Thermoremendable Styrenic Polymers by Controlled Radical Copolymerization of Styrene with bioderived 2-vinylfuran

Thermoremendable Styrenic Polymers by Controlled Radical Copolymerization of Styrene with bioderived 2-vinylfuran A. Grassi,* A. Buonerba, C. Capacchione, S. Milione Department of Chemistry and Biology “Adolfo Zambelli”, University of Salerno – Italy CIRCC - Interuniversity Consortium on Chemical Reactivity and Catalysis *Corresponding author: agrassi@unisa.it Keywords: Biosourced olefins, functional olefin copolymer, furan-maleimide Diels Alder reaction. Abstract 2-vinylfuran (2VF) is a bioderived olefin synthesized by Peterson methylenation of furfural, a cheap platform molecule resulting from acid catalyzed hydrolysis and dehydration of pentosanes from lignocellulosic biomass. Ideal ATR copolymerization of styrene with 2VF yielded random copolymers (S-co-2VFs) in a wide range of composition and high monomer conversion.[1] The S-co-2VFs are stable for years in solution and solid state at room temperature; radical oxidation of the furan moieties starts in air at temperature higher than 120°C whereas thermal degradation occurs at 380°C. Diels Alder (DA) cycloaddition reaction of S-co-2VFs with bismaleimide (BMI) produces thermorevesible crosslinks: the thermodynamic and kinetic parameters of this reaction were investigated by NMR and FT-IR spectroscopy to assess the optimal condition for high crosslink degree and self healing conditions. The mechanical properties of the S-co-2VFs, before and after reaction with BMI, were compared using INSTRON analysis and nanoidentation of polymeric thin films by Atomic Force Microscopy.[2] Moreover simple thermal treatment of mechanically fractured films of S-co-2VFs reacted with BMI allowed full repairing in 80 min (Figure 1). Scheme. Diels Alder reaction of S-co-2VFs with BMI. Figure 1. Fractured (a) and healed (b) polymer film of S-co-2VF crosslinked with BMI after thermal annealing at 150°C. References [1] S. Ortega Sáncheza, F. Marra, A. Dibenedetto, M. Aresta, A. GrassiMacromolecules 2014, 47, 7129−7137. [2] A. Grassi, A. Buonerba, C. Capacchione, S. Milione ACS National Meeting San Diego (USA) 2016.