Toughened aromatic poly-(decylene terephthalate) copolyesters with two renewable eugenol-based components via a random copolymerization method
writer：Keling Hu, Dongping Zhao, Guolin Wu* and Jianbiao Ma*
keywords：Renewable, Eugenol, Tougheness, Poly-(decylene terephthalate)
source：期刊
specific source：Polymer Chemistry
Issue time：2016年
Poly-(decylene terephthalate) PDT homopolyester and two series of thermoplastic PDT1-xM1x and PDT1-xM2x copolyesters with varying molar compositions (x = 0%, 20%, 40%, 60%, 80%, 100%) were prepared via random copolymerization of dimethyl terephthalate (DMT) and 1,10-decanediol, with renewable eugenol-based subunits providing toughener properties. These eugenol-based tougheners were synthesized via a thiol-ene click reaction and subsequent nucleophilic substitutions. The obtained copolyesters exhibit averaged molecular weights (Mws) ranging between 26800 and 55300 g mol-1, together with dispersity (D) values between 1.8 and 2.2. 1H NMR, 13C NMR and FTIR spectroscopic analyses were carried out as structural characterization techniques. The quantitative 13C NMR spectra of PDT1-xM1x indicate that the copolyesters feature random microstructures. The results from thermogravimetric analysis (TGA) show that thermal stabilities of both PDT1-xM1x and PDT1-xM2x species gradually decrease with increasing toughener contents. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were carried out in order to study the thermo-mechanical properties of the polyesters. The toughener content proves to have no significant influence on the glass transition temperatures (Tgs) of the copolyesters, despite the fact that an inconspicuous Tg value was observed for the PDT homopolyester. Furthermore, the gradually diminishing melting enthalpy (ΔHm) results from a decreasing crystallinity upon increase of the toughener unit content, suggesting that the incorporation of eugenol-based tougheners into PDT reduces the crystallinity in a significant manner. Isothermal crystallization and wide X-ray diffraction (WXRD) techniques provide evidence for this conclusion as well. The amount of eugenol-based units significantly influences the observed toughening effect. Strong tenacity of the brittle PDT was realized from the tensile and impact assays, with the content of the tougheners up to 20%. Specifically, the impact strength increases up to 16.4 and 15.8 kJ m-2 for PDT80%M120% and PDT80%M220%, respectively. Simultaneously, the ultimate strength decreases 2.6-4.3 MPa from 16.8 MPa to 12.5-14.2 MPa and elongation at break increases from approximately 5% to 18-20%. The findings described herein prove to be particularly important from a commercial point of view to meet the strict requirements for a variety of potential applications of such polyester species in structural materials.