Trans-2-Butene-1,4-Diol as an Olefinic Building Block to Prepare Biobased Unsaturated Copolyesters with High Molecular Weight: Synthesis, Characterization, and Physical Properties

Abstract

A series of biobased poly(butylene succinate-co-trans-butene succinate) (PBStBS) was prepared by copolymerizing biobased trans-2butene-1,4-diol(tB), succinic acid, and 1,4-butanediol via a two-step polycondensation. NMR and gel permeation chromatography characteristics indicated that the isomerization and branching side reactions were prevented in PBStBS synthesis. Random copolyesters with high number average molecular weights (M n ) over 40 kDa were achieved. Despite being random, these PBStBS can crystallize in the whole composition range, exhibiting a eutectic region on the copolyesters with around 70−76 mol % trans-butane succinate (tBS) content. In combination with WAXD analysis, PBStBS showed an unexpected isodimorphism, in which the crystallization rate of PtBS was very slow, but could also show typical isodimorphism with PBS after isothermal crystallization for a long time. The isodimorphism between PBS and PtBS was further investigated by thermodynamics. The tensile test result demonstrated that PBStBS copolyesters had excellent mechanical properties, considering their satisfactory thermal and crystal properties; thus, PBStBS was promising as linear biobased unsaturated polymers for a wide range of applications. This work suggested that tB is a suitable diol for the direct synthesis of linear unsaturated copolyesters, and the fully biobased PBStBS can potentially replace the common packaging materials of PBAT and PE from fossil resources.

Ring opening copolymerization of δ-valerolactone with 2-methyl-1,3-dioxane-4-one towards poly(3-hydroxypropionate-co-5-hydroxyvalerate) copolyesters

“…Thus, we tried to use theoretical models (ES12-ES17) for the random copolymers for the calculation of the crystal compatibility of HP and HV. 52,53 As shown in Fig. 9(C), the experimental T 0 m values highly match with the insertion-rejection theory (Wendling-Suter model).…”

Temperature-Dependent Polymorphic Crystallization and Crystalline Structure of Unsaturated Polyesters Derived from cis-2-Butene-1,4-diol

“…Thus, it is further demonstrated that no branching reaction occurred during polymerization. In addition, only the proton of cis double bond is detected, indicating no isomerization of the double bonds taking place during polycondensation. , Hence, 1 H NMR and GPC results confirm the successful synthesis of the desired linear unsaturated polyesters without the branching or the isomerization of double bonds.…”

“…In addition, only the proton of cis double bond is detected, indicating no isomerization of the double bonds taking place during polycondensation. 50,53 Hence, 1 H NMR and GPC results confirm the successful synthesis of the desired Cooling and Heating Thermograms. The nonisothermal crystallization and subsequent melting process of the prepared unsaturated polyesters were investigated via DSC, as shown in Figure 2.…”

Effects of Different Isomers of Thiophenedicarboxylic Acids on the Synthesis and Properties of Thiophene-Based Sustainable Polyesters

“…Although several attempts (like high-temperature crystallization, solution crystallization, and stretch-induced crystallization) have been made, no crystallization phenomenon of it could be observed. This stereo-isomer effect on the crystallization behavior is attributed to the main difference between 3,4-TFDCA and 2,5-TFDCA being the lower symmetry of the former, and the difference in polyester’s δ value also influences the crystallization ability to some degree. − Additionally, these polyesters both exhibited a one-step thermal decomposition process under a N 2 atmosphere (Figure d). The related results of TGA experiments indicated that the position (2,5/3,4) of the carboxylic acid groups hardly affected the thermal stability of TFDCA-based polyesters.…”