ATR Copolymerization of Styrene with 2‑Vinylfuran: An Entry to Functional Styrenic Polymers Sheila Ortega Sa ́ nchez, †,‡ Francesco Marra, § Angela Dibenedetto, ∥ Michele Aresta, ‡ and Alfonso Grassi* ,† † Dipartimento di Chimica e Biologia and NANO_MATES Research Centre for NANOMAterials and NanoTEchnology, Universita ̀ degli Studi di Salerno, Via Giovanni Paolo II, 84084 Fisciano (SA), Italy ‡ CIRCC Interuniversity Consortium of Chemical Catalysis and Reactivity, Via Celso Ulpiani 27, 70126 Bari, Italy § Dipartimento di Ingegneria Industriale, Universita ̀ degli Studi di Salerno, Via Giovanni Paolo II, 84084 Fisciano (SA), Italy ∥ Dipartimento di Chimica, Universita ̀ degli studi di Bari “Aldo Moro”, Via E. Orabona, 4, 70125 Bari, Italy * S Supporting Information ABSTRACT: Samples of styrene-co-(2-vinylfuran) polymers (S-co-2VFs) were obtained in a wide range of composition via ATRP catalyzed by Cu(I)-PMDETA using 1-phenylethyl bromide (1-PEBr) as initiator. Investigation of the copoly- merization kinetics allowed evaluating the reactivity ratios r s and r VF (r s =k S‑S /k S‑VF ;r VF =k VF‑VF /k VF‑S ; M S = styrene; M VF = 2VF) using the Fineman−Ross, Kelen−Tudos, extended Kelen−Tudos, and Meyer−Lowry methods; a quasi-ideal copolymerization behavior was found with reactivity ratios values r s and r VF of 1.21−1.30 and 0.98−1.10, respectively, and reactivity ratio products of ≈1.3−1.6. 1 H NMR investigation of the polymerization solution showed that the reaction of 2VF with the Cu(I)-PMDETA/1-PEBr catalyst causes a reduced efficiency in radical initiation reaction; broadening of the average molecular weight distribution was thus observed at short polymerization time. The T g values of the S-co-2VFs range from 105 °C of PS to 54 °C for the S-co-2VF with 2VF mole fraction x 2VF of 0.60 (S-co-2VF 60 ); the thermal decomposition of the copolymers starts at about 360 °C in air. The S-co-2VFs are stable in solution and solid state at room temperature, but gelation occurs at 100 °C in 10% w/w tetrachloroethane solution in air. Diels− Alder reaction of S-co-2VF with 1,1′-(methylenedi-4,1-phenylene)bismaleimide (BMI) readily yields a thermoreversible gel at room temperature. ■ INTRODUCTION A challenge for the future of polymeric materials is the possibility of creating macromolecules with well-defined architecture which are able to develop specific functions and are reusable, for the same or other use applications, using simple transformations not consuming excessive energy and chemicals. This interest significantly increases when the monomers arise from renewable resources, as in the case of bioderived plastics, thus producing a positive balance in the CO 2 management of the synthetic process. 1 Atactic polystyrene (PS) is one of the most important polymers produced after polyethylene, poly(vinyl chloride), and polypropylene. PS is a thermoplastic polymer with a T g of 105 °C; it softens when heated above this temperature and is commonly shaped under a wide variety of forms ranging from sheet, films, foams, to items by injection molding for everyday life applications. 2 Pure PS is brittle but can be softened when styrene is copolymerized with 1,3-butadiene to yield high impact polystyrene (HIPS). This styrenic copolymer exhibits improved flexibility, hygiene, and good visual appearance. 3 The discovery of metal-catalyzed syndiotactic specific styrene polymerization opened novel approaches to the synthesis of stereoregular styrenic-based copolymers with improved physical and mechanical properties. 4 We contributed to this field with styrene-conjugated diene copolymers which are examples of novel thermoplastic elastomers or HIPS, containing crystalline styrene polymer segments of both isotactic or syndiotactic type. 5−8 In this framework we were interested in developing novel styrenic copolymers for value added applications. The increased sensibility toward environmental concerns moved many major plastics manufacturers, as well as several smaller players, to invest heavily in researching and developing plastics derived from biological feedstock to avoid environment pollution and preserve fossil fuels feedstock. Bioderived plastics are currently priced above their petroleum-based counterparts, and thus value-added applications have to be designed to make them competitive vs fossil fuel-based polymeric materials. Furfural is a cheap biomass-derived platform molecule resulting from dehydration of the not edible fraction of vegetables. Polysaccharides can be converted into furan Received: July 11, 2014 Revised: October 3, 2014 Article pubs.acs.org/Macromolecules © XXXX American Chemical Society A dx.doi.org/10.1021/ma501431u | Macromolecules XXXX, XXX, XXX−XXX