Synthesis, Characterization, and Biodegradability of Novel Fully Biobased Poly(decamethylene-co-isosorbide 2,5-furandicarboxylate) Copolyesters with Enhanced Mechanical Properties

Abstract

This study spotlighted a successful synthesis of a novel series of biobased poly(decamethylene-co-isosorbide 2,5-furandicarboxylate)s (PDIsFs) copolyesters from dimethylfuran-2,5-dicarboxylate (DMFD), isosorbide (Is), and 1,10-decanediol (1,10-DD) by melt polycondensation, using titanium(IV) isopropoxide (TTIP). The chemical structure and composition of prepared polymers were confirmed in detail by 1 H NMR and FTIR spectroscopies. Satisfactory weight-average molecular weights (M w ) in the 55,300−84,500 g/mol range and random microstructures were obtained for PDIsFs. It was shown that Is unit incorporation into the copolyesters molecular chains was dramatically effective in increasing the glass transition temperatures (T g ) and in delaying the onset decomposition temperatures of PDIsFs. Hence, an excellent improvement of the thermal stability exceeding 405 °C for all copolymers was obtained. In addition, the degradation behavior in soil as well as the mechanical properties of PDIsFs were duly investigated in detail. The biodegradation rate of the copolyesters depended on the comonomer ratio. Rotational rheometry characterization of polymer melts revealed prevailing viscous properties for all formulations, whereas the presence of isosorbide favored a Newtonian behavior. Oxygen induction time (OIT) measurements by chemiluminescence (CL) demonstrated that isosorbide incorporation also dramatically increases polymer thermo-oxidative stability. Taking advantage of their features, PDIsFs have the potential to serve as promising and innovative biobased polymers for practical applications such as ecofriendly and sustainable plastic packaging.

Tuning the Properties of Furandicarboxylic Acid-Based Polyesters with Copolymerization: A Review

“…Generally, when copolymers are synthesized, the T g of the materials can be found at intermediate temperatures between the respective T g of the two homopolymers. Especially for amorphous random copolymers, a monotonic change in the T g that depends on the composition can be observed [ 50 , 52 , 100 ]. This phenomenon has been described by several mathematical models that take different parameters under consideration.…”

“…This phenomenon has been described by several mathematical models that take different parameters under consideration. Among the studies referenced in this review, the most employed model [ 28 , 45 , 50 , 65 , 68 , 70 , 73 , 77 , 78 , 79 , 84 , 97 , 99 , 100 ] is the Fox equation [ 109 ]. However, it does not always fit adequately the experimental values, since it is a rather simplified mathematical model that only considers the T g of the pristine materials and the composition of the copolymer.…”

“…On the other hand, when two diols are used to prepare copolymers from 2,5-FDCA, two main strategies can be singled out. The use of cyclic diols such as isosorbide [ 68 , 97 , 99 , 100 ], CHDM [ 59 , 65 ], and CBDO [ 34 ] leads to increased T g , since the chain mobility of the end products is severely hindered. At the same time, increasing the length of aliphatic diols used always leads to higher chain mobility and thus to lower T g values.…”

“…To induce crystallizability in PIsF-based copolymers, Chebbi et al inserted 1,10-decanediol in the polymerization mixture [ 100 ]. Low isosorbide contents seemed to enhance tensile properties, and the main factor that influenced them was concluded to be chain rigidity.…”

Synthesis of hydroxyl‐bearing polyurethanes from naturally occurring myo‐inositol

“…Such targets meet the current need to reduce the consumption of fossil fuel feedstocks, as well as the evolution of carbon dioxide, which is vital to making society more sustainable . Among the various high‐performance polymers synthesized from naturally occurring compounds so far, those synthesized from monosaccharide‐derived diols, such as isohexides and bis‐acetals of hexitols, which bear cyclic, and thus, rigid cores, have attracted much attention, because these diols are versatile substrates for polycondensation and polyaddition. Furthermore, the resulting polymers, such as polyesters and polyurethanes, exhibit high glass transition temperatures because of the incorporation of the rigid cores in the repeating units of the polymer.…”