ATR Copolymerization of Styrene with 2-Vinylfuran: An Entry to Functional Styrenic Polymers

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 copolymerization kinetics allowed evaluating the reactivity ratios rs and rVF (rs = kS-S/kS-VF; rVF = kVF-VF/kVF-S; MS = styrene; MVF = 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 rs and rVF of 1.21–1.30 and 0.98–1.10, respectively, and reactivity ratio products of ≈1.3–1.6. 1H 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 Tg values of the S-co-2VFs range from 105 °C of PS to 54 °C for the S-co-2VF with 2VF mole fraction x2VF of 0.60 (S-co-2VF60); 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.