Synthesis and Catalytic Applications of Novel Thiolated and Sulfonated Polymers Resulting by Functionalization of Multiblock Syndiotactic Polystyrene-co-1,4-cis-Polybutadiene

IND-OR-18 Synthesis and Catalytic Applications of Novel Thiolated and Sulfonated Polymers Resulting by Functionalization of Multiblock Syndiotactic Polystyrene-co-1,4-cis-Polybutadiene. Antonio Buonerba,a Rosa Vitiello,b Martino Di Serio,b Alfonso Grassi,a Elio Santacesariab a Dipartimento di Chimica e Biologia, Università degli Studi di Salerno, via Ponte don Melillo, 84084 Fisciano (SA), Italy b Dipartimento di Chimica, Università di Napoli “Federico II”, Via Cinthia, 80126 Napoli, Italy abuonerba@unisa.it Hydrocarbon polymers carrying side chain functional groups are attractive materials because of their specific chemical reactivity or physicochemical properties. Their direct synthesis by copolymerization of suitable monomers is often impracticable because of incompatibility of the transition metal catalysts with the polar monomers; thus postfunctionalization is often required to yield these polymer products of interest. In this work the controlled radical thioacetylation of polybutadiene segments in multiblock copolymers syndiotactic polystyrene-co-1,4-cispolybutadiene (sPSB) is described. sPSB are semicrystalline polymers (Tg = 100°C, Tm = 250°C) which exhibit, when shaped as thin film by spin coating, a phase separated morphology, ranging from irregular hard lamellae of sPS in PB to spheres of PB embedded into the sPS phase[1]. The selective functionalization of the PB domains by thioacetylation followed by thioester cleavage lead to thiol functionalized sPSB (sPSB-T). The direct thioester oxidation by in situ synthesized performic acid leads to sulfonated sPSB (sPSB-SA) in quantitative yield. sPSB-SAs with high degree of sulfonation were successful tested as strongly acidic catalysts in esterification reactions. [1] a) A.Buonerba, C.Cuomo, V.Speranza, A.Grassi, Macromolecules 43, 2010, 367; b) C.Cuomo, M.C.Serra, M.Gonzalez Maupoey, A.Grassi, Macromolecules 40, 2007, 7089.