalysis in Nitrogen Heterocycles Synthesis to Polymer Nanocomposites Interface Design

Research reported in this thesis was carried out thanks to a strong partnership between the laboratory of organic chemistry of Prof. Enrico Marcantoni at the University of Camerino and R and D laboratory of Delta S.r.l. in Montecassiano. It was conducted between January 2012 and December 2013 and between August 2014 and December 2014 in the laboratory of Prof. Enrico Marcantoni at the University of Camerino and in the R and D laboratory of Delta S.r.l. in Montecassiano. Research conducted during the visiting period (January 2014 August 2014) at the Prof. Brian Benicewicz research group at University of South Carolina, Columbia, SC (USA) is also presented. The work concerns two main fields, divided in polymer and organic synthesis, sharing a common leitmotif, namely the importance of surface's modification both in heterogeneous catalysis for heterocycles synthesis and in the design and preparation of polymer nanocomposites. In the first part a brief overview over Controlled Radical Polymerization (CRP) techniques is given, displaying main techniques the advantages they brought to polymer chemistry and also relative limitations. This section is followed by a deeper focus on Reversible Addition Fragmentation Chain Transfer polymerization (RAFT), its mechanism and the role and importance of the Chain Transfer Agent (CTA). Furthermore, applications of RAFT to surface modification are described and the importance of these modifications on interface science in polymer nanocomposites chemistry is reported. In particular are herein reported studies over 2-vinylpyridine and 4-vinylpyridine RAFT polymerization and more attention has been paid to kinetics of RAFT solution polymerization and RAFT surface initiated polymerization reaction of both monomers. Are herein reported successful synthesis and characterization of monomodal P2VP-g-SiO2 and bimodal P2VP-g-SiO2-g-PS polymer brushes. In the second part, the importance of the interface modification theme is followed from the organic synthesis point of view. Key features of heterogeneous catalysis are briefly reported, followed by examples and explanation of heterogeneous catalysis given by cerium-based promoting systems in many organic reactions. In particular we focused onto the application of an innovative Ce(III)/Cu(I) cooperative system in the synthesis of nitrogen containing heterocycles. With this purpose, procedures involving this cocatalyzed reaction are reported in the preparation of several benzimidazoles and dihydropyridones moieties containing heterocycles.